Talanta 80 (2010) 12571263

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Talanta
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A modied acid digestion procedure for extraction of tungsten from soil

A.J. Bednar a, , W.T. Jones a , M.A. Chappell a , D.R. Johnson a , D.B. Ringelberg b
a
U.S. Army Engineer Research and Development Center, Environmental Laboratory, 3909 Halls Ferry Rd., Vicksburg, MS 39180, United States
b
U.S. Army Engineer Research and Development Center, Cold Regions Research and Engineering Laboratory, 72 Lyme Rd., Hanover, NH 03755, United States

a r t i c l e i n f o a b s t r a c t

Article history: Interest in tungsten occurrence and geochemistry is increasing due to increased use of tungsten com-
Received 10 July 2009 pounds and its unknown biochemical effects. Tungsten has a complex geochemistry, existing in most
Received in revised form 9 September 2009 environmental matrices as the soluble and mobile tungstate anion, as well as poly- and heteropoly-
Accepted 10 September 2009
tungstates. Because the geochemistry of tungsten is substantially different than most trace metals,
Available online 12 September 2009
including the formation of insoluble species under acidic conditions, it is not extracted from soil matrices
using standard acid digestion procedures. Therefore, the current work describes a modication to a com-
Keywords:
monly used acid digestion procedure to facilitate quantication of tungsten in soil matrices. Traditional
Tungsten
Acid digestion
soil digestion procedures, using nitric and hydrochloric acids with hydrogen peroxide yield <1 up to 50%
Extraction procedures recovery on soil matrix spike samples, whereas the modied method reported here, which includes the
addition of phosphoric acid, yields spike recoveries in the 7698% range. Comparison of the standard and
modied digestion procedures on National Institute of Standards and Technology Standard Reference
Materials yielded signicantly improved tungsten recoveries for the phosphoric acid modied method.
The modied method also produces comparable results for other acid extractable metals as the standard
methods, and therefore can be used simultaneously for tungsten and other metals of interest.
Published by Elsevier B.V.

1. Introduction One of the most fundamental pieces of information needed to

Recently, interest in tungsten geochemistry and occurrence in
groundwater has increased due to specic human toxicological
events, related to local natural deposits of tungsten ore [13]. Addi-
tionally, industrial (e.g. tungsten carbide tools), mining, civilian
recreational (e.g. lead shotshell replacement), and military (e.g.
kinetic penetrators and small arms ammunition) activities are
potential sources of tungsten in the environment [24]. Tungsten
metal is not found in nature, but oxyanion species of tungsten
are found in a variety of minerals, which can dissolve to yield
the thermodynamically stable tungstate in most environmental
matrices [24]. The chemistry of tungstate is not limited to the sol-
uble monomeric species, as polymerization with other common
oxyanions, such as molybdate, phosphate, and silicate, can yield a
plethora of ill-dened poly-species with variable biogeochemical
properties [3,57]. Because of the complex speciation of tungsten,
particularly the anionic nature, it does not behave as traditional
cationic metals in soils [3,6]. Tungsten sorption to soil has been
studied, and tungsten species have been shown to be more mobile
under alkaline conditions, similar to other anionic compounds, such
as arsenic [811].
Corresponding author. Tel.: +1 601 634 3652.
E-mail address: Anthony.J.Bednar@usace.army.mil (A.J. Bednar).
investigate geochemistry of metals in the environment is quanti-
tation of the amount of the metal present, or at least the fraction of
that metal that could become environmentally relevant [12]. How-
ever, due to the complex chemistry of tungsten, traditional acid
digestion techniques do not extract tungsten from soil that could
become mobile under normal environmental conditions, primarily
due to the precipitation of insoluble tungstates or the polymeriza-
tion of tungstates onto soil particles [6,11,13].
Traditional acid digestion techniques often use nitric and
hydrochloric acids, usually with hydrogen peroxide, to solubilize
metals for analysis by inductively coupled plasma atomic emission
spectroscopy or inductively coupled plasma mass spectrometry
(ICP-AES and ICP-MS) [12]. Due to the precipitation of insoluble
species, low extraction efciencies and matrix spike recoveries
are observed for tungsten using these procedures [13]. Total dis-
solution procedures are also reported which can dissolve the
entire sample matrix, yet usually involve hydrouoric acid or other
complex and potentially hazardous acid cocktails, and require spe-
cialized digestion and analytical equipment (e.g. uoropolymer
vessels and sample introduction systems) [1416].
Some researchers have also investigated the use of alkaline
extractions, however, these procedures often do not extract all
tungsten species with equal effectiveness, and do not work well
for simultaneous extraction of other metals, necessitating at least
two digestions/analyses be performed for a complete metals char-
acterization [13,14,17]. Furthermore, alkaline digestion is more

0039-9140/$ see front matter. Published by Elsevier B.V.

doi:10.1016/j.talanta.2009.09.017
1258 A.J. Bednar et al. / Talanta 80 (2010) 12571263
effective with sodium versus ammonium hydroxide, which can
lead to plasma instabilities and interferences necessitating sample
dilution which raises analyte reporting limits [14,17].
The modied procedure described in the current work capi-
talizes on tungstens ability to polymerize with oxyanion acids,
particularly phosphoric acid, to yield acid soluble tungsten species
for measurement by ICP-AES or ICP-MS, while simultaneously
allowing determination of other metals extracted during the
digestion procedure. The modication involves the addition of
phosphoric acid to a standard nitric acid and hydrogen peroxide
digestion procedure to promote tungsten solublization [1214].
The phosphoric acid modied procedure was tested on standard
reference materials and test eld soils. Results were compared for
tungsten and other metals routinely measured by ICP-AES follow-
ing acid digestion. Tungsten recoveries are greatly improved using
the modied procedure, with only minor differences observed for
some metals between the modied and standard digestion proce-
dures.
2. Experimental
2.1. Reagents
All chemicals used were of trace metal grade purity and used
without further purication; the deionized (DI) water used had a
resistivity of 18.3 M cm. Trace metal grade nitric acid, hydrochlo-
ric acid, phosphoric acid, and hydrogen peroxide were purchased
from Fisher Scientic (Pittsburg, PA) and used as received. Single
element and mixed analyte standards for tungsten and other met-
als were purchased from SPEX CertiPrep (Metuchen, NJ) and CPI
(Santa Rosa, CA).
2.2. Soil sample preparation
Standard reference soil materials (SRM 2709 and 2710) were
purchased from the National Institute of Standards and Technology
(NIST), and used as received. A tungsten-spiked soil was formed by
mixing a Grenada Loring soil (GL) with metallic tungsten (<1 m
particles). The soil was aged approximately 3 years to oxidize the
metallic tungsten. The silty loam soil of the Grenada Loring series
(Allsols order) was collected from the Brown Loam Experimental
Station, Learned, MS. The use of this soil in other geochemical inves-
tigations of tungsten has been previously described [10,11,18].
Finally, eld soil 1 (FS-1), and eld soil 2 (FS-2) were collected
from training ranges where tungsten munitions have been previ-
ously used [19]. The soils were collected in bulk, mixed, and sieved
(<1 cm) to remove plant debris and rocks. FS-1 is an iron-rich clay
and FS-2 is a sandy soil. The three test soils were air-dried, ground
Table 1
Procedures for the three acid digestions compared in the current work.
Nitric acid
Sample mass and digestion vessel 0.5 g in PTFE vessels
1st acid addition 5 mL of 1:1 nitric acid
Heating 30 min at 95 C
Acid additions 42.5 mL concentrated nitric acid each
with 30 min heating
Heating 120 min at 95 C
1st hydrogen peroxide addition 3 mL 30% hydrogen peroxide
Heating 15 min at 95 C
2nd hydrogen peroxide addition 2 mL 30% hydrogen peroxide
Heating 120 min at 95 C
Hydrochloric acid addition
Heating
Dilution to volume Filter and dilute to 50 mL with 1% nitric
acid
with a mortar and pestle, and sieved through a #40 ASTM sieve to
improve sample homogeneity similar to the NIST reference soils
[20].
2.3. Digestion procedures
Three digestion procedures were compared for the present
work, two published versions of US EPA method 3050B [12], and a
third modied from the standard procedures by adding phosphoric
acid to the acid cocktail, as described below and outlined in Table 1.
All acid digestions were conducted on a DigiPrep hotblock digestion
system (SCP Science, Champlain, NY), using uoropolymer diges-
tion vessels to prevent tungsten polymerization onto borosilicate
glass vessel walls. Each digestion batch included a matrix blank,
blank spike, and NIST standard reference soils, as well as the three
test soils (GL, FS-1, FS-2), digested in triplicate.
2.3.1. Nitric acid digestion
The rst procedure follows the US EPA method 3050B nitric
acid and hydrogen peroxide digestion protocol [12]. Briey, one
half gram of dried, ground, and sieved soil was placed in a u-
oropolymer digestion vessel, to which 5 mL of 1:1 nitric acid:DI
water was added and the mixture heated at 95 C for 30 min. Then,
4 sequential additions of 2.5 mL of concentrated nitric acid were
added, with 30 min of heating between each acid addition. After
the nal nitric acid addition, the mixture was heated for 2 h. The
samples were allowed to cool to room temperature before 3 mL of
30% hydrogen peroxide was added, followed by heating for 15 min.
Finally, 2 mL of hydrogen peroxide were added, and the mixture
heated for an additional 2 h. Five milliliters of hydrogen peroxide
was generally sufcient for complete reaction with the samples
tested, although more can be added as needed for other soil matri-
ces. The digestate was then cooled to room temperature and ltered
through a Whatman #40 lter and diluted to 50 mL with 1% nitric
acid.
2.3.2. Nitric and hydrochloric acids digestion
The second digestion procedure also follows USEPA 3050B
where hydrochloric acid is added to increase the solubility of cer-
tain elements for ICP-AES determination [12]. A second 0.5 g aliquot
of each of the solid samples was weighed into uoropolymer ves-
sels and digested following the above described procedure, except
that after the second 2 h heating period, 5 mL of concentrated
hydrochloric acid was added to the digestion vessel with a nal
15 min of heating. After cooling, the digestates were ltered and
diluted to volume as described above.
Nitrichydrochloric acids Phosphoricnitric acids
0.5 g in PTFE vessels 0.5 g in PTFE vessels
5 mL of 1:1 nitric acid 5 mL 1:1 nitric acid + 1 mL concentrated
phosphoric acid
30 min at 95 C 30 min at 95 C
42.5 mL concentrated nitric acid each 42.5 mL concentrated nitric acid each
with 30 min heating with 30 min heating
120 min at 95 C 120 min at 95 C
3 mL 30% hydrogen peroxide 3 mL 30% hydrogen peroxide
15 min at 95 C 15 min at 95 C
2 mL 30% hydrogen peroxide 2 mL 30% hydrogen peroxide
120 min at 95 C 120 min at 95 C
5 mL concentrated hydrochloric acid
15 min at 95 C
Filter and dilute to 50 mL with 1% nitric Filter and dilute to 50 mL with 1% nitric
acid acid
 A.J. Bednar et al. / Talanta 80 (2010) 12571263 1259

2.3.3. Phosphoric and nitric acids digestion
The third digestion procedure was developed specically to
increase tungsten extraction. A third 0.5 g aliquot of each of the
solid samples was weighed into uoropolymer vessels and digested
following the above described nitric acid procedure, with the mod-
ication of adding 1 mL of concentrated phosphoric acid with the
initial 5 mL of 1:1 nitric acid:deionized water. The digestate was
then ltered and diluted as described above.
Aliquots of the 50 mL digestate solutions were further diluted
with 1% nitric acid prior to analysis as needed such that analyte
concentrations were within the calibration range of the analytical
instrumentation (generally 1:4 dilution).
2.4. Instrumentation
Metal concentrations in the diluted digestates, including tung-
sten, were determined by Inductively Coupled Plasma Atomic
Emission Spectroscopy (ICPAES, following modications of EPA
Method 6010C [21]), using a PerkinElmer (Wellesley, MA) Optima
5300DV equipped with a MiraMist nebulizer and cyclonic spray
chamber. The plasma was operated at 1400 W and nebulizer
gas ow rate of 0.65 mL/min. Tungsten was quantied using the
207.912 nm emission line with analyte conrmation at 224.876 nm
using axial plasma viewing. Due to the low concentration of
tungsten in the standard reference soil 2709, tungsten was also
measured by Inductively Coupled Plasma Mass Spectrometry (ICP-
MS following modications of EPA Method 6020A [21]), using a
PerkinElmer Elan DRC-II equipped with a MiraMist nebulizer and
Scott spray chamber. The ICP-MS plasma was operated at 1250 W
and nebulizer gas ow of 0.85 mL/min. Tungsten was quantied at
m/z 182 with conrmation using m/z 184 after correction for 184 Os.
2.5. Calibration and quality control
The ICP-AES was calibrated using NIST-traceable calibration
standards. Scandium, added on-line using a mixing-T, was used as
an internal standard to correct for instrumental drift during analy-
sis. Calcium, magnesium, sodium, potassium, aluminum, and iron
were calibrated using mixed analyte standards containing 0, 0.100,
1.000, 10.00, and 100.0 mg/L of each analyte. All other analytes,
including tungsten, were calibrated using mixed analyte stan-
dards containing 0, 0.100, 1.000, and 10.00 mg/L of each element.
The ICP-MS was calibrated using standards containing 0, 0.001,
0.010, and 0.100 mg/L tungsten, and used holmium as the internal
standard.
All calibration responses were linear and had correlation coef-
cients of at least 0.9999. A second source calibration verication
standard was analyzed immediately after calibration following
standard US EPA Method 6010C procedures [21]; analyte recoveries
were within 10% of the nominal value (4.000 and 0.040 mg/L for
ICP-AES and ICP-MS, respectively). Continuing calibration verica-
tion standards and blanks were analyzed periodically throughout
the analytical batch, with recoveries within 10% of the nominal
value (5.000 and 0.050 mg/L for ICP-AES and ICP-MS, respectively)
and subsequent blanks below the instrument reporting limits
(<0.020 and <0.001 mg/L for ICP-AES and ICP-MS, respectively).
3. Results and discussion
3.1. Tungsten
The tungsten concentrations measured in the two standard
reference materials, using the three digestion procedures, and
associated quality control samples are listed in Table 2. The diges-
tion blanks for all three procedures were below the instrument
reporting limit (<0.040 mg/L including dilution factor), indicat-
ing that contamination was not present in the acids or vessels
used. However, the blank spike sample, consisting of aque-
ous 10 mg/L tungsten from a NIST-traceable standard shows a
marked difference among the three digestion procedures. The
nitric acid method yielded a blank spike recovery of 39%, while
the nitrichydrochloric acid procedure recovery was 43%, both
were well below the phosphoricnitric procedure recovery of 98%.
The nitric and nitrichydrochloric procedures produced a yel-
low precipitate consisting of insoluble tungstic and polytungstic
acids that was captured by the ltration process resulting in poor

Table 2
Comparison of the modied digestion procedure to two standard methods for extraction of tungsten from two standard reference materials and three test soils. Concentrations
are in mg/kg standard deviation of triplicate digestions for soils and mg/L for liquid quality control samples determined by ICP-AES, values in parentheses were determined
by ICP-MS.

Tungsten concentration (mg/kg) Tungsten concentration (mg/L) Reported value recovery (%) Matrix spike recovery (%)

Sample Nitric acid

Digestion blank <0.04
Digestion blank spike (10 mg/L) 3.9 39
SRM 2709 (2 mg/kg) <4 (<0.1) NA (NA)
SRM 2710 (93 mg/kg) 27.4 29
Grenada Loring 210 30 39
Field soil 1 90.2 11 0.4
Field soil 2 440 28 47
Sample Nitrichydrochloric acids
Digestion blank <0.04
Digestion blank spike (10 mg/L) 4.3 43
SRM 2709 (2 mg/kg) <4 (0.2) NA (10)
SRM 2710 (93 mg/kg) 50.0 54
Grenada Loring 221 25 56
Field Soil 1 190 22 3.7
Field Soil 2 737 145 25
Sample Phosphoricnitric acids
Digestion blank <0.04
Digestion blank spike (10 mg/L) 9.8 98
SRM 2709 (2 mg/kg) <4 (0.5) NA (25)
SRM 2710 (93 mg/kg) 79.9 86
Grenada Loring 762 44 98
Field soil 1 483 191 76
Field soil 2 1695 203 79

NAconcentration measured is below instrument reporting limit.

1260 A.J. Bednar et al. / Talanta 80 (2010) 12571263
spike recovery [6,22]; the phosphoricnitric digestion produced no
precipitate, and therefore the soluble phosphotungstates formed
during the modied phosphoricnitric digestion procedure were
not removed by ltration. Improved recoveries for the nitric and
nitrichydrochloric acid procedures were not obtained by rinsing
the ltrate with 2% phosphoric acid, indicating that the precipitates
are stable once formed.
The NIST standard reference soil material results listed in Table 2
show a similar trend as the blank spike samples. The reference
soil 2709 has a total tungsten concentration determined by Neu-
tron Activation Analysis reported by NIST of 2 mg/kg, which is
below the ICP-AES reporting limit for the current study, although,
this demonstrates that matrix interferences are not present, which
could yield a false positive. However, ICP-MS analysis indicated
that increased tungsten recoveries in reference soil 2709 were
obtained using the phosphoricnitric digestion procedure com-
pared to the standard techniques. The phosphoricnitric procedure
yielded 0.5 mg/kg tungsten, which is approximately 25% of the
reported value, however, this is a higher recovery than either the
nitric or nitrichydrochloric digestions.
The reference soil 2710 has a total tungsten concentration
determined by Neutron Activation Analysis reported by NIST
of 93 mg/kg. The nitric acid digestion procedure yielded a con-
centration of 27.4 mg/kg, whereas the nitrichydrochloric acid
digestion yielded 50 mg/kg, which represent 29 and 54% recov-
ery, respectively. The phosphoricnitric acid procedure yielded a
concentration of approximately 80 mg/kg, or 86% recovery. These
recoveries are in line with values reported by others when standard
acid digestion procedures are used for tungsten determinations
[13,17].
It should be noted that all three acid digestion procedures tested
are not intended to be total dissolutions, but rather are strong
extractions, therefore, 86% tungsten recovery for the reference soil
2710 by the phosphoricnitric method compared to Neutron Acti-
vation Analysis is considered acceptable. Furthermore, some of the
tungsten may be present in these samples in silicate phases, which
would normally only be extracted by a total dissolution technique
(e.g. hydrouoric acid, [15,16]), or a solid phase analysis technique,
such as Neutron Activation or X-ray Fluorescence Spectroscopy.
This likely explains the low recovery observed in the reference
soil 2709, even with the phosphoricnitric digestion procedure.
However, in light of the two standard acid digestion procedures
extracting less tungsten in all matrices, the phosphoricnitric acid
procedure performs well. Additionally, the tungsten concentra-
tions reported by NIST are not certied values, but presented for
information purposes only, and therefore may have some inherent
error associated with them. A total dissolution procedure using a
four acid cocktail, including hydrouoric acid [16], was performed
on the reference soils 2709 and 2710 to verify the NIST reported
concentrations. Reference soil 2709 yielded a tungsten concentra-
tion of 2.2 0.05 mg/kg determined by ICP-MS, while reference soil
2710 yielded a tungsten concentration of 97.8 0.4 mg/kg deter-
mined by ICP-AES. These values are 110 and 105% of the NIST
reported concentrations, respectively.
The three digestion procedures are also compared in Table 2 on
the three test soils, with similar trends in tungsten extraction and
matrix spike recovery observed. The nitric acid procedure yielded
tungsten concentrations of 210 30, 90.2 11, and 440 28 mg/kg
for the GL, FS-1, and FS-2 samples, respectively. Tungsten con-
centrations in the nitrichydrochloric digestion procedure samples
were approximately the same for the GL soil (220 25 mg/kg) as the
nitric acid procedure, although the concentrations measured for the
FS-1 and FS-2 samples were about a factor of two higher than those
measured with the nitric acid procedure. The phosphoricnitric
procedure yielded the highest tungsten concentrations, 762 44,
483 191, and 1695 203 mg/kg for the GL, FS-1, and FS-2 soils,
respectively, further suggesting that the two standard methods
have a low bias for tungsten extraction.
The lower concentrations determined by the standard methods
explains the poor matrix spike recovery values listed in Table 2.
The nitric acid digestion yielded a spike recovery of 39% for the GL
soil, but less than 1% for FS-1, and 47% for the FS-2 sample. The
nitrichydrochloric acid procedure yielded slightly higher tung-
sten recoveries than the nitric acid procedure, with the GL spike
recovery being 56%, but only 4 and 25% for the FS-1 and FS-2
samples, respectively. Finally, the matrix spike recoveries for the
phosphoricnitric procedure were 98, 76, and 79% for the GL, FS-1,
and FS-2 samples, respectively, substantially higher than the stan-
dard methods. FS-1 contains a high amount of iron, and therefore
it is possible that an irontungstate phase is causing exceptionally
low extraction of tungsten, even lowering the phosphoricnitric
digestion, which was 76%. The FS-2 sample is a sandy soil, which
could facilitate the formation of polytungstates on the silicon diox-
ide particles, resulting in low tungsten recovery, although the
phosphoricnitric procedure yielded 79% recovery. These experi-
ments demonstrate that the phosphoricnitric modied procedure
greatly improves tungsten extraction from soils compared to the
unmodied standard procedures.
3.2. Other metals
In addition to tungsten, other metal analyses in soils may also
be required simultaneously, therefore, the digestate solutions were
analyzed for 20 other metals to determine the comparability of
the three procedures for determination of other metals. The addi-
tion of phosphoric acid could potentially lower recoveries of metals
that form insoluble phosphate salts, such as lead, aluminum, iron,
nickel, and cobalt, therefore, extraction efciencies and matrix
spike recoveries were tested and compared.
The digestion blanks listed in Table 3 show only 2 analyte detec-
tions, 0.081 mg/L iron in the phosphoricnitric digestion solution,
and 0.104 mg/L calcium in the nitrichydrochloric acid digestion
solution. However, these major cations are present at several orders
of magnitude higher concentrations in soil matrices, suggesting
these blank levels are acceptable. The blank spike recoveries listed
in Table 3 for all elements measured from the three digestion
procedures are within 10% of the nominal spike concentration
indicating no bias among the three digestion procedures for the
elements determined.
Table 3 lists other metal concentrations for the two NIST
standard reference soils determined using the three digestion pro-
cedures. The acid leachable metals concentrations reported by NIST
are not certied values (only the total metals concentrations are
certied by NIST), but are listed for information purposes only.
However, the recoveries listed generally agree among the three
procedures, indicating that low recoveries are not an issue for these
soil matrices and that the phosphoricnitric procedure can be used
for simultaneous determination of other metals. For example, Co
determined by the nitric acid procedure yielded 90 and 101% recov-
ery for the standard reference soils 2709 and 2710, respectively,
in agreement with recoveries obtained for the nitrichydrochloric
procedures (93 and 100%, respectively). In comparison, the
phosphoricnitric procedure produced cobalt recoveries of 105
and 102% for the reference materials 2709 and 2710, respectively,
indicating similar extraction efciencies for the three digestion pro-
cedures. Similar agreement is observed for other analytes listed in
Table 3 (e.g. arsenic, barium, calcium, cadmium, lead, strontium,
and zinc). Elements such as chromium, copper, iron, potassium,
magnesium, molybdenum, and nickel appear to have a slightly
higher extraction efciency by the phosphoricnitric procedure,
compared to the standard digestion procedures, although the dif-
ference is generally less than a 10% increase.
Table 3
Comparison of the modied digestion procedure to standard methods for extraction of other metals from two standard reference materials.

Elements 2709 2710 Nitric acid Nitrichydrochloric acids Phosphoricnitric acids

reporteda reporteda
(mg/kg) (mg/kg)

Digestion Digestion 2709 2710 Digestion Digestion 2709 2710 Digestion Digestion 2709 2710
blank blank spikeb (% recovery) (% recovery) blank blank spikeb (% recovery) (% recovery) blank blank spikeb (% recovery) (% recovery)
(mg/L) (% recovery) (mg/L) (% recovery) (mg/L) (% Recovery)

A.J. Bednar et al. / Talanta 80 (2010) 12571263

Al 26000 18000 <0.08 90 70 80 <0.08 90 71 78 <0.08 92 116 109
As <20 590 <0.08 91 NA 89 <0.08 93 NA 85 <0.08 98 NA 94
Ba 398 360 <0.08 98 86 81 <0.08 98 86 78 <0.08 99 94 82
Ca 15000 4100 <0.08 NS 83 86 0.104 NS 83 81 <0.08 NS 85 80
Cd <1 20 <0.08 101 NA 71 <0.08 99 NA 68 <0.08 96 NA 76
Co 12 8.2 <0.08 100 90 101 <0.08 99 93 100 <0.08 100 105 102
Cr 79 19 <0.08 102 75 81 <0.08 101 77 80 <0.08 105 100 106
Cu 32 2700 <0.08 96 75 91 <0.08 97 83 92 <0.08 103 89 99
Fe 30000 27000 <0.08 100 86 87 <0.08 99 86 86 0.081 103 98 100
K 3200 4500 <0.08 NS 97 99 <0.08 NS 101 95 <0.08 NS 147 120
Mg 14000 5700 <0.08 NS 75 79 <0.08 NS 78 75 <0.08 NS 88 93
Mn 470 7700 <0.08 98 88 92 <0.08 97 89 87 <0.08 99 93 94
Mo <2 20 <0.08 NS NA 57 <0.08 NS NA 63 <0.08 NS NA 73
Na 680 540 <0.08 NS 85 87 <0.08 NS 88 83 <0.08 NS 86 78
Ni 78 10.1 <0.08 100 83 97 <0.08 100 83 95 <0.08 100 91 117
Pb 13 5100 <0.08 94 NA 90 <0.08 95 NA 86 <0.08 92 NA 87
Sr 101 100 <0.08 NS 90 91 <0.08 NS 90 87 <0.08 NS 89 81
Ti 380 1000 <0.08 NS 58 74 <0.08 NS 65 77 <0.08 NS 155 45
V 62 43 <0.08 95 84 87 <0.08 95 87 89 <0.08 97 126 110
Zn 100 5900 <0.08 98 83 85 <0.08 97 86 80 <0.08 100 91 87

NAconcentration measured by one of the digestion procedures is below instrument reporting limit. NSmatrix spike solution did not contain this analyte.
a
Acid leachable metal concentrations are reported by NIST for information purposes only, they are not certied values.
b
Spike levels (mg/L): Al = 10, As = 0.5, Ba = 2.5, Cd = 0.25, Co = 1, Cr = 1, Cu = 1, Fe = 5, Mn = 1, Ni = 1, Pb = 0.5, V = 1, Zn = 2.5.

1261
 1262 A.J. Bednar et al. / Talanta 80 (2010) 12571263

There appears to be a signicant increase in extraction ef-

nitrichydrochloric
ciency for titanium and vanadium in standard reference soil 2709
when using the phosphoricnitric procedure. A similar trend is
also observed for reference soil 2710, which has increased tita-
digestion

nium extraction by the phosphoricnitric procedure. These results

suggest that reference material 2709, in particular, may possess
% of

128

139

124

113
172
115
102

117

113
147
125
107

107
NA

NA
NA

NA

NA
89

94
a refractory vanadium and titanium phase that is sensitive to the
presence of phosphoric acid.
% of nitric

digestion

Listed in Table 4 are the additional metals concentrations in

acid

128

134
177
120

115
101

113

121

111
168
145
130
the three test soils determined using the three digestion proce-
NA

NA
NA
NA

NA

NA
85

83
dures. Because there are no reference values for the concentrations
Field soil 2 metals Matrix spike
recovery (%)

of metals in these soils, as there is with the NIST standard ref-

erence materials, the values obtained for the standard nitric and

-207
nitrichydrochloric acid procedures are used as the reference
108

-67
NS

NS
NS

NS
NS

NS
NS
83
91

91

93

88
91
90

91
40

90
values. The concentrations determined by the phosphoricnitric
(mg/kg) standard

procedure are listed in Table 4, and the relative recovery of each

analyte compared to the standard digestion procedures.
nitrichydrochloric concentration

The matrix spike recoveries for the Grenada Loring soil are all
6481 222
4742 42

9438 69

996 339
deviation

583 6.9
689 2.7

197 5.9
within 20% of the nominal value except for aluminum, iron, and
337 75

43 5.5
13 0.2

47 0.6
10 0.2

11 0.2

11 0.8
40 0.1

manganese, primarily due to the spike concentrations being less

<10

<10
<10

<10

<10

than 10% of the sample concentration for aluminum and iron, and
less than 20% of the manganese concentration in the samples. Sim-
ilarly, the matrix spike recoveries for most elements in the FS1 and
2 samples are acceptable (20%) except where the spike concen-
Metal concentrations and matrix spike recoveries in the three test soils obtained using the modied phosphoricnitric acids digestion procedure.

digestion

tration was small relative to the amount of metal present in the

sample (e.g. aluminum, iron, copper, lead, and zinc in FS-1, and
% of

227

146

261
189

114
107
105

123

111
282
105

106
NA

NA
NA

NA

NA
99

95

95

copper, iron, and lead in FS-2).

Aluminum, chromium, copper, potassium, magnesium, sodium,
% of nitric

digestion

nickel, titanium, and vanadium tend to have higher extraction ef-

ciencies by the phosphoricnitric procedure in at least one of the
acid

231

144

111
125
267
105

146

111
385
131
111
190
105
NA

NA
NA

NA

NA
95

96

test soil matrices compared to the nitric or nitrichydrochloric

Field soil 1 metals Matrix spike

digestion procedures. However, chromium, copper, and nickel are

recovery (%)

only elevated in the GL soil, which has relatively low concentra-

-4667

tions of these elements (<20 mg/kg), suggesting that this could be

615

268
294

615
105
NS

NS
NS

NS
NS

NS
NS
81
91

91
92

94

92

94

a matrix anomaly, or an effect of being near the instrument report-

ing limit. For example, the agreement between the three digestion
(mg/kg) standard

procedures is excellent for copper in the eld soils 1 and 2 that have
NAconcentration measured by one of the digestion procedures is below instrument reporting limit.
nitrichydrochloric concentration

10852 1620

much higher concentrations.

13409 351

8023 1250
199 13.1

135 29.7

It is also possible that the phosphoric acid improves extraction

deviation

114 1.1

56 10.0
415 92

305 50
13 4.4
23 1.5
91 3.1

45 1.1

26 4.3

21 1.4

24 1.0

efciency of anionic species, such as vanadium, due to surface com-

<10
<10

<10

<10

plexation competition. The major cations (aluminum, potassium,

magnesium, and sodium) could also be elevated due to the presence
of additional acid (phosphoric) in the digestion cocktail, although
a similar trend would be expected for the nitrichydrochloric pro-
cedure compared to the nitric acid only procedure, which is not
digestion

observed. However, the anomalies observed with the major cations

% of

182

143

163
145
117
263
154

162
114
105

131
143
109

408
NA

NA
NA

NA

NA
NA

only indicate a potential increased efciency extraction, toward

the recoveries of a total dissolution method, and therefore are not
% of nitric

digestion

necessarily a negative effect, the comparability of the modied

phosphoricnitric procedure for the determination of metals still
acid

173

151
158

261
149
160

101

123
135

446
145
102

110
NA

NA

NA
NA

NSmatrix spike solution did not contain this analyte.

89

75

47

demonstrates its utility.

Matrix spike
recovery (%)

4. Conclusions
233

An acid digestion method modied from standard procedures

NS

NS
NS

NS
NS

NS
NS
86
94

92
91
96
94
18

91
83

92
95
50

is described for the quantitative recovery of tungsten from soil

matrices. The modied method involves the addition of phosphoric
metals concentration
Element Grenada Loring soil

(mg/kg) standard

acid to the acid cocktail to form stable polymeric phospho-

tungstate species for the acid solubilization of tungsten from
15369 350

15446 705

soils. The method was tested on NIST standard reference soils

1651 37
1589 29
deviation

388 4.9
852 11

628 65
12 1.1
94 5.9

12 5.2

81 1.3
19 0.6

14 0.2

35 1.0
29 0.5
10 0.2

and three test soils and shown to improve tungsten solubiliza-

8 0.2

tion and yield acceptable matrix spike recoveries. Additionally,

<10

<10

<10

other common metals were determined in the digestate solu-

tions with similar recoveries obtained to the standard methods,
Table 4

although some anomalies were observed. However, the modied

Mn
Mo
Mg

Na
Cu
Cd

Zn
Co

Pb
Ba
Ca
As

Ni
Fe
Cr
Al

Sr
Ti
V
K

procedure generally performed similarly to the standard digestion

 A.J. Bednar et al. / Talanta 80 (2010) 12571263
procedures and can be used for tungsten and other metals simul-
taneously.
Acknowledgments
The use of trade, product, or rm names in this report is for
descriptive purposes only and does not imply endorsement by
the U.S. Government. The tests described and the resulting data
presented herein, unless otherwise noted, were obtained from
research conducted under the Environmental Quality Technology
Program of the United States Army Corps of Engineers by the
USAERDC. Permission was granted by the Chief of Engineers to
publish this information. The ndings of this report are not to be
construed as an ofcial Department of the Army position unless
so designated by other authorized documents. The authors also
thank Jennifer Seiter and Frances Hill of the USACE for their editorial
comments.
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