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Biogenic Sulfur Compounds and the Global SulfurCycleViney P. Aneja a , Arun P. Aneja b & Donald F. Adams ca General Electric Companyb Monsanto Triangle Park Development Center, Inc.c University of IdahoPublished online: 12 Mar 2012.

To cite this article: Viney P. Aneja , Arun P. Aneja & Donald F. Adams (1982) Biogenic Sulfur Compounds and the GlobalSulfur Cycle, Journal of the Air Pollution Control Association, 32:8, 803-807, DOI: 10.1080/00022470.1982.10465466

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Biogenic Sulfur Compounds and theGlobal Sulfur Cycle

Viney P. AnejaGeneral Electric Company

Arun P. AnejaMonsanto Triangle Park Development Center, Inc.

Donald F. AdamsUniversity of Idaho

Sulfur compounds of biogenic origin are thought to constitute a significantfraction of the atmospheric sulfur burden. Experimental determinationof the biogenic fluxes of these compounds into the atmosphere is requiredto assess accurately the relative contributions of the anthropogenic andthe biogenic fraction of the natural sources to such important phenomenaas the atmospheric sulfate burden and acid precipitation.

A review of the literature describing field measurements of biogenic sul-fur compounds at different kinds of emission locales to include both gener-ation processes (sulfate reduction and plant decomposition) of volatile sul-fur production show a great variation in the emission rate measurementsassociated primarily with wide variations in the surface and climatic envi-ronments of the various study sites. Although the maximum emission ratemeasurements balance the global sulfur cycle, the average measurementvalues do not, indicating the need for more experimental investigations inorder to characterize the biogenic process adequately.

Field measurements describe biogenic,gaseous sulfur compounds emitted fromdifferent kinds of locales and show agreat variation both in absolute con-centrations and in emission rates. Thesevariations can be explained partially bythe wide differences among the surfaceand climatic environments. Althoughthe maximum emission rates would ap-pear high enough to balance the globalsulfur cycle, the average measurementsdo not, indicating the need for moreexperimental investigations to charac-terize adequately the biogenic processes.These studies are needed for an under-standing of such important phenomenaas the atmospheric sulfate content andacid precipitation.

The rational development of emissioncontrol strategies for sulfur require the

Dr. V. P. Aneja is with GeneralElectric Company, Corporate Re-search and Development Center,Schenectady, NY 12301. Dr. A. P.Aneja is with Monsanto TrianglePark Development Center, Inc., Re-search Triangle Park, NC 27709. Dr.Adams is President of the Air Pollu-tion Control Association.

identification and characterization of allmajor sources of atmospheric sulfurcompounds, both natural and anthro-pogenic (Figure I). Natural sulfursources include sea spray, volcanic ac-tivity, decay of animal and plant tissue,marine algae, anaerobic microbiologicalactivity, and other in-situ inland soilprocesses.

Anthropogenic sourcesATMOSPHERE

[Automobile exhausufossil fuel burning,

[refineries, etc. I

Figure 1. Sources of sulfur compounds.

Biogenic sulfur compounds originatefrom nonspecific bacterial reduction oforganic sulfur, i.e. plant decomposition,and from specific sulfate reducing bac-teria. The latter organisms are strictlyanaerobic, while nonspecific reducersmay be found in anaerobic or aerobicenvironments. Both processes requirethe presence of organic material andmoisture. Because the biogenicallyproduced fraction of the natural sulfuremissions has not been well character-ized, either qualitatively or quantita-

tively, the total amount of sulfur thatbiogenic sources supply to the atmo-sphere per year has been estimated bydifference. The amount of atmosphericsulfur contributed per year from an-thropogenic sources, from volcanoes,and from sea spray is known. It is as-sumed that the sulfur content of theatmosphere does not change in the timescale of one year, and the biogenicemission rate is set equal to the sourcedeficit usually found.

Ambient Air ConcentrationMeasurements

Early field investigation of biogenicsulfur compounds involved measuringthe concentrations of H2S, DMS, CS2,COS, and SO2 in ambient air. The valuesfor H2S, DMS, CS2 and COS togetherwith their ranges are presented in Tablej 1-19 T n e jj2g concentrations foundprior to 1970 should be treated withcaution because they were obtained withunreliable sampling and analyticaltechniques. For these early valuesbackground concentrations have beenassumed to be of the order of 0.3 ng/m3

or less.

Natural sources Sulfate sea spray ~ 10%Volcanic activity ~ 10%Biogenic activity ~ 80%

Prior to Natusch, analytical methodscould not measure H2S concentrationsless than about 0.15 /ig/m3. In 1972,Natusch etal.4 reported a fluorescencemethod with a sensitivity of 0.002 /ig/m3.Using this method at a remote mountainski area in Boulder, CO under westerlywind conditions, they found H2S con-centrations averaging 0.04 /ig/m3.

Years later, Delmas et al.10 employedthis method of Natusch and gas chro-matography and observed that the H2SCopyright 1982-Air Pollution Control Association

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Table I. Atmospheric concentrations of sulfur compounds.

Reference

Smith et al.1 (1961)Lodge and Pate2 (1966)Axelrod e t a / . 3 (1969)Natusch etal.4 (1972)Breeding et al.5 (1973)Slatt etal.6 (1978)Jaeschkeeia/.7(1978)Georgii8 (1978)

Delmase£a/.9(1978)Delamsetaf.1 0(1979)Denmead11 (1962)

Graedeletal.1 2 (1974)Hitchcock et al.u

(1977)Slatt etal.6 (1978)

Maroulis, Bandy14

(1977)Hanst etal.15 (1975)Sandall & Penkett16

(1977)Maroulis etal.11 (1977)

Maroulis etal.17 (1977)

Maroulis et al.17 (1977)Torres e ta / . 1 8 (1978)

Inn et al.19 (1979)

Location

U.S.PanamaPanamaU.S. (CO)U.S. (IL, MO)Miami, FLW. GermanyIsland of Sylt

(North Sea)Ivory CoastFranceAbove Polluted Air

New ZealandPolluted Air USAU.S. (NC) Polluted

MarshMiami, FL

polluted airU.S. (VA Coast)

U.S. AtmosphereUK Atmosphere

Philadelphia, PA(U.S.)

Wallops Island, VA(U.S.)

Lawton, OK (U.S.)Latitude Range

67°N-57°S38°N-119°W

(15.2 km)

H2S

0.15-0.451.0

0-0.480.04

0.12-0.30.008-0.080.035-1.65

0.1

0.1-8.70.017-0.17

1 X10 3

I X 103

80

0.17-1.15

Atmosphericconcentrations,

Mg/m3

DMS CS2 COS

0.15

0.27-0.800.24-1.26 1.29-1.50

1.17 ± 0.07

1.21 db 0.083

1.37 ± 0.0961.37 ± 0.16

1.31-140

air concentration in the temperate zoneof France was close to that in Boulder,-CO; it ranged from 0.017-0.17 jtg/m3.These same investigators found that theatmospheric H2S was much higher inthe equatorial region of the Ivory Coast,ranging from 0.1-8.7 /*g/m3. It is notedthat urban air in Miami, FL had an H2Sconcentration much lower than this—0.17-0.15 jig/m3.6

In areas where high H2S concentra-tions are suspected, very high concen-trations have been found. Hitchock etal.13 measured H2S in the air above atidal marsh in North Carolina and foundthe concentration to be as high as 80ixg/m3. These data may be unreliable,however, because they were possiblyinfluenced by a nearby sewage treat-ment plant. At a sampling station0.4-11.3 km away from industrialsources, Graedel et al.12 measuredlong-term H2S concentrations exceeding1 X 103 /ug/m3. Denmead11 found H2Sconcentrations approaching 1 X 103

jug/m3 above the highly polluted, shallowbackwaters of a harbor.

Originally H2S was considered to bethe only biogenic form of sulfur. In 1972DMS was found in sea water and in theheadspace gas of soils and organic mat-ter stored under several laboratoryconditions.20

In 1975 Hanst et al.15 used a cryogenicprocedure for concentrating trace gases

in the atmosphere and analysis bymeans of long-path infrared absorptionspectroscopy and observed COS in theNorth Carolina atmosphere at concen-trations of 0.49 /ig/m3. In 1977 Sandallsand Penkett16 employed cryogenicsample concentration and subsequentgas chromatographic analysis to findatmospheric COS and CS2 in Harwell,England at concentrations of 1.25 and0.59 ^ug/m3, respectively. In the sameyear Maroulis and Bandy14 found aver-age DMS concentrations as high as 0.15/Lig/m3 at two sites along the coast ofVirginia.

Because all sulfur species are even-tually oxidized to SO2 and sulfates, theconcentration of atmospheric SO2 givesa general indication of the original totalconcentration of other sulfur com-pounds. Therefore, instead of measuringthe other sulfur compounds individu-ally, the atmospheric reaction productSO2 is sometimes determined. In a re-mote, moist equatorial forest of theIvory Coast, Delmas et al.9'10 measuredthe atmospheric SO2 concentration andfound it to be ~30 jig/m3. This SO2 is thesecondary reaction product from thedecomposition of organic litter andhumus. The concentration is compara-ble to SO2 levels in industrial zones andhigher than those reported for ruralzones in the U.S. and Europe. In com-parison, marine concentrations of SO2

in the air near the Ivory Coast are low(0.1-0.5 jug/m3).

Sulfur Flux Measurements

Recently, comprehensive experi-mental measurements have been re-ported for earth atmosphere fluxes ofbiogenic sulfur compounds.7'9"10'14'21-29

Table 117,10,17,21-26,30,31 p resents thesemeasurements as published values fornatural biogenic sulfur emissions fromsalt and fresh water marshes (i.e. bybacterial reduction of sulfate), fromvarious inland soils and vegetative cover,and from the decomposition of tropicalvegetation.

Although these measurements showwide variations from site to site, thedifferences may, in part, be associatedwith the temperature range at the timeof sampling and the type of soils wherethe measurements were made. Some ofthe variations in measured fluxes maybe due to the different sampling andanalytical methods used by these in-vestigators.

Measurements over Marshes,Swamps, and Intertidal Zones

The first direct measurements ofemission fluxes were reported byAneja21 and published by Hill et al.22

The latter reported that the biogenicH2S fluxes above a Long Island saltmarsh varied from below detection limitto 42 gS/m2/yr with a strong seasonalvariation. When these values are cor-rected for seasonal (i.e. temperature)and tidal variations, the average H2Sflux is ~0.5 gS/m2/yr for this marsh.Other sulfur gases were found in the fluxfrom this marsh. The maximum fluxesmeasured were: CH3SH, 1.92 gS/m2/yr;DMS, 3.84 gS/m2/yr; and (CH3)2S2,0.81gS/m2/yr.

Hansen et al.23 observed copiousquantities of H2S in two shallow, coastalareas of Denmark. Here the peak emis-sion rates were ~89 to ~2000 gS/m2/yrwith diurnal averages equivalent to ~19to ~470 gS/m2/yr. Aneja et al.24 re-ported peak H2S flux values from saltmarshes at Cox's Landing, NC of ~100gS/m2/yr with an average over the mudflat zone of ~0.5 gS/m2/yr.

At the same locale over the Spartinaalterniflora zone, the average DMS fluxvalues were found to be ~0.66 gS/m2/yr-24,25 c s 2 and COS flux values werealso measured from the same salt marshby Aneja et a/.26"29-32 who reported theestimated emission rates as ~0.2 gS/m2/yr and ~0.03 gS/m2/yr, respectively.Adams et al.sl working at this locationunder different climatic and surfaceconditions and excluding emissions fromtide water surfaces, observed quite dif-ferent CS2 and COS emission rates—1.13 and 6.36 gS/m2/yr, respectively.

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Table II. Biogenic emissions of sulfur compounds. Emission rate gS/m2/yr.

Reference

Aneja21 (1975) Hill, Aneja,Felder22 (1977)

Maroulis,Bandy (1977)

Aneja eta/.24-26

(1979)Aneja et a/.30

Adams et al.31 (1979)Adams et a/.31 (1979)

Jaeschke7 et al. (1978)

Hansene£a/.23(1978)

Delmas et al.10 (1979)

Delmas et al.w (1979)

Source

Salt Marsh, NY

Atlantic Ocean,VA

Salt Marsh, NC

Fresh WaterMarsh, NC

Salt Marsh, NCInland Soils

U.S.Swamps and tidal

flatsSediments of

shallow coastalarea, Denmark

Soils of humidequatorial forestsIvory Coast (neara salt marsh)

Soils of temperateregions, France

H2SAvg.

0.55

0.5

0.6

720.001

0.044

~19 ~

0.07

0.044

Max.

41.5

100

1.27

381

2000

2.6

0.24

DMS DMDSAvg. Max. Avg. Max.

3.84 0.81

0.006

0.66 2.5

0.093 0.0040.001 0.001

CH3SH CS2 COSAvg. Max. Avg. Max. Avg.

1.92

0.2

6.56 1.130.001 0.002

Max.

0.03

6.36

A year later Adams et al.27~29 re-ported a peak H2S flux value of ~381gS/m2/yr with an average value of ~71gS/m2/yr in the intertidal salt marsh atCox's Landing. (Incidentally, these re-searchers observed average CH3SHemissions from this marsh of ~6.5 gS/m2/yr, corroborating the earlier findingsof Aneja21 and Hill et al.22)

Measurements over Land

Aneja et al.30 measured H2S flux ratesfrom a fresh water marsh soil in NorthCarolina and found an emission ratevarying between ~0.08 and 1.27 gS/m2/yr with an average value of 0.6 gS/m2/yr. Adams et al.31 studied the emis-sions from a North Carolina histosol soilproduced from an ancient, fresh-waterCyprus swamp and reported an averageH2S emission of 0.018 gS/m2/yr.

Jaeschke et al.1 calculated a H2S fluxof 0.044 gS/m2/yr for the Island of Sylt(off the shore of Denmark). This studyalso showed that the flux of H2S aboveaerobic soils is negative, i.e. these soilsare a sink for H2S.

In a broad and diverse inland studyarea in the eastern and southern U.S.,Adams et a/.

27-29.31>33-34 reported H2Sfluxes consistent with Jaeschke's7 val-ues, ranging from 0.01-0.17 gS/m2/yr, inaddition to the fluxes of several othersulfur gases including DMS, CS2, andCOS. Although the fluxes of all of thesegases are much lower than fluxes overmarshes, swamps, and intertidal zonesof more limited area, measurements atmore than 30 sites indicate that theseinland soils contribute up to 58% of thetotal biogenic sulfur over this inlandarea.

Delmas et al.10 measured H2S emit-ted by anaerobic soils of humid equa-torial forests of the Ivory Coast and es-timated the flux to be between ~0.3 and~2.6 gS/m2/yr. They also measured H2Semissions from three aerobic, grass-covered (lawn) soils between 43 and 47N latitude in France and found them tobe low in contrast, varying between0.007 and 0.24 gS/m2/yr with an averagevalue of 0.04 gS/m2/yr. At five sites atthe same latitude in New York, Michi-gan, Wisconsin, Massachusetts, andMinnesota, Adams et al.u measuredsulfur fluxes and found them to be con-sistent with the Delmas et al. data.9'10

The H2S flux was found to range fromundetectable to 0.16 gS/m2/yr with anaverage flux of 0.04 gS/m2/yr for all fivesites. (These investigations were a partof the extensive Sulfate Regional Ex-periment Study, (SURE.35) In addition,the total sulfur flux from these five U.S.sites ranges from 0.013-0.33 gS/m2/yr.34

Thus, approximately 30-50% of the totalmeasured sulfur flux at these five sitesconsists of organo-sulfur compounds—primarily CS2, COS, and DMS, the re-mainder being H2S.

The Stratospheric Aerosol Layer

In order to describe the global sulfurcycle adequately, the sulfur content ofboth the troposphere and the strato-sphere must be taken into consideration.In 1961 Junge36>37 suggested that sulfurcould be found in the stratosphere andmeasurements were made to confirm itspresence. Because all gaseous sulfurcompounds except for COS and CS2 areoxidized rapidly in the troposphere, itwas decided that COS and CS2 are re-

sponsible for the presence of sulfur inthe stratosphere.

Two studies consider the possiblecontribution of COS and CS2 from saltmarshes to the stratospheric sulfateaerosol layer.26-38 It can be calculatedthat CS2 and COS from salt marshesaccount for more than 100% of thestratospheric sulfur. This calculation isbased on the following synthesis. Ac-cording to Crutzen's39 estimate, a flux of1.8 X 10~4 gS/m2/yr into the strato-sphere accounts for the entire strato-spheric sulfate aerosol layer.

Applying Junge's37 one-dimensionaleddy diffusion model to the troposphere,and using the mean sum of CS2 and COSmaximum emission rates for globalmarshes (Table II) and CS2 and COSatmospheric lifetimes (Table III),16'40-45

the mean maximum contribution due toCS2 and COS can be computed to begreater than 100% (Table IV). (This

Table III. Atmospheric residence times ofCS2andCOS.

Reference

Sandals, Penkett16

(1977)Kurylo40 (1978)Atkinson et al.41

(1978)Logan et al.42

(1979)Ravishankara

eia/.43(1980)Cox, Sheppard44

(1980)Turcoeia/.45

(1980)

Atmosphericresidence time,

daysCS2 COS

365 7300

5034134

60 200

19290 3288

723

45 365

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Meanaverage~10.7

4.1 X 106

~ 1 %

Meanmaximum

-373.1

~142 X 106

>1OO%

Table IV. Contribution of biogenic sulfur compounds to the global sulfur cycle.

Biogenic emissions oftotal sulfur species (2S)gS/m2/yr (Table II)

Biogenic contribution of(2S) to the troposphereton/yr

Biogenic contribution ofCOS + CS2 to stratosphericsulfate aerosol layer

calculation assumes zero CS2 and COSconcentrations at 15 km height.)

The Biogenic Contribution

It is interesting to speculate on thepossible role of biogenically producedH2S, DMS, DMDS, CH3SH, CS2, andCOS in the sulfur cycle of the tropo-sphere and the stratosphere. The esti-mated biogenic contribution to balancethe global sulfur cycle ranges from 40 X106-230 X 106 tons of gaseous sulfur peryear.36-46"51 It has been assumed that thereal value may lie somewhere betweenthese limits. Measurements of sulfurremoved from the troposphere by rain-water (as sulfate) indicate that 100 X 106

tons of gaseous sulfur, put into the at-mosphere by biogenic processes, is re-moved from the troposphere by rain-water.48

It has been calculated that the con-tribution from salt marshes is mean ~4.1X 106 ton/yr and maximum ~142 X 106

ton/yr by making the following as-sumptions:

• All salt marshes emit uniformly.• The total salt marsh area is 3.8 X 105

km2.52

• The total sulfur (2S) emission ratefor salt marshes is mean arithmeticaverage US = ~10.3 gS/m2/yr andmean arithmetic maximum 2S =~361 gS/m2/yr. Using a total annualturnover of 100 X 106 ton of biogenicsulfur, it can be seen that marshescontribute mean ~4% and maximum~100% of the biogenic sulfur com-pounds.

In conclusion, when biogenic sulfurcompounds from both sulfate reductionand plant decomposition generationprocesses are considered, there is a greatvariation in the measured emission ratesfor different kinds of locales. While themaximum emission rate measurementsfrom salt marshes certainly make a sig-nificant contribution to the global sulfurcycle, the mean average values do not.Adams34 reported that nearly 58% of thebiogenic sulfur emissions from theSURE study area originated from inlandsoils which represent nearly 90% of thestudy area. Obviously, additional fieldmeasurements at carefully defined lo-

cales are needed to characterize globalprocesses adequately. A large body ofbiogenic sulfur flux data is becomingavailable for the temperate zone, par-ticularly in the northern hemisphere.However, very limited data are availablefrom the tropics which may be thegreatest source of biogenic sulfur gasesdue to the tropical wetlands, the highbiomass, and the high ambient temper-atures.

Methods for Measuring Flux

Two methods are used to measureearth-atmosphere fluxes of gases. In thechamber method (Figure 2, direct mea-surement), an open-bottom chamber isplaced over the surface to capture thegases emanating from the surface. Acarrier gas is introduced into the cham-ber and mixed with these gases. The ef-fluent gas is sampled and analyzed forthe compounds of interest and the fluxis estimated by mass balance.

In the micrometeorological method(Figure 3, indirect measurement), theconcentration of the gas of interest ismeasured at various altitudes above thesource along with the wind speed anddirection. Estimates of flux are made byapplying turbulent diffusion theory tothe concentration profile data.

Acknowledgment

Before publication, this feature articlewas read and commented on for tech-

nical accuracy by Dr. Allan Lazrus,Atmsopheric Chemistry and AeronomyDivision of the National Center for At-mospheric Research (NCAR), Boulder,CO.

References

1. A. F. Smith, D. G. Jenkins, D. E. Cun-ningworth, "Measurements of tracequantities of hydrogen sulfide in indus-trial atmosphere," J. Appl. Chem. 11:317 (1961).

2. J. P. Lodge, J. B. Pate, "Atmosphericgases and particulates in Panama,"Science 153: 408 (1966).

3. M. C. Axelrod, J. H. Cary, J. E. Bonelli,J. P. Lodge, Jr., "Fluorescence determi-nation of sub parts per billion hydrogensulfide in the atmosphere," Anal. Chem.41:1850 (1969).

4. D. F. S. Natusch, M. B. Klonis, H. D.Axelrod, R. J. Teck, J. P. Lodge, Jr.,"Sensitive method for the measurementof atmospheric hydrogen sulfide," Anal.Chem. 44: 2067 (1972).

5. R. J. Breeding, J. P. Lodge, Jr., J. B. Pate,D. C. Sheesley, H. B. Klonis, B. Fogle, J.A. Anderson, T. R. Englert, P. L. Haag-enson, A. F. Wartburg, "Backgroundtrace gas concentrations in the centralUnited States." J. Geophys. Res. 78:7057 (1973).

6. B. J. Slatt, D. F. S. Natusch, J. M. Pros-pero, D. L. Savoie, "Hydrogen sulfide inthe atmosphere of the northern equato-rial Atlantic Ocean and its relation to theglobal sulfur cycle," Atmos. Environ. 12:981 (1978).

7. W. Jaeschke, H. M. Georgii, H. Claude,H. Malewski, "Contributions of H2S tothe atmospheric sulfur cycle," Pure andAppl. Geophys. 116(2/3): 463 (1978).

8. H. W. Georgii, "Large-scale spatial andtemporal distribution of sulfur com-pounds." Atmos. Environ. 12: 681(1978).

- 9. R. Delmas, J. Bandet, J. Servant, "Ademonstration of the natural sources ofsulfate in a moist tropical environment,"TELLUS 30:158 (1978).

10. R. Delmas, J. Bandet, J. Servant, R. Ba-ziard, "Emissions and Concentration ofHydrogen Sulfide in the Air of theTropical Forest of the Ivory Coast and ofTemperate Regions in France," FourthInternational Conference of the Com-mission of Atmospheric Chemistry andGlobal Pollution, University of Colorado,Boulder, CO, 1979.

11. C. F. Denmead, "Air Pollution by Hy-drogen Sulfide from a Shallow PollutedTidal Inlet, Auckland, New Zealand," in

Emission rate, n=F-AC

F=Steady volumetric flow rate of gas through the chamberAC=Concentration increase

A=Area of emitting surface covered by the chamber

Rotameter Emission flux reactor

Ambientair)ient —*4 "7ir f~\

.To GC foranalysis

Ground level

Figure 2. Layout of field experiment using emission flux reactor with ambient air carrier gas.24

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4-

2 3-

Z 2 -

1-

At each sampling port (1, 2, 3, 4—) measurepollutant concentration, wind speed, winddirection and temperature

Tower

TVegetation canopy

^ M M M ^ ^ ^ ^ i — M r r Ground level

Figure 3. Micrometeorological method. Emission rate n = Kz. AC/AZ, whereKz = vertical diffusivity and A C / A Z = vertical pollutant concentration gra-dient.

Proc. Clean Air Conference, Universityof New South Wales, Paper No. 4, FirstTechnical Session, 1962.

12. T. E. Graedel, B. Kleiner, C. C. Patterson,1974. "Measurements of extreme con-centration of tropospheric hydrogensulfide," J. Geophys. Res. 79: 4467(1974).

13. D. R. Hitchcock, L. L. Spiller, W. E.Wilson, "Biogenic Sulfides in the At-mosphere in a North Carolina TidalMarsh," Paper presented at the NewOrleans American Chemical SocietyMeeting, March 1977.

14. P. J. Maroulis, A. R. Bandy, "Estimate ofthe contribution of biologically produceddimethyl sulfide to the global sulfurcycle," Science 196: 647 (1977).

15. P. L. Hanst, L. L. Spiller, D. M. Watts, J.W. Spence, M. F. Miller, "Infrared mea-surements of fluorocarbons, carbon tet-rachloride, carbonyl sulfide, and otheratmospheric trace gases," JAPCA 25:1220 (1975).

16. F. J. Sandalls, S. A. Penkett, "Measure-ments of carbonyl sulfide and carbondisulfide in the atmosphere," Atmos.Environ. 11:197 (1977).

17. P. J. Maroulis, A. L. Torres, A. R. Bandy,"Atmospheric conditions of carbonylsulfide in the south-western and easternUnited States," Geophys. Res. Lett. 4:510 (1977).

18. A. L. Torres, P. J. Maroulis, A. B. Gold-berg, A. R. Bandy, "Measurement ofTropospheric COS on the 1978 GAME-TAG Flights," EOS-Trans. Amer. Geo-phys. Union 59:1082 (1978).

19. E. C. Y. Inn, J. F. Vedder, B. J. Tyson,"COS in the stratosphere," Geophys.Res. Lett. 6:191 (1979).

20. J. E. Lovelock, R. J. Maggs, R. A. Ras-mussen, "Atmospheric dimethyl sulfideand the natural sulfur cycle," Nature237:452 (1972).

21. V. P. Aneja, "Characterization of Sourcesof Biogenic Atmospheric Sulfur Com-pounds," M.S. Thesis, Department ofChemical Engineering, North CarolinaState University, Raleigh, NC, 1975.

22. F. B. Hill, V. P. Aneja, R. M. Felder, "Atechnique for measurement of biogenicsulfur emission fluxes," Environ. Sci.Technol. 13:199 (1978).

23. M. H. Hansen, K. Ingvoren, Jorgensen,"Mechanisms of hydrogen sulfide releasefrom coastal marine sediments to theatmosphere," Limnology Oceanology23(1): 66 (1978).

24. V. P. Aneja, E. W. Corse, L. T. Cupitt, J.

C. King, J. H. Overton, Jr., R. E. Rader,M. H. Richards, H. J. Sher, R. J. Whit-kus, "Biogenic Sulfur Sources StrengthField Study." Northrop Services, Inc.Report No. ESC-TR-79-22, ResearchTriangle Park, NC, 1979, p. 189.

25. V. P. Aneja, J. H. Overton, Jr., L. T. Cu-pitt, J. L. Durham, W. E. Wilson, "Directmeasurements of emission rates of someatmospheric biogenic sulfur com-pounds," TELLUS 31(2): 176 (1979).

26. V. P. Aneja, J. H. Overton, Jr., L. T. Cu-pitt, J. L. Durham, W. E. Wilson, "Car-bon disulfide and carbonyl sulfide frombiogenic sources and their contributionto the global sulfur cycle," Nature282(5738): 493 (1979).

27. D. F. Adams, "Estimates of NaturalSource Strengths," Chapter in Atmo-spheric Sulfur Deposition: Environ-mental Impact and Health Effects, Ed.D. S. Shiner, Ann Arbor Science Pub-lishers, Inc., Ann Arbor, MI, 1980.

28. D. F. Adams, S. O. Farwell, E. Robinson,M. R. Pack, "Assessment of BiogenicSulfur Emissions in the SURE Area,"EPRI Final Report, No. EA-1516, Elec-tric Power Research Institute, Palo Alto,CA, Sept. 1980.

29. D. F. Adams, S. 0. Farwell, E. Robinson,M. R. Pack, "Biogenic sulfur gas emis-sions from soils in eastern and south-eastern United States," JAPCA 31:1083(1981).

30. V. P. Aneja, J. H. Overton, A. P. Aneja,"Emission survey of biogenic sulfur fluxfrom terrestrial surfaces," JAPCA 31:256(1981).

31. D. F. Adams, S. O. Farwell, M. R. Pack,W. L. Bamesberger, "Preliminary mea-surements of biogenic sulfur-containinggas emissions from soils," JAPCA 29:380(1979).

32. V. P. Aneja, J. H. Overton, Jr., L. T. Cu-pitt, J. L. Durham, W. E. Wilson, "Mea-surements of emission rates of carbondisulfide from biogenic sources and itspossible importance to the stratosphericaerosol layer," Chem. Eng. Communi-cations 4(6): 721 (1980).

33. D. F. Adams, S. O. Farwell, M. R. Pack,E. Robinson, "An Initial Emission In-ventory of Biogenic Sulfur Flux fromTerrestrial Surfaces," Paper No. 78-16Presented at the Annual Meeting ofPNWIS/APCS, Portland, OR, 1978.

34. D. F. Adams, S. O. Farwell, E. Robinson,M. Pack, W. L. Bamesburger, "BiogenicSulfur Source Strength," Paper No.81-15.3 Presented at the Annual Meeting

of APCA, Philadelphia, PA, 1981.35. R. M. Perhac, "Sulfate regional experi-

ment in northeastern United States: The"SURE" program," Atmos. Environ. 12:641 (1978).

36. C. E. Junge, Air Chemistry and Radio-activity, Academic Press, New York, 382pp.

37. C. Junge, 1963, "Sulfur Budget of theStratospheric Aerosol Layer," in Pro-ceedings of the International Confer-ence of Structure, Composition andGeneral Circulation of the Upper andLower Atmospheres and Possible An-thropogenic Perturbations, Melbourne,Australia, 1974.

38. V. P. Aneja, "Direct Measurements ofEmission Rates of Some AtmosphericBiogenic Sulfur Compounds and TheirPossible Importance to the StratosphericAerosol Layer," Chapter in AtmosphericSulfur Deposition: Environmental Im-pact and Health Effects, Ed. D. S.Shriner, Ann Arbor Science Publishers,Inc., Ann Arbor, MI 1980.

39. P. J. Crutzen, "The possible importanceof COS for the sulfate layer of thestratosphere," Geophys. Res. Letters3(2): 73 (1976).

40. M. J. Kurylo, 1978. "Flash photolysisresonance fluorescence investigation ofthe reactions of OH radicals with COSand CS2," Chem. Phys. Lett. 58: 238(1978).

41. R. Atkinson, R. A. Perry, J. N. Pitts, Jr.,1978. "Rate constant for the reaction ofOH radicals with COS, CS2, andCH3SCH3 over the temperature range299-430K," Chem. Phys. Lett. 54: 14(1978).

42. J. A. Logan, M. B. McElroy, S. C. Wofsy,M. J. Prather, "Oxidation of CS2 andCOS: sources for atmospheric SO2,"Nature 281:185 (1979).

43. A. R. Ravishankara, N. M. Kreutter, R.C. Shah, P. H. Wine, 1980. "Rate of re-action of OH with COS," Geophys. Res.Letters 7(11): 861 (1980).

44. R. A. Cox, D. Sheppart, "Reactions of OHwith gaseous sulfur compounds," Nature284:330 (1980).

45. R. P. Tui-co, R. C. Whitten, O. D. Toon,E. C. Y. Inn, P. Hamill, "Stratospherichydroxyl radical concentrations: newlimitations suggested by observations ofgaseous and particulate sulfur," to bepublished.

46. E. J. Conway, "Mean geochemical datain relation to ocean evolution," Proc.Royal Irish Academy, A, 48: 119(1943).

47. E. Eriksson, "The yearly circulation ofsulfur in nature," J. Geophys. Res. 68:4001 (1963).

48. E. Robinson, R. C. Robbins, "Sources,Abundance, and Fate of Gaseous Atmo-spheric Pollutants," SRI Project ReportPR-6755, prepared by American Petro-leum Institute, New York, 1968, 123pp.

49. W. W. Kellogg, R. D. Cadle, E. R. Allen,A. L. Lazrus, E. Martell, "The sulfurcycle," Science 175:587 (1972).

50. J. P. Friend, "The Global Sulfur Cycle,"in Chemistry of the Lower AtmosphereS. I. Rasool, Ed., Plenum Press, NewYork, 1973. pp. 221-241.

51. L. Granat, R. O. Hallberg, H. Rodhe,1976. "The Global Sulfur Cycle," in B. H.Svensson and R. Soderlund, Eds.—Ni-trogen, Phosphorus and Sulfur-GlobalCycles, SCOPE Report 7. Ecol. BullStockholm 22: 39 (1976).

52. G. M. Woodwell, P. M. Rich, C. A. A.Hall, 1973. "Carbon and the Biosphere,"E. M. Woodwell and E. V. Pecan, Eds.,AEC Symposium, 30, U.S. Departmentof Commerce, 1973. pp. 221-241.

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