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2021
TESIS DOCTORAL
La conformidad del director/es de la tesis consta en el original en papel de esta Tesis Doctoral
2021
A mis padres, hermana y Jose
La realización de esta Tesis Doctoral ha sido posible gracias a la concesión de un
contrato predoctoral para formación de Doctores en los centros públicos de I+D
pertenecientes al Sistema Extremeño (Ref. PD16021), financiada por la Consejería de
Economía e Infraestucturas de la Junta de Extremadura y el Programa Operativo del
Fondo Social Europeo. Así como el apoyo económico prestado por el Ministerio de
Ciencia, Innovación y Universidades y la Agencia Estatal de Investigación, Junta de
Extremadura, co-financiados a su vez por los Fondos Europeos de Desarrollo Regional
(FEDER).
Agradecimientos
En el desarrollo de esta Tesis Doctoral son muchas las personas de las que he
recibido apoyo, por ello no puedo dar por finalizado este trabajo sin aprovechar estas
líneas para agradecérselo
¿Han llegado “los niños” del campo? Así llamaba Antonio a David y Damián. Con
ellos comencé en el laboratorio y me enseñaron junto con el Dr. Ángel Albarrán Liso, un
experto en HPLC, las labores en el campo de ensayo, gracias por todo y por evitarme los
temidos “barrenazos”. En estos cuatro años he visto como Damián culminaba sus
esfuerzos con el título de doctor, tienes que estar muy orgulloso. David eres un currante,
los años de esfuerzo y constancia en algún momento se verán compensados, estoy segura
que conseguirás todo lo que te propongas.
Más tarde llegaron mis “polluelos” Carmen, Jaime y Luis. Llegaron para volverme
loca en el laboratorio pero para darme el mayor apoyo, gracias por el buen ambiente de
trabajo, por las risas y confidencias. Espero teneros siempre como amigos. Con esfuerzo y
ganas también conseguiréis vuestra meta de llegar a ser doctores, como siempre os digo
“haceros caso de madre”.
Mi agradecimiento también a todo el personal del Área de Edafología y Química
Agrícola y de la Facultad de Ciencias. En especial a Pepa, gracias por tu cercanía y por
dejarme aprender a tu lado, ha sido un auténtico placer.
Fuera de la Universidad también hay vida, por ello quisiera agradecer todo el
apoyo que he tenido de mis amigas del pueblo; Loli, Mari, Marta, Isa, Fátima y Maite,
cada rato con vosotras era un chute de energía para continuar cada vez que volvía a
Badajoz. Mi Lola, ella ha sido conocedora de mis agobios, mis nervios y mi día a día de
estos cuatro años por eso no podía pasar sin darte las gracias por tu apoyo. A mi amiga
Ana María Chávez, hace mucho que terminamos la carrera pero gracias por permanecer
en mi vida y por estar siempre dispuesta ayudarme en todo, nos debemos muchos cafés.
“En la vida no existe nada que temer, solo cosas que comprender”
Marie Curie
Prólogo
ÍNDICE GENERAL
Abstract ............................................................................................................................... 1
Resumen .............................................................................................................................. 5
I.1.3. Pesticidas............................................................................................................... 27
I.1.3.2. Herbicidas....................................................................................................... 29
Bispyribac-sodio ..................................................................................................... 33
Clomazona .............................................................................................................. 34
MCPA ..................................................................................................................... 35
Volatilización................................................................................................... 55
Capítulo IV. How the environmental fate of clomazone in rice fields is influenced by
amendment with olive-mill waste under different regimes of irrigation and tillage ....... 129
Capítulos I y II
Capítulo III
Table S1. Selected properties of original soil (0-20 cm depth) and compost. ................ 126
Capítulo IV
Table 1. Effect of different treatments on the soil’s physicochemical properties. .......... 136
Table 2. Effect of different treatments on Clomazone sorption–desorption parameters. 139
Table 3. Effect of different treatments on dehydrogenase activity and clomazone
dissipation parameters. ..................................................................................................... 143
Table 4. Effect of different treatments on clomazone leaching parameters. ................... 147
Capítulo V
Capítulos I y II
Figura 1.1 Labor de “fangueo” en una parcela dedicada al cultivo de arroz. ................... 13
Figura 1.2 Empleo de agricultura de conservación en el cultivo de arroz. ....................... 17
Figura 1.3 Proceso de elaboración del aceite de oliva según los distintos sistemas. ........ 24
Figura 1.4 Porcentaje global de ventas de pesticidas a nivel mundial en el año 2018. .... 28
Figura 1.5 Evolución de la cantidad de herbicidas empleados en España a lo largo de los
últimos años. ...................................................................................................................... 30
Figura 1.6 Factores y procesos que afectan a la dinámica de los plaguicidas en el suelo 38
Figura 2.1 Localización del ensayo de campo en las Vegas Bajas del Guadiana............. 73
Figura 2.2 Diseño y distribución de los diferentes tratamientos en el ensayo de campo..75
Figura 2.3 Aplicación del compost de alperujo en las subparcelas del ensayo de campo 79
Figura 2.4 Fórmula semi-desarrollada del herbicida bispyriac-sodio............................... 85
Figura 2.5 Fórmula semi-desarrollada del herbicida clomazona. ..................................... 86
Figura 2.6 Fórmula semi-desarrollada del herbicida MCPA. ........................................... 86
Figura 2.7 Disposición de muestras al 80 % de la capacidad de campo y condición de
inundación para el estudio de disipación y actividad microbiana en la cámara de
incubación. ......................................................................................................................... 90
Figura 2.8 Diseño esquemático del montaje de columnas alterada, empleadas en el
estudio de lixiviación. ........................................................................................................ 93
Capítulo III
Figure S1. The symbols indicate the experimental data points of clomazone dissipation
studies whereas the lines correspond to the fits to first-order dissipation kinetics for those
experimental data.. ........................................................................................................... 157
Figure S2. Effects of treatments on the clomazone sorption and desorption isotherms..158
Capítulo V
Figure 1. Effect of different crop management regimens on the MCPA sorption and
desorption isotherms. Solid and dashed lines connect sorption and desorption points,
respectively ...................................................................................................................... 170
Figure 2. Effect of different crop management regimens on the MCPA dissipation and
dehydrogenase activity under aerobic and anaerobic incubation conditions. .................. 174
Figure 3. Effect of different crop management regimens on the relative (above) and
cumulative (below) breackthrough curves of MCPA.. .................................................... 179
ABREVIATURAS
AD Actividad deshidrogenasa
AF Ácidos fúlvicos
AH Ácidos húmicos
CA Compost de alperujo
CE Conductividad eléctrica
Ce Concentración de equilibrio
Ci Concentración inicial
D Porcentaje de desorción
GP Grado de polimerización
H Histéresis
IH Índice de humificación
IG Índice de germinación
INT 2-p-iodofenil-3-p-nitrofenil-5-feniltetrazolio
Kd Coeficiente de distribución
Kf Coeficiente de adsorción
LC Laboreo convencional
nf Intensidad de adsorción
NT Nitrógeno total
SD Siembra directa
Abstract
Rice (Oryza sativa L.) is the staple food of more than 50% of the world's
population. However, its production is carried out in a traditional way under conditions of
intensive labour and flooding, a situation that has associated with it a number of
environmental risks such as soil degradation, pesticide contamination of soil and water,
greenhouse gas emissions, and high water consumption, calling into question the
sustainability of the crop, especially in countries such as Spain. Our country is the second
producer in Europe after Italy, and the availability of water resources is a growing issue.
It is therefore necessary to develop alternative methods to mitigate the problems
associated with rice cultivation. For instance, rice production under aerobic conditions
together with the application of organic amendments and conservation agricultural
techniques such as direct seeding could reduce the environmental risks associated with
traditional methods. Organic amendments could not only improve soil quality, but also
could balance the water deficit under aerobic conditions since it increases the soil's water
retention capacity and consequently the productivity. But adoption of these alternative
methods could lead to the proliferation of weeds, making greater use of herbicides
essential.
The overall objective of the present work was to evaluate the effects produced by
the implementation of different irrigation systems (spraying and flooding) in combination
with different tillage methods (direct seeding and conventional tillage) and application of
organic amendment (composted olive mill waste, i.e., alperujo compost) on the dynamics
of herbicides used in rice cultivation, such as bispyribac-sodium (BYS), clomazone
(CLO), and MCPA. In order to analyse the direct and residual effect of the application of
alperujo compost, it was applied in only the first year of study, at a dosage of 80 Mg ha-1.
A field study was carried out during 2015, 2016, and 2017 in a rice growing area
of Las Vegas del Guadiana (Extremadura). Six treatments were established: SD (direct
seeding and spray irrigation); SDC (direct seeding and spray irrigation with application of
compost); LC (conventional tillage and spray irrigation); LCC (conventional tillage and
spray irrigation with application of compost); LCI (conventional tillage and flood
irrigation); LCIC (conventional tillage and flood irrigation with application of compost).
~1~
Abstract
Adsorption-desorption studies were carried out using batch experiments. The half-lives
(t1/2) of the different herbicides were determined from dissipation studies under aerobic
and anaerobic conditions, with the dehydrogenase enzymatic activity (DA) also being
monitored. Finally, leaching studies were performed with disturbed-soil columns (hand-
filled with homogenized soil).
The adsorption studies showed the low adsorbability of BYS and MCPA
compared with CLO. The application of compost significantly increased the adsorption of
CLO, regardless of the management system, but this was not the case for BYS or MCPA.
Unlike CLO, whose adsorbability was strongly correlated with total organic carbon
(TOC), BYS and MCPA adsorption depended on soil pH. The desorption results in
general showed that the spray-irrigation soils can retain the herbicides more strongly,
regardless of the herbicide and the tillage system implemented, especially when alperujo
compost was applied as organic amendment, reflecting the importance of humic acids
(HA) in desorption processes.
The shortest half-life corresponded to the MCPA herbicide (t1/2 = 1.38 – 9.42
days), and the longest to BYS (t1/2 = 27.4 – 86.5 days). With respect to the original soils,
for BYS, the greatest persistence corresponded to the SD soil, coinciding with the highest
pH and thus suggesting that chemical hydrolysis could be the main process in BYS
degradation. For CLO and MCPA, regardless of the management system, the fastest
dissipation corresponded to anaerobic conditions, coinciding with the highest DA values
recorded. This is probably due to the adaptation of the microbial communities to flooded
conditions, since this irrigation system had been used for more than ten years in the study
field. The application of compost affected the dissipation of herbicides in all management
systems, although differently depending on the incubation conditions the selected active
matter, and the year of study. In the particular case of BYS, the application of compost
increased persistence under aerobic conditions regardless of the management system,
indicating that microorganisms could be using organic matter from the amendment as a
source of carbon instead of the herbicide. Under anaerobic incubation conditions,
however, the results were different. While in the direct year there was a decrease in the
values of t1/2, in the residual year these values increased, probably due to the lack of
adaptation of microbial communities to anoxic conditions after three years of non-
flooding management. In the same way, this lack of adaptation could explain the CLO t1/2
~2~
Abstract
values observed in the residual year, with increased persistence for spray-irrigated
management systems but decreased persistence for the flooded system, especially under
anaerobic incubation conditions. Nevertheless, the application of the alperujo compost
increased the dissipation of MCPA under both incubation conditions independently of the
management system or year of study, suggesting that the dissipation of this compound is
mainly due to biological processes.
With regard to the results obtained in the leaching studies, these were conditioned
by the different solubilities of the herbicides, as well as by the adsorption-desorption and
dissipation processes. In the particular case of BYS, this showed high mobility in all
management systems, from 55.3% to 40.2% for original soils and from 50.6% to 32.3%
for amended soils, confirming the high risk of groundwater contamination by BYS due to
its low adsorbability, long persistence, and high solubility in water. Of the three
herbicides CLO had the lowest leaching values, not surpassing in any management
system the value of 30% of total leached herbicide, and being the herbicide with the
lowest solubility in water. The application of the alperujo compost, regardless of the
management system and the year of study, led to a significant decrease in CLO leaching,
reflecting increased adsorption of this active compound following the implementation of
the amendment. The results were similar for MCPA, with significant decreases in the
total percentage of leached herbicide following the application of alperujo compost in
those treatments irrigated by spraying, regardless of the type of tillage used and the year
of study, showing the importance of wetted organic matter in the mobility of this active
compound.
~3~
Resumen
Resumen
El objetivo general de este trabajo fue evaluar los efectos producidos por la
implantación de diferentes sistemas de riego (aspersión e inundación), en combinación
con diferentes técnicas de laboreo (siembra directa y laboreo convencional) y aplicación
de enmienda orgánica (compost de alperujo), en la dinámica de herbicidas ampliamente
utilizados en el cultivo del arroz: bispyribac-sodio (BYS), clomazona (CLO) y MCPA.
Para analizar el efecto directo y residual de la aplicación del compost de alperujo, este fue
aplicado solamente el primer año de estudio a una dosis de 80 Mg ha−1. Para ello, se
realizó un estudio de campo durante los años 2015, 2016 y 2017 en una zona arrocera de
las Vegas del Guadiana (Extremadura), donde se establecieron seis tratamientos: SD
(siembra directa y riego por aspersión); SDC (siembra directa y riego por aspersión con
aplicación de compost); LC (laboreo convencional y riego por aspersión); LCC (laboreo
convencional y riego por aspersión con aplicación de compost); LCI (laboreo
~5~
Resumen
Al comparar los valores de t1/2 obtenidos para los diferentes herbicidas pudo
observarse que los valores más bajos se registraron en el herbicida MCPA (t1/2 = 1.38 –
9.42 días), mientras que los más elevados se presentaron en BYS (t1/2 = 27.4 – 86.5 días).
Con respecto a los suelos originales, en el caso particular del herbicida BYS la mayor
persistencia se observó en el tratamiento SD coincidiendo con el mayor valor de pH,
pudiendo sugerir que la hidrólisis química podría ser el proceso principal de degradación
de BYS. En el caso particular de CLO, independientemente del sistema de manejo, la
mayor tasa de disipación fue observada bajo condiciones de anaerobiosis. Este hecho
coincidió con un mayor incremento de la actividad microbiana bajo estas condiciones,
corroborado por los mayores valores de AD registrados. Similarmente, la disipación de
MCPA fue más rápida bajo condiciones anaeróbicas debido, probablemente, a la posible
adaptación de las comunidades microbianas a las condiciones de inundación, sistema de
riego empleado durante más de diez años de antigüedad en la parcela de estudio. La
~6~
Resumen
~8~
Capítulo I.1. INTRODUCCIÓN
Capítulo I.1. Introducción
La producción media de arroz en España está próxima a las 800 000 toneladas de
arroz cáscara, de las cuales alrededor del 80 % se producen en las comunidades
autónomas de Andalucía, Cataluña y Extremadura (Tabla 1.1). Concretamente, en el caso
particular de Extremadura, se cosecha de forma anual sobre 19 000 ha con una
producción que ronda los 150 000 toneladas de arroz cáscara, y un rendimiento medio,
por tanto, de 7 800 kg ha-1. Solamente en la región extremeña, este cultivo genera una
mano de obra de aproximadamente 235 000 peonadas al año, y una facturación bruta
anual superior a 44 millones de euros, sin contabilizar la facturación de empresas de
fitosanitarios y de servicios, poniendo de manifiesto el gran interés económico y social
que representa este cultivo en el contexto regional.
~ 11 ~
Capítulo I.1. Introducción
~ 12 ~
Capítulo I.1. Introducción
que analizaron el efecto del cambio climático sobre las producciones de arroz,
concluyeron que los países mediterráneos son una zona de fuerte riesgo debido al
fenómeno de la sequía, situación que podría ocasionar importantes descensos en el
rendimiento agronómico del cultivo. Por este motivo, sistemas de riego alternativos a la
inundación son necesarios para reducir el consumo de agua en la producción de arroz
(Okami et al., 2014; Singh et al., 2018a; Devkota et al., 2020), sobre todo si se tiene en
cuenta que existen estudios que cifran que la cantidad de agua improductiva empleada en
condiciones de inundación ronda el 70 % (IRRI, 2007, Sánchez-Llerena et al., 2016;
Chenz et al., 2021).
~ 13 ~
Capítulo I.1. Introducción
~ 14 ~
Capítulo I.1. Introducción
~ 16 ~
Capítulo I.1. Introducción
~ 17 ~
Capítulo I.1. Introducción
Con respecto al caso concreto del cultivo de arroz, investigaciones previas han
mostrado que, en comparación con los sistemas de laboreo convencional, mientras la
implantación de laboreo reducido no afectó el rendimiento agronómico del mismo
(Rognoni, et al., 2014), la utilización de sistemas de no laboreo provocó una disminución
del rendimiento entre el 10 y el 20 % (Moretti, et al., 2019). Sin embargo, en un estudio
realizado por Naresh et al. (2014), en la India, se observó que los rendimientos
agronómicos del arroz mediante técnicas de no laboreo y siembra en seco fueron similares
a los obtenidos con técnicas convencionales (laboreo e inundación), pero con un
incremento significativo en la productividad del agua. Del mismo modo, Tao et al. (2006)
también observaron que la utilización de cobertura vegetal permitía un importante ahorro
de agua, aunque también observaron una reducción de la producción con respecto al
sistema tradicional. Das et al. (2020) observaron que el uso de técnicas de agricultura de
conservación en el cultivo del arroz mejoró la productividad, rentabilidad y eficiencia en
el uso de los recursos, especialmente cuando se realizan rotaciones con otros cultivos.
esta técnica es de buena calidad siempre que las prácticas de manejo, como la gestión del
agua, malezas, y nutrición, se ejecuten correctamente.
Por tanto, para la implementación con éxito del arroz aeróbico, es necesario
desarrollar estrategias adecuadas y efectivas para el control de malezas que sean, además
viables económicamente. En este sentido, la eliminación manual de malas hierbas implica
enormes costos, por tanto, el uso de herbicidas además de estar permitido es
recomendado. El control de malezas mediante la aplicación de herbicidas preemergentes a
menudo no tiene éxito en el arroz aeróbico debido a la aparición de brotes tardíos de
malezas, pues la ventana de tiempo para la aplicación es muy estrecha y, a menudo, no se
realiza en su punto óptimo (Mahajan y Chauhan, 2015). Mahajan y Chauhan (2013)
revelaron que las aplicaciones secuenciales de herbicidas, antes y después de la
emergencia, proporcionaron un mejor control de los brotes tempranos y tardíos de
malezas, que la aplicación única en arroz cultivado bajo el sistema de siembra directa. Sin
embargo, existe la necesidad de reducir la carga de herbicidas en el medio ambiente
debido a que el uso excesivo de éstos puede tener efectos negativos sobre la salud
humana y el medio ambiente (Huang et al., 2016; Malyan et al., 2019). Además, las malas
~ 19 ~
Capítulo I.1. Introducción
hierbas pueden generan mecanismos de resistencia a los herbicidas cuando estos no son
aplicados en su dosis requerida (Munda et al., 2017; Li et al., 2020).
La movilidad de los herbicidas desde la superficie del suelo hasta capas más
profundas reduce su efectividad y, además, incrementan el riesgo de contaminación de
aguas subterráneas por plaguicidas, como se ha puesto de manifiesto en sistemas
agrícolas de distintos países (Herrero-Hernández et al., 2017; Gosetti et al., 2019). Los
cambios en el riego y las prácticas agrícolas, como el empleo de la agricultura de
conservación, pueden inducir cambios en las propiedades del suelo, y estos a su vez
también pueden modificar el comportamiento ambiental de los pesticidas aplicados
(López-Piñeiro et al., 2016; 2019).
Por tanto, el arroz aeróbico puede ser una alternativa interesante al sistema
convencional, pues puede disminuir, significativamente, el consumo de agua en relación
con los sistemas convencionales al reducir la percolación, filtración y pérdidas por
evaporación incrementando, así, la productividad del agua empleada (Liu et al., 2015;
Dari et al., 2017). Sin embargo, los resultados sobre el rendimiento agronómico, como ya
se ha comentado anteriormente, son frecuentemente contradictorios, por lo que se necesita
un mayor conocimiento para implementar correctamente estas técnicas (Nie et al., 2012).
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Capítulo I.1. Introducción
avanzar hacia una economía circular, en la que se reincorporen al proceso productivo una
y otra vez los materiales que contienen los residuos para la producción de nuevos
productos o materias primas. Se establece que la prevención debe ser la prioridad
principal en relación con la política de residuos, seguida por este orden: reutilización,
reciclado, otras formas de valorización, incluida la valorización energética, siendo la
eliminación de residuos, fundamentalmente a través del depósito en vertedero, la última
opción de la jerarquía para gestionar estos materiales. Entre los planes de gestión de los
residuos orgánicos se contempla la valorización de estos residuos, mediante su aplicación
como enmienda orgánica, directamente en los suelos o mediante un proceso de
compostaje.
La materia orgánica es un factor clave en la fertilidad del suelo; actúa sobre las
propiedades físicas (porosidad, capacidad de retención hídrica, estabilidad de agregados,
etc.), y sobre las químicas, aportando nutrientes mediante los procesos de mineralización,
y a través de su capacidad de intercambio iónico actúa como una reserva nutricional.
También influye sobre las propiedades biológicas, manteniendo la actividad microbiana
del suelo (López-Piñeiro et al., 2011a; Bastida et al., 2015; Peña et al., 2019). Por ello, la
utilización de residuos orgánicos como enmiendas en agricultura es una práctica común
desde la antigüedad (Aranda et al., 2015) y ha atraído un interés considerable en los
últimos años (Scotti et al., 2015; Han et al., 2020).
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Capítulo I.1. Introducción
Aceitunas
Molienda y batido
Aceite de oliva
Aceite de oliva
Aceite de oliva
Figura 1.3 Proceso de elaboración del aceite de oliva según los distintos sistemas. Fuente:
Alburquerque et al., 2004; Cegarra y Paredes, 2008.
~ 24 ~
Capítulo I.1. Introducción
La industria oleícola, al menos en España, ha optado de manera casi generalizada por los
sistemas de extracción de dos fases, en busca de una simultánea reducción de costes y
mejora de la calidad (Rincón et al., 2016). Entre las ventajas de este nuevo sistema de
extracción, cabe señalar que permite obtener un aceite cualitativamente superior debido a
su mayor contenido en agentes antioxidantes, lo que le otorga una mayor estabilidad
frente a los fenómenos oxidativos (Ranalli y Martinelli, 1995), consigue un caudal de
trabajo similar o superior al de tres fases y una importante reducción del consumo de agua
(65 -70 %), con el consiguiente ahorro en energía de calefacción (Roig et al., 2006). Sin
embargo, la ventaja más importante de este sistema es que no genera alpechín,
reduciéndose el efluente acuoso producido, básicamente, al agua de lavado de los aceites
y, en menor cuantía, al agua de lavado de las aceitunas y limpieza general de la
maquinaria, originando como subproducto únicamente el orujo de dos fases, también
llamado alperujo o bien orujo húmedo, en una proporción estimada de unos
800 a 950 kg por tonelada de aceituna procesada (Serrano et al., 2017). Como principales
inconvenientes del sistema de dos fases cabe citar el aumento considerable del volumen
de alperujo producido, debido a la incorporación de la fracción acuosa, así como el difícil
manejo y aprovechamiento del mismo.
tanto en COT como en COH aplicando alperujo fresco en diferentes tipos de suelos y a
diferentes dosis, aunque observaron que la germinación L. perenne fue menor tras la
aplicación de alperujo fresco en comparación con el alperujo compostado, situación que
fue atribuída al mayor contenido en polifenoles en la enmienda fresca que en la
compostada. De hecho, varios experimentos realizados con subproductos y desechos de
almazara han relacionado su fitotoxicidad con la concentración de fenoles (Alburquerque
et al., 2006; Pinho et al., 2017; Enaime et al., 2019). En general, y según Canet et al.
(2008), debido a sus propiedades químicas, no es recomendable la aplicación directa al
suelo del alperujo, menos aún en cultivos herbáceos. Por tanto, para evitar posibles
efectos fitotóxicos ocasionados por este residuo orgánico, la valorización del alperujo,
mediante el proceso de compostaje, ha sido ampliamente propuesto (Alfano et al., 2011;
Proietti et al., 2015; Tortosa et al., 2020).
I.1.3. Pesticidas
Los pesticidas deben cumplir una serie de requisitos para poder alcanzar un uso
amplio en la agricultura: ser efectivos contra la plaga sobre la que actúan, no tener efectos
~ 27 ~
Capítulo I.1. Introducción
negativos sobre otros organismos de la flora o fauna del terreno, su uso debe producir
beneficios económicos que superen el gasto que conllevan, no deben ser tóxicos para la
salud del hombre ni animales, etc. (Early, 2018). Además, la tendencia actual está dirigida
a disminuir las dosis de pesticidas necesarias mediante el desarrollo de formulaciones de
compuestos más eficaces que actúan de manera más específica.
1.7 %
11.6 % 2%
32.3 % África
América
52.4 % Asia
Europa
Oceanía
Figura 1.4 Porcentaje global de ventas de pesticidas a nivel mundial en el año 2018
(FAO, 2018).
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Capítulo I.1. Introducción
I.1.3.2. Herbicidas
~ 29 ~
Capítulo I.1. Introducción
20000
16000
12000
Toneladas
8000
4000
0
2007 2008 2009 2010 2011 2012 2013 2014 2015 2016 2017 2018
Años
Los herbicidas pueden ser clasificados de acuerdo a varios criterios, siendo los
más comúnmente usados: época de aplicación, selectividad, tipo de movilidad en la
planta, familia química y modo y mecanismo de acción (Tabla 1.2).
.
~ 30 ~
Capítulo I.1. Introducción
La clasificación más útil de los herbicidas es por su modo de acción (Senero, 2011;
HRAC, 2020). El modo de acción es la secuencia que culmina provocando algún daño en
la planta, que eventualmente (pero no necesariamente) puede ser la muerte de la misma.
Este modo de acción depende de la inmovilización del principio activo en las distintas
estructuras celulares, metabolización, etc. Los herbicidas con el mismo modo de acción
tienen el mismo comportamiento de absorción y transporte, y producen síntomas
similares en las plantas tratadas (Gunsolus y Curran, 1996). Además, la clasificación de
los herbicidas según su modo de acción permite predecir, de forma general, su espectro de
control de maleza, época de aplicación, selectividad a cultivos y persistencia en el suelo.
Ashton y Craft (1981) y Cobb y Reade (2010), distinguen siete grandes grupos, dentro de
los cuales a su vez se incluyen uno o más mecanismos de acción. Este tipo de
clasificación permite un control químico más eficiente, así como mitigar, en parte, los
efectos negativos que estas sustancias pueden tener sobre el medio ambiente (Regehr y
Morishita, 1989).
~ 31 ~
Capítulo I.1. Introducción
Tabla 1.3 Clasificación de los herbicidas por el modo de acción (HRAC, 2020).
~ 32 ~
Capítulo I.1. Introducción
Bispyribac-sodio
~ 33 ~
Capítulo I.1. Introducción
Clomazona
Entre las especies que CLO controla destacan: Digitaria sanguinalis (pata de
gallina), Echinochloa crus-galli (arroz silvestre), Eleusine indica (pata de gallo), Setaria
sp. (cola de zorra) entre las malas hierbas gramíneas y, entre las malas hierbas
dicotiledóneas: Abutilon theophrasti (abutión), Amaranthus hybridus (quelite), Bidens
pilosa (mozote), Chenopodium álbum (cenizo blanco), Datura stramonium (estramonio),
Galinsoga parviflora (jarilla), Galium aparine (lapa), Polygonum sp. (albohol), Portulaca
oleracea (verdolaga), Sida spinosa (malva de escoba), Solanum nigrum (hierba mora),
etc.
~ 34 ~
Capítulo I.1. Introducción
MCPA
~ 35 ~
Capítulo I.1. Introducción
0.5 μg L-1. El Reglamento (CE) número 1107/2009 del parlamento europeo, por el que se
deroga la directiva 91/414/CEE, establece las normas aplicables a la autorización de
productos fitosanitarios en su presentación comercial, y a su comercialización, utilización
y control en la Unión Europea. La finalidad de este reglamento es garantizar la protección
de la salud humana y animal, así como el medio ambiente, además de mejorar la
producción agrícola. En la actualidad, sin embargo, se ha observado la presencia de
residuos de herbicidas en suelos y aguas en diferentes países del mundo en niveles más
altos de los permitidos (López et al., 2015; Zheng et al., 2016; Herrero-Hernández et al.,
2017; Khan et al., 2020). Por ello, es importante conocer el destino ambiental y dinámica
de los herbicidas empleados en suelos, e intentar buscar posibles alternativas para
minimizar o evitar la contaminación de aguas y suelos por su uso.
~ 37 ~
Capítulo I.1. Introducción
~ 38 ~
Capítulo I.1. Introducción
I.1.3.3.1.1. Adsorción-Desorción
~ 39 ~
Capítulo I.1. Introducción
La adsorción está controlada, por un lado, por la incompatibilidad del soluto con
la fase fluida, y por otro, por un conjunto de interacciones con la fase sólida. Las fuerzas
atractivas entre las moléculas de soluto y las moléculas de la fase sólida o adsorbente
pueden ser de distinto tipo, pero todas ellas tienen su origen en la interacción entre los
núcleos y los electrones. Dependiendo del tipo de fuerza atractiva predominante,
podemos distinguir entre interacciones físicas o químicas. En la mayoría de los casos, en
la mayor parte de los plaguicidas suelen influir varios tipos de interacciones (Bi et al.,
2006), teniendo lugar cambios de entropía y entalpía en el sistema que favorecen la unión
entre adsorbato y adsorbente (Niederer et al. 2006). Los tipos de interacción adsorbato-
adsorbente más importantes son:
• Fuerzas de Van der Walls: atracciones débiles, de pequeño alcance, entre dipolo-
dipolo o dipolo-dipolo inducido. Las interacciones entre plaguicidas no polares y
no iónicos y moléculas de ácidos húmicos (AH) son de particular relevancia. Son
relativamente débiles y disminuyen de intensidad rápidamente a medida que
aumenta la distancia.
~ 40 ~
Capítulo I.1. Introducción
El estudio del proceso de adsorción permite conocer los mecanismos que regulan
dicho proceso y la posibilidad de comparar, tanto entre adsorbatos diferentes (herbicidas)
como entre adsorbentes diferentes (suelos) y en diversas condiciones (das Chagas et al.,
2019). Los procesos de adsorción y desorción son dinámicos e intrínsecamente
relacionados, teniendo lugar de manera continuada a lo largo del tiempo, donde las
moléculas orgánicas se adsorben y desorben, alcanzando un estado final denominado
equilibrio dinámico de la adsorción.
~ 41 ~
Capítulo I.1. Introducción
𝑪𝑪𝒆𝒆 ⇌ 𝑪𝑪𝒔𝒔
(𝐶𝐶𝑖𝑖 − 𝐶𝐶𝑒𝑒 ) ∙ 𝑉𝑉
𝐶𝐶𝑠𝑠 =
𝑚𝑚
𝐶𝐶𝑠𝑠
𝐾𝐾𝑑𝑑 =
𝐶𝐶𝑒𝑒
Isotermas de adsorción-desorción
~ 42 ~
Capítulo I.1. Introducción
Modelos de adsorción
Freundlich
𝑛𝑛
𝐶𝐶𝑠𝑠 = 𝐾𝐾𝑓𝑓 ∙ 𝐶𝐶𝑒𝑒 𝑓𝑓
~ 43 ~
Capítulo I.1. Introducción
~ 44 ~
Capítulo I.1. Introducción
𝐾𝐾𝑑𝑑
𝐾𝐾𝑐𝑐𝑐𝑐 =
𝐶𝐶𝐶𝐶 (%)
𝑛𝑛𝑓𝑓 𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎ó𝑛𝑛
𝐻𝐻 =
𝑛𝑛𝑓𝑓 𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑
~ 45 ~
Capítulo I.1. Introducción
atraídos rápidamente por componentes cargados negativamente del adsorbente, como son
minerales de la arcilla y sustancias húmicas. Por el contrario, plaguicidas cargados
negativamente en disolución o aniónicos son repelidos por dichos componentes, pero a su
vez atraídos por otro tipo de componente como los óxidos de hierro. Si la distribución de
carga no es muy pronunciada, se produce una pequeña polaridad; si por el contrario la
carga es fuerte la molécula puede llegar a disociarse y, por tanto, la adsorción dependerá
en mayor medida del pH (Spadotto et al., 2020). En el caso de herbicidas no cargados,
pero con una cierta polaridad en su estructura, estos pueden interaccionar con la
superficie del adsorbente mediantes enlaces de Van der Waals, enlaces de hidrógeno, etc.
Por otro lado, en las moléculas con un carácter apolar marcado, las interacciones
hidrofóbicas jugarán un papel fundamental.
La fracción coloidal inorgánica del suelo está constituida por los minerales
cristalinos y los óxidos e hidróxidos cristalizados y amorfos del suelo cuyo tamaño de
~ 46 ~
Capítulo I.1. Introducción
partícula es inferior a 2 μM. La carga eléctrica superficial de los coloides inorgánicos les
permite unirse a compuestos con cargas de signo opuesto, lo que le confiere una gran
importancia en los procesos de adsorción que ocurren en el suelo. Los componentes
cristalinos de esta fracción son los filosilicatos (caolinita, haloisita, montmorillonita,
vermiculita, etc.), silicatos fibrosos (sepiolita y paligorskita), minerales no laminares
(feldespatos, óxidos de hierro y carbonatos) y los compuestos amorfos que son alófanas y
óxidos amorfos. En los procesos de adsorción son los filosilicatos los que presentan
mayor interés (Bordón et al., 2017), por ello nos centraremos en estos minerales, los
cuales están constituidos por láminas formadas a su vez por capas o estratos de dos tipos:
Tetraédrica: formadas por tetraedros de sílice unidos por las bases. Estos
tetraedros poseen un átomo de Si en el centro y átomos de oxígeno o hidroxilo en los
vértices. Se disponen en un enrejado hexagonal con las bases en un mismo plano y los
vértices señalando todos en un mismo sentido.
Ambas capas cuando van unidas, para formar la lámina, lo hacen compartiendo
oxígenos y/o hidroxilo en los vértices. Según el número de capas que forman su lámina
característica, los filosilicatos se clasifican en filosilicatos 1/1 (capa tetraédrica y capa
octaédrica) y filosilicatos 2/1 (dos capas tetraédricas y una octaédrica). En algunos
filosilicatos del tipo 2/1, las sustituciones isomórficas de Si4+ por Al3+ en la capa
tetraédrica y de Al3+ por Mg2+ en la octaédrica originan la aparición de un exceso de carga
negativa en las láminas que se compensa con la entrada de cationes externos (Ca2+, Na+,
Mg2+) que actúan de puente entre las láminas. La cantidad de cationes que es necesario
intercalar en dicho espacio determina la capacidad de intercambio catiónico (CIC), y es
característica de cada filosilicato. Esta propiedad es fundamental en la adsorción de
compuestos orgánicos catiónicos (Calvet, 1989).
Por otra parte, y dentro de la fracción coloidal mineral, se debe considerar a los
óxidos metálicos, que tienen también propiedades importantes en cuanto a la adsorción de
compuestos orgánicos, y al igual que los filosilicatos, presentan una alta superficie
específica y reactividad. La forma cargada de estos compuestos depende, en gran medida,
~ 47 ~
Capítulo I.1. Introducción
Estructuralmente, los ácidos húmicos y los ácidos fúlvicos son muy similares,
diferenciándose sólo en el peso molecular y en el contenido en grupos funcionales. La
carga de las sustancias húmicas es variable dependiendo del pH. Normalmente las
sustancias húmicas tienen carga negativa debido a la disociación de los grupos
funcionales de carácter ácido como los grupos carboxílicos y fenólicos, lo que les
confiere una elevada capacidad de intercambio catiónico (CIC). Sin embargo, en suelos
muy ácidos pueden tener carga positiva, adsorbiendo en ese caso sustancias de carácter
aniónico.
~ 49 ~
Capítulo I.1. Introducción
En caso de plaguicidas ácidos, que son aquellos que en disolución acuosa dan
reacción ácida, si el pH del suelo es ácido, la mayor parte de la molécula se encuentra sin
disociar, y si el pH se eleva por encima del pKa, aumenta la disociación, por lo que la
adsorción del plaguicida disminuye (García-Jaramillo et al., 2020). Estudios realizados
por Barriuso et al. (1994) determinaron que la adsorción presenta un máximo para valores
de pH próximos al pKa del plaguicida, aunque este máximo también puede depender de
otras propiedades. Los cambios de pH que con el tiempo sufre el suelo debido a diferentes
prácticas (fertilización, irrigación, enmiendas orgánicas, etc.) pueden afectar al
comportamiento de los herbicidas en el suelo (Peña et al., 2019).
d) Otros factores
Humedad: el contenido de agua o humedad del suelo tiene una gran importancia
en el proceso de adsorción dado que su variación afectará a la relación sólido/disolución
del suelo y, por tanto, a la magnitud de la adsorción (Grover y Hance, 1970). Una
disminución en el contenido de agua generalmente aumenta la adsorción del compuesto
orgánico, sobre todo en sistemas donde las moléculas de agua compitan por los sitios de
adsorción (menor competencia y mayor número de sitios libres de adsorción). Además, la
~ 50 ~
Capítulo I.1. Introducción
mayor concentración de soluto hace más probable las colisiones entre adsorbato-
adsorbente necesarias para que se dé el proceso de adsorción. Sin embargo, al disminuir
el contenido de agua, también se afecta a la cantidad de compuesto orgánico disponible
para la adsorción, ya que su precipitación o cristalización se verá favorecida, afectando
así a la magnitud de adsorción del mismo.
I.1.3.3.1.2. Lixiviación
Este proceso está producido por el agua procedente de las precipitaciones o del
riego de los cultivos que arrastra o disuelve el herbicida produciéndose, así, un
movimiento vertical a lo largo del perfil del suelo. La lixiviación tiene implicaciones
tanto en la efectividad del herbicida como en la contaminación de aguas subterráneas por
estos productos (Li et al., 2014; Herrero-Hernández et al., 2017).
~ 51 ~
Capítulo I.1. Introducción
contaminación de las aguas subterráneas (Albarrán et al., 2003; Cabrera et al., 2009;
Fenoll et al., 2015; García-Delgado et al., 2020).
La adsorción del herbicida por los coloides del suelo es el principal proceso que
retarda su movimiento a través del perfil edáfico (Takeshita et al., 2020), ya que si los
plaguicidas se encuentran adsorbidos no pueden ser arrastrados en disolución por las
aguas de lluvia o de riego. De la misma forma, si el herbicida tiene una gran solubilidad
en agua, la lixiviación será mayor (Dechene et al., 2014). Por tanto, se puede afirmar que
la movilidad del herbicida, en general, es proporcional a su solubilidad e inversamente
~ 52 ~
Capítulo I.1. Introducción
por lo que estas prácticas influyen en la movilidad de los herbicidas (Aslam et al., 2015;
López-Piñeiro et al., 2017).
I.1.3.3.1.3. Escorrentía
~ 54 ~
Capítulo I.1. Introducción
En el cultivo del arroz, la volatilización directa desde la lámina de agua que cubre
el suelo en arrozales inundados es una importante ruta de pérdida de herbicidas (Ampong-
~ 55 ~
Capítulo I.1. Introducción
~ 56 ~
Capítulo I.1. Introducción
I.1.3.3.2.1. Biodegradación
~ 57 ~
Capítulo I.1. Introducción
La adsorción del herbicida a los coloides del suelo puede tener un efecto doble ya
que puede proteger al herbicida de la degradación química, pero también puede
potenciarla, como en el caso de reacciones catalizadas por la superficie de los
componentes coloidales. Los procesos de degradación química más frecuentes son las
reacciones de hidrólisis y oxidación-reducción, estando afectados por factores como pH,
~ 58 ~
Capítulo I.1. Introducción
a) Reacciones de hidrólisis
b) Reacciones de oxidación-reducción
I.1.3.3.2.3. Fotodegradación
~ 60 ~
Capítulo I.1. Introducción
Dado que la intensidad de la luz solar es el principal factor que controla la tasa de
fotólisis de herbicidas en el suelo, cabe esperar variaciones de este parámetro en función
de la localización geográfica y la estación del año. Las estimaciones de las vidas medias
de plaguicidas fotosensibles indican que las reacciones fotolíticas son más rápidas en
zonas en las que la intensidad de la radiación solar es más uniforme a lo largo del año
(Racke et al., 1997).
~ 61 ~
Capítulo I.1. Introducción
a los cultivos sucesivos (Scursoni et al., 2017; Palhano et al., 2018), además de suponer
un elevado riesgo de contaminación para las aguas subterráneas (Pinasseau et al., 2020).
En el caso particular del uso del alperujo compostado como enmienda orgánica, se
ha observado como su aplicación puede aumentar la adsorción de los herbicidas en el
suelo reduciendo, así, el riesgo de lixiviación (Cañero et al., 2012; López-Piñeiro et al.,
2013; García-Jaramillo et al., 2014; Peña et al., 2019). Peña et al. (2019) encontraron que,
tras aplicar diferentes tipos de residuos de almazaras como enmiendas orgánicas, la
capacidad de adsorción del suelo incrementó considerablemente para el herbicida
S-metolacloro. Sin embargo, la lixiviación dependió del tipo de residuo, pues el COH,
más abundante en las enmiendas frescas, facilitaba el movimiento del herbicida en el
perfil del suelo. De hecho, existen estudios con diferentes materias activas y en diferentes
tipos de suelo, que relacionan la mayor movilidad de los pesticidas con la materia
orgánica soluble de las enmiendas (Cox et al., 2007; Calderón et al., 2015). Por tanto, el
comportamiento de los herbicidas en suelos enmendados es un tema complejo porque los
efectos dependen de muchos factores, como el tipo de suelo y de enmiendas, el contenido
en materia orgánica y su grado de madurez, la dosis de enmienda, pH, actividad
microbiana, etc (García-Delgado et al., 2019).
predecir los impactos ambientales que ejercen la implantación de los diferentes sistemas
de manejo sobre el comportamiento de los mismos (Alletto et al., 2010; Marín-Benito et
al., 2018b).
~ 66 ~
Capítulo I.2. OBJETIVOS
Capítulo I.2. Objetivos
El presente trabajo tiene como objetivo global evaluar, en el cultivo del arroz, el
impacto que la implementación de diferentes sistemas de manejo (siembra directa y
laboreo convencional) y riego (aspersión e inundación), por si mismos o en combinación
de compost (obtenido a partir de subproductos de almazara), ejerce en la dinámica de
herbicidas ampliamente utilizados en el mismo: bispirybac-sodio, clomazona y MCPA.
Este objetivo global se concreta en los siguientes objetivos específicos:
~ 69 ~
Capítulo II. MATERIALES Y MÉTODOS
Capítulo III. Materiales y Métodos
Figura 2.1 Localización del ensayo de campo en las Vegas Bajas del
Guadiana.
~ 73 ~
Capítulo III. Materiales y Métodos
Se realizaron ensayos de campo durante los años 2015, 2016 y 2017 en un suelo
clasificado como Antrosol Hidrágico (FAO, 2006) que consistía en 50.3 % de arena,
28.9 % de limo y 20.8 % de arcilla en la zona de las Vegas Bajas del Guadiana. Se trata,
por tanto, de una zona de clima mediterráneo con precipitación media anual y temperatura
de 460 mm y 16.2 °C, respectivamente, (AEMET, 2020). El suelo donde se desarrollaron
las investigaciones pertenecía a una parcela donde se había cultivado arroz en
monocultivo de forma tradicional (técnicas de laboreo convencional junto con sistemas de
riego por inundación) durante unos 11 años de antigüedad. El mes de Enero del año 2015,
la parcela experimental se dividió en dieciocho subparcelas, cada una de 180 m²
(18m × 10 m) en donde se implementarron seis tratamientos, cada uno de ellos por
triplicados (Figura 2.2), los cuales se detallan a continuación:
~ 74 ~
Capítulo III. Materiales y Métodos
Aspersión Inundación
2m
4m
10 m
71 m 35 m
~ 75 ~
Capítulo III. Materiales y Métodos
~ 76 ~
Capítulo III. Materiales y Métodos
Tabla 2.1 Cantidades de agua aportadas al cultivo (m3 ha-1) en cada tratamiento y año de
estudio.
~ 77 ~
Capítulo III. Materiales y Métodos
Propiedades Compost
COT (g kg-1) 382
COH (g kg-1) 23.6
-1
AH (g kg ) 47.9
-1
AF (g kg ) 18.9
IH (g kg-1) 12.5
NT (g kg-1) 21.7
C/N 17.6
pH 7.71
CE (mS/cm) 2.32
IG (%) 109
Fenoles
3.38
Hidrosolubles (g kg-1)
MO: Materia Orgánica; COT: Carbono Orgánico Total; COH: Carbono Orgánico
Hidrosoluble; AH: Ácidos Húmicos; AF: Ácidos Fúlvicos; IH: Índice de Humificación;
NT: Nitrógeno total; C/N: Relación Carbono Nitrógeno; CE: Conductividad Eléctrica; IG:
Índice de Germinación.
~ 78 ~
Capítulo III. Materiales y Métodos
Figura 2.3 Aplicación del compost de alperujo en las subparcelas del ensayo de campo.
Previo a la implantación del ensayo (marzo 2015), se llevó a cabo una calicata en
la parcela de estudio para conocer el tipo de suelo y obtener una información completa
del mismo.
Una vez aplicado el compost en las subparcelas que representan los tratamientos
SDC, LCC y LCIC, y previo al cultivo (abril 2015) se tomaron manualmente muestras de
suelo de todos los tratamientos al azar de hasta una profundidad de 20 cm con las que se
realizó un análisis de los parámetros edáficos más relevantes. Para asegurar la
representatividad y minimizar errores derivados de la variabilidad natural del terreno se
tomaron cuatro submuestras en cada una de las tres réplicas de los seis tratamientos
~ 79 ~
Capítulo III. Materiales y Métodos
considerados (SD, SDC, LC, LCC, LCI, LCIC) para posteriormente ser mezcladas con el
fin de obtener una muestra representativa para cada uno de los tratamientos estudiados.
Anualmente, y tras la finalización del ciclo del cultivo, se procedió a la toma de muestras
de suelo siguiendo el mismo criterio, con el objetivo de monitorizar los posibles cambios
que los distintos tratamientos pudieran haber inducido en las propiedades del suelo.
~ 80 ~
Capítulo III. Materiales y Métodos
Tabla 2.3 Propiedades edáficas de los diferentes horizontes presentes en el perfil del
suelo.
COT: Carbono Orgánico Total; NT: Nitrógeno total; CIC: Capacidad de Intercambio
Catiónico; CE: Conductividad Eléctrica.
~ 81 ~
Capítulo III. Materiales y Métodos
M.O: Materia Orgánica; COT: Carbono Orgánico Total; COH: Carbono Orgánico
Hidrosoluble; AH: Ácidos Húmicos; AF: Ácidos Fúlvicos; IH: Índice de Humificación;
GP: Grado de Polimerización; CE: Conductividad Eléctrica; NT: Nitrógeno total.
~ 82 ~
Capítulo III. Materiales y Métodos
Carbono Orgánico Hidrosoluble (COH): fue extraído con agua destilada en una
proporción 1:100 (p/v) para el suelo y de 1:1000 (p/v) para el compost. Después se
procedió a una oxidación parcial del carbono con dicromato potásico 1 N en un medio de
ácido sulfúrico. Posteriormente se cuantificó en un espectrofotómetro a λ=590 nm (Sims
y Haby, 1971).
pH: se determinó sobre una suspensión de suelo con agua destilada en relación
1:1 (p/v) para el suelo y 1:5 (p/v) para el compost, realizándose la medida con un pH-
metro modelo Crison-501 con electrodo de vidrio.
~ 83 ~
Capítulo III. Materiales y Métodos
II.4. Herbicidas
~ 84 ~
Capítulo III. Materiales y Métodos
II.4.1. Bispyribac-sodio
II.4.2. Clomazona
~ 85 ~
Capítulo III. Materiales y Métodos
II.4.3. MCPA
~ 86 ~
Capítulo III. Materiales y Métodos
Los estudios de dinámica de herbicidas se llevaron a cabo en los suelos (0-20 cm)
de los diferentes tratamientos seleccionados, tomándose al finalizar el ciclo del cultivo en
el año 2015 (efecto directo) y el año 2017 (efecto residual).
(𝐶𝐶𝑖𝑖 − 𝐶𝐶𝑒𝑒 ) ∙ 𝑉𝑉
𝐶𝐶𝑠𝑠 =
𝑚𝑚
~ 87 ~
Capítulo III. Materiales y Métodos
𝐶𝐶𝑠𝑠
𝐾𝐾𝑑𝑑 =
𝐶𝐶𝑒𝑒
~ 88 ~
Capítulo III. Materiales y Métodos
𝑛𝑛𝑓𝑓 𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎ó𝑛𝑛
𝐻𝐻 =
𝑛𝑛𝑓𝑓 𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑
~ 89 ~
Capítulo III. Materiales y Métodos
interior del tubo falcon) y la incubación se llevó a cabo en oscuridad a una temperatura
ambiente de 20 °C (Figura 2.7). En el interior del tubo falcon, las condiciones de
humedad preestablecidas se mantuvieron registrando su peso semanalmente, y añadiendo
la cantidad de agua necesaria en cada caso.
A intervalos periódicos (dos horas tras la aplicación de los herbicidas, tres días,
cinco días, siete días y, a partir de ese momento, semanalmente hasta los cuarenta y nueve
días de incubación) se retiraron muestras por triplicado para su análisis mediante HPLC.
El herbicida presente en las muestras de suelo (tanto bajo condiciones de inundación
como condiciones aeróbicas) fue extraído añadiendo 10 mL de disolución extractante en
cada uno de los tubos falcon, con una relación, por tanto, 1:2 (p/v). Cada herbicida tuvo
su propia fase extractante siendo: 60 % agua destilada más 40 % metanol en el caso de
BYS, 100 % metanol para CLO, y 60 % metanol y 40 % ácido ortofosfórico 1N (pH=2)
para MCPA. Una vez añadido los 10 mL de la fase extractante, las suspensiones se
agitaron durante 24 horas a 200 rpm y posteriormente se centrifugaron 10 minutos a
4000 rpm. Independientemente del tipo de herbicida seleccionado, ensayos previos de
~ 90 ~
Capítulo III. Materiales y Métodos
𝑡𝑡
𝐶𝐶
𝑑𝑑𝑑𝑑 𝐶𝐶0
� − = 𝑘𝑘 � 𝑑𝑑𝑑𝑑 → 𝑙𝑙𝑙𝑙 = 𝑘𝑘𝑘𝑘
𝐶𝐶0 [𝐶𝐶] 𝐶𝐶
0
ln 𝐶𝐶 = ln 𝐶𝐶0 − 𝑘𝑘𝑘𝑘
𝐶𝐶0
Dado que por definición de tiempo de vida media 𝐶𝐶 = ; siendo C0 la
2
ln 2
Por lo que el tiempo de vida media de la materia activa aplicada sería 𝑡𝑡1/2 = 𝑘𝑘
,
~ 91 ~
Capítulo III. Materiales y Métodos
~ 92 ~
Capítulo III. Materiales y Métodos
~ 93 ~
Capítulo III. Materiales y Métodos
La fase estacionaria utilizada para los tres herbicidas fue la columna Nova Pack
C18 de Waters de 150 mm de longitud y 3.9 mm de diámetro interno. La temperatura del
horno fue de 30 °C y el volumen de inyección de 25 μL, con un flujo constante de
1 mL min-1.
~ 94 ~
Capítulo III. Materiales y Métodos
longitud de onda para su detección fue 228 nm. Los límites de detección (cantidad o
concentración mínima de una sustancia que puede ser detectada con fiabilidad), y los
límites de cuantificación (cantidad más pequeña de una sustancia que se pueda cuantificar
dentro de los límites especificados de precisión y exactitud), se han calculado como las
concentraciones de herbicida que resultan en relaciones señal/ruido de 3:1 y 10:1
respectivamente (Gámiz et al., 2019). Para el herbicida BYS, los límites de detección y
cuantificación fueron de 0.0068 y de 0.0226 μM, respectivamente. Para el herbicida CLO,
los límites de detección y cuantificación fueron de 0.015 y 0.047 μM, respectivamente.
En el caso del MCPA los límites de detección y cuantificación fueron 0.021 y 0.068 μM,
respectivamente.
Los análisis estadísticos fueron llevados a cabo utilizando el programa IBM SPSS
Statistics 19 para Windows. Los datos fueron sometidos a ANOVAS de un factor para
encontrar diferencias significativas entre los tratamientos estudiados y test post hoc
Duncan para obtener grupos homogéneos. Además, se realizaron dos ANOVA de un
factor para cada variable dependiente teniendo en cuenta el factor Año y el factor
Tratamiento por separado, con el objetivo de encontrar diferencias significativas entre
tratamientos dentro de un mismo año y entre años dentro de un mismo tratamiento. Así
mismo, se realizaron los test post-hoc de Duncan, con el fin de obtener grupos
homogéneos.
~ 95 ~
Capítulo III. Behaviour of bispyribac-sodium
in aerobic and anaerobic rice-growing conditions
with and without olive-mill waste amendment
Soraya Gómez 1, Damián Fernández 1, David Peña 1, Ángel Albarrán 2, Antonio López-
Piñeiro 1*
1
Área de Edafología y Química Agrícola, Facultad de Ciencias – IACYS,
Universidad de Extremadura, Avda de Elvas s/n, 06071 - Badajoz, Spain.
² Área de Producción Vegetal, Escuela de Ingenierías Agrarias – IACYS,
Universidad de Extremadura, Ctra de Cáceres, 06071 - Badajoz, Spain.
Abstract
~ 99 ~
Capítulo III. Bispyribac-sodium
persistence was significantly reduced in NTA and TA when OW was added to the soil,
but in TF it was enhanced. Conversely, in the third year the persistence of BYS was
significantly increased in NTA and TA by OW addition, but decreased under TF
management. BYS leaching was similar under the aerobic (TA and NTA) and anaerobic
(TF) treatments in the first year, but was less under the TF treatment at the end of the
experiment. Independently of the water and tillage management, the addition of OW
significantly influenced BYS sorption and persistence, reducing the amount of the
herbicide leached, although the magnitude of the effect depended on the time elapsed
after its application to the soil. The use of OW could be considered as a strategy with
which to reduce water contamination by BYS under aerobic and anaerobic rice-growing
conditions, especially in the short term after application of this organic amendment.
1. Introduction
Traditionally, rice (Oryza sativa L.) has been cultivated worldwide under flooding
management with tillage, involving the intensive use of fertilizers and pesticides which
can contribute to increased greenhouse gas emissions, soil degradation, and water
contamination. The production of rice under flooding conditions is threatened by the
progressive decline in water availability, especially in Mediterranean countries such as
Italy and Spain, the two countries which account for most of Europe's rice production.
Therefore, alternatives to the traditional management system for rice production are
needed that will allow water requirements to be reduced while maintaining productivity.
Since rice production under non-flooding (aerobic) conditions requires less water than
conventional tillage with flooding (anaerobic) conditions, it has been considered as a
potential management practice for sustainable rice cropping (Kumar et al., 2013; Singh et
al., 2018a), and has recently been implemented in Mediterranean countries under
no-tillage practices (Facchi et al., 2017; Sánchez-Llerena et al., 2016; Spanu et al., 2018).
Implementing these practices strongly influences not only the properties of the soil, but
also the activity, composition, and diversity of its microbial community since these are
strongly dependent on whether the conditions are anaerobic or aerobic (Vasquez et al.,
2011). Thus, it is well established that in the medium- and long-terms the adoption of no-
~ 100 ~
Capítulo III. Bispyribac-sodium
tillage usually increases the soil's total organic carbon and lowers its pH (Soane et al.,
2012; Li et al., 2015), although higher soil pH values have been reported in reduced
tillage than in conventional tillage (Denardin et al., 2019; Šimanský and Kováčik, 2015).
Increased microbial activity and community size have also been reported under reduced
tillage and aerobic conditions (Jørgensen and Spliid, 2016; Lupwayi et al., 2017).
While similar or even greater rice grain yields have been found under aerobic than
anaerobic rice conditions in the medium- and long-terms (Kumar et al., 2013; Sánchez-
Llerena et al., 2016), in the short-term, lower yields have been observed in rice grown
under aerobic conditions in southern Europe (Sánchez-Llerena et al., 2016). These results
have been attributed to the lower soil organic matter content in the aerobic system at the
beginning of its implementation (Xue et al., 2008). Therefore, the use of organic
amendments could compensate for these initial low levels of soil organic matter,
increasing the soil's water holding capacity (Rawls et al., 2003; Stevenson, 1994), and
hence also water efficiency and crop productivity under aerobic conditions, even in the
short-term.
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Capítulo III. Bispyribac-sodium
with the consequent very high yield losses (Ramesh et al., 2017; Singh et al., 2018b).
Herbicides are therefore required to provide effective weed control for this management
practice to be viable. In this sense, bispyribac-sodium (BYS) (sodium 2,6-bis[(4,6-
dimethoxypyrimidine- 2-yl)oxy]benzoate) is a pyrimidinyl carboxy herbicide that is
intensively used in rice agroecosystems for post-emergence control of grasses and broad-
leaf weeds. Indeed, the registration certificates and sales volume of BYS have been
increasing rapidly (Wang et al., 2019) and it is in the sixth position among the herbicides
of the greatest economic weight in rice-growing in the world (McDougal, 2017).
However, BYS is considered hazardous for the environment, having very toxic effects on
non-target terrestrial and aquatic organisms (Bera and Ghosh, 2013; Lajmanovich et al.,
2013; Stenert et al., 2018). Furthermore, due to its high solubility in water (64. g L-1),
BYS has a major potential for contaminating water through leaching or run-off. Indeed,
BYS has been found (up to 3.5 μg L-1) in water samples collected from regions of
irrigated rice crops (Vieira et al., 2016). Although there have been very few studies
conducted on the behaviour of BYS in soils, the trends those studies have reported appear
to be contradictory. Thus, while Chirukuri and Atmakuru (2015) and López-Piñeiro et al.
(2016) found that BYS sorption was negatively correlated with soil pH and positively
with soil organic matter, Singh and Singh (2015) found that this sorption was positively
correlated with soil pH and showed no correlation with soil organic matter.
Despite it being known that water and tillage management practices alone or in
combination with OW amendments can alter soil properties, and may therefore also
modify the behaviour of soil-applied BYS, we could find no published research
contrasting the impact of different regimes of water and tillage rice management in
combination with organic amendments on this herbicide's environmental fate. Such
information would be invaluable from the agricultural and environmental perspective of
BYS management in rice agroecosystems. The objective of this work was therefore to
evaluate the sorption, persistence, and leaching of BYS under anaerobic and aerobic rice-
growing conditions with and without OW amendment. Since the quantity and quality of
the OW organic matter change with time after the amendment has been applied to a soil,
we studied the "direct" (first year) and "residual" (third year, two years after application)
effects. We also evaluated the effect on each soil's microbial activity by monitoring the
dehydrogenase activity.
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Capítulo III. Bispyribac-sodium
BYS of purity 98.3% was supplied by Dr Ehrenstorfer, GmbH. Its properties were
452.4 g mol-1 molecular weight, 5.5×10-6 mPa vapour pressure at 20ºC, 64.0 g L-1 water
solubility at 20°C, and a pKa of 3.35 at 25ºC (BPDB, 2019). Its concentrations in samples
were determined by high-performance liquid chromatography (HPLC), model Waters
600E, using a chromatograph coupled to a diode-array detector (model Waters 966). The
following conditions were used: Nova-Pack C18 column (150 × 3.9 mm, 4.5 µm particle
size), column temperature 30 °C, 25 µL injection volume, mobile phase of a 55:45
acetonitrile/water (v/v) mixture containing 0.1% phosphoric acid at a flow rate of
1 mL min-1, and UV detection at 248 nm. Under these conditions, the retention time of
BYS was 2.23 minutes. Additional details of the method validation are given in Text S1
of Supplementary Material.
Field experiments were conducted from 2015 to 2017 in southern Spain (38°55'N;
6°57'W) on a loam soil which consisted of 50.3% sand, 28.9% silt, and 20.8% clay, in a
region of Mediterranean climate with mean annual rainfall and temperature of 460 mm
and 16.2 °C, respectively. Prior to the study, the cropping system in the experimental area
had consisted of an 11-year succession of irrigated rice (O. sativa L.) monocropping,
following the practices traditional in the region (deep ploughing and flooding). After the
harvest in December 2014, the field was divided into eighteen plots of 180 m²
(18 m × 10 m) to be subjected to six treatments in triplicate: no-tillage and sprinkler
irrigation (aerobic) without (NTA) and with first-year application of composted OW
(NTAOW), tillage and aerobic without (TA) and with first-year application of composted
OW (TAOW), and tillage and flooding without (TF) and with first-year application of
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Capítulo III. Bispyribac-sodium
composted OW (TFOW). The NTAOW, TAOW, and TFOW treatments received a dose
of 80 t ha-1 of compost obtained from a mixture (9:1) of OW and olive leaves. The
relevant properties of the compost and soils prior to the study are given in Table S1 of the
Supplementary Material.
After harvest in each of the two years of the study (2015 representing the "direct"
effects, and 2017 the "residual" effects), soil samples were taken (0-20 cm) from each
plot for the sorption-desorption, leaching, and dissipation determinations. The electrical
conductivity (EC), pH, total organic carbon (TOC), humic acids (HA), fulvic acids (FA),
and water soluble organic carbon (WSOC) were measured in the soils and OW
(sieved < 2mm) as described by Cabrera et al. (2010). The values of the selected soil
properties for 2015 and 2017 years are presented in Table 1.
TOC WSOC HA FA pH EC
(g kg-1) (mg kg-1) (g kg-1) (g kg-1) (H2O) (dS m-1)
2015
NTA 10.2aA 210cA 1.62bA 1.10cB 5.77cA 2.14aA
NTAOW 21.3dB 448dA 2.35dA 1.29dA 6.58eA 3.69bA
TA 10.7aA 137bA 1.34aA 0.97bA 5.64bA 3.74bA
TAOW 15.7bA 497eB 2.02cA 1.29dA 5.99dA 4.19cA
TF 10.9aA 72.8aA 1.50abA 0.85aA 4.93aA 3.60bA
TFOW 20.3cB 489eB 1.60bA 1.02bA 6.06dB 4.46cB
2017
NTA 15.1cB 316bB 1.44aA 0.95aA 6.08cB 3.96cB
NTAOW 19.1eA 498dA 2.24cA 1.24dA 6.61eA 3.44abA
TA 13.1aB 336bcB 1.55aB 1.48eB 5.61aA 4.62dB
TAOW 18.2dB 395cA 2.40cB 1.13cA 6.35dB 3.73bcA
TF 13.9bB 220aB 1.48aA 1.03bB 5.65aB 3.37aA
TFOW 19.1eA 325bA 1.88bB 1.19cdB 5.80bA 3.29aA
Y *** ** ** *** *** *
M *** *** *** *** *** ***
YxM *** *** *** *** *** ***
ANOVA factors are Y: year; M: management regime; Y x M: interaction year x management regime; *, **,
and *** significant at a levels of 0.05, 0.01, and 0.001, respectively; NS: not significant. Different letters
indicate significant differences (p < 0.05) between management regimes in the same year (lower case
letters) and between years within the same management regime (upper case letters).
~ 104 ~
Capítulo III. Bispyribac-sodium
The detailed method followed for the dissipation study can be found in López-
Piñeiro et al. (2016). Briefly, 5 g aliquots of the soil of each treatment were weighed out
into glass tubes, and supplemented with sterile distilled water to obtain non-flooded (80%
field capacity; aerobic) and flooded (1:1.25 w/v soil/water; anaerobic) moisture
conditions. BYS was applied in an amount to correspond to a field dose rate of
0.5 kg ha-1. Triplicate soil samples were periodically removed for analysis until 49 days
after preparation. Therefore, a total of 360 tubes (6 treatments × 3 replicate × 10 time
intervals × 2 experimental conditions) were used for these studies. For BYS extraction,
5 g of soil in triplicate were extracted with 10 mL of a 60:40 (v/v) mixture of distilled
water/methanol by shaking mechanically at 200 revolutions per minute and 20 ºC ± 2 ºC
for 24 hours. After centrifuging, the supernatants were filtered and assayed by HPLC.
Data were fitted to a first-order kinetics equation, and t1/2 (time required for 50% of the
~ 105 ~
Capítulo III. Bispyribac-sodium
initial dose of pesticide to be dissipated) was calculated. Additional details of this study
are given in Text S3 of Supplementary Material.
For the leaching experiments, PVC disturbed soil columns (30-cm length × 5-cm
i.d.) were used as described by López-Piñeiro et al. (2016). BYS at a rate of 0.5 kg ha-1
was applied to the top of the columns. Each day, the columns were leached with 50 mL of
0.01 M CaCl2 until herbicides were no longer detected in the leachates. BYS leachates
were assayed by HPLC. The soil columns were sectioned into 5-cm deep portions after
the leaching experiment to determine the herbicides remaining at different depths. The
extraction procedure was as described above in Sec. 2.4. Additional details of these
studies are given in Text S5 of Supplementary Material.
Statistical analyses were performed using the SPSS software package (22.0). The
data were subjected to a one-way ANOVA. The Duncan test was applied for multiple
comparisons. Pearson's correlation coefficient was employed to find possible correlations
between selected parameters. Differences between the results at a p < 0.05 level were
considered statistically significant.
~ 106 ~
Capítulo III. Bispyribac-sodium
BYS sorption-desorption isotherms for the direct (2015) and residual (2017) years
are shown in Fig. S1 of Supplementary Material. For all treatments, the sorption
isotherms were satisfactorily described by the Freundlich equation with R² > 0.928. The nf
values were < 1 (Table 2), indicating that the sorption of BYS depended on its initial
solution concentration. The Kf values ranged from 0.674 to 1.531 and from 0.716 to 1.846
for the direct and residual years, respectively (Table 1). These values are of the same
order as those reported by López-Piñeiro et al. (2016) and Chirukuri and Atmakuru
(2015) who found values ranging 0.488 to 2.05 for rice soils in Spain with pH's of 5.1-6.2
and slightly lower TOC contents (6.8-16.2 g kg-1), and values of 0.5 to 2.0 for several
European soils with TOC's of 5-20 g kg-1 but higher pH values (6.3-7.9). However, our
values are much lower than those of 4.8 and 5.6 found by these latter authors for soils
from the Netherlands and USA with 44 and 33 g kg-1 TOC and pH values of 5.2 and 6.3,
respectively. Our Kf values are however greater than those reported by Singh and Singh
(2015) and Gámiz et al. (2017) who found values ranging from 0.37 to 0.87 for Indian
soils with pH of 5.2-7.9 and much lower TOC content (3.0-6.3 g kg-1), and the value of
0.2 for a soil in Spain with pH 7.9 and a TOC of 13 g kg-1. The treatments significantly
(p < 0.001) influenced the BYS sorption, with different effects in the direct and residual
years as shown by the treatment × year interaction (p < 0.001; Table 1). In the non-
amended soils, the Kf values were significantly greater in TF than in [NTA and TA] for
the direct and residual years of the experiment by factors of [1.5 and 2.3] and [1.6 and
1.2], respectively, suggesting that the implementation of aerobic instead of anaerobic
conditions could reduce BYS sorption under no-tillage and tillage management, at least in
the short- and medium-terms. These results agree with those of López-Piñeiro et al.
(2016) for a rice-cropping loam soil also in Spain which found medium-term BYS Kf
values of up to 2.4 times greater under anaerobic than aerobic management.
~ 107 ~
Capítulo III. Bispyribac-sodium
~ 108 ~
Capítulo III. Bispyribac-sodium
nf Kf R2 H
µmol 1-nf -1
kg L nf
2015
NTA 0.883±0.024aA 0.988±0.061bB 0.972 432aA
NTAOW 0.867±0.008aA 0.928±0.005bA 0.996 628bA
TA 0.929±0.026aA 0.674±0.031aA 0.996 699bB
TAOW 0.861±0.017aA 0.896±0.024aA 0.998 680bA
TF 0.876±0.012aA 1.53±0.059cB 0.997 322aA
TFOW 0.866±0.029aA 0.989±0.020bA 0.998 392aB
2017
NTA 0.889±0.015aA 0.716±0.040aA 0.994 573cdB
NTAOW 0.880±0.013aA 0.876±0.024abA 0.996 684bcA
TA 0.851±0.060aA 0.955±0.135bcA 0.985 500bcA
TAOW 0.921±0.014aA 0.836±0.010abA 0.996 834dA
TF 0.894±0.037aA 1.14±0.072cA 0.918 376abA
TFOW 0.931±0.019aA 1.85±0.019dB 0.998 254aA
Y NS * - *
M NS *** - **
YxM NS *** - *
ANOVA factors are Y: year; M: management regime; Y x M: interaction year x management regime; *, **,
and *** significant at a levels of 0.05, 0.01, and 0.001, respectively; NS: not significant. Different letters
indicate significant differences (p < 0.05) between management regimes in the same year (lower case
letters) and between years within the same management regime (upper case letters).
~ 109 ~
Capítulo III. Bispyribac-sodium
Figure 1 shows the BYS dissipation and the dehydrogenase activity (DHA) for
each management system. The experimental data fit first-order kinetics, with R² > 0.801
and R² > 0.895 under anaerobic and aerobic incubation conditions, respectively (Table 3).
For all treatments, the values of DHA before (DHAB) and two hours after (DHAA) BYS
application and determined by considering all incubation times (DHAT) were much lower
under aerobic than anaerobic incubation conditions (Table 3). This agrees with Wolińska
and Bennicelli (2010) who found DHA to be greater as the aeration and potential redox of
their soils decreased. Positive correlations were found between TOC and DHAA and
DHAT under aerobic (r = 0.787** and r = 0.836**) and anaerobic (r = 0.465** and
r = 0.639**) incubation conditions, indicating that total organic matter was representative
of the microbial activity of these soils regardless of the tillage and irrigation management.
The DHAA and DHAT values were also correlated with soil pH under aerobic
(r = 0.499** and r = 0.529**) incubation conditions, although under anaerobic incubation
conditions the correlations were not significant (p > 0.05). This indicates a reduction of
microbial activity with decreasing soil pH (Kah et al., 2007; Zhang et al., 2019) at least
when oxygen is present.
~ 110 ~
Capítulo III. Bispyribac-sodium
2015
8 8 TF 8
100 NTA 100 TA 100
Bispyribac-sodium (%) 80 6 80 6 80 6
Aerobic conditions
60 60 60
-1 -1
40 40 40
2 2 2
20 20 20
0 0 0 0 0 0
0 10 20 30 40 50 0 10 20 30 40 50 0 10 20 30 40 50
80 6 80 6 80 6
60 60 60
4 4 4
40 40 40
2 2 2
20 20 20
0 0 0 0 0 0
0 10 20 30 40 50 0 10 20 30 40 50 0 10 20 30 40 50
NTA 8 8 8
100 100 TA 100 TF
Anaerobic conditions
80 6 80 6 80 6
Bispyribac-sodium (%)
60 60 60
-1 -1
40 40 40
2 2 2
20 20 20
0 0 0 0 0 0
0 10 20 30 40 50 0 10 20 30 40 50 0 10 20 30 40 50
80 6 80 6 80 6
60 60 60
4 4 4
40 40 40
2 2 2
20 20 20
0 0 0 0 0 0
0 10 20 30 40 50 0 10 20 30 40 50 0 10 20 30 40 50
8 8 8
100 NTA 100 TA 100 TF
Anaerobic conditions
80 80 6 80
6 6
Bispyribac-sodium (%)
4
-1 -1
60 60 60
4 4
40 40 2 40
2 2
20 20 0 20
0 0 0 0 0
0 10 20 30 40 50 0 10 20 30 40 50 0 10 20 30 40 50
8 8 8
100 NTAOW 100 TAOW 100 TFOW
80 80 6 80
6 6
60 60 4 60
4 4
40 40 2 40
2 2
20 20 0 20
0 0 0 0 0
0 10 20 30 40 50 0 10 20 30 40 50 0 10 20 30 40 50
~ 111 ~
Capítulo III. Bispyribac-sodium
In the non-amended soils, the BYS t1/2 values ranged from 35.5 to 75.7 d and from
27.4 to 73.3 d for aerobic and anaerobic incubation conditions, respectively (Table 3). These
values are much greater than those reported by Chirukuri and Atmakuru (2015) of 5.3-16.2 d
or by Gámiz et al. (2017) of 21 d in soils under aerobic incubation conditions, but these were
studies in which the moisture content of the samples was adjusted to 33% field capacity
instead of the 80% in the present work. Also for rice-growing soils, López-Piñeiro et al.
(2016) reported BYS t1/2 values that, compared to those presented here (Table 3), were
slightly greater under aerobic (31-51.5 d) but lower under anaerobic (45.4-131.8 d)
conditions. The treatments significantly (p < 0.001) influenced BYS dissipation, with their
effects being different in the two years, as shown by the significant (p < 0.001)
treatment × year interaction (Table 3). In non-amended soils, the BYS dissipation rates were
significantly influenced by the tillage and irrigation regime. Thus, BYS persistence at the end
of the experiment was significantly longer in NTA, with t1/2 values being greater than those
corresponding to TA and TF by factors of 1.4 and 1.7 for the aerobic incubation conditions,
and 1.1 and 1.4 for the anaerobic conditions, both respectively. These results suggest that
BYS dissipation may be slower under no-flooding conditions, especially when the crop is
managed with reduced tillage (Table 3). This could be attributable to a greater availability of
carbon under NTA than under TA management (Table 1), which may defer the use of BYS as
a source of carbon and therefore its dissipation. Also, longer persistence of BYS in the non-
amended soils may be attributable to higher pH's, since the shortest persistence corresponded
to TF and the longest to NTA (see Table 1 for the pH values). This suggests that chemical
hydrolysis, which in sulfonylurea herbicides is favoured under acidic conditions, may be the
major process of BYS degradation under both experimental conditions tested. This would
agree with Hultgren et al. (2002) who found that t1/2 values of prosulfuron herbicide were
highly correlated with the pH values of ten different soils, and reporting that dissipation of
this sulfonylurea herbicide is favoured by lower pH's because hydrolysis rates are reduced at
higher pH values.
~ 112 ~
Capítulo III. Bispyribac-sodium
Table 3. Effect of different management regimes on dehydrogenase activity and bispyribac-sodium dissipation parameters.
t1/2 80% (days) R2 80% t1/2 1:1.25 (days) R2 1:1.25 DHAB80% DHAA80% DHAT80% DHAB1:1.25 DHAA1:1.25 DHAT1:1.25
(µg INTF g-1 h-1)
2015
NTA 35.5aA 0.987 53.9cA 0.800 0.345aA 0.625aA 4.59aA 2.42aA 4.54bcA 23.1bB
NTAOW 59.0dA 0.901 27.6aA 0.810 0.718bA 1.34cB 12.6cB 5.85bA 8.75dB 53.3dB
TA 36.0abA 0.989 69.5dA 0.846 0.337aA 0.683abA 5.20aB 1.62aA 2.93aB 16.1aB
TAOW 44.5cA 0.955 40.9bA 0.825 0.650bA 0.967bA 7.44bA 4.83bA 5.49cB 30.3cB
TF 39.0abA 0.949 27.4aA 0.931 0.269aA 0.595aA 4.71aA 2.30aA 3.81abA 16.0aA
TFOW 57.3dB 0.933 38.1abA 0.899 0.710bA 1.48cA 14.9dB 4.38bA 5.57cA 57.6dB
2017
NTA 75.7dB 0.971 73.3dB 0.817 0.79bcB 0.73aA 6.01bB 4.53bB 3.06bA 12.6bA
NTAOW 67.1cB 0.967 86.5eB 0.876 1.04eB 1.06bA 8.51dA 6.15bA 3.05bA 17.7cA
TA 53.7bB 0.952 68.5cA 0.852 0.47aB 0.58aA 4.05aA 1.34aA 0.91aA 5.83aA
TAOW 80.1dB 0.895 82.5eB 0.835 0.84cA 0.98bA 7.60cA 4.52bA 2.84bA 14.1bA
TF 44.7aB 0.948 52.8bB 0.940 0.76bB 1.18bcB 7.65cB 8.20cB 6.33cB 27.0dB
TFOW 47.7aA 0.965 40.0aA 0.913 0.96dB 1.35cA 9.89eA 9.76cB 8.88dA 38.5eA
Y *** - *** - *** * ** *** ** ***
M *** - *** - *** *** *** *** *** ***
YxM *** - *** - ** *** *** *** *** ***
Half-lives: t1/2 80% in soils at 80% field water capacity; t1/2 1:1.25 in soils with 1:1.25 (w/v) (soil/water) moisture content. DHA: dehydrogenase activity two hours
before (B) and after (A) the application of the herbicide to soils conditioned to 80% field capacity and 1:1.25 (w/v) (soil/water) moisture content. DHAT: total dehydrogenase
activity considering all the incubation times in soils conditioned to 80% field capacity and 1:1.25 (w/v) (soil/water) moisture content. ANOVA factors are Y: year; M:
management regime; Y x M: interaction year x management regime; *, **, and *** significant at a levels of 0.05, 0.01, and 0.001, respectively; NS: not significant. Different
letters indicate significant differences (p < 0.05) between management regimes in the same year (lower case letters) and between years within the same management regime
(upper case letters).
~ 113 ~
Capítulo III. Bispyribac-sodium
With regard to the determinations under anaerobic incubation conditions however, the
findings were different. In particular, for soils of the direct year, the field addition of OW led
to significant decreases in BYS persistence (t1/2) by factors of 1.9 and 1.7 in NTAOW and
TAOW relative to their corresponding non-amended soils (NTA and TA), respectively. There
was an apparent contrary increase in the TFOW/TF case, but it was not statistically
significant (p > 0.05). For soils of the residual year, BYS persistence significantly increased
by a factor of 1.2 in NTAOW and TAOW relative to NTA and TA, respectively, and
decreased by a factor of 1.3 in TFOW relative to TF (Table 2). These results could be
explained by the non-amended and amended NTA and TA soil microbial communities
naturally not having any adaptation to anoxic conditions after the three years of non-flooding
management (Table 3). Contrary to the results observed under aerobic incubation conditions,
the differences in the BYS dissipation rates under anaerobic incubation conditions could be
attributable to the differences in their DHA values. Indeed, t1/2 was negatively and strongly
correlated with DHAA (r = -0.685**) and DHAT (r = -0.664**), suggesting that BYS was
~ 114 ~
Capítulo III. Bispyribac-sodium
preferably degraded by biotic processes. Longer BYS persistence was observed in the
residual than in the direct year, especially in the non-flooding management regimes,
regardless of whether or not OW was applied as organic amendment. This could also be
attributable to a lack of any adaptation of the non-flooded soils' microbial communities to
anoxic conditions (Unger et al., 2009; Vallée et al., 2016), as is suggested by the significant
decrease (on average, by a factor of 2.4) observed in the DHAT values for these treatments in
the residual compared to the direct year (Table 3).
Figure 2 shows the relative and cumulative BYS breakthrough curves. Table 4
presents the total BYS leached as well as the remaining percentage extracted from the soil
columns after the leaching experiment. Overall, BYS breakthrough was below one pore
volume (Fig. 2) in both years, indicating very great mobility of the compound (Beck et al.,
1993). In the non-amended soils, the total BYS leached ranged from 40.2% to 55.3% of the
amount initially applied (Table 4; Fig. 2). Amounts of leached BYS within the range of our
study (49%) or somewhat lower (18.7%-51.7%) were found by Gámiz et al. (2017) and
López-Piñeiro et al. (2016), respectively. It is interesting to note that the lower amount of
BYS leached in the latter study corresponded to a soil managed under no-tillage and sprinkler
irrigation in use for 10 years with a Kf value of 2.1, much higher than those observed in the
present study (Table 2). Much greater leaching losses of BYS (100%) were reported,
however, by Singh and Singh (2015), although in an alkaline soil (pH = 7.9) very poor in
organic matter (TOC = 3.9 g kg-1). These results were to be expected since the sorption of
sulfonylurea herbicides generally decreases with increasing soil pH and decreasing TOC. The
effect of the treatments on BYS leaching was different in the first and the third years of the
experiment (p < 0.01 treatment × year interaction; Table 4). With regard to the non-amended
soils, while in the first year no significant differences were observed among treatments, after
three years of the trial the amount of leached BYS was significantly lower in TF (42.0%) than
in NTA (51.3%) and TA (55.3%) (Table 4). The greater sorption and lesser persistence may
explain the greater decrease of BYS in the leachates corresponding to the TF management.
Our results are consistent with those found by López-Piñeiro et al. (2016) who also reported a
~ 115 ~
Capítulo III. Bispyribac-sodium
lower amount of BYS leached in TF than in NTA and TA managements, which was
attributed to the higher Kf value observed under flooding management. Although there were
no significant differences between the amounts of BYS leached in NTA and TA, a slightly
greater amount of the compound was observed at the end of the trial in TA, which may be
consistent with its lower H value (i.e., greater reversibility; Table 2 and Table 4) and its lower
t1/2 value (Table 3). The field addition of OW significantly influenced the amount of BYS
leached regardless of the water and tillage management implemented, although its effect was
dependent on the time elapsed after the herbicide's application (Table 4). Thus, while in the
direct year the amount of BYS leached showed significant decreases after OW addition,
being 1.3, 1.2 and 1.5 times greater in NT, TA and TF than in NTOW, TAOW and TFOW,
respectively, there was no such clear change in the residual year, with the apparent decreases
not reaching statistical significance (p > 0.05). In neither year were there any significant
differences between the three amended treatments. These results are consistent with those
described above for the dissipation study in that the OW addition led to a major increase in
DHAT, and consequently a decrease in the BYS half-life values, especially in the first year
under anaerobic incubation conditions (Table 3), therefore reducing the amount of BYS
potentially available to be leached (Table 4). Indeed, the correlation study found that, under
anaerobic conditions, the percentage of BYS leached was correlated negatively with TOC
(r = -0.353*) and ADTT (r = -0.779**), and positively with t1/2 (r = 0.585**). To the best of
our knowledge, although no work has yet been conducted to evaluate how the leaching of
BYS is influenced by amendment with OW, López-Piñeiro et al. (2013b) also observed a
similar positive correlation between the amount of herbicide leached and t1/2 values in OW-
amended soils, although for different a compound (metribuzin) applied only in soils under
conventional tillage. Our findings suggest that the implementation of non-flooding
management in rice production could increase BYS leaching in the medium-term, especially
when conventional tillage is applied, and that, at least in the short-term (our direct year
results), the use of OW may reduce the amount of the compound leached regardless of the
water and tillage managements applied.
~ 116 ~
Capítulo III. Bispyribac-sodium
2015
14 14 14
NTA TA TF
12 NTAOW 12 12 TFOW
TAOW
10 10 10
Bispyribac-sodium leached (%)
8 8 8
6 6 6
4 4 4
2 2 2
0 0 0
0 2 4 6 8 0 2 4 6 8 0 2 4 6 8
60 60 60
50 50 50
40 40 40
30 30 30
20 TA 20 TF 20
TF
10 TAOW 10 TFOW 10 TFOW
0 0 0
0 2 4 6 8 0 2 4 6 8 0 2 4 6 8
Watter added (pore volumes) Watter added (pore volumes) Watter added (pore volumes)
2017
14 14 14
NTA TA TF
12 12 12
NTAOW TAOW TFOW
10 10 10
Bispyribac-sodium leached (%)
8 8 8
6 6 6
4 4 4
2 2 2
0 0 0
0 2 4 6 8 0 2 4 6 8 0 2 4 6 8
60 60 60
50 50 50
40 40 40
30 30 30
20 20 20 TF
TF TA
10 TFOW 10 TAOW 10 TFOW
0 0 0
0 2 4 6 8 0 2 4 6 8 0 2 4 6 8
Watter added (pore volumes) Watter added (pore volumes) Watter added (pore volumes)
Figure 2. Effect of different crop management regimens on the relative (above) and
cumulative (below) breakthrough curves of bispyribac-sodium. Vertical bars represent one
standard error of the mean.
The effect of the treatments on the BYS recovered at the end of the leaching study
was different in the direct and residual years (p < 0.01 treatment × year interaction; Table 4).
Thus, whereas in the direct year there remained none of the BYS initially applied to the soil
columns, in the residual year significant differences between treatments were observed
~ 117 ~
Capítulo III. Bispyribac-sodium
(Table 4). The use of OW decreased the amount of BYS recovered in all treatments,
particularly in TFOW where the proportion of herbicide recovered was 3.3 times less than in
the TF treatment (Table 4). These results are also coherent with those described above for the
dissipation study, with the smaller amount of BYS recovered in TFOW being attributable to
its higher DHAT, especially under anaerobic conditions (Table 3). Indeed, under anaerobic
incubation conditions there was a significant negative correlation of the BYS recovered with
ADTT (r = -0.459**) and positive with the t1/2 values (r = 0.554**).
4. Conclusions
and organic matter quantity and quality). While the sorption of BYS was found to be
significantly greater under flooding irrigation management, the persistence, under aerobic and
anaerobic conditions, and leaching were significantly greater in the tillage and non-tillage
managements under non-flooding irrigation. Only in the direct year (when the amendment
was added) did the addition of OW significantly influence BYS sorption and persistence,
reducing the amount of the herbicide leached in all treatments. Therefore, although the
implementation of non-flooding irrigation management regimes may increase the risk of
water contamination by BYS in Mediterranean rice-growing ecosystems, the use of OW as
organic amendment may counteract it, but only in the short-term after its application.
Nonetheless, future dissipation and leaching studies under field conditions are needed.
Acknowledgements
Support for this work was provided by Spain's Ministries of Science and Innovation
(AGL 2010-21421-CO2-02) and of Economics and Competitiveness (AGL2013-48446-C3-2-
R), and by the Junta of Extremadura (GR18011; IB16075), co-financed by the European
Regional Development Fund. Soraya Gómez is the recipient of a grant from the Consejería of
Economía, Comercio e Innovación of the Junta of Extremadura (PD16021). Damian
Fernández is the recipient of a subvention for the promotion of the hiring of research support
personnel from the SEXPE of the Junta de Extremadura, co-financed by the European
Regional Development Fund.
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Text S1. The BYS concentration was quantified against a linear calibration curve of
chromatographic peak area versus BYS standards between 0.05 µM and 20 µM (external
calibration). The repeatability was evaluated by six repeated injections of BYS standards.
This test was also carried out on a different day and in different media (distilled water, CaCl2
~ 124 ~
Capítulo III. Bispyribac-sodium
0.01 M, and on extracting agent) in order to verify the reproducibility. Adequate linearity and
precision (R2 ≥ 0.9991 and relative standard deviation < 2%) were obtained. The
measurements with control samples (without BYS) at the band maxima of UV spectra for
BYS, showed that there were no interfering peaks at the retention times of the herbicide. The
limits of detection and quantification, calculated as the herbicide concentrations resulting in
signal-to-noise ratios of 3:1 and 10:1 respectively, were 0.007 μM and 0.022 μM,
respectively.
Text S2. Soil samples (5 g) were treated by mechanical shaking at 20±1 °C for 24 h
with 10 mL of solutions in 0.01M CaCl2 of BYS at initial concentrations (Ci) of 0.5, 1, 2.5,
5, 10, and 20 µM. According to OECD guideline 106, preliminary kinetics studies were
carried out to determine the optimal soil:solution ratio and the equilibrium time (OECD,
2000). Equilibrium concentrations in the supernatants were determined by high-performance
liquid chromatography (HPLC). The amount of BYS sorbed (Cs) was calculated from the
difference between the initial (Ci) and the equilibrium (Ce) solution concentrations. The
measurements with control samples containing only BYS but no soil showed that there were
no losses of the herbicide due to microbial activity, volatilization, or sorption onto the surface
of the tubes.
Text S3. Prior to the BYS addition, the soils were pre-incubated for 7 days in the dark
at 20±1 °C to allow the soil microorganisms to adapt to the incubation conditions, and also to
allow the development of reducing conditions in the flooded soils. Then BYS dissolved in
distilled water was applied at a rate equivalent to 0.5 kg ha 1, and the tubes were incubated in
the dark at 20±1 °C for 49 days. Moisture was maintained at a constant level throughout the
experiment by adding distilled water as necessary. Three replicate tubes were periodically (at
2 h, 2 days, 5 days, and 7 days after herbicide application, and then at 7-day intervals for
49 days) removed from each treatment to measure the herbicide concentrations. Recoveries
were greater than 95% of the herbicide applied to the soil. The BYS dissipation curves in
soils and water were fitted to first-order kinetics, C = Co e kt, where C is the BYS
concentration at time t (days), Co is the initial herbicide concentration, and k (day 1) is the
degradation constant, and the half-lives (t1/2) were calculated.
~ 125 ~
Capítulo III. Bispyribac-sodium
Text S4. To measure the dehydrogenase activity (DHA), three replicate tubes were
removed periodically from each treatment at the same times as for the dissipation experiment.
The tubes were incubated for 20 h at 20±1 °C in the dark with 1 mL of 0.4% 2-p-iodophenyl-
3p-nitrophenyl-5 tetrazolium chloride (INT) as substrate. At the end of the incubation, the
iodonitrotetrazolium formazan (INTF) produced was extracted with methanol, and the
absorbance was measured at 490 nm.
Text S5. Leaching studies were carried out using disturbed soil columns. To minimize
losses of soil during the experiment, the top 5 cm of the columns was filled with sea sand and
the bottom 5 cm with sea sand plus glass wool. The remaining 20 cm was hand-packed with
air-dried soil. The soil columns were saturated with 0.01 M CaCl2 and allowed to drain for 24
h. Leachates containing the BYS were collected daily, filtered, and assayed by HPLC.
Table S1. Selected properties of original soil (0-20 cm depth) and compost.
~ 126 ~
Capítulo III. Bispyribac-sodium
2015
20
NTA
Cs (µmol kg-1)
NTAOW
15 TA
TAOW
TF
10 TFOW
0
0 5 10 15
Cs (µmol kg-1) Cs (µmol kg-1)
20 NTA
20 TA
20 TF
15 15 15
10 10 10
5 5 5
0 0 0
0 5 10 15 0 5 10 15 0 5 10 15
20 NTAOW
20 TAOW 20 TFOW
15 15 15
10 10 10
5 5 5
0 0 0
0 5 10 15 0 5 10 15 0 5 10 15
Ce (µmol L-1) Ce (µmol L-1) Ce (µmol L-1)
2017
20 NTA
NTAOW
Cs (µmol kg-1)
TA
15 TAOW
TF
TFOW
10
0
0 5 10 15
Cs (µmol kg-1) Cs (µmol kg-1)
20 NTA
20 TA
20 TF
15 15 15
10 10 10
5 5 5
0 0 0
0 5 10 15 0 5 10 15 0 5 10 15
20 NTAOW
20 TAOW 20 TFOW
15 15 15
10 10 10
5 5 5
0 0 0
0 5 10 15 0 5 10 15 0 5 10 15
Ce (µmol L-1) Ce (µmol L-1) Ce (µmol L-1)
Figure S1. Effect of different crop management regimens on the bispyribac-sodium sorption
and desorption isotherms. Vertical bars representing one standard error of the mean were
smaller than the symbols in all cases.
~ 127 ~
Capítulo IV. How the environmental fate of
clomazone in rice fields is influenced by
amendment with olive-mill waste under different
regimes of irrigation and tillage
Damián Fernández 1, Soraya Gómez 1, Ángel Albarrán 2, David Peña1, María Ángeles Rozas2,
J.M. Rato-Nunes 3, Antonio López-Piñeiro 1*
1
Área de Edafología y Química Agrícola, Facultad de Ciencias – IACYS,
Universidad de Extremadura, Avda de Elvas s/n, 06071 - Badajoz, Spain.
² Área de Producción Vegetal, Escuela de Ingenierías Agrarias – IACYS, Universidad
de Extremadura, Ctra de Cáceres, 06071 - Badajoz, Spain.
3
Instituto Politécnico de Portalegre, Escola Superior Agrária de Elvas, Apartado 254,
7350-Elvas, Portugal.
Abstract
1. Introduction
Traditionally, rice (Oryza sativa L.) has been grown worldwide under anaerobic
(continuous flooding irrigation with tillage) conditions. These can contribute to increased soil
degradation and water contamination, and decreased productivity of water use.1-3 In the
European Union, the area under rice cultivation is 475 000 ha, with 80% corresponding to
two countries – Spain (30%) and Italy (50%). In both of these countries, limited water
availability is leading to a steady decline in the area used for rice cultivation. For this reason,
aerobic (non-flooding) rice production with and without conservation agriculture practices
(i.e., no tillage) has recently been implemented in European countries as a productive and
sustainable alternative to the traditional rice flooding system.4,5 Indeed, Sánchez-Llerena et
al.2 found similar rice yields under aerobic and anaerobic management regimes using no-
tillage, but with the advantage of on average 75% water savings in the former. However,
lower short-term rice grain yields have been found under non-flooding than flooding
regimes.2 This has been described as due to lower soil organic carbon (SOC) in the soils of
the former of these two management regimes at the beginning of its implementation.6
~ 132 ~
Capítulo IV. Clomazone
Also, greater soil aggregate stability and lower penetration resistance have been reported for
no-tillage soils relative to tilled soils.10,11 Although the adoption of no-tillage has often been
shown to raise the organic carbon content and lower the pH of a soil,12,13 significantly lower
pH's have been also reported in conventional than in no-tillage systems.14-16 The main soil
characteristics determining the influence of the tillage practice will have on SOC (and indeed
other soil properties are the texture and the initial SOC level17,18 Furthermore, the increase in
SOC under no-tillage is usually accompanied by concomitant increases in microbial activity
and community size, and these depend strongly on how anoxic the systems are.19-21 Whereas
significant reductions in both the organic matter content and the pH have often been reported
in irrigated soils,22 there are differences according to whether the irrigation regime is
sprinkler or flooding. In particular, soil organic matter losses are found to be greater in the
former case due to its higher rate of organic matter decomposition, which may lead to higher
values of pH, reflecting the importance of which method of irrigation is used in determining
the soil's properties.2
One of the principal processes used worldwide for olive oil extraction is two-phase
centrifugation. In Mediterranean nations alone, it generates greater than 11 000 000 Mg yr-1
of waste. This waste can be an invaluable resource for use as organic amendment, improving
crop productivity by impacting positively on the properties of the soil.23 Because of its high
content in organic matter (>85%), the use of composted olive-mill waste (W) as organic
amendment could compensate the initial low organic matter levels observed under non-
flooding conditions in rice soils, also increasing water and crop productivity,24 enhancing
therefore the sustainability of this crop in regions with limited water availability.
Changes in irrigation systems may greatly impact the persistence and environmental
behaviour of pesticides frequently used in rice cropping.25 Although sprinkler irrigation has
been considered as a viable non-flooding option for rice cultivation in zones in which the
limiting factor is water, this alternative may often be associated with very high yield losses as
a consequence of the difficulty in controlling weeds. In this sense, the isoxazolane herbicide
clomazone (2-[(2-chlorophenyl) methyl]-4,4-dimethyl-3-isoxazolidinone) is intensively
applied worldwide in rice fields owing to its effectiveness in controlling broadleaf weeds and
grasses. Due to its long dissipation half-life (28-84 d), minimal volatility
-4
(Pv=1.44×10 mm Hg), slow degradation by photolysis or hydrolysis, and great water
~ 133 ~
Capítulo IV. Clomazone
solubility (1100 mg L-1), this herbicide has a great potential to contaminate surface and
ground waters. Indeed, it is one of the most frequently detected herbicides in water sampled
in rice-growing areas,26,27 with reported concentrations greater than 3.7 μg L-1 (e.g.,
Marchesan et al. 28). Furthermore, several studies have shown that clomazone may negatively
impact non-target organisms such as nitrogen-fixing bacteria29 and invertebrates30, some of
which are essential for sustainable rice production.31
Various studies using W as organic amendment have highlighted its beneficial effects
in that it increases the soil's adsorption of pesticides, and consequently reduces the risk of
water contamination.32, 33 Nonetheless, these effects depend on the compound's properties and
the soil type.34 Furthermore, the transformation of W in the field may modify the compound's
future interactions with the amended soil. Although the implementation of conservation
farming practices may enhance a soil's adsorption of pesticides because of the greater total
organic carbon content, the results of studies of pesticide behaviour in soils under different
tillage management regimes have often been contradictory.35
With respect to clomazone specifically, we could find no literature evaluating how its
behaviour might be affected by different irrigation and tillage management regimes with and
without organic amendment. The aim of this work therefore was to assess the persistence,
sorption, and leaching of clomazone in rice-growing under different water and tillage
management regimes influenced by W amendment. We also evaluated the residual and direct
effects in years one and three after the W application.
~ 134 ~
Capítulo IV. Clomazone
An experiment in the field was carried out from 2015 to 2017 in southern Spain
(38°55'N; 6°57'W) on a 20.8% clay, 28.9% silt, and 50.3% sand soil, in a semi-arid region of
the Mediterranean with mean annual rainfall and temperature of 460 mm and 16.2 °C,
respectively. This experimental area had already been cropped for eleven years with rice (O.
sativa L.) with deep ploughing and flooding, however clomazone had not been previously
applied in this area. The experiment involved eighteen plots (18 m × 10 m) with six
treatments in triplicate: conventional tillage and sprinkler irrigation without (ST) or with first-
year of W application (STW), no-tillage and sprinkler irrigation without (SNT) or with first-
year of W application (SNTW), and continuous flooding irrigation and tillage without (FT) or
with first-year of W application (FTW). The W was obtained from a mixture of 10% olive
leaves and 90% two-phase olive-mill waste. It had the following properties: total organic
carbon (TOC) 382 g kg-1; pH 7.71; total nitrogen 21.7. g kg-1; and electrical conductivity
(EC) 2.32 dS m-1. The W application rate in the STW, SNTW, and FTW treatments was
80 Mg ha-1. After harvest in November 2015 and 2017, four subsamples of soil were taken
from each of the plots (20 cm depth) for sorption-desorption, leaching, and dissipation
determinations in laboratory experiments. The sub-samples from each plot were mixed and
homogenized to get a composite sample for every plot. The measurements done in 2015 and
2017 constituted the "direct" and "residual" effects, respectively. Measurements were also
made of the soil pH, EC, TOC, and water soluble organic carbon (WSOC), fulvic acids (FA),
and humic acids (HA) contents as described by López-Piñeiro et al.36 and briefly in Text S2.
Table 1, which is adapted from Gómez et al..37, presents the values of selected soil properties
for the direct and residual years.
~ 135 ~
Capítulo IV. Clomazone
TOC WSOC HA FA pH EC
(g kg-1) (mg kg-1) (g kg-1) (g kg-1) (H2O) (dS m-1)
2015
SNT 10.2aA 210cA 1.62bA 1.10cB 5.77cA 2.14aA
SNTW 21.3dB 448dA 2.35dA 1.29dA 6.58eA 3.69bA
ST 10.7aA 137bA 1.34aA 0.97bA 5.64bA 3.74bA
STW 15.7bA 497eB 2.02cA 1.29dA 5.99dA 4.19cA
FT 10.9aA 72.8aA 1.50abA 0.85aA 4.93aA 3.60bA
FTW 20.3cB 489eB 1.60bA 1.02bA 6.06dB 4.46cB
2017
SNT 15.1cB 316bB 1.44aA 0.95aA 6.08cB 3.96cB
SNTW 19.1eA 498dA 2.24cA 1.24dA 6.61eA 3.44abA
ST 13.1aB 336bcB 1.55aB 1.48eB 5.61aA 4.62dB
STW 18.2dB 395cA 2.40cB 1.13cA 6.35dB 3.73bcA
FT 13.9bB 220aB 1.48aA 1.03bB 5.65aB 3.37aA
FTW 19.1eA 325bA 1.88bB 1.19cdB 5.80bA 3.29aA
Y *** ** ** *** *** NS
M *** *** *** *** *** ***
YxM *** *** *** *** *** ***
ANOVA factors are Y: year; M: management regime; Y x M: interaction year x management regime; *, **, and
*** significant at a levels of 0.05, 0.01, and 0.001, respectively; NS: not significant. Different letters indicate
significant differences (p < 0.05) between management regimes in the same year (lower case letters) and
between years within the same management regime (upper case letters).
~ 136 ~
Capítulo IV. Clomazone
The clomazone dissipation studies were conducted under non-flooded (aerobic) and
flooded (anaerobic) incubation conditions. Clomazone additions were applied so as to reach
an initial concentration of 3.3 µg g-1 soil (equivalent to 1 kg ha-1). For each treatment,
triplicate samples were periodically removed to determine the herbicide's residual
concentration. Clomazone was extracted from the soil samples with methanol (10 mL). After
centrifuging, residues of clomazone were analysed in the supernatants by HPLC. A kinetics
equation of first order was fitted to the data corresponding to dissipation (Fig. S1), followed
by calculation of the respective half-lives (t1/2). Further information can be found in Text S4
of SM.
Dehydrogenase activity (DA) determinations were made under aerobic and anaerobic
incubation conditions following García et al.39 as detailed in SM (Text S4).
For each treatment, PVC disturbed-soil columns (5-cm i.d. × 30-cm length) in
triplicate were used to measure clomazone leaching in accordance with OECD40. After
saturating with a solution of 0.01 M CaCl2, the columns were allowed to drain for 24 h.
Clomazone was then applied at a 1 kg ha-1 dose to the top of each column. Each day, an
additional 50 mL 0.01 M CaCl2 was poured into the top of the columns, and the leachates
were recovered as long as the herbicide was detected. These leachates were analysed by
HPLC to determine their clomazone concentration. When the monitoring period concluded,
each soil column was partitioned into sections of 5-cm depth to determine the clomazone
remaining at four different depths. The extraction procedure followed was that described
above in the Dissipation studies subsection. Further information about these leaching
experiments is given in SM (Text S5).
~ 137 ~
Capítulo IV. Clomazone
The statistical analysis was carried out using the SPSS statistics software package
version 22.0. After having verified the normality distribution (Shapiro-Wilk method) and
homoscedasticity (Levene test) of the data, these were subjected to a one-way ANOVA.
Duncan test was applied to compare inter-treatment differences (p<0.05). A Pearson's
correlation analysis was applied to measure relationships between selected variables.
The clomazone sorption-desorption isotherms for direct and residual years are
presented in SM (Fig. S2). For both years, the sorption isotherms fitted appropriately the
Freundlich equation (R² > 0.956; Table 2), showing that the herbicide's sorption was
concentration-dependent (nf values <1; Table 2). The clomazone Kd values for the direct
(1.54-3.05) and residual (1.24-2.95) years are of the same order as those found by Xu et al.41
of 1.11-3.26 for soils from China with and without burned rice straw amendment. However, a
wider range of Kd values (2.3-11.0) was found by Gunasekara et al.42 for rice soils from
California (USA). The different treatments significantly (p<0.001) influenced the clomazone
sorption, with different effects in the direct and residual years since the treatment × year
interaction was found to be significant (Table 2). For the unamended soils, in the direct year
the Kd values were 1.2 times lower in ST than in SNT and FT. In the residual year, however,
these values were significantly greater in FT than in SNT and ST by factors of 1.4 and 1.2,
respectively, indicating that the timing of the implementation of different water and tillage
management regimes is of major importance for the sorption behaviour of this herbicide.
These results are contrary in part than those reported by Gómez et al.37 which found sorption
values greater in FT than in SNT and ST in both the direct and residual years, although for
bispyribac-sodium (BS) herbicide.
~ 138 ~
Capítulo IV. Clomazone
nf R2ads Kd H R2des
2015
SNT 0.893bB 0.999 1.85bB 301cA 0.968
SNTW 0.837aA 0.999 3.05eB 221aA 0.970
ST 0.903bA 0.999 1.54aB 318cA 0.983
STW 0.879bB 0.998 2.27cB 261bA 0.996
FT 0.953cB 0.998 1.81bA 247bA 0.998
FTW 0.906bB 0.999 2.82dA 218aA 0.996
2017
SNT 0.775aA 0.994 1.24aA 420cB 0.999
SNTW 0.806aA 0.988 2.06dA 290aB 0.999
ST 0.797aA 0.956 1.42bA 383bcB 0.999
STW 0.778aA 0.995 2.06dA 318abA 0.975
FT 0.794aA 0.994 1.69cA 341abA 0.988
FTW 0.852aA 0.994 2.95eA 263aA 0.998
Y *** - *** *** -
M * - *** *** -
YxM NS - *** NS -
ANOVA factors are Y: year; M: management regime; Y x M: interaction year x management regime; *, **, and
*** significant at a levels of 0.05, 0.01, and 0.001, respectively; NS: not significant. Different letters indicate
significant differences (p < 0.05) between management regimes in the same year (lower case letters) and
between years within the same management regime (upper case letters).
different treatments in the direct year and in the residual year. In the unamended soils, the
lowest H values observed corresponded to the FT treatment, indicating lower reversibility of
sorbed clomazone under non-flooding than flooding management, especially when no-tillage
is implemented (Table 2). These results are consistent with those of various workers who
report lower reversibility of different pesticides under no-tillage management (e.g., Reddy
and Locke46). Furthermore, for both years the H values were significantly lower after W
application, with again the lowest values corresponding to FTW (Table 2). These results
show that sorbed clomazone may be retained more strongly in soils that are under non-
flooding management, especially when W has been applied as organic amendment. Greater
reversibility of clomazone in soils under flooding conditions may be a result of the significant
falls in their HA values, especially for the amended soils whose HA values were up to
1.5 and 1.3 times lower under flooding than non-flooding conditions in the direct and residual
years, respectively (Table 1). This is consistent with Gunasekara et al.42 who also reported
that HA compounds limited clomazone desorption in rice soils from California (USA).
The clomazone dissipation curves and the dehydrogenase activity (DA) are presented
in Figure 1. The data fit first-order kinetics under anaerobic and aerobic experimental
conditions, giving values of R² > 0.858 and R² > 0.824 in the direct and residual years,
respectively (Table 3). For both years, the values of DA determined before (DAB) and two
hours after (DAA) clomazone application and by considering all 50 d of incubation time
(DAT) were much lower under aerobic than anaerobic conditions (Table 3). This agrees with
Gómez et al.37 who also found values of DA much lower under aerobic than anaerobic
conditions in the same unamended and amended soils of the present study, but after
application of BS herbicide. Similar results have been also reported for MCPA and
bensulfuron-methyl herbicides in different unamended rice-field soils,47 which also agreed
with a study finding a reduction in DA with increasing soil aeration and redox potential.48
~ 140 ~
Capítulo IV. Clomazone
2015
100 SNT 8 100 ST 8 100 FT 8
Aerobic conditions 80 6 80 6 80 6
SNT 8 8 FT 8
100 100 ST 100
Anaerobic conditions
4
40 2 40 2 40
20 0 20 0 20 2
0 0 0 0
0 10 20 30 40 50 0 10 20 30 40 50 0 10 20 30 40 50
2017
100 SNT 8 100 ST 8 100 FT 8
Aerobic conditions
80 80 6 80
40 40 40
20 2 20 2 20 2
0 0 0 0 0 0
0 10 20 30 40 50 0 10 20 30 40 50 0 10 20 30 40 50
80 6 80 6 80 6
60 4 60 4 60 4
Clomazone (%)
40 40 40
20 2 20 2 20 2
0 0 0 0 0 0
0 10 20 30 40 50 0 10 20 30 40 50 0 10 20 30 40 50
Except for aerobic experimental conditions in the direct year, the clomazone
dissipation rates were significantly influenced by the tillage and irrigation regime. This was
particularly evident under anaerobic experimental conditions for which clomazone
persistence was significantly shorter in FT, with t1/2 values being lower than those
corresponding to SNT and ST by factors of 1.6 and 3.1 for the direct year, and 1.8 and 2.5 for
the residual year, both respectively (Table 3). The longer persistence of clomazone observed
in ST compared to SNT for both direct and residual years under anaerobic conditions may be
attributable to these soils' lower microbial activity as indicated by their DA values. Indeed,
the DAT values in ST were 1.7 times lower than those corresponding to SNT for both years
(Table 3). This is consistent with Dalal et al.51 and Biederbeck et al.52 who also found that
microbial biomasses were smaller under conventional tillage management than under no-
tillage.
~ 142 ~
Capítulo IV. Clomazone
Table 3. Effect of different treatments on dehydrogenase activity and clomazone dissipation parameters.
t1/2 80% R2 80% t1/2 1:1.25 R2 1:1.25 DAB80% DAA80% DAT80% DAB1:1.25 DAA1:1.25 DAT1:1.25
(days) (days) (µg INTF g-1 h-1)
2015
SNT 36.3cA 0.976 5.40bA 0.934 0.344aA 0.535aA 4.39aA 2.42aA 4.81bB 23.7bB
SNTW 21.1abA 0.953 3.56aA 0.957 0.718bA 1.79cB 13.8cB 5.85bA 7.60dB 52.0dB
ST 33.5cA 0.949 10.8cA 0.858 0.337aA 0.585aB 5.36aB 1.62aA 3.43aB 13.5aB
STW 29.7bA 0.976 5.44bA 0.956 0.650bA 1.06bA 9.22bA 4.83bA 6.06cA 29.6cB
FT 33.1cA 0.904 3.43aA 0.980 0.269aA 0.573aA 4.53aA 2.30aA 2.54aA 11.8aA
FTW 18.1aA 0.917 3.06aA 0.986 0.710bA 2.05cB 17.1dB 4.38bA 7.33dA 50.2dA
2017
SNT 54.6abB 0.888 14.7cB 0.961 0.793bcB 0.901cA 6.41bB 4.53bcB 2.04aA 10.5bA
SNTW 64.1cB 0.873 21.3dB 0.857 1.04eB 0.999cA 9.31dA 5.43cA 4.59bA 19.4cA
ST 52.7aB 0.959 20.5dB 0.868 0.472aB 0.444aA 4.33aA 1.34aA 1.18aA 6.04aA
STW 63.4cB 0.888 23.2eB 0.879 0.838cB 0.792abA 8.61dA 3.79bA 5.38bA 20.9cA
FT 62.6bcB 0.885 8.23bB 0.824 0.762bB 0.984cA 7.58cB 8.19dB 8.50cB 36.8dB
FTW 60.3bcB 0.895 2.53aA 0.984 0.962dB 0.761abA 7.51cA 9.76eB 7.66cA 43.2eA
Y *** - *** - *** ** *** *** * ***
M * - *** - *** *** *** *** *** ***
YxM ** - *** - ** *** *** *** *** ***
Half-lives: t1/2 80% in soils at 80% field water capacity; t1/2 1:1.25 in soils with 1:1.25 (w/v) (soil/water) moisture content. DA: dehydrogenase activity two hours before (B)
and after (A) the application of the herbicide to soils conditioned to 80% field capacity and 1:1.25 (w/v) (soil/water) moisture content. DAT: total dehydrogenase activity
considering all the incubation times in soils conditioned to 80% field capacity and 1:1.25 (w/v) (soil/water) moisture content. ANOVA factors are Y: year; M:
management regime; Y x M: interaction year x management regime; *, **, and *** significant at a levels of 0.05, 0.01, and 0.001, respectively; NS: not significant.
Different letters indicate significant differences (p < 0.05) between management regimes in the same year (lower case letters) and between years within the same
management regime (upper case letters).
~ 143 ~
Capítulo IV. Clomazone
In the residual year, DAT values were also much higher in the amended than in
unamended soils in anaerobic and aerobic incubation conditions (Table 3). However, contrary
to the results for the direct year, for the residual year, clomazone persistence was significantly
increased in SNT and ST when W was applied under both anaerobic and aerobic incubation
~ 144 ~
Capítulo IV. Clomazone
conditions, but it was decreased in FT management, although only this decrease was
significant under anaerobic incubation conditions (Table 3). Thus, while the t1/2 values were
greater by a factor of 1.2 in SNTW and STW than in the corresponding unamended soils
(SNT and ST) under aerobic incubation conditions, and by factors of 1.4 and 1.1 in SNTW
and STW, respectively, these values were lower by a factor of 3.2 in TFW than in the
corresponding unamended soils under anaerobic incubation conditions (Table 3). Our
findings could be explained by the unamended and amended SNT and ST soil microbial
communities naturally not having any adaptation to anoxic conditions after years of non-
flooding management implementation (Table 3). This finding is concordant with those of
Tomco et al.27 who report the importance of anaerobic bacteria degrading clomazone.
Our results are contrary in part to what we found in a previous work for BS37 in rice
soils after w addition in which BS persistence increased in the direct and residual years under
aerobic conditions. However, under anaerobic conditions, while BS persistence decreased in
the direct year, it increased in the residual year except for FT treatment.
~ 145 ~
Capítulo IV. Clomazone
could be enhanced in soils with conventional tillage regardless of the water irrigation system
implemented. The lower amount of clomazone in the leachates corresponding to the SNT
treatment may be consistent with its higher TOC (Table 1) and H values (i.e., lower
reversibility; Tables 2 and 4). However, these results contrast with those found in a previous
study37 in which the amount of BS leached was lower in FT than in SNT and NT. This effect
was explained by the greater sorption and lesser persistence of BS in FT than in SNT and NT
treatments.
2015
Clomazone leached (%)
FT
30 SNT 30 ST 30 FTW
SNTW STW
25 25 25
20 20 20
15 15 15
10 10 10
5 5 5
0 0 0
0 2 4 6 8 0 2 4 6 8 0 2 4 6 8
2017
Clomazone leached (%)
30 SNT 30 ST 30 FT
SNTW STW FTW
25 25 25
20 20 20
15 15 15
10 10 10
5 5 5
0 0 0
0 2 4 6 8 0 2 4 6 8 0 2 4 6 8
Water added (pore volumes) Water added (pore volumes) Water added (pore volumes)
The addition of W significantly reduced the quantity of clomazone that leached in the
direct and residual years (Table 4). Thus, the amount of clomazone in the leachates was
lessened by factors of 1.8, 2.4, and 2.8 in SNTW, STW, and FTW, respectively, than in the
corresponding unamended soils (SNT, ST, and FT) in the direct year, and by factors of 1.3,
1.6 and 2.6 in SNTW, STW, and FTW than in their corresponding unamended soils in the
~ 146 ~
Capítulo IV. Clomazone
residual year (Table 4). While in the direct year there were no significant differences among
amended treatments, the amount of clomazone leached in the residual year was significantly
lower in FTW (1.6 times less) than in SNTW and STW (Table 4). These results may be
attributable to the greater values of Kd observed in amended compared to unamended soils
(Tables 2 and 4). Indeed, the amount of clomazone leached had a significant negative
correlation with Kd (r=-0.785, p <0.01). Furthermore, the lesser persistence may explain the
greater fall in the quantity of clomazone in the FTW leachates in the residual year, compared
to those observed in SNTW and STW (Tables 2, 3 and 4). These results suggest that using W
as organic amendment in rice production strongly decreases clomazone leaching in the short-
term, regardless of the irrigation and tillage management implemented. However, in the
medium-term, this effect was much more evident under flooding irrigation with conventional
tillage (Table 4), as was expected according to the above sorption-desorption and dissipation
results. Similarly, Gómez et al.37 also observed that the use of W reduced the amount of BS
leached in the same treated soils, although only at the short-term (direct year), indicating that
the effects of this organic amendment can be different for different types of pesticides.
~ 147 ~
Capítulo IV. Clomazone
At the termination of the trial, the total amount of clomazone recovered from the soil
columns was significantly influenced by the treatments, with their effects differing between
the two years, as shown by the significance (p<0.05) of the treatment × year interaction
(Table 4). For all treatments and both years, clomazone was retained in the all four soil
columns sections. In the unamended soils, while in the direct year no significant differences
between treatments were observed, in the residual year the amounts of clomazone recovered
were significantly lower in FT than in SNT and ST by factors of 1.9 and 2.1, respectively.
For the direct year, the addition of W significantly decreased the amount of clomazone
recovered in all treatments (Table 4). However, in the residual year the amounts of the
herbicide extracted increased in all treatments, although this only was significant in FT. For
both years, the results are consistent with those of the dissipation experiment described
above, especially under anaerobic incubation conditions (Tables 3 and 4). Indeed, a
significant positive correlation of the clomazone recovered was observed with the t1/2 values
under anaerobic conditions (r=0.705, p <0.01). The greater Kd value (Table 2) may explain
the significant increase of clomazone retained in FTW in the residual year compared to that
observed in FT (Table 4), despite its lower persistence (Table 3).
4. Conclusions
~ 148 ~
Capítulo IV. Clomazone
basis of our previous studies for BS37, amending soils with W may have different effects on
the environmental fate of pesticides depending of their characteristics. Therefore, future
studies are needed evaluating how the behaviour of each pesticide used in rice production is
affected by amendment with W under different tillage and water management practices.
Acknowledgements
Support for this work was provided by the Spanish Ministry of Economics and
Competitiveness (AGL2013-48446-C3-2-R) and Ministry of Science, Innovation and
Universities (RTI2018-095461-B-I00), and by the Extremadura Regional Government
(GR18011; IB16075) with co-financing from the Fondo Europeo de Desarrollo Regional.
Soraya Gómez is the recipient of a grant awarded by the Consejería of Economía, Comercio e
Innovación of the Extremadura Regional Government (PD16021). Damian Fernández is the
recipient of a grant-in-aid to promote research support personnel hiring, awarded by the
SEXPE of the Extremadura Regional Government, with co-financing from the Fondo
Europeo de Desarrollo Regional.
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3 Vieira DC, Noldin JA, Deschamps FC, Resgalla C, Ecological risk analysis of
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Capítulo IV. Clomazone
8 Busari MA, Kukal SS, Kaur A, Bhatt R, Dulazi AA, Conservation tillage impacts
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13 Li S, Jiang X, Wang X, Wright AL, Tillage effects on soil nitrification and the
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19 Cookson WR, Murphy DV, Roper MM, Characterizing the relationships between
soil organic matter components and microbial function and composition along a tillage
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20 Lupwayi NZ, Larney FJ, Blackshaw RE, Kanashiro DA, Pearson DC,
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organic carbon on soil water retention. Geoderma 116: 61-76 (2003).
26 Mattice JD, Skulman BW, Norman RJ, Gbur EE, Jr Analysis of river water for
rice pesticides in eastern Arkansas from 2002 to 2008. J. Soil Water Cons 65: 130–140
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34 Ahangar AG, Smernik RJ, Kookana RS, Chittleborough DJ, Separating the effects
of organic matter-mineral interactions and organic matter chemistry on the sorption of diuron
and phenanthrene. Chemosphere 72(6): 886-890 (2008).
41 Xu C, Liu W, Sheng GD, Burned rice straw reduces the availability of clomazone
to barnyardgrass. Sci Total Environ 392(2-3): 284-289 (2008).
42 Gunasekara AS, Dela Cruz IDP, Curtis MJ, Claassen VP, Tjeerdema RS, The
behavior of clomazone in the soil environment. Pest Manag Sci 65(6): 711-716 (2009).
44 Li LF, Li GX, Yang RB, Guo ZY, Liao XY, Clomazone dissipation, adsorption
and translocation in four paddy topsoils. J Environ Sci-China 16(4): 678-682 (2004).
45 Pereira GAM, Rodrigues DA, Fonseca LABV, Passos ABRJ, da SILVA MRF,
Silva DV, da SILVA AA, Sorption and desorption behavior of herbicide clomazone in soils
from Brazil [Comportamento de sorção e dessorção do clomazone em solos do Brasil. Biosci
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4 Proposed New Uses and Other Communcations on Clomazone, EPA-HQ-OPP-2006-0113
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51 Dalal RC, Henderson PA, Glasby JM, Organic matter and microbial biomass in a
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52 Biederbeck VO, Campbell CA, Hunter JH, Tillage effects on soil microbial and
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Capítulo IV. Clomazone
Text S1. The herbicide was assayed by HPLC, using a chromatograph (Waters 600E)
coupled to a diode-array detector (Waters 996). The conditions used were: Nova-Pack
column (150 × 3.9 mm, 4.5 µm particle size), acetonitrile:water (70:30) mobile phase at a
flow rate of 1 mL min-1, 25 µL injection volume, and UV detection at 214 nm. The limits of
detection and quantification, calculated as the herbicide concentrations resulting in signal-to-
noise ratios of 3:1 and 10:1 respectively, were 0.015 μM and 0.047 μM, respectively.
Text S2. Total organic carbon content (TOC) was determined by dichromate
oxidation. Water-soluble organic carbon (WSOC) was extracted with de-ionized water at a
3:1 (water to soil) ratio. Humic and fulvic acids (HA and FA, respectively) were extracted by
a solution of 0.1 M Na4P2O7 + NaOH using a ratio of extractant to sample of 10:1, and to
precipitate humic acid the supernatant was acidified to pH 2 with H2SO4. The WSOC and the
total organic carbon associated with each fraction of HA and FA were determined by
dichromate oxidation and absorbance at 590 nm to detect Cr3+ formation. The pH was
measured in a 1:1 (w/v) soil/water using a combination electrode. Electrical conductivity
(EC) was measured in a saturation extract.
Text S3. Soil samples (5 g) were treated by mechanical shaking at 20±1 °C for 24 h
with 10 mL of solutions of clomazone in 0.01M CaCl2 at initial concentrations (Ci) of 5, 10,
20, 40, and 50µM. Equilibrium concentrations in the supernatants were determined by high-
performance liquid chromatography (HPLC). The amount of clomazone sorbed (Cs) was
calculated from the difference between the initial (Ci) and the equilibrium (Ce) solution
concentrations. The values of Kd were calculated from the fit of the experimental sorption
isotherms (Kd = Cs/Ce) at a selected Ce (20 μM). The measurements with control samples
containing only clomazone but no soil showed that there were no losses of the herbicide due
to microbial activity, volatilization, or sorption onto the surface of the tubes. Hysteresis
coefficients (H) were calculated: H = (nfa/nfd)×100, where nfa and nfd are the Freundlich
nf constants obtained from the sorption and desorption isotherms, respectively.
~ 154 ~
Capítulo IV. Clomazone
Text S4. For each treatment, triplicate soil samples (5 g) were weighed into 50 mL
glass tubes. Soils were supplemented with distilled water to obtain non-flooded (80% field
capacity) and flooded (soil-to-water ratio 1:1.25, w/v) moisture conditions. Prior to the
clomazone addition, the soils were pre-incubated for 7 days in the dark at 20±1 °C to allow
the soil microorganisms to adapt to the non-flooded (aerobic) and flooded (anaerobic)
incubation conditions, and also to allow the development of reducing conditions in the
flooded soils. Then clomazone dissolved in distilled water was applied at a rate equivalent to
1 kg ha-1, and the tubes were incubated in the dark at 20±1 °C for 49 days. Moisture was
maintained at a constant level throughout the experiment by adding distilled water as
necessary. Three replicate tubes were removed (at 2 h and at 2 days after herbicide
application, and then at 7-day intervals for 49 days) from each treatment to measure the
herbicide concentrations. The soils (5 g) were extracted with methanol (10 mL) by shaking
mechanically on an end-over-end shaker at 20±1°C for 24 h followed by centrifugation, and
the residues of the herbicide in the extracts were determined by HPLC. Recoveries were
greater than 95% of the herbicide applied to the soil. Clomazone residues from water samples
were also determined by HPLC. The clomazone dissipation data in soils and water were fitted
to a first-order kinetics equation, C = Co e-kt, where C is the clomazone concentration at time
t (days), Co is the initial herbicide concentration, and k (day-1) is the degradation constant,
and the half-lives (t1/2) were calculated.
To measure the dehydrogenase activity (DA), another three replicate soil samples of
each treatment were weighed out into glass tubes, and supplemented with sterile distilled
water to obtain aerobic (80% field capacity) and anaerobic (1:1.25 w/v soil/water) moisture
conditions. From each treatment, the tubes were removed before clomazone application and
at the same times as for the dissipation experiment. The tubes were incubated for 20 h at
20±1 °C in the dark with 1 mL of 0.4% 2-p-iodophenyl-3p-nitrophenyl-5 tetrazolium chloride
(INT) as substrate. At the end of the incubation, the iodonitrotetrazolium formazan (INTF)
produced was extracted with methanol, and the absorbance was measured at 490 nm.
Text S5. For the leaching studies, PVC was used to prepare disturbed soil columns
(5-cm i.d. × 30-cm length). To minimize losses of soil during the experiment, the top 5 cm of
the columns was filled with sea sand and the bottom 5 cm with sea sand plus glass wool. The
remaining 20 cm was hand-packed with air-dried soil. The soil columns were saturated with
~ 155 ~
Capítulo IV. Clomazone
0.01 M CaCl2 and allowed to drain for 24 h. Then, clomazone was applied to the top of the
soil columns at a rate equivalent to 1 kg ha-1. Leachates containing the clomazone were
collected daily, filtered, and assayed by HPLC. After the leaching experiments, the soil
columns were left to drain for 24 h and then sectioned into the follow depths: 0-5 cm, 5-10
cm, 10-15 cm, and 15-20 cm. In order to determine the residual amounts of clomazone, the
soils (5 g) from different depths were extracted with methanol (10 mL) by shaking for 24 h at
20±1°C, and assayed by HPLC.
~ 156 ~
Capítulo IV. Clomazone
2015
Aerobic conditions
Ln Clomazone extracted
Anaerobic conditions
Ln Clomazone extracted
2017
Aerobic conditions
Ln Clomazone extracted
Anaerobic conditions
Ln Clomazone extracted
Figure S1. The symbols indicate the experimental data points of clomazone dissipation
studies whereas the lines correspond to the fits to first-order dissipation kinetics for those
experimental data. Error bars denote standard errors of triplicate measurements. Treatments
are: No-tillage and sprinkler irrigation without (SNT) or with compost application (SNTW);
conventional tillage and sprinkler irrigation without (ST) or with compost application (STW),
continuous flooding irrigation and tillage without (FT) or with compost application (FTW).
~ 157 ~
Capítulo IV. Clomazone
2015
Cs (µmol kg-1)
SNT ST FT
60 60 60
40 40 40
20 20 20
0 0 0
0 5 10 15 20 25 30 0 5 10 15 20 25 30 0 5 10 15 20 25 30
Cs (µmol kg-1)
40 40 40
20 20 20
0 0 0
0 5 10 15 20 25 30 0 5 10 15 20 25 30 0 5 10 15 20 25 30
SNT ST FT
60 60 60
40 40 40
20 20 20
0 0 0
0 5 10 15 20 25 30 0 5 10 15 20 25 30 0 5 10 15 20 25 30
Cs (µmol kg-1)
40 40 40
20 20 20
0 0 0
0 5 10 15 20 25 30 0 5 10 15 20 25 30 0 5 10 15 20 25 30
Figure S2. Effects of treatments on the clomazone sorption and desorption isotherms.
Vertical bars representing one standard error of the mean were smaller than the symbols in all
cases. Ce: equilibrium clomazone concentration; Cs: amount of clomazone sorbed.
Treatments are: No-tillage and sprinkler irrigation without (SNT) or with compost application
(SNTW); conventional tillage and sprinkler irrigation without (ST) or with compost
application (STW), continuous flooding irrigation and tillage without (FT) or with compost
application (FTW).
~ 158 ~
Capítulo V. Olive mill sludge may reduce water
contamination by 4-chloro-2-methylphenoxyacetic
acid (MCPA) in non-flooding but enhance it in
flooding rice cropping agroecosystems
Keywords: flooding rice cultivation, MCPA behaviour, non-flooding rice cultivation, olive
mill sluge
Capítulo V. MCPA
1
Área de Edafología y Química Agrícola, Facultad de Ciencias – IACYS,
Universidad de Extremadura, Avda de Elvas s/n, 06071 - Badajoz, Spain.
² Área de Producción Vegetal, Escuela de Ingenierías Agrarias – IACYS, Universidad
de Extremadura, Ctra de Cáceres, 06071 - Badajoz, Spain.
Abstract
A field experiment covering three years was conducted to evaluate how composted
olive mill sludge (OS) influenced MCPA's environmental fate in rice soils under six
combinations of tillage and irrigation cultivation techniques: tillage and sprinkler irrigation
without (TS) or with (TSOS) the addition of OS (80 Mg ha-1), no-tillage and sprinkler
irrigation without (NTS) or with (NTSOS) OS, and tillage and continuous flooding without
(TF) or with (TFOS) OS. The measurements made in the first and third years after OS
application were taken to constitute the "direct" and "residual" effects, respectively. After OS
amendment, Kd (partition coefficients) values in the direct year were lower by factors of 1.1,
1.3, and 1.9 in TSOS, NTSOS, and TFOS, respectively, relative to the corresponding
unamended soils, and in the residual year by factors of 1.1 and 1.5 in TSOS and NTOS, but
greater by a factor of 1.5 in TFOS, than in the corresponding unamended soils, respectively.
The dissipation of MCPA was very fast under both anaerobic (t1/2=1.80–5.29 d) and aerobic
(t1/2=2.23–9.42 d) incubation conditions. The field application of OS led to a decrease in
MCPA persistence under both incubation conditions, especially in the TF case. However,
while under aerobic conditions the half-life (t1/2) decreased after OS addition in the direct and
residual years, under anaerobic condition it only decreased in the direct year. While the
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Capítulo V. MCPA
application of OS in TS and NTS led to less leaching of MCPA, in TF it led to 1.4 and 1.2
times more leaching losses of the herbicide for the direct and residual years, respectively.
Therefore, the use of OS in rice production could be considered an effective strategy for
reducing water contamination by MCPA in at least the short- and medium-terms after its
application, but only under non-flooding crop management regimes irrespective of the tillage
practice implemented.
1. Introduction
In the European Union (EU), rice (Oryza sativa L.) production is concentrated in three
Mediterranean countries: Italy, Greece, and Spain. Spain is the second largest of these
producers, accounting for 30% of EU production. Traditionally, rice has been cultivated
under tillage plus continuous flooding irrigation. These practices can lead to water
contamination, decline in water productivity, and deterioration of the soil's properties.
Furthermore, they contribute to the increasing emission of greenhouse gases, especially by
highest CH4 fluxes measured under flooding in reference to non-flooding regimes (Janz et al.,
2019). In Mediterranean countries, where the aforementioned practices remain commonplace,
there has recently been a decline in the area of rice cultivation in several producing regions
where water supplies for this crop cannot always be guaranteed. For instance, in
Extremadura, the second largest rice producing region in Spain, recent severe water shortages
have resulted in a steady decline in rice area, reaching more than 27% in the last decade
(MAPA, 2019). Therefore, crop management alternatives that improve water-use efficiency
are needed to ensure the sustainability of rice production in Mediterranean areas in which it is
a strategically important sector. One such alternative is non-flooding rice production, with or
without tillage, (Jabran et al., 2015; Mukherjee et al., 2017). In the mid- and long-terms, the
yields are similar but the water requirements can be reduced by up to 75%, (Sánchez-Llerena
et al., 2016) and through the use of non-flooding the global warming potential was reduced
versus flooded irrigation about 40% (Fangueiro et al., 2017). In the short-term however, our
previous studies have found lower yields under non-flooding management, with this being
attributable to the lower soil organic matter (OM) content observed with this system during
the first two years of its implementation (Sánchez-Llerena et al., 2016). The application of
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Capítulo V. MCPA
organic amendments could compensate for this OM deficiency, and the resulting
enhancement in rice productivity might also ensure the crop's sustainability in the short-term
in areas where water availability is scarce.
Weed infestation is the major constraint to rice production under both flooding and
non-flooding cropping conditions, with potentially very high yield losses (>50%) if weeds are
not appropriately controlled (Rao et al., 2007; Singh et al., 2018). To this end, 4-chloro-2-
methylphenoxyacetic acid (MCPA) is one of the most commonly used herbicides worldwide
for effective post-emergence control of broad-leaved weeds in a range of crops, including rice
(Wu et al., 2018). This herbicide has good selectivity, low cost, and compatibility with other
herbicides (Marczewska et al., 2010). However, it is considered to be environmentally
hazardous, and may have toxic effects on non-target organisms including humans, being
possibly mutagenic and carcinogenic (IARC, 1983). Furthermore, its weak adsorption by
soils makes MCPA one of the most frequently detected herbicides in groundwater, lakes, and
rivers. The concentrations may exceed the EU threshold (0.1μg L-1) for drinking water
(Comoretto et al., 2007; Espel et al., 2019; Palma et al., 2018), which can negatively affect
ecosystem functions (Schäfer et al., 2007).
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Capítulo V. MCPA
Irrigated soils have significantly lower pH and OM content than rain-fed soils, an effect
that for OM is stronger under sprinkler than flooding irrigation, but for pH is weaker
(Sánchez-Llerena et al., 2016). It is also widely recognized that the transition from anaerobic
to aerobic cropping conditions may alter the soil's microbial activity, and consequently the
degradation of pesticides (e.g., López-Piñeiro et al., 2016). Moreover, the addition of organic
amendments may alter a soil's properties and hence the environmental fate of pesticides
(Delgado-Moreno et al., 2017; López-Piñeiro et al., 2013; Peña et al., 2019). For instance, an
increase in soil OM content enhances pesticide sorption and biodegradation, thus reducing
the amount of pesticide potentially available to be leached, and therefore limiting its
environmental availability (e.g., Nemeth-Konda et al., 2002). This is particularly relevant in
the Mediterranean region whose soils are very poor in OM content (Cabrera et al., 2007;
Cañero et al., 2012; Peña et al., 2016). But contradictory trends have also been reported,
reflecting the dependence of the fate of pesticides in amended soils on the type of soil, on the
dosage, type, and degree of maturity of the amendment, and on the properties of the specific
pesticide (Cox et al., 2007; García-Delgado et al., 2019).
We could find no studies analyzing how different rice cropping systems influence on
MCPA behaviour, other than our previous research, but in soils with quite different properties
to the soils used in the present work (López-Piñeiro et al., 2019), in spite of the extensive use
of MCPA in rice agroecosystems and its potential for water contamination. Moreover, we
found no work contrasting how organic amendment might impact this compound's
environmental fate under different rice irrigation and tillage management regimes. The aim of
the present work therefore was to assess how amendment with OS (a sludge whose disposal
may constitute an environmental problem in Mediterranean countries) influences the
~ 164 ~
Capítulo V. MCPA
persistence, sorption, and leaching of MCPA in rice soils under different water and tillage
management regimes. Because the interactions between soils and pesticides may be affected
by the transformation of the OS organic matter under field conditions, we also evaluated the
residual and direct effects in years one and three after its application.
2.1. Herbicide
The MCPA (97.8% purity) herbicide used in the sorption, leaching, and dissipation
experiments was supplied by Dr Ehrenstorfer, GmbH (Germany). The herbicide
concentrations were determined by high-performance liquid chromatography (HPLC) as
detailed in Text S1 of Supplementary Material (SM).
A field experiment on a rice soil was carried out from 2015 to 2017 in southern Spain
(38°55'N; 6°57'W), in a semi-arid Mediterranean region with mean annual rainfall and
temperature of 460 mm and 16.2°C, respectively. The soil's composition was 20.8% clay,
28.9% silt, and 50.3% sand, with 12.6 g kg-1 organic carbon, 1.28 g kg-1 total N, and pH 4.42.
This experimental area had been under rice cropping for 11 years, applying deep ploughing
and flooding. The experiment involved eighteen plots (18 m × 10 m) with six crop
management regimes in triplicate: tillage and sprinkler irrigation without (TS) or with
(TSOS) first-year composted OS addition, no-tillage and sprinkler irrigation without (NTS)
or with (NTSOS) first-year composted OS addition, and tillage and continuous flooding
without (TF) or with (TFOS) first-year composted OS addition. The composted OS was made
from a mixture of 10%olive leaves and 90% fresh two-phase olive-mill sludge. Its main
properties were the following: total organic carbon (TOC) 382 g kg-1; pH 7.71; total nitrogen
~ 165 ~
Capítulo V. MCPA
21.7 g kg-1; and electrical conductivity (EC) 2.32 dS m-1. The composted OS addition dosage
in the TSOS, NTSOS, and TFOS treatments was 80 Mg ha-1.
After harvest in 2015 and 2017, four subsamples of soil were taken from each of the
plots (20 cm depth) for sorption-desorption, leaching, and dissipation determinations. The
measurements done in 2015 and 2017 constituted the "direct" and "residual" effects,
respectively. Measurements were also made of the soil pH, TOC, water soluble organic
carbon (WSOC), and fulvic acid (FA) and humic acid (HA) contents, as described in López-
Piñeiro et al. (2016). Table 1, which is adapted from Gómez et al. (2019), presents the values
of selected soil properties for both the direct and residual year.
TOC WSOC HA FA pH
(g kg-1) (mg kg-1) (g kg-1) (g kg-1) (H2O)
2015
TS 10.7 aA 137 bA 1.34 aA 0.97 bA 5.64 bA
TSOS 15.7 bA 497 eB 2.02 cA 1.29 dA 5.99 dA
NTS 10.2 aA 210 cA 1.62 bA 1.10 cB 5.77 cA
NTSOS 21.3 dB 448 dA 2.35 dA 1.29 dA 6.58 eA
TF 10.9 aA 72.8 aA 1.50 abA 0.85 aA 4.93 aA
TFOS 20.3 cB 489 eB 1.60 bA 1.02 bA 6.06 dB
2017
TS 13.1 aB 336 bcB 1.55 aB 1.48 eB 5.61 aA
TSOS 18.2 dB 395 cA 2.40 cB 1.13 cA 6.35 dB
NTS 15.1 cB 316 bB 1.44 aA 0.95 aA 6.08 cB
NTSOS 19.1 eA 498 dA 2.24 cA 1.24 dA 6.61 eA
TF 13.9 bB 220 aB 1.48 aA 1.03 bB 5.65 aB
TFOS 19.1 eA 325 bA 1.88 bB 1.19 cdB 5.80 bA
Y F-values 194 *** 9.67 ** 21.8 ** 43.2 *** 80.7 ***
M F-values 544 *** 522 *** 55.0 *** 48.1 *** 448 ***
Y x M F-values 94.3 *** 21.5 *** 20.1 *** 64.6 *** 46.1 ***
ANOVA factors are Y: year; M: management regime; Y x M: interaction year x management regime. F-values
indicate the significance levels * p < 0.05, **p < 0.01, and ***p < 0.001, respectively, and NS: not significant.
Different letters indicate significant differences (p < 0.05) between management regimes in the same year
(lower case letters) and between years within the same management regime (upper case letters).
The technique used to determine MCPA adsorption isotherms in unamended and OS-
amended soils was batch equilibration in accordance with OECD guideline 106 (OECD,
~ 166 ~
Capítulo V. MCPA
2000) as described in López-Piñeiro et al. (2016). The adsorption-desorption data were fitted
to a Freundlich equation. Further information can be found in Text S2 of SM.
The MCPA dissipation studies in unamended and OS-amended soils were conducted
under non-flooded (aerobic) and flooded (anaerobic) incubation conditions. MCPA additions
were applied so as to reach an initial concentration of 5 μg g-1 soil (dry weight). For each
treatment, triplicate samples were periodically removed to determine the herbicide's residual
concentration until 49 days from preparation. MCPA was extracted by adding 10 mL of a
60:40 (v/v) mixture of methanol/diluted H3PO4 (pH 2). After centrifuging, residues of MCPA
in the supernatants were assayed by HPLC. A first-order kinetics equation was fitted to the
dissipation data, followed by calculation of the respective half-lives. Detailed information is
given in Text S3 of SM.
For each treatment, PVC disturbed-soil columns (5-cm i.d. × 30-cm length) in triplicate
were used to measure MCPA leaching in both unamended and OS-amended soils in
accordance with OECD (2004). After saturating with a solution of 0.01 M CaCl2, the
columns were allowed to drain for 24 h. MCPA was then applied at a 1.5 kg ha-1 dosage to
~ 167 ~
Capítulo V. MCPA
the top of each column. Each day, an additional 50 mL 0.01 M CaCl2 was poured into the top
of the columns, and the leachates were recovered as long as the herbicide was detected. These
leachates were assayed by HPLC to determine their MCPA concentration. When the
monitoring period had concluded, each soil column was partitioned into sections of 5-cm
depth to determine the MCPA remaining at four different depths. The extraction procedure
followed was that described above in Sec. 2.4. Further information about these leaching
experiments is given in Text S4 of SM.
Statistical analyses were done using the SPSS statistics software package version 22.0.
An analysis of variance (ANOVA) followed by the Duncan test was applied to compare inter-
treatment differences. Pearson's correlation coefficient was employed to find possible
correlations between selected parameters. Differences between the results at a p<0.05 level
were considered statistically significant.
The MCPA sorption-desorption isotherms (direct and residual years) for all treatments
are presented in Figure 1. For both years, the sorption isotherms fitted appropriately the
Freundlich equation with (R² >0.980). The MCPA Kd (partition coefficients) values for
unamended and OS-amended soils in the direct (Kd=0.424–1.074) and residual (Kd=0.260–
0.847) years (Table 2) are similar to those found by López-Piñeiro et al. (2019) with values
ranging from 0.404 to 0.976 for different unamended rice soils from Spain with pH's of 5.15-
6.24 but with lower TOC content (6.8–16.2 g kg-1). Our Kd values were, however, much
lower than those reported by Jacobsen et al. (2008) and Piwowarczyk & Holden (2013) who
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Capítulo V. MCPA
found values ranging from 1.30 to 9.27 for Danish agricultural soils with pH's of 4.1–6.3 and
TOC contents of 13–64 g kg-1, and of 1.50 and 1.96 for Irish soils under tillage and grassland
management, with pH's of 5.7 and 5.1 and TOC contents of 36 and 39 g kg-1, respectively.
Also, MCPA was more weakly adsorbed in our soils than in the Chinese soils studied by Wu
et al. (2018) who found Kf values of 2.74 and 4.24 for soils with pH's 5.8 and 5.7 and TOC
contents of 6.8 and 10.1 g kg-1. These results indicate a higher risk of MCPA leaching and
water contamination for the soils of this present study compared with other types of soil.
The different treatments significantly influenced MCPA sorption, with differences also
between the two years as shown by the significant (p<0.001) treatment × year interaction
(Table 2). For the soils without OS amendment, the TF Kd values were significantly greater
than those of the TS and NTS treatments (Table 2) for both years. This is consistent with
López-Piñeiro et al. (2019) who, in a three-year study of only unamended soils, also reported
that the transition from flooding to non-flooding rice growing conditions could increase
MCPA's mobility as a consequence of the decrease in its sorption. However, in 2015 the TF
Kd was 2.5 and 1.6 times greater than the TS and NTS values, respectively, but in 2017 these
factors were 1.4 and 2.3, indicating that not only the management regime itself but also the
timing of its implementation are important factors for MCPA's sorption behaviour.
~ 169 ~
Capítulo V. MCPA
2015
40
TS
TSOS
Cs (µmol kg-1)
30 NTS
NTSOS
TF
20 TFOS
10
0
0 10 20 30 40
40 40 40
Cs (µmol kg-1)
TS NTS TF
30 30 30
20 20 20
10 10 10
0 0 0
0 10 20 30 40 0 10 20 30 40 0 10 20 30 40
40 40 40
Cs (µmol kg-1)
20 20 20
10 10 10
0 0 0
0 10 20 30 40 0 10 20 30 40 0 10 20 30 40
30 NTS
NTSOS
TF
20 TFOS
10
0
0 10 20 30 40
40 40 40
NTS TF
Cs (µmol kg-1)
TS
30 30 30
20 20 20
10 10 10
0 0 0
0 10 20 30 40 0 10 20 30 40 0 10 20 30 40
40 40 40
Cs (µmol kg-1)
20 20 20
10 10 10
0 0 0
0 10 20 30 40 0 10 20 30 40 0 10 20 30 40
Figure 1. Effect of different crop management regimens on the MCPA sorption and
desorption isotherms. Solid and dashed lines connect sorption and desorption points,
respectively. Vertical bars representing one standard error of the mean were smaller than the
symbols in al cases.
~ 170 ~
Capítulo V. MCPA
The OS field application significantly influenced MCPA sorption (p<0.001). But while
sorption was affected negatively in both the direct and residual years in the non-flooded
treatments, in the flooded treatments it was affected negatively in the direct year but
positively in the residual year (Table 2). Thus, for the direct year the MCPA Kd values were
lower than in the corresponding unamended soils by factors of 1.1, 1.3, and 1.9 in TSOS,
NTSOS, and TFOS, respectively, and for the residual year, by factors of 1.1 and 1.5 in TSOS
and NTOS but greater by a factor of 1.5 in TFOS than in the corresponding unamended soils.
Gómez et al. (2019), however, found different trends for the herbicide bispyribac-sodium.
They reported that, while there were no differences between the sorption values of amended
and unamended soils under non-flooding conditions, they were significantly greater in
amended than in unamended soils under flooding conditions in both the direct and residual
years. This fact reflects the importance of the specific properties of the pesticide involved
when evaluating how its environmental fate might be impacted by OS amendment. Specific
studies are therefore necessary for each pesticide that is applied in rice production under
different cropping systems. The differences in MCPA sorption found in the present study
could be attributable to the increase in soil pH as a consequence of the OS addition. Indeed,
Kd was significantly negatively correlated with soil pH (r=-0.649**), indicating that an
increase in pH may lead to a decrease in the proportion of neutral herbicide molecules which
could be attracted and more readily adsorbed by negatively charged soil particles (Hyun et
al., 2003; López-Piñeiro et al., 2016). This is to be expected for most Mediterranean rice
soils, whose unamended and OS amended pH values would be greater than this herbicide's
pKa (pKa=3.7) (Gardiner & Radford, 1980; Piwowarczyk & Holden, 2013). Our findings are
consistent with other studies which concluded that the pH is one of the most important soil
properties determining MCPA sorption (e.g., Cabrera et al., 2011), and in rice soils in
particular (Wu et al., 2018; López-Piñeiro et al., 2019). But the pH values do not explain the
significant increase in MCPA sorption observed in the residual year for the treatment under
flooding irrigation management after OS application, with Kd values of 0.568 and 0.824, and
pH's of 5.65 and 5.80 for TF and TFOS, respectively (Tables 1 and 2). With similar pH
values, this greater MCPA sorption could be attributable to increased TOC and HA (Table 1)
following the OS addition, in agreement with previous studies finding that MCPA sorption is
affected not only by soil pH but also by both the quality (López-Piñeiro et al., 2013) and
quantity (Paszko et al., 2016; Wu et al., 2018) of the soil's OM content.
~ 171 ~
Capítulo V. MCPA
As shown in Table 2, the MCPA desorption data were also satisfactorily fitted by the
Freundlich model (R²>0.903). For soils without OS amendment, the desorption values (D)
were significantly influenced by the different treatments, but only in the year 2017, with the
TF treatment having the greatest D values (Table 2), indicating greater reversibility of sorbed
MCPA under flooding than under non-flooding cultivation regardless of the tillage practice
implemented (Table 2). The application of OS influenced the D values, although this was
only significant (p<0.05) in the residual year for which the greatest D values corresponded to
the TFOS treatment. On the contrary, the values were lower for TSOS and NTSOS compared
to the corresponding unamended treatments (TS and NTS). Our findings suggest that, three
years after the OS field application, the MCPA sorbed in the amended soils might be more
strongly retained under non-flooding management, especially in a no-tillage regime. Lower
reversibility of MCPA in amended soils under non flooding conditions may be a result of the
significant increases in their HA values. Indeed, while these values were 1.5 and 1.6 times
higher in TSOS and NTSOS, they were 1.1 times lower in TFOS compared to the TS, NTS,
and TF treatments, respectively. Furthermore, there was a significant negative correlation
~ 172 ~
Capítulo V. MCPA
(r=-0.688**) between the D and HA values, confirming the importance of the HA content in
the MCPA sorption-desorption process. This contrasts with the report in López-Piñeiro et al.
(2019) of a greater role played by FA than by HA in MCPA desorption also under both
flooding and non-flooding rice growing conditions, but in a study which only tested
unamended soils for which the HA content was on average 1.7 times lower than in the
present study.
The dehydrogenase activity (DHA) and MCPA dissipation curves are shown in
Figure 2. The data fit first-order kinetics under both aerobic and anaerobic experimental
conditions, giving values of R² >0.849 and R² >0.845 in the direct and residual years,
respectively (Table 3). Similar to the results reported by López-Piñeiro et al. (2019) in a
study using only unamended rice soils, the DHA values were much lower under non-flooding
than under flooding conditions, with values considering all 50 d of incubation time (DHAA)
up to 7.2 and 7.3 times higher in the anoxic condition for the direct and residual years,
respectively (Table 3). Our findings are also consistent with those of Wolińska & Bennicelli
(2010) who reported increasing DHA with decreasing soil moisture content and higher redox
potential. Overall, in both years there was a significant increase in DHAA (2 h after MCPA
application), indicating that this compound would not constitute a toxicity risk for
microorganisms, at least at the dosage applied in the present work (1.5 kg ha-1). Similarly,
Yousaf et al. (2013) reported that microbial activity in two soils of Pakistan was unaffected
for 15 days after MCPA application, although in that study only the aerobic condition was
investigated.
~ 173 ~
Capítulo V. MCPA
2015
10 10 10
100 TS 100 NTS 100 TF
8 8 8
80 80 80
Aerobic conditions
60 6 60 6 60 6
4
DA (µg INTF g h )
40 40 4 40 4
-1
MCPA (%)
20 2 20 2 20 2
-1
0 0 0 0 0 0
0 10 20 30 40 50 0 10 20 30 40 50 0 10 20 30 40 50
10 10 10
100 TSOS 100 NTSOS 100 TFOS
8 8 8
80 80 80
60 6 60 6 60 6
40 4 40 4 40 4
20 2 20 2 20 2
0 0 0 0 0 0
0 10 20 30 40 50 0 10 20 30 40 50 0 10 20 30 40 50
10 10 10
100 TS 100 NTS 100 TF
8 8 8
Anaerobic conditions
80 80 80
60 6 60 6 60 6
DA (µg INTF g h )
-1
40 4 40 4 40 4
MCPA (%)
-1
20 2 20 2 20 2
0 0 0 0 0 0
0 10 20 30 40 50 0 10 20 30 40 50 0 10 20 30 40 50
10 10 10
100 TSOS 100 NTSOS 100 TFOS
8 8 8
80 80 80
60 6 60 6 60 6
40 4 40 4 40 4
20 2 20 2 20 2
0 0 0 0 0 0
0 10 20 30 40 50 0 10 20 30 40 50 0 10 20 30 40 50
2017
10 10 10
100 TS 100 NTS 100 TF
8 8 8
80 80 80
Aerobic conditions
60 6 60 6 60 6
4
DA (µg INTF g h )
40 40 4 40 4
-1
MCPA (%)
20 2 20 2 20 2
-1
0 0 0 0 0 0
0 10 20 30 40 50 0 10 20 30 40 50 0 10 20 30 40 50
10 10 10
100 TSOS 100 NTSOS 100 TFOS
8 8 8
80 80 80
60 6 60 6 60 6
40 4 40 4 40 4
20 2 20 2 20 2
0 0 0 0 0 0
0 10 20 30 40 50 0 10 20 30 40 50 0 10 20 30 40 50
10 10 10
100 TS 100 NTS 100 TF
8 8 8
Anaerobic conditions
80 80 80
60 6 60 6 60 6
DA (µg INTF g h )
-1
40 4 40 4 40 4
MCPA (%)
-1
20 2 20 2 20 2
0 0 0 0 0 0
0 10 20 30 40 50 0 10 20 30 40 50 0 10 20 30 40 50
10 10 10
100 TSOS 100 NTSOS 100 TFOS
8 8 8
80 80 80
6
60 6 60 6
4 60
40 4 40 40 4
2
20 2 20 0 20 2
0 0 0 0 0
0 10 20 30 40 50 0 10 20 30 40 50 0 10 20 30 40 50
Figure 2. Effect of different crop management regimens on the MCPA dissipation ( ) and
dehydrogenase activity ( ) under aerobic and anaerobic incubation conditions. Vertical bars
representing one standard error of the mean were smaller than the symbols in some cases.
~ 174 ~
Capítulo V. MCPA
For both unamended and amended soils, the treatments significantly (p<0.001)
influenced MCPA half-lives (t½), with there being differences between the direct and residual
years as indicated by the significant (p<0.001) treatment × year interaction (Table 3). For
soils without OS addition, the MCPA t½ values ranged from 2.23 to 9.42 d for aerobic and
from 1.80 to 5.29 d for anaerobic incubation conditions (Table 3), indicating that dissipation
of this herbicide was very fast, especially under anoxic experimental incubation conditions
(Table 3). This agrees with López-Piñeiro et al. (2019) who also found lower MCPA
dissipation under aerobic than anaerobic conditions in different unamended rice soils of
Spain. Contrarily, Sørensen et al. (2006) reported that MCPA was not degraded in surface
and subsurface soil samples under anoxic conditions, although in that study the soils were not
dedicated to rice growing, and one of them had been without any exposure to MCPA for the
preceding 20 years. In the present study, however, the soils had been managed for the
preceding eleven years under flooding rice production conditions including treatment with
MCPA, a compound whose dissipation rates are known to strongly depend on the history of
its application to soils (Paszko et al., 2016). Therefore, these factors may have contributed to
soil microorganism populations adapting to degrade MCPA also under anoxic conditions,
allowing greater dissipation rates of this compound without oxygen, especially under the
traditional management regime (TF) for rice production in the region of this study. This is in
concordance with Vallée et al. (2016) who also found faster dissipation of six herbicides
including MCPA under anaerobic than aerobic conditions in sediments with microbial
communities adapted to flooded conditions.
The MCPA t½ values were similar to those found in other studies using unamended
topsoils from different countries such as China (Hu et al., 2012), Spain (Peña et al., 2015),
and Germany (Saleh et at., 2016), which were incubated with a wide range of moisture
contents, but not under anaerobic conditions. Overall, MCPA persistence was longer in TF
than in the rest of the treatments for both 2015 and 2017, an effect that was particularly
evident under the aerobic experimental conditions. Thus, under anaerobic conditions,
significant (although small) differences in persistence between treatments were only found in
year 2015. But under aerobic conditions, the t½ values for TF were greater than those
corresponding to TS and NTS by factors of 2.9 and 3.2 for 2015, and by 2.2 and 2.1 for 2017,
respectively (Table 3), suggesting that the changes from flooding to non-flooding rice
growing conditions could increase MCPA's persistence, especially in the short-term. As was
~ 175 ~
Capítulo V. MCPA
suggested above, the greater persistence of MCPA in TF that was particularly notable under
aerobic experimental conditions could be attributable to a lack of adaptation of the TF soil
microbial communities to non-flooding after more than eleven years under flooding
irrigation. Despite DHAA being significantly greater in NTS than TS under anaerobic
experimental conditions for year 2015, there was a significantly longer persistence of MCPA
in the no-tillage treatment. This could be explained by the significantly greater WSOC value
observed in NTS than in TS (Table 2), with this organic substrate probably being preferably
consumed by the soil microorganisms as a carbon and energy source instead of the herbicide,
at least under anoxic conditions (Table 3).
The field OS application led to an increase in MCPA dissipation in all treatments under
both aerobic and anaerobic experimental incubation conditions, although substantial
differences were observed between the direct and residual years (Table 3). Thus, regarding
the determinations in the direct year, MCPA persistence decreased after OS addition in both
experimental conditions, although this decrease was only significant in the TF management
regime with t½ values being 2.4 and 1.4 times lower in TFOS than in the corresponding
unamended TF under aerobic and anaerobic conditions, respectively. In the residual year,
under aerobic conditions MCPA persistence significantly decreased in NTS and TF with t½
values 1.7 and 2.1 times lower in NTSOS and TFSOS than in the corresponding unamended
NTS and TF management regimes, respectively. However, under anaerobic conditions the
differences between unamended and amended soils were not significant in this year,
irrespective of the irrigation and tillage systems implemented (Table 3). These results suggest
that, while in the short-term MCPA dissipation may be faster in the non-flooded and flooded
amended soils, in the medium-term this effect would be limited to the non-flooding OS-
amended soils, especially in the soils which had traditionally been cultivated previously
under tillage and flooding irrigation (i.e., the TF treatment).
~ 176 ~
Capítulo V. MCPA
Table 3. Effect of different crop management regimes on dehydrogenase activity and MCPA dissipation parameters.
2017
TS 2.23 bA 0.927 1.95 abA 0.856 0.472 aB 0.43 aA 3.66 aA 1.34 aA 1.76 aA 6.91 aA
TSOS 1.95 abA 0.911 1.93 abA 0.869 0.838 cB 1.42 cA 7.53 cB 3.79 bA 4.53 bA 26.2 cA
NTS 2.37 bA 0.902 2.18 bA 0.932 0.793 bcB 0.59 aA 5.51 bA 4.53 bB 3.92 bA 14.1 bA
NTSOS 1.38 aA 0.865 1.66 abA 0.875 1.04 eB 0.91 bA 7.60 cA 5.34 bA 6.00 cA 24.3 cA
TF 4.99 cA 0.925 2.38 bA 0.845 0.762 bB 1.28 cB 7.05 cB 8.19 cB 5.93 cA 41.8 dB
TFOS 2.23 bA 0.904 2.03 bA 0.908 0.962 dB 1.95 dB 9.18 dA 9.76 cB 7.48 dA 52.1 eA
Y F-values 60.2 *** - 745 *** - 185 *** 4.82 * 36.9 *** 184 *** 65.4 *** 481 ***
M F-values 110 *** - 10.5 *** - 26.8 *** 223 *** 227 *** 14.2 *** 26.4 *** 264 ***
Y x M F-values 10.5 *** - 16.3 *** - 6.66 ** 54.0 *** 146 *** 51.4 *** 5.68 ** 150 ***
Half-lives: t1/2 80% in soils at 80% field water capacity; t1/2 1:1.25 in soils with 1:1.25 (w/v) (soil/water) moisture content. DHA: dehydrogenase activity two hours before (B)
and after (A) the application of the herbicide to soils conditioned to 80% field capacity and 1:1.25 (w/v) (soil/water) moisture content. DHAT: total dehydrogenase
activity considering all the incubation times in soils conditioned to 80% field capacity and 1:1.25 (w/v) (soil/water) moisture content. ANOVA factors are Y: year; M:
management regime; Y x M: interaction year x management regime. F-values indicate the significance levels * p < 0.05, **p < 0.01, and ***p < 0.001, respectively, and
NS: not significant. Different letters indicate significant differences (p < 0.05) between management regimes in the same year (lower case letters) and between years
within the same management regime (upper case letters).
~ 177 ~
Capítulo V. MCPA
According to Paszko et al. (2016), the differences in DHA values could explain the
trends in MCPA dissipation rates. Indeed, a significant correlation between t½ and DHAA
was found, although only under aerobic experimental conditions (r=-0.359*). This is
consistent with various previous studies with unamended and amended soils which found
similar correlations between MCPA's t½ and DHA, also under only aerobic conditions (e.g.,
López-Piñeiro et al., 2013), suggesting that the degradation of this compound is mainly a
biological process. Furthermore, under both experimental conditions, the relative order of
MCPA dissipation values reflects a direct relationship with the compound's sorption. Indeed,
t½ was significantly correlated with Kd under aerobic (r=0.756**) and anaerobic (r=0.594**)
incubation conditions, indicating that greater sorption values as a consequence of OS field
addition could reduce the concentration of MCPA in aqueous solution, thereby limiting its
bioavailability for degradation by microorganisms (Dyson et al., 2002; Katayama et al., 2010;
Hiller et al., 2012). However, the significant differences in MCPA dissipation rates between
TF and TFOS in the residual year under aerobic conditions would not be explained by the
differences in their Kd values, since Kd was 1.4 times greater in TFOS than in TF, while t½
was 2.3 times lower (Tables 2 and 3). This may be due to the greater biological activity in the
amended treatment as reflected in the DHAA values, which were significantly greater by a
factor of 1.3 in TFOS than in TF (Table 3).
The relative and cumulative MCPA breakthrough curves for each treatment are shown
in Figure 3. Tabla 4 presents the total MCPA leached and the percentage that was extracted
from the soil columns at the end of the leaching experiment. MCPA breakthrough ranged
from 0.372 to 1.00 and from 0.355 to 1.06 pore volumes for unamended and amended soils,
respectively, indicating very high mobility of the herbicide (Figure 3).
~ 178 ~
Capítulo V. MCPA
2015
NTS
MCPA leached (%) 16 TS 16 16 TF
TSOS NTSOS TFOS
12 12 12
8 8 8
4 4 4
0 0 0
0 2 4 6 0 2 4 6 0 2 4 6
TS NTS TF
MCPA leached (%)
2017
NTS TF
MCPA leached (%)
16 TS 16 16
TSOS NTSOS TFOS
12 12 12
8 8 8
4 4 4
0 0 0
0 2 4 6 0 2 4 6 0 2 4 6
TS NTS TF
MCPA leached (%)
Figure 3 Effect of different crop management regimens on the relative (above) and
cumulative (below) breackthrough curves of MCPA. Vertical bars represent one standard
error of the mean.
For both unamended and amended soils, the crop management regimes significantly
(p<0.01) influenced the total MCPA leached, although no significant differences between the
direct and residual years were observed (p>0.05; Table 3). For the unamended soils, the total
~ 179 ~
Capítulo V. MCPA
MCPA leached ranged from 31.6% to 47.4% and from 34.4% to 43.7% of the amount applied
for the direct and residual years, respectively (Table 3; Figure 3). Greater leaching of MCPA
was reported by Socias Viciana et al. (1999) and Tatarková et al. (2013) who found the
leachates to contain 56% and 99% of the compound initially applied, respectively, although
both of these studies were of alkaline agricultural soils (pH>7.60), and the soil of the latter of
the two studies was also very poor in organic matter content (TOC=1.8 g kg-1). Greater
leaching of MCPA (41.8%–83.8%) was also reported by López-Piñeiro et al. (2019) in
unamended rice soils under different cropping regimes, although with TOC, HA, and FA
values much lower than those of the present study. The leaching of MCPA in TS was
significantly greater by factors of 1.5 and 1.4 in the year 2015, and by factors of 1.2 and 1.3
in the year 2017 than in the NTS and TF treatments, respectively. Moreover, the maximum
concentration of MCPA in the leachate was greater in TS than in the NTS and TF treatments
by factors of 2.0 and 2.4 (year 2015) and 1.4 and 1.9 (year 2017), respectively. These results
suggest that conventional tillage might enhance the leaching of MCPA in unamended soils,
but only under non-flooding irrigation. The above findings might in part be a reflection of the
lower Kd values observed in TS than in NTS and TF, except for NTS in the year 2017 in
which the differences in MCPA sorption between TS and NTS were not significant (Tables 2
and 4). One explanation for this could be the differences in the microbial activity of the soils
as shown in their DHA values under anaerobic conditions, with DHAB and DHAA being
3.4 and 2.2 times greater in NTS than in TS, respectively (Table 3). This could have
contributed to greater MCPA degradation in NTS than in TS, and hence leaving less to be
leached.
The application of OS significantly influenced MCPA leaching in both the direct and
the residual years. But while it led to a decrease for the non-flooded soils, the contrary was
the case for the flooded soils (Table 4). In particular, while the amount of MCPA leached was
lower by factors of 1.3 and 1.6 and by 2.9 and 2.7 in TSOS and NTSOS than in TS and NTS
for the direct and residual years, respectively, it was greater by factors of 1.4 and 1.2 in TFOS
than in TF for the direct and residual years, respectively. For the non-flooding cases, the
increase in HA content may explain the decrease of MCPA leaching in the amended soils
(TSOS and NTSOS; Tables 1 and 4). Indeed, the amount of MCPA leached was negatively
correlated with HA (r=-0.604**). Similarly, López-Piñeiro et al. (2019) reported decreasing
MCPA leaching with increasing HA. This was also in rice soils under different tillage and
~ 180 ~
Capítulo V. MCPA
irrigation systems, but without OS application. Our results also agree with those of Ćwieląg-
Piasecka et al. (2018) who found a strong affinity between HA and ionic herbicides of which
MCPA is an example, so that this could reduce the risk of its leaching. However, the leaching
behaviour in the flooded-treatment soils (TF and TFOS) cannot be attributed to their HA
contents. Instead, for these treatments the explanation may lie in the differences in sorption.
That there was more MCPA leaching in TFOS than in TF in the direct but not in the residual
year may reflect the differences in their D values. In particular, while this parameter showed
no significant differences between TF and TFOS in the direct year, in the residual year the D
value was 1.4 times lower in the former (Table 2).
At the end of the trial, MCPA retention was observed in all the soil columns, with the
greatest amounts of herbicide recovered from the bottom layer (15–20cm) (data not shown).
Significant differences (p<0.001) were found between treatments, although the amounts of
MCPA recovered were small: under flooding, <6.4%; and especially under non-flooding,
<2.8% (Table 4). In the direct year, OS application did not influence the amount of MCPA
~ 181 ~
Capítulo V. MCPA
recovered from the soils irrespective of the tillage and irrigation regimes. In the residual year,
however, while the total amounts of MCPA recovered were significantly greater in NTSOS
than in NTS, they were lower in TFOS than in TF (Table 4). These findings are consistent
with those described above for the sorption-desorption and dissipation studies. Indeed, the
total amount of MCPA extracted was negatively correlated with Kd (r=-0.501**) and
positively with t½ (r=0.643**) as measured under aerobic conditions.
4. Conclusions
With or without the application of OS in the field, non-flooding rice production under
conventional and no-tillage management may alter the soil's properties and have a major
impact on the environmental behaviour of the herbicide MCPA. As a consequence of their
decreased capacity for sorption, leaching of MCPA might be enhanced in soils under
conventional tillage in the short- and medium-terms, but only in those under non-flooding
cultivation. After OS application, we found a decrease in MCPA dissipation (especially in the
short-term) in the soils under tillage and flooding irrigation. This could potentially contribute
to reducing this herbicide's activity in amended but traditionally cultivated rice soils. While
the field application of OS led to less MCPA being leached from soils under non-flooding
irrigation, irrespective of the tillage management applied, it had the contrary effect in soils
cultivated under flooding in both the direct and the residual years.
Differences in HA content and in the Kd and D values were found to be the major
factors contributing to MCPA's leaching behaviour in OS-amended soils. Therefore, although
the risk of water contamination by MCPA used in rice growing may be raised by the
transition from flooding to non-flooding irrigation, particularly under conventional tillage, the
use of OS as organic amendment could help reduce it. Nevertheless, if flooding is maintained
as the management regime, there could be a greater risk of water being contaminated by
MCPA if OS is added to the soil as an amendment.
~ 182 ~
Capítulo V. MCPA
Acknowledgements
Support for this work was provided by the Spanish Ministry of Economics and
Competitiveness (AGL2013-48446-C3-2-R) and Ministry of Science, Innovation and
Universities (RTI2018-095461-B-I00), and by the Extremadura Regional Government
(GR18011; IB16075) with co-financing from the Fondo Europeo de Desarrollo Regional.
Soraya Gómez is the recipient of a grant awarded by the Consejería of Economía, Comercio e
Innovación of the Extremadura Regional Government (PD16021). Damián Fernández is the
recipient of a grant-in-aid to promote research support personnel hiring, awarded by the
SEXPE of the Extremadura Regional Government, with cofinancing from the Fondo Europeo
de Desarrollo Regional.
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Text S1. The herbicide was assayed by HPLC, using a chromatograph (Waters 600E)
coupled to a diode-array detector (Waters 996). The conditions used were: Nova-Pack column
(150 × 3.9 mm, 4.5 µm particle size), methanol/diluted H3PO4 (pH 2) (60:40) mobile phase at
a flow rate of 1 mL min-1, 25 µL injection volume, column temperature 30°C, and UV
detection at 228 nm. The limits of detection and quantification, calculated as the herbicide
concentrations resulting in signal-to-noise ratios of 3:1 and 10:1 respectively, were 0.021 μM
and 0.068 μM, respectively.
Text S2. The MCPA sorption-desorption experiments were done in triplicate. Soil
samples (5 g± 0.001 g) were treated by mechanical shaking with the thermostatic chamber
Thermo Scientific MaxQ 4000 at 20±1 °C for 24 h with 10 mL of solutions of MCPA in
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Capítulo V. MCPA
0.01M CaCl2 at initial concentrations (Ci) of 5, 10, 20, 40, and 50 µM. Equilibrium
concentrations in the supernatants were assayed following the method presented in Text S1.
The amount of MCPA sorbed (Cs) was calculated from the difference between the initial (Ci)
and the equilibrium (Ce) solution concentrations. Following the adsorption experiment,
MCPA desorption was studied using the tubes to which the highest initial concentration
(50 µM) had been added, replacing the 5 mL of the supernatant removed for the adsorption
analysis herbicides with 5 mL of 0.01 M CaCl2, and then following the same operating
procedure as in the adsorption experiment. The data were fitted to the Freundlich equation,
Cs = Kf Ce1/nf, where Cs is the amount (µM kg-1) sorbed at equilibrium concentration Ce, and
Kf and nf are the Freundlich coefficient and linearity parameter, respectively. Partition
coefficients, Kd (L kg-1), where Kd = Cs/Ce, and the percentage, D, of MCPA desorbed with
respect to that previously adsorbed were also calculated.
Text S3. For each treatment, triplicate soil samples (5 g± 0.001 g) were weighed into
50 mL glass tubes. Soils were supplemented with distilled water to obtain non-flooded (80%
field capacity) and flooded (soil-to-water ratio 1:1.25, w/v) moisture conditions. Prior to the
MCPA addition, the soils were pre-incubated for 7 days in the dark at 20±1 °C to allow the
soil microorganisms to adapt to the non-flooded (aerobic) and flooded (anaerobic) incubation
conditions, and also to allow the development of reducing conditions in the flooded soils.
Then MCPA dissolved in distilled water was applied at a dosage equivalent to 1.5 kg ha-1, and
the tubes were incubated with the Memmert Peltier-cooled incubator IPP260 in the dark at
20±1°C for 49 days. Moisture was maintained at a constant level throughout the experiment
by adding distilled water as necessary. Three replicate tubes were removed (at 2 h and
at 2 days after herbicide application, and then at 7-day intervals for 49 days) from each
treatment to measure the herbicide concentrations. The soils were extracted with 10 mL of a
60:40 (v/v) mixture of methanol/diluted H3PO4 (pH 2) by shaking mechanically on an end-
over-end shaker at 20±1°C for 24 h followed by centrifugation, and the residues of the
herbicide in the extracts were determined following the method presented in Text S1. MCPA
residues from water samples were also determined as indicated in Text S1. The MCPA
dissipation data in soils and water were fitted to a first-order kinetics equation, C=Co e-kt,
where C is the MCPA concentration at time t (days), Co is the initial herbicide concentration,
and k (day-1) is the degradation constant, and the half-lives (t½) were calculated.
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Capítulo V. MCPA
To measure the dehydrogenase activity (DHA), another three replicate soil samples of
each treatment were weighed out into glass tubes, and supplemented with sterile distilled
water to obtain aerobic (80% field capacity) and anaerobic (1:1.25 w/v soil/water) moisture
conditions. For each treatment, the tubes were removed before MCPA application and at the
same times as for the dissipation experiment. They were then incubated for 20 h at 20±1°C in
the dark with 1 mL of 0.4% 2-piodophenyl-3p-nitrophenyl-5 tetrazolium chloride (INT) as
substrate. At the end of incubation, the iodonitrotetrazolium formazan (INTF) produced was
extracted with methanol, and the absorbance was measured at 490 nm with the Shimadzu
UV/Vis 1603 spectrophotometer. The limits of detection (0.093 mg L-1) and quantification
(0.310 mg L-1) were calculated using the formulae LOD = 3 σ/s and LOQ = 10 σ/s, where σ is
the standard deviation of ten reagent blank measurements and s is the slope of the
corresponding calibration graph.
Text S4. For the leaching studies, PVC cylinders (5-cm i.d. × 30-cm length) were
used to prepare disturbed soil columns. To minimize soil losses during the experiment, the
top 5 cm of the columns was filled with sea sand and the bottom 5 cm with sea sand plus
glass wool. The remaining 20 cm was hand-packed with air-dried soil. The soil columns were
saturated with 0.01 M CaCl2 and allowed to drain for 24 h. Then, MCPA was applied to the
top of the soil columns at a dosage equivalent to 1.5 kg ha-1. Leachates containing the MCPA
were collected daily, filtered, and assayed as indicated in Text S1. After the leaching
experiments, the soil columns were left to drain for 24 h and then sectioned into the following
depths: 0–5 cm, 5–10 cm, 10–15 cm, and 15–20 cm. To determine the residual amounts of
MCPA, 5-g aliquots of soil from different depths were extracted by adding 10 mL of a 60:40
(v/v) mixture of methanol/diluted H3PO4 (pH 2) and shaking for 24 h at 20±1°C, and assayed
as indicated in Text S1.
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Capítulo VI. DISCUSIÓN GENERAL
Capítulo VI. Discusión general
En los capítulos III, IV y V se presenta una copia de los diferentes artículos que
forman parte de esta Tesis Doctoral por compendio de publicaciones. En dichos artículos, se
exponen los resultados obtenidos en los estudios de adsorción-desorción, disipación y
lixiviación de tres herbicidas en un suelo dedicado al cultivo de arroz bajo diferentes sistemas
de manejo de agua y laboreo, con y sin aplicación de compost de alperujo (CA). Por tanto, en
este apartado, se pretende llevar a cabo un breve análisis de los resultados más relevantes, así
como una comparativa en el comportamiento de los tres herbicidas bajo los diferentes
sistemas de manejo, ya que propiedades de éstos como su estructura molecular y tamaño,
constante de disociación, y solubilidad en agua son factores importantes en su dinámica
(Mendes et al., 2016).
~ 195 ~
Capítulo VI. Discusión general
Con respecto a la desorción de CLO, en los suelos sin enmendar, los valores de H más
bajos correspondieron a LCI, independientemente del año estudio, indicando una menor
reversibilidad en la adsorción bajo condiciones de riego por aspersión, especialmente cuando
se utilizan prácticas de siembra directa. Además, también independientemente del año de
estudio, los valores de H fueron significativamente más bajos en los tratamientos
enmendados, observándose que dichos valores fueron más elevados en LCC y SDC que en
LCIC. Estos resultados indican que CLO podría ser retenido más fuertemente en los sistemas
productivos aeróbicos que en los anaeróbicos, especialmente tras la aplicación de la
enmienda orgánica.
Para el herbicida MCPA, considerando sólo los suelos originales, los valores de Kd
fueron significativamente mayores en el tratamiento bajo riego por inundación que en los de
~ 196
Capítulo VI. Discusión general
Con respecto a la desorción del MCPA, para los suelos sin enmendar, los valores de
desorción (D) indicaron una mayor reversibilidad del herbicida adsorbido bajo condiciones
de inundación que en las de aspersión, independientemente del tipo de sistema de laboreo
utilizado para el año residual. La aplicación de enmienda orgánica influyó sobre los valores
de D sugiriendo que, trascurridos tres años desde su aplicación, el MCPA adsorbido podría
ser más fuertemente retenido bajo condiciones aeróbicas que anaeróbicas, especialmente bajo
un régimen de labranza cero.
Los resultados obtenidos en los estudios de desorción de los tres herbicidas mostraron
una mayor reversibilidad bajo condiciones de inundación, indicando que el herbicida
adsorbido podría retenerse más débilmente en suelos de sistemas de producción de arroz
anaeróbicos que aeróbicos, independientemente de la utilización del compost de alperujo
como enmienda. Estos resultados fueron atribuidos a los descensos significativos observados
en los valores de ácidos húmicos de los suelos regados por inundación, siendo estos más
evidentes en aquellos suelos que recibieron la aplicación de la enmienda.
Con respecto a los estudios de disipación, los datos experimentales para los tres
herbicidas se ajustaron a una cinética de primer orden, tanto para la experimentación en
condiciones de incubación anaeróbicas como aeróbicas. Además, independientemente del
sistema de manejo y del herbicida seleccionado, los valores de actividad deshidrogenasa
(AD) antes (ADB), dos horas después (ADA) de la aplicación de cada uno de los herbicidas y
considerando la AD total tras los 50 días de incubación (ADT), fueron inferiores bajo
condiciones de incubación aeróbicas que anaeróbicas, en consonancia con otros estudios que
encontraron una reducción en AD tras un incremento en los potenciales redox y en suelos con
mayor tasa de aireación.
Para el herbicida BYS, las tasas de disipación en los suelos no enmendados fueron
influenciadas significativamente por el sistema de laboreo y riego. Así, en el año residual los
valores de t1/2 para este herbicida en el tratamiento SD fueron superiores a los observados en
LC y LCI bajo condiciones de incubación aeróbicas y anaeróbicas. Estos resultados sugieren
~ 198
Capítulo VI. Discusión general
que la disipación de BYS puede ser más lenta en sistemas productivos con riego por
aspersión, especialmente cuando el cultivo se maneja mediante técnicas de agricultura de
conservación. Este hecho fue atribuido a una mayor disponibilidad de carbono en los suelos
del tratamiento SD, que podría haber afectado al uso de BYS por parte de los microrganismos
como fuente de carbono y, por tanto, a su disipación. También, la mayor persistencia de BYS
coincidió con los valores de pH más altos 5.77 y 6.08 observados en SD en el año directo y
residual, respectivamente. Por otro lado, los valores de persistencia más bajos se observaron
en los suelos del tratamiento LCI, coincidiendo con aquéllos que mostraron los valores de pH
más ácidos. Estos resultados parecen indicar que la hidrólisis química pudo ser la principal
vía de degradación del herbicida tanto para condiciones de incubación aeróbicas como
anaeróbicas.
Con respecto al herbicida CLO, para los suelos originales, los resultados obtenidos
reflejan una degradación más rápida del herbicida bajo condiciones anaeróbicas que
~ 199 ~
Capítulo VI. Discusión general
aeróbicas. La persistencia de CLO fue menor en el tratamiento LCI que en SD y LC, tanto en
el año directo como residual. Además, la mayor persistencia de CLO observada en LC con
respecto a SD en condiciones de incubación anaeróbica y para los dos años del estudio,
fueron atribuidos a la menor actividad microbiana de estos suelos, reflejada en sus valores de
AD.
Con respecto al herbicida BYS en los suelos no enmendados, aunque en el primer año
no se observaron diferencias significativas entre tratamientos, transcurridos tres años la
cantidad de BYS lixiviada fue menor en LCI que en SD y LC, resultado que fue atribuido a la
mayor adsorción y menor persistencia que presenta el herbicida en el tratamiento con laboreo
convencional y riego por inundación. En los tratamientos regados por aspersión, se observó
una cantidad de BYS lixiviada ligeramente mayor en LC que en SD, coincidiendo con su
valor más bajo de H (es decir, mayor reversibilidad). La aplicación de CA influyó en la
cantidad de BYS lixiviado independientemente del sistema de manejo empleado, aunque su
efecto dependió del tiempo transcurrido tras la aplicación de la enmienda. Así, mientras que
en el año directo la cantidad de BYS lixiviado se redujo en los tratamientos que incorporaron
la enmienda, en el año residual no hubo diferencias significativas en el porcentaje de
herbicida total lixiviado entre los tratamientos con y sin aplicación de CA, aunque en los
tratamientos irrigados mediante aspersión la enmienda provocó un descenso en la cantidad de
~ 201 ~
Capítulo VI. Discusión general
BYS lixiviada. Los descensos del porcentaje de herbicida lixiviado tras la aplicación de la
enmienda con respecto a los suelos originales, concuerda con los resultados obtenidos en el
estudio de disipación, donde la aplicación de CA provocó un aumento importante en ADT y,
en consecuencia, un descenso en los valores de t1/2 para BYS en el primer año bajo
condiciones de incubación anaeróbicas reduciendo, así, la cantidad de BYS potencialmente
disponible para ser lixiviado. Por tanto, aunque a medio plazo la implementación de sistemas
productivos con riego por aspersión pudiera aumentar la lixiviación de BYS, especialmente
cuando se aplica la labranza convencional, la aplicación de CA como enmienda orgánica
puede reducir la cantidad del compuesto lixiviado independientemente del sistema de manejo
empleado.
implementado. Sin embargo, en el año residual, este efecto fue mucho más evidente bajo
riego por inundación con labranza convencional, en consonancia con los resultados
observados en los procesos de adsorción-desorción y disipación comentados anteriormente.
que en LCI. Estos resultados concuerdan con los descritos anteriormente para los estudios de
adsorción-desorción y disipación.
Todo ello pone de manifiesto, al igual que ocurría para los estudios de adsorción-
desorción y disipación, que el proceso de lixiviación es un proceso complejo gobernado por
múltiples factores, entre ellos las características físicas y químicas de las propias materias
activas, situación que no permite establecer una tendencia general en cuanto a la dinámica de
herbicidas en los suelos, y particular en el proceso de lixiviación.
~ 204
Capítulo VII. CONCLUSIONES
Capítulo VII. Conclusiones
4. Mientras que la aplicación del compost en sistemas con riego por aspersión,
tanto en el efecto directo como en el residual, no afectó a la adsorción de BYS, esta enmienda
provocó descensos en la de MCPA. Si embargo, en los sistemas con riego por inundación, la
aplicación del compost incrementó la capacidad de adsorción de ambos herbicidas, aunque
solamente en su efecto residual, revelándose el pH edáfico como el factor más determinante
en la adsorción de estas materias activas.
~ 207 ~
Capítulo VII. Conclusiones
11. En relación con los suelos sin enmendar, en general y a corto plazo, la
implementación de sistemas alternativos al cultivo tradicional del arroz no afectó al proceso
de lixiviación de los herbicidas seleccionados. Sin embargo, a medio plazo, mientras que el
sistema de riego por aspersión en combinación con técnicas de agricultura de conservación
minimizó la lixiviación de CLO, este mismo sistema incrementó la de BYS y MCPA,
especialmente bajo laboreo convencional.
~ 208 ~
Capítulo VII. Conclusiones
12. Excepto en el caso del MCPA en el sistema con riego por inundación, la
aplicación del compost provocó descensos en las cantidades de BYS, CLO y MCPA
lixiviadas en todos los sistemas de manejo y años de estudio, revelándose la materia orgánica
del suelo y de su fracción humificada como los factores más determinantes en el proceso de
lixiviación de estos herbicidas.
~ 209 ~
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