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Halocarbon and dimethyl sulphide studies around the


Mascarene Plateau
D. Smythe-Wright, S. M. Boswell, C. H. Lucas, A. L. New and M. S. Varney

Phil. Trans. R. Soc. A 2005 363, doi: 10.1098/rsta.2004.1485, published 15 January 2005

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Phil. Trans. R. Soc. A (2005) 363, 169185


doi:10.1098/rsta.2004.1485
Published online 12 November 2004

Halocarbon and dimethyl sulphide


studies around the Mascarene Plateau
By D. Smythe-Wright, S. M. B o s w e l l, C. H. L u c a s,
A. L. N e w a n d M. S. Varney
Southampton Oceanography Centre, European Way,
Southampton S014 3ZH, UK (dsw@soc.soton.ac.uk)

Airsea exchange is thought to be one of the major routes by which halocarbons and
dimethyl sulphide reach the troposphere and stratosphere. Once there, in dierent
ways, they participate in chemical reactions that have implications for ozone deple-
tion and climate change. The gases are released by phytoplankton and other algae,
but our present understanding of the sources and sinks is insucient to establish
a balanced global budget. Published data suggest that there are regions of coastal
and ocean waters that constitute a major source, but, for halocarbons, in other
regions the ocean is a net sink. For example, in many open oceanic areas, the rate
of degradation of methyl bromide outweighs production.
Here we present data from the Central Indian Ocean, a region considered to be
low in terms of biological productivity. Little is known about trace-gas release from
the Central Indian Ocean and without such data it is impossible to even hazard a
guess at the global ocean source to the atmosphere.
Keywords: Indian Ocean; methyl chloride; methyl iodide;
methyl bromide; dimethyl sulphide; phytoplankton

1. Introduction
Over the last 20 years much has been learned about anthropogenic and natural chem-
ical changes in the atmosphere and their relation to ozone depletion and greenhouse
warming. Concerns over the environmental eects of a number of halogenated com-
pounds such as chlorouorocarbons (CFCs), carbon tetrachloride, methyl chloroform
and methyl bromide resulted in the Montreal Protocol. This instigated the curtail-
ment of anthropogenic production and use of these compounds, the development of
hydrochlorouorocarbons (HCFCs), with further restrictions following subsequent
amendments to the Protocol.
Probably of more interest, however, is the natural source of halogenated com-
pounds. Together, the anthropogenic CFCs and the replacement HCFCs con-
tribute about 60% of the equivalent chlorine in the atmosphere, but the largest
secondary source is natural methyl bromide and methyl chloride, which together

One contribution of 24 to a Discussion Meeting Atmosphereoceanecology dynamics in the Western


Indian Ocean.


c 2004 The Royal Society
169
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170 D. Smythe-Wright and others

contribute about 25%. The oceanic source of methyl chloride has long been recog-
nized, with initial estimates suggesting it was the largest single natural source to
the atmosphere. Rened estimates now suggest it is responsible for about 31%, with
biomass burning at 43% (Harper 2000) being the predominant source, and fungi
and salt marshes (both 8%) being lesser contributors. The oceanic source of methyl
bromide, however, is still the subject of much debate.
Initially, it was thought that the ocean contributed a large ux of methyl bromide
to the atmosphere, explaining the missing source in global budgets (Butler 1995,
1996). Further data implied that the ocean was a sink (Lobert et al . 1995). New
data now suggest that the ocean can be both (King et al . 2000; Smythe-Wright &
Boswell 2001), depending on temporal and spatial variability.
Atmospheric iodine chemistry has also been the focus of recent attention. There
is clear evidence of high iodide concentrations in the tropical troposphere that have
implications for tropospheric ozone and its greenhouse eect (Vogt et al . 1999). In
addition, there is also evidence for the rapid upward transport of a tropical source
impinging on stratospheric ozone concentrations. The high iodide concentrations
probably result from an oceanic source of methyl iodide. Lovelock (1974) was the rst
to suggest the importance of ocean-derived methyl iodide in atmospheric chemistry.
Once in the atmosphere, methyl iodide is either attacked by OH radicals, or, more
importantly, undergoes photodecomposition, liberating iodine.
The importance of dimethyl sulphide (DMS) in atmospheric chemistry has been
known for some time, as it contributes the main natural source (about 60%) of
atmospheric sulphur (Lovelock et al . 1972; Andreae 1986). A cocktail of sulphur
compounds, including sulphate and methane sulphonic acid, which inuence climati-
cally important processes such as the backscatter of sunlight and cloud condensation
(Bates et al . 1987; Ayers & Gras 1991), form from DMS. These processes increase
the Earths albedo, causing planetary cooling and hence aect our climate (Charlson
et al . 1987).
In short, airsea exchange is one of the major routes by which halocarbons and
DMS reach the troposphere and stratosphere. However, it is dicult to quantify
the temporal and geographical extent of the sources and to establish the processes
responsible for them. There have been a number of investigations regarding trace-
gas release in the Atlantic and Pacic Oceans (see, for example, Belviso et al . 2003;
Aranami et al . 2002; Yvon-Lewis et al . 2002; King et al . 2000; Moore & Groszko
1999; Groszko & Moore 1998; Moore et al . 1996; Malin et al . 1993), and some work
at Amsterdam Island (Putaud et al . 1992) and in the Arabian Sea (Hatton et al .
1999), but relatively little is known about the Central Indian Ocean.
Since there is evidence of halocarbon and DMS production by phytoplankton in
laboratory culture (see, for example, Peckett 2001; Zang et al . 1999; Saemundsdottir
& Matrai 1998; Scarratt & Moore 1999, 1998, 1996; Tait & Moore 1995; Simo et al .
1998; Malin et al . 1998; Malin & Kirst 1997), it is not unreasonable to suggest that
phytoplankton are, in part, responsible for oceanic production. Other possibilities
are nucleophilic substitution of halides, e.g. the formation of methyl chloride from
methyl bromide and iodide (Zariou 1975), and photochemistry, particularly the
latter for methyl iodide (Moore & Zariou 1994; Happell & Wallace 1996). Here
we present data from the Central Indian Ocean, an area considered to be low in
nutrients and biological productivity. It would therefore seem reasonable to expect
that the oceanic release of halocarbons and DMS is low from these regions. Data

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Halocarbons and DMS around the Mascarene Plateau 171

5 S Seychelles

10 S

western section

15 S central section

eastern section

20 S
Mauritius
Runion

55 E 60 E 65 E
Figure 1. Map showing the sections occupied during the SCIPIO cruise with station positions.

from the SCIPIO (Satellite Calibration and Interior Physics of the Indian Ocean)
cruise, completed in July 2002 and presented here, contradict this and suggest that
even regions considered to be oligotrophic may be sources of halocarbons to the
atmosphere.

2. Data and methodology


The SCIPIO cruise took place during June/July 2002 on the RRS Charles Darwin,
between 3z circ and 20 S and 55 and 70 E (New 2003). A total of 64 stations were
occupied along ve sections (see gure 1), spaced ca. 6080 miles apart. Trace-gas
measurements were made primarily along the central and western sections during
the second leg of the cruise, with only limited measurements at the southern end of
the eastern section.
All trace-gas samples were collected directly from the hydrographic bottles
into 250 ml ground-glass syringes, which were stored in the dark, under a constant
stream of running water, prior to analysis, to prevent contamination from the ships
environment. The samples were analysed on board, using purge-and-trap gas chro-
matography/mass spectrometry (HP 6890GC/5973 MSD, tted with 30 m CB Sil-5,

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172 D. Smythe-Wright and others

0 175
(a) 150
50

pmol l1
125
depth (m)

100
100
75
50
150
25

200 0
0 8
(b)
50 6
depth (m)

pmol l1
100 4

150 2

200 0
0 40
(c)
50 30
depth (m)

pmol l1
100 20

150 10

200 0
0 12
(d )
10
50
nmol l1

8
depth (m)

100 6
4
150
2
200 0
0 10 12 14 16 18 20
latitude
Figure 2. The distributions of (a) methyl chloride, (b) methyl bromide,
(c) methyl iodide and (d) DMS along the central section.

0.32 mm, 5 m lm-thickness column). Air samples were also collected and analysed
during the cruise. All samples were calibrated by injection of known quantities of
calibrated gas using xed-volume sample loops. Two sources of gas were used: one
from a cylinder calibrated by NOAA/CMDL and cross-calibrated to the Weiss scale,
the other from a Kin-Tek standards generator. Details of the analytical techniques
are given in Smythe-Wright (2000) and New (2003).

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Halocarbons and DMS around the Mascarene Plateau 173

0 350
(a)
300
50 250

% saturatiom
depth (m)

200
100
150

150 100
50
200 0
0 500
(b)
50 400

% saturatiom
depth (m)

300
100
200
150
100

200 0
0 2500
(c)
50 2000

% saturatiom
depth (m)

1500
100
1000
150
500

200 0
0 25 000
(d )
50 20 000
depth (m)

% saturatiom

15 000
100
10 000
150
5 000

200 0
8 10 12 14 16 18 20
latitude
Figure 3. Percentage saturations of (a) methyl chloride, (b) methyl bromide, (c) methyl iodide
and (d) DMS with respect to the atmosphere along the central section.

Water samples were also collected and prepared for plant-pigment analysis and
phytoplankton identication and stored either frozen to liquid-nitrogen tempera-
tures or preserved with Lugols iodine and formaldehyde. These samples were later
analysed for plant pigments, using the high-pressure-liquid chromatography tech-
niques detailed by Barlow et al . (1997), and for species identication by microscopy
and ow cytometry (Carr et al . 1996), but the species data are not presented here.

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174 D. Smythe-Wright and others

3. Trace-gas distributions
A total of 22 gases with natural and/or anthropogenic sources were measured during
the cruise. Here we concentrate on methyl chloride, methyl iodide, methyl bromide
and DMS and compare results from the central and western sections in the top 200 m;
concentrations below 200 m are close to zero. Figure 2 shows the distribution of
the four compounds along the central section. Not unexpectedly, concentrations are
patchy, with some coincidence between the high spots of the four compounds, espe-
cially around 12 S. In general, methyl bromide and DMS are at low levels in the
southern part of the section, whereas methyl chloride and methyl iodide appear to
be more uniformly spread. Figure 3 shows the same data expressed as percentage
saturation with respect to the atmosphere. These saturations were calculated fol-
lowing Sander (1999), using Henrys law constants derived by Moore et al . (1995)
for methyl chloride and methyl iodide, Wilhelm et al . (1977) for methyl bromide
and De Bruyn et al . (1995) for DMS. Mean atmospheric concentrations of 588 pptv
for methyl chloride, 10.2 pptv for methyl bromide, 12 pptv for methyl iodide and
100 pptv for DMS were used in the calculations. While bearing in mind that not all
the gas in the surface water will escape to the atmosphere, release being constrained
by wind stress, wave action, etc., percentage saturation does give an indication of
the potential ocean source. Furthermore, because of the very short atmospheric life-
time of methyl iodide compared with methyl bromide and methyl chloride, it will
invariably appear supersaturated compared with the other two halides, which can
be undersaturated in some ocean regions.
Figures 4 and 5 give the data for the western section. Concentrations here are
lower than along the central section, but again there is some coincidence between
the distribution of the four compounds, particularly between 14 and 16 S and in the
distributions of the three methyl halides at 20 S. More detailed descriptions of the
individual compounds and implications regarding oceanic sources to the atmosphere
follow.

(a) Methyl chloride


The observed concentrations of methyl chloride range from below detection lev-
els to 175 pmol l1 , with the maximum concentration centred around 12 S along
the central section (see gure 2a). The highest concentrations range from ca. 110
to 175 pmol l1 (corresponding to almost 350% saturation (see gure 3a)) and cover
a band between 10 and 14 S, extending to 75 m in depth. There is also a second
relatively high spot at 16 S at 100 m. Either side of these high areas, concentrations
fall to ca. 75 pmol l1 , with a distinct trend for higher concentrations to penetrate
deeper at the southern end of the section. South of 18 S, concentrations in the
surface begin to fall away, approaching equilibrium with the atmosphere.
Along the western section, concentrations reach a maximum of ca. 150 pmol l1
(gure 4a), corresponding to 250% saturation (gure 5a) at 12 S, and extend only
to 35 m. There is a distinct feature, with concentrations of more than 100 pmol l1 ,
between 14 and 16 S extending below 100 m (see gure 4a). Moving southward,
concentrations fall away to 50 pmol l1 and can be considered to be in equilibrium
with the atmosphere, before rising sharply at 20 S around 60 m.

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Halocarbons and DMS around the Mascarene Plateau 175

(b) Methyl bromide


The distributions of methyl bromide (see gures 2b and 4b) along the central and
western sections are broadly similar to those of methyl chloride (gures 2a and 4a).
High concentrations up to 8 pmol l1 (almost 500% saturation with respect to the
atmosphere), extending to 75 m, are centred around 12 S on the central section (see
gures 2b and 3b). There is also a relatively high patch extending southwards at 50 m
between 14 S and 18 S, which is about 200% saturated, but this does not extend as
deep as the corresponding patch for methyl chloride. South of 18 S, concentrations
fall away to ca. 2 pmol l1 , which is approaching atmospheric equilibrium.
Along the western section (see gure 4b), concentrations are lower, reach-
ing ca. 5 pmol l1 (200300% saturation (see gure 5b)), and again there is a deep
feature, with concentrations approaching 4 pmol l1 between 14 and 16 S, followed
by minimum levels at around 18 S. There is also a distinct front at about 20 S,
with concentrations reaching 6 pmol l1 (almost 400% saturation) at 30 and 120 m.

(c) Methyl iodide


The distribution of methyl iodide along the central section (see gure 2c) shows
a distinctive high patch stretching from just south of 10 S to almost 16 S, extend-
ing to 60 m. Within this patch, concentrations at the surface exceed 40 pmol l1 ,
with concentrations to the south in the top 100 m falling away to 20 pmol l1 . Both
regions represent a signicant potential source to the atmosphere with saturations
over 1000% (see gure 3c).
Along the western section (see gure 4c), concentrations are lower, with maxima
of ca. 30 pmol l1 centring on 12 S, but are still suciently high to represent an
ocean source. Like the other halides, there are high values, reaching 35 pmol l1 , at
the southern end of the section.

(d ) Dimethyl sulphide
The concentrations of DMS are three orders of magnitude higher than those of the
halocarbons. Between 12 and 14 S along the central section they reach 12 nmol l1
and are a striking 25 000% saturated with respect to the atmosphere (see gures 2d
and 3d). South of 14 S, concentrations fall away rapidly to less than 1 nmol l1 , but
are still at about 30005000% saturation.
Along the western section (see gures 4d and 5d), the higher concentrations appear
to extend further south than on the central section, but fall sharply at 17 S. Unlike
the halides, there is no corresponding high at 20 S.

4. Discussion
The high trace-gas concentrations observed at 1214 S along the central section, and
the feature between 14 and 16 S along the western section are likely to be related
to the ow of the South Equatorial Current as it crosses the Mascarene Plateau.
The Plateau forms a natural restriction to the westward owing current, with ow
constrained through narrow gaps in the bottom topography. The main convergence
zone is between the Nazareth and Saya de Malha Banks at 1214 S. The acoustic-
Doppler-current-proler data from the cruise, at 27 and 51 m (see gure 6), show a

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176 D. Smythe-Wright and others


0 175
(a)
150
50
125

pmol l1
depth (m)

100
100
75

150 50
25
200 0
0
8
(b)
50 6
depth (m)

pmol l1
100 4

150 2

200 0
0 40
(c)
50 30
depth (m)

pmol l1
100 20

150 10

200 0
0 12
(d )
10
50
8
depth (m)

nmol l1

100 6
4
150
2
200 0
10 12 14 16 18 20
latitude
Figure 4. The distributions of (a) methyl chloride, (b) methyl bromide,
(c) methyl iodide and (d) DMS along the western section.

strong westward ow in this region along the central section that appears to move
southward to 1416 S as it crosses the western section. Work by New et al . (2005)
shows that this convergence is a critical boundary between nutrient rich northern
water and nutrient poor waters to the south.
Studies of mesoscale processes such as internal wave action (Morozov & Vlasenko
1996; Schott & McCreary 2001) and gyres (Williams & Follows 1998a, b) have shown

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Halocarbons and DMS around the Mascarene Plateau 177


0
350
(a)
300
50
250

% saturatiom
depth (m)

200
100
150
150 100
50
200 0
0 500
(b)
50 400

% saturatiom
depth (m)

300
100
200
150 100

200 0
0
(c) 2500

% saturatiom
50 2000
depth (m)

1500
100
1000
150 500
0
200
0
25 000
(d ) % saturatiom
50 20 000
depth (m)

15 000
100
10 000
150 5 000

200 0
10 12 14 16 18 20
latitude
Figure 5. Percentage saturations of (a) methyl chloride, (b) methyl bromide, (c) methyl iodide
and (d) DMS with respect to the atmosphere along the western section.

nutrient replenishment in surface waters that can lead to isolated areas of produc-
tivity in regions considered to be a desert. Internal wave studies by Konyaev et al .
(1995) and by Morozov & Vlasenko (1996), together with the work of Schott et al .
(2002), and Schott (2005) regarding Ekman suction, suggest that the region of the
Mascarene Plateau might be such an anomalous area. The data in New et al . (2005)
and in gure 7 show water of a higher nutrient content to the north of 12 S just

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178 D. Smythe-Wright and others

2
(a) (b)
4 Seychelles Seychelles

10 Saya de Malha Saya de Malha


Bank Bank

12

14 Nazareth Nazareth
Bank Bank

16

18

20
Mauritius Mauritius
Runion 50 cm s1 Runion 50 cm s1
22
55.0 58.0 61.0 64.0 55.0 58.0 61.0 64.0
longitude longitude
Figure 6. Velocities (cm s1 ) derived from acoustic
Doppler current proler at (a) 27 and (b) 51 m.

extending to the surface. This water is thought to originate from northern water
masses as well as from upwelling in the Central Indian Ocean due to Ekman suction
(see New et al . 2005).
We believe that it is the upward inux of nutrients from lower depths that inu-
ences productivity in this region, and hence the higher trace-gas production. But
what is curious is that the high trace-gas concentrations seen between 12 and 14 S
are not well correlated with the SeaWiFS composite image for chlorophyll-a (see
gure 8 in New et al . 2005). The low chlorophyll-a presence in the 1214 S region
along the central section and the 1416 S band along the western section is con-
rmed from in situ chlorophyll-a plant-pigment data shown in gure 8. In general,
the high trace-gas concentrations appear to be on the southerly boundary within the
more nutrient poor waters.
While it could be argued that trace-gas production in clear tropical waters is due to
photochemical action, particularly for methyl iodide (Richter 2004; Moore & Zariou
1994), we do not believe that it can account for the high concentrations observed here.
Using incubation experiments for tropical waters, Richter (2004) has calculated daily
photoproduction rates for methyl iodide of 0.10.2 nmol m3 h1 that equate well
with those of Moore & Zariou (1994) when dierences in irradiation time between

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Halocarbons and DMS around the Mascarene Plateau 179

Table 1. The taxonomic signicance of plant-pigment markers

pigment taxonomic signicance

chlorophyll-a phytoplankton biomass


chlorophyll-b green algae (chlorophytes/euglenophytes)
divinyl chlorophyll a prochlorophytes
fucoxanthin diatoms
19 hexanoyloxyfucoxanthin prymnesiophytes
peridinin photosynthetic dinoagellates
phaeophorbides zooplankton grazing/cell senescence
zeaxanthin cyanophytes/prochlorophytes/chlorophytes

the two studies are taken into account. Equating the net daily photochemical methyl
iodide production of 40.3 nmol m3 d1 to concentration, using a relationship with
wind speed and Schmidt number, Richter (2004) has shown that net production
would result in surface sea-water (top 30 m) concentrations of 14 pmol l1 at wind
speeds of 6.6 m s1 , and 28 pmol l1 at wind speeds of 4.5 m s1 . The data presented
here from the SCIPIO cruise were collected in the track of the southeast trade winds,
when wind speeds were in excess of 10 m s1 and between 15 and 20 m s1 for most
of the cruise. Taking an average wind speed of 15 m s1 would reduce the surface
concentration resulting from net photochemical production to 1.6 pmol l1 . In fact,
constant wind speeds of less than 2 m s1 would be needed to maintain surface
concentrations at our observed level. Consequently, photochemistry cannot account
for the methyl iodide concentrations of up to 40 pmol l1 observed here, and an
alternative source must be investigated.
Plant-pigment analysis provides markers for dierent phytoplankton species, as
shown in table 1. While the concentrations of chlorophyll-a are low in the 1014 S
region, those of zeaxanthin, divinyl chlorophyll-a, peridinin and fucoxanthin are rel-
atively high and show some coincidence with the trace-gas distributions (see g-
ure 9). These pigments are markers for prochlorophytes, cyanophytes, dinoagellates
and diatoms, all of which have been shown to correlate with methyl halide produc-
tion in the Atlantic Ocean (Smythe-Wright & Boswell 2001). Prochlorophytes and
cyanophytes, in particular, are known to dominate the Northwestern/tropical Indian
Ocean (Sorokin et al . 1985). Their small size (picoplankton) provides them with
a high surface-area-to-volume ratio, making them adaptable to oligotrophic water
(Gibb et al . 2001).
In contrast to the halocarbons, the oceanic production of DMS is fairly well under-
stood, originating from the precursor dimethyl sulphoniopropionate (DMSP) that is
synthesized by certain marine algal groups for cellular osmoregulation and by bacte-
ria (Stefels 2000). While several mechanisms have been postulated for the conversion
of DMSP to DMS, the exact nature of the process and reasons why it occurs are
still unclear. Factors that are known to inuence DMS production are physical dis-
turbance, osmotic shock, pathogen attack by viruses and bacteria and zooplankton
grazing (Burkill et al . 2002; Archer et al . 2001; Malin et al . 1994). One of the phyto-
plankton groups known to contain high DMSP cellular concentrations are members
of the algae class prymnesiophyceae (Malin et al . 1994; Liss et al . 1994) that have
the marker pigment 19 hexanoyloxyfucoxanthin. While levels of DMS are particu-

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180 D. Smythe-Wright and others

0 30
(a) 25
50

depth (m)

mol l1
20
100 15
10
150 5
200 0
0 1.50
(b) 1.25
depth (m)

mol l1
50
1.00
100 0.75
0.50
150
0.25
200 0
0 50
(c) 40
50
depth (m)

mol l1
30
100
20
150 10
200 0
8 S 10 S 12 S 14 S 16 S 18 S 20 S
latitude
Figure 7. The distributions of (a) nitrate, (b) phosphate and
(c) silicate (mol l1 ) along the central section.

0
(a)
0.25
50
0.20
mol l1
depth (m)

100 0.15
0.10
150
0.05

200 0
8 10 12 14 16 18 20
0
(b) 0.25
50
0.20
mol l1
depth (m)

100 0.15
0.10
150
0.05

200 0
10 12 14 16 18 20
latitude
1
Figure 8. Chlorphyll-a distributions (mol l ) along (a) the central and (b) western sections.

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Halocarbons and DMS around the Mascarene Plateau 181

0 0.10
(a)
0.08
depth (m)
50

mol l1
0.06
100
0.04
150 0.02
200 0
0 0.175
(b)
50 0.150
depth (m)

mol l1
0.125
100 0.100
0.075
150 0.050
200 0.025
0 0.012
(c)
50 0.010
depth (m)

mol l1
0.007
100
0.005
150 0.002
200 0
0 0.040
(d ) 0.035
50
depth (m)

0.030

mol l1
0.025
100 0.020
150 0.015
0.010
200 0.005
0 0.175
(e)
50 0.150
mol l1
depth (m)

0.100
100
0.075
150 0.050
200 0.025
8 10 12 14 16 18 20
latitude
Figure 9. The distributions of (a) zeazanthin, (b) divinyl chlorophyll-a, (c) peridinin,
(d) fucoxanthin and (e) 19 hexanoyloxyfucoxanthin along the central section.

larly high in the 1214 S region along the central section, there seems to be little
relationship with the occurrence of this pigment.

5. Conclusions
It is clear that there are sources of halocarbons and DMS in regions of the Southwest-
ern Indian Ocean normally considered to be low in productivity. Concentrations of
up to 175 pmol l1 methyl chloride, 8 pmol l1 methyl bromide, 40 pmol l1 methyl
iodide and 12 nmol l1 DMS were observed, primarily in a band between 10 and
16 S. South of this, concentrations are lower and in equilibrium with the atmo-

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182 D. Smythe-Wright and others

sphere for methyl chloride and methyl bromide and in line with reported open ocean
values for DMS. While the lowest observed values of methyl iodide still represent a
signicant source to the atmosphere, they could possibly be explained by photochem-
ical reaction. The maximum values of all the traces gases appear to correlate with
the presence of pico- and micro-algae, suggesting a biological rather than physical
source (photochemistry or substitution). We believe that the observed distributions
are related to the inuence of the South Equatorial Current, which forms a bound-
ary between more nutrient-rich water originating to the north of the region and
oligotrophic regions to the south. Nutrient-rich water crosses this boundary at depth
and its inuence just extends to the surface north of 12 S. Since the observed chloro-
phyll levels suggest productivity is still relatively low, we believe that picoplankton,
known to be ubiquitous in the region and able to survive in low-nutrient regions,
may be responsible for the trace-gas source. We therefore conclude that regions nor-
mally considered to be oligotrophic cannot be discounted as an oceanic source of
biologically produced trace gases. This suggests that the global oceanic production
of some environmentally important gases may be considerably higher than originally
thought.
The authors express their thanks for the help and support given by the scientic party and
ships company of Charles Darwin Cruise 141 during the collection of this dataset. This work
was partly supported by the Royal Geographical Society (with IBG)Royal Society Shoals of
Capricorn programme, Western Indian Ocean, 19982001. This is Shoals Contribution no. PO48.
We also acknowledge the use of the computer program Ocean Data View (Schlitzer 2004) in
this work.

References
Andreae, M. O. 1986 The ocean as a source of atmospheric sulphur compounds. In The role of
airsea exchange in geochemical cycling (ed. P. Buat-Menaud). NATO ASI Series C Mathe-
matical and Physical Science, vol. 186. Dordrecht: Reidel.
Aranami, K., Watanabe, S., Tsunogai, S., Ohki, A., Miura, K. & Kojima, H. 2002 Chemical
assessment of oceanic and terrestrial sulfur in the marine boundary layer over the North
Pacic during summer. J. Atmos. Chem. 41, 4966.
Archer, S. D., Stelfox-Widdicombe, C. E., Burkill, P. H. & Malin, G. 2001 A dilution approach
to quantify the production of dissolved dimethyl sulphoniopropionate and dimethyl sulphide
due to microzooplankton herbivory. Aquat. Microbial Ecol. 23, 131145.
Ayers, G. P. & Gras, J. L. 1991 Seasonal relationship between cloud condensation nuclei and
aerosol methane sulphonate in marine air. Nature 353, 834835.
Barlow, R. G., Mantoura, R. F. C., Cummings, D. G. & Fileman, T. W. 1997 Pigment chemotax-
onomic distributions of phytoplankton during summer in the western Mediterranean. Deep-
Sea Res. 44, 833850.
Bates, T. S., Charleston, R. J. & Gammon, R. H. 1987 Evidence for the climatic role of marine
biogenic sulphur. Nature 329, 319321.
Belviso, S., Sciandra, A. & Copin-Montegut, C. 2003 Mesoscale features of surface water DMSP
and DMS concentrations in the Atlantic Ocean o Morocco and in the Mediterranean Sea.
Deep-Sea Res. 50, 543555.
Burkill, P. H., Archer, S. D., Robinson, C., Nightingale, P. D., Groom, S. B., Tarran, G. A.
& Zubkov, M. V. 2002 Dimethyl sulphide biogeochemistry within a coccolithophore bloom
(DISCO): an overview. Deep-Sea Res. 49, 28632885.
Butler, J. H. 1995 Methyl bromide under scrutiny. Nature 376, 469470.

Phil. Trans. R. Soc. A (2005)


Downloaded from rsta.royalsocietypublishing.org on June 4, 2013

Halocarbons and DMS around the Mascarene Plateau 183

Butler, J. H. 1996 Scientic uncertainties in the budget of atmospheric methyl bromide. Atmos.
Environ. 30, iiii.
Carr, M. R., Tarran, G. A. & Burkill, P. H. 1996 Discrimination of marine phytoplankton species
through statistical analysis of their ow cytometer data. J. Plankton Res. 18, 12251238.
Charlson, R. J., Lovelock, J. E., Andreae, M. O. & Warren, S. G. 1987 Oceanic phytoplankton,
atmospheric sulphur, cloud albedo and climate. Nature 326, 655661.
De Bruyn, W., Swartz, E., Hu, J. H., Shortner, J. A., Davidovits, P., Worsnop, D. R., Zahniser,
M. S. & Kolb, C. E. 1995 Henrys law solubilities and Setchenow coecients for biogenic
reduced sulphur species obtained from gasliquid uptake measurements. J. Geophys. Res.
100, 72457251.
Gibb, S. W., Cummings, D. G., Irigoien, X., Barlow, R. G. & Mantoura, F. R. C. 2001 Phyto-
plankton pigment chemotaxonomy of the northeastern Atlantic. Deep-Sea Res. 48, 795823.
Groszko, W. & Moore, R. M. 1998 Oceanatmosphere exchanges of methyl bromide: NW
Atlantic and Pacic studies. J. Geophys. Res. 103, 1673716741.
Happell, J. D. & Wallace, D. W. R. 1996 Methyl iodide in the Greenland/Norwegian Seas and
the tropical Atlantic Ocean: evidence for photochemical production. Geophys. Res. Lett. 23,
21052108.
Harper, D. B. 2000 The global chloromethane cycle: biosynthesis, biodegradation and metabolic
role. Nat. Prod. Rep. 17, 337348.
Hatton, A. D., Malin, G. & Liss, P. S. 1999 Distribution of biogenic sulphur compounds during
and just after the southwest monsoon in the Arabian Sea. Deep-Sea Res. 46, 617632.
King, D. B., Butler, J. H., Montzka, S. A., Yvon-Lewis, S. A. & Elkins, J. W. 2000 Implications
of methyl bromide supersaturations in the temperate North Atlantic Ocean. J. Geophys. Res.
105, 19 76319 769.
Konyaev, K. V., Sabinin, K. D. & Serebryany, A. N. 1995 Large-amplitude internal waves at
the Mascarene Ridge in the Indian Ocean. Deep-Sea Res. 42, 207.
Liss, P. S., Malin, G., Turner, S. M. & Holligan, P. M. 1994 Dimethyl sulphide and phaeocystis:
a review. J. Mar. Syst. 5, 4153.
Lobert, J. M., Butler, J. H., Montzka, S. A., Geller, L. S., Myers, R. C. & Elkins, J. W. 1995 A
net sink for atmospheric CH3 Br in the East Pacic Ocean. Science 267, 10021005.
Lovelock, J. E. 1974 Atmospheric halocarbons and stratospheric ozone. Nature 252, 292294.
Lovelock, J. E., Maggs, R. L. & Rassmussen, R. A. 1972 Atmospheric dimethyl sulphide and
the natural sulphur cycle. Nature 237, 452453.
Malin, G. & Kirst, C. O. 1997 Algal production of dimethyl sulphide and its atmospehric role.
J. Phycol. 33, 889896.
Malin, G., Turner, S. M., Liss, P. S., Holligan, P. & Harbour, D. 1993 Dimethyl sulphide and
dimethyl sulphoniopropionate in the Northeast Atlantic during the summer coccolithophore
bloom. Deep-Sea Res. 40, 14871508.
Malin, G., Liss, P. S. & Turner, S. M. 1994 Dimethyl sulphide; prodution and atmospheric con-
sequences. In The Haptophyte algae (ed. J. C. Green & B. S. C. Leadbeater). Oxford Scientic
Publications Systematics Association Special Volume 51, pp 303320. Oxford: Claredon.
Malin, G., Wilson, W. H., Bratbak, G., Liss, P. S. & Mann, N. H. 1998 Elevated production
of dimethylsulde resulting from viral infection of cultures of Phaeocystis pouchetti. Limnol.
Oceanogr. 43, 13891393.
Moore, R. M. & Groszko, W. 1999 Methyl iodide distribution in the ocean and uxes to the
atmosphere. J. Geophys. Res. 104, 11 16311 171.
Moore, R. M. & Zariou, O. C. 1994 Photochemical production of methyl iodide in seawater.
J. Geophys. Res. 99, 16 41516 420.
Moore, R. M., Green, C., G. & Tait, V. K. 1995 Determination of Henrys law constants for a
suite of naturally occurring halogenated methanes in seawater. Chemosphere 30, 11831191.

Phil. Trans. R. Soc. A (2005)


Downloaded from rsta.royalsocietypublishing.org on June 4, 2013

184 D. Smythe-Wright and others

Moore, R. M., Groszko, W. & Niven, S. J. 1996 Oceanatmosphere exchange of methyl chloride:
results from NW Atlantic and Pacic Ocean studies. J. Geophys. Res. 101, 28 52928 538.
Morozov, E. G. & Vlasenko, V. I. 1996 Extreme tidal internal waves near the Mascarene Ridge.
J. Mar. Syst. 9, 203210.
New, A. L. 2003 RRS Charles Darwin Cruise 141, 01 June11 July, 2002. Satellite calibration
and interior physics of the Indian Ocean: SCIPIO. Southampton Oceanography Centre, Cruise
Report 41.
New, A. L., Stanseld, K., Smythe-Wright, D., Smeed, D. A., Evans, A. J. and Alderson, S. G.
2005 Physical and biochemical aspects of the ow across the Mascarene Plateau in the Indian
Ocean. Phil. Trans. R. Soc. A363, 151168.
Peckett, C. F. 2001 An investigaton into the release of methyl halides by phytoplankton cultures,
2001. MPhil thesis, School of Ocean and Earth Science, University of Southampton.
Putaud, J. P., Mihalopoulus, N., Nguyen, B. C., Campin. J. M. & Belviso, S. 1992 Seasonal
variations of atmospheric sulfur dioxide and dimethylsulde concentrations at Amsterdam
Island in the southern Indian Ocean. J. Atmos. Chem. 15, 17131.
Richter, U. 2004 Factors inuencing methyl iodide production in the ocean and its ux to the
atmosphere. Dissertation zur Erlangung des Doktorgrades der Mathematisch-Naturwissen-
schaftlichen Fakult at der Christian-Albrechts-Universit at zu Kiel. (Available at E.diss.uni-
Keil.de/diss 1024/d1024.pdf.)
Saemundsdottir, S. & Matrai, P. A. 1998 Biological production of methyl bromide by cultures
of marine phytoplankton. Limnol. Oceanogr. 43, 8187.
Sander, R. 1999 Compilation of Henrys law constants for inorganic and organic species of poten-
tial importance in environmental chemistry. (Available at http://www.mpch-mainz.mpg.de/
sander/res/henry.html.)
Scarratt, M. G. & Moore, R. M. 1996 Producton of methyl chloride and methyl bromide in
laboratory cultures of marine phytoplankton. Mar. Chem. 54, 263272.
Scarratt, M. G. & Moore, R. M. 1998 Producton of methyl chloride and methyl bromide in
laboratory cultures of marine phytoplankton II. Mar. Chem. 59, 311320.
Scarratt, M. G. & Moore, R. M. 1999 Production of chlorinated hydrocarbons and methyl iodide
by the red micralgae, Porphyridium Purpureum. Limnol. Oceanogr. 44, 703707.
Schlitzer, R. 2004 Ocean Data View. (Available at http://www.awi-bremerhaven.de/GEO/
ODV.)
Schott, F. A. 2005 Shallow overturning circulation of the Western Indian Ocean. Phil. Trans.
R. Soc. A 363, 143149.
Schott, F. A. & McCreary Jr, J. P. 2001 The monsoon circulation of the Indian Ocean. Prog.
Oceanogr. 51, 1123.
Schott, F. A., Dengler, M. & Schoenefeldt, R. 2002 The shallow overturning circulation of the
Indian Ocean. Prog. Oceanogr. 53, 57103.
Simo, R., Hatton, A. D., Malin, G. & Liss, P. S. 1998 Particulate dimethyl sulphoxide in seawater:
production by microplankton. Mar. Ecol. 167, 291296.
Smythe-Wright, D. 2000 Planktonic sources of biogenic gases: a mesocosm study in Ranefjorden,
Norway. Southampton Oceanography Centre Internal document 63.
Smythe-Wright, D. & Boswell, S. M. 2001 Climatically active halogenated gases in the ocean;
their measurement and distribution SOC Research and Consultancy Report 53.
Sorokin, Y. I., Kopylov, A. I. & Mamaeva, N. V. 1985 Abundance and dynamics of microplankton
in the central tropical Indian Ocean. Mar. Ecol. 24, 2741.
Stefels, J. 2000 Physiological aspects of the production and conversion of DMSP in marine algae
and higher plants. J. Sea Res. 43, 183197.
Tait, V. K. & Moore, R. M. 1995 Methyl chloride production in phytoplankton cultures. Limnol.
Oceanogr. 40, 189195.

Phil. Trans. R. Soc. A (2005)


Downloaded from rsta.royalsocietypublishing.org on June 4, 2013

Halocarbons and DMS around the Mascarene Plateau 185

Vogt, R., Sander, R., Von Glasgow, R. & Crutzen, P. J. 1999 Iodine chemistry and its role in
halogen activation and ozone loss in the marine boundary layer: a model study. J. Atmos.
Chem. 32, 375395.
Wilhelm, E., Battino, R. & Wilcock, R. J. 1977 Low pressure solubitites of gases in liquid water.
Chem. Rev. 77, 219226
Williams, R. G. & Follows, M. J. 1998a Eddies make ocean deserts bloom. Nature 394, 228229.
Williams, R. G. & Follows, M. J. 1998b The Ekman transfer of nutrients and maintenance of
new production over the North Atlantic. Deep-Sea Res. 45, 461489.
Yvon-Lewis, S. A., Butler, J. H., Saltzman, E. S., Matrai, P. A., King, D. B., Tokarczyk, R.,
Moore, R. M. & Zhang, J. Z. 2002 Methyl bromide cycling in a warm-core eddy of the North
Atlantic Ocean. Global Biogeochem. Cycles 16, 88.188.6.
Zariou, O. C. 1975 Reaction of methyl halides with seawater and marine aerosols. J. Mar. Res.
33, 7581.
Zang, M.-P., Cui, Z., Cui, W., Wang, F., Zhang, H.-Z. & Sheng, P. 1999 Study on the dimethyl
sulphide and dimethyl sulfoniopropionate in algae by laboratory batch cultures. Chin. J.
Oceanol. Limnol. 17, 366370.

Phil. Trans. R. Soc. A (2005)


Downloaded from rsta.royalsocietypublishing.org on June 4, 2013

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