Th< GIo>baJ BioFo<h<m"'" S.lphur C,ekE<j'l<d l>l' M. V. I,..",. an<l1 R r",,,,,~

<;l 1983 S<",o"fo< e-m;,... OIl Problem. of 11", Eo,.,,""""'_' (SCOPE)

CHAPTER 4The Atmospheric Sulphur Cycle

A. G. RY!lOOSIl!lPKO

4.1 l'TROOUCTION

Compared to other grospheres. lhe armosphere is 8 ,'ery mobile system inwhich lhe predomin81ing proces..,s occur during no more than a f.w d8YS,11>0 ,Io,,"'e'l proce.""'s. which 18h months or yea~ are tM lr8nsfor of 8irbc:lv.'••n hemispheres 8nd lhe SIf3tOSphere-tropospMr. ox~h8nge. Tho highmobiliry of 1M S)"Slem ~'u..,s high ....tes of transfer and redislribulion ofsulphur compounds in Spil. of rel8tively S1n811 8'erag~ concentralions in lilealmosphere. In this ..,n'" the atlIlOSphere differs sharpll' from lhe otherre..,rvoirs.

11>0 almospheric pan 01 the global sulphur c)'cl~ has during r.cent y.ars beena focus 01 attention since it is undergoing drastic changes due 10 the induslria]aeti'ily 01 man. As will be 'hown below, the anthropogenic sources of sulphurare comparable in size "'ilh lhe natural global .missions 10 lhe atmosphere.and in 5Om~ r~gions 01 the gk>be th~ .nthropog~nk SOurC~S m.y be mOre lhanIO lime. higher than natural soure.s.

Eriksson (I %0) made the fim syst~maticstudy of the almospheric sulphurcycle. Some of his estimates ar~ still valid. "'hile Others ha'-e been sub­stanliall)' re"sed. One 01 the lat~SI publications On lhe global sulphur C)'CI~ isthe repon 01 SCOPE made by the Swedish SCientiSIS, GranalttaJ. (l976). Weshall allempt 10 improv~ SOm~ of the Cilimates using relati"ely inaccesoibledala lrom Sm'iel investigalOrs a$ well as re$ults published in world literalur~

during lhe period 1976-80.

4.l CONCE1Io"lllATION A....O ~tASS OF SULPHUR COMPOUNDS INTHE "TMOSPHERE

We shall review the lileralure on conct-ntrations of three basic fonn' 01sulphur: r~duced ~ulphur compound.. sulphur dio1ido. and sulphate in lhetroposphere. Since tbe.., concentrations may vary O'-er a wide rang. depend·

'"

Ju icaJ Sulphur Cych~ Global Bwgeoc m

TM Almaspllnle Sulphur Cyd~ 205

ing on location. we 'hall group data separatel~' for oceanic. conlinental. andindustrial and urban regions. Similar re~iews were undertaken by Granat elill. (1976). Georgii (1978). and Me"",ros (197gb). 1bese region. ar~ markedin Fig, 4.1. tile deri~ation of "hich will be discussed later. The stratosphericsulphate laler will be eonsidered >eparately. To 'tandardize unit' throughoutthe text. "'e .hall expre.. concentration .. the ma.. of ,ulphur per uni' vol­ume of air under normal cond,tion. (273 K. 1 bar) "gS m-'. the sulphurcontent in individual re"",,,·oi.. ll'l TgS. and Ouus as TgS year·'.(1 Tg-IO"g).

4.2.1 Con«ntTtltion of Reduced Sulpltur Compound,

Red~d (sulphide) sulphur is present in the atmosphere in "",veral com­pound•. 1be ';mple.t (and at the same time the most common) a", hydrogensulphide H,s. dimethyl Sulphide CH,SCH" carbon di,ulphide CS,. and car­bonyl .ulphide Des. Other more complicated compound. of sulphide sulphurOCCur in the atrrK>Sphere. e.g. mercaptans and dimeth~'l disulphide. We 'hancon,;der only those comjXIunds which contribute substantially to sulphurfluxes bel\<'een "'>ervoirs or ,,'hose atmospheric content i. ",Iatively large.

In the o,idizing condition' of the atmosphere. h~'drogen sulphide anddimethyl sulphide are chemicall)' unstable and degrade quickly; we shalldescribe these a, shon-li'ed red~d sulphur comjXIund$. Carbon di.ulphideand carbonyl sulphide are more ",,;'tant to o'idation; "'e oIIall describe themll'l reduced sulphur comjXIund. with a long residence time.

Reduced sulphur comjXIunds enter the atmosphere as a result of biologicaland decompo.ition processes both on land and in ",ater and to some extentthrough "oleanic and anthrojXIgenic activity. Red~d sulphur comjXIundsOCCUr in rather low concentrations in the atmosphere except fo, narrow tidalzones along coasts whe'" tile local concentrations are so high that undercenain weather conditions they con he detecred by their characteristic odou"

Table 4.1 contains data on concentrations of both dlS""'s of reduced sul­phur compounds in the atmosphere over different regions, (Note that thelong_lived reduced ,ulphu, compounds ore Ie.. variable in space.)

Direct measurements of reduced sulphur compounds have been made onlyin recenl yea.. and they are not )'et sufficiently numerouS to elucidate thetime and space variations.

Over ocean regions with high bioproductivity. i.e. in up",el1ing are.. andnear OO-aSlS. the concentration of reduced sulphur compound, in the atmos­phere can be SUbstantially higher than ove, the open ocean (e.g, the dit«tobservations of Jaeschke el ai, (1979) in coastal regions of the Nonh .sea)From the limited data available (Sian et al.. 1978; Marou!i' and Bandy. 1977;Graedel, 1979) "'e assume that m'er the oJ>¢n regions of the world's ocean,and in polar area~ the concentration of h)'drogen $ulphilk "

Table 4.' Rcdoe<:d ""Iphn' in ,he olon<:><pb<ro

C"n,:onl,.'ioo (~gS nl "Typ< of 3l"""phcro \l.o!;on C"mpound Ihng< Me,n \l.okr<oc< C"mmon"

0<."",,,,' Ce"",1 All,..,,,, 1I .~ 11,007-11,07 IUWJ SI,"" "I (1~7X) Dire"'1 ""'.""0""'''''E."ern «,." of tbe OMS 0.08.1 ' 0.003 Mamnl" .",1 Il,ndy DiICo, m,,,,urcm,,,,'"

USA. Wind from (1~77)

~'"C"",;'",n'.1. Including Con'13' USA Ill''' O.O)-(I.()\I N""",b rt uf. ('~72)indn"riol ",p.n,

Cen",' USA ill'S 0.17-(1.4~ 032 Ilreed'n~,,"', (1'i13)Con",1 Eurnpe Ill''' 1.0 Ooo'gi, (I'i7M)Enl:i"nd ill'S o 14-(1.~4 Smi'h " "I. (1%1)We" r;c<"""y. n",.1 ill'S 0'-1.03 J;",,,,II~e " "I,.'U', !~'ll' (IY78)

We" Oorma"y, ,"'. II ." O..H_I,SS ho",hke" "I I\"'il>l<: "n'hr",~,!,c,"o

b<twe<:n "'I.;", (l97g) effect

""d w"""'de"We.. Ge,many, l1000l il,S " Jae<;<hk<:" ~I. O<'obe,,", (1978)... J..",h~e" ~I. M,,"'h

(1978)

, " Jac",h~c" "I. M"y(1~7M)

'" J",,"'hke rt ../. July(197M)

N"f1bc", We" O.OS Jaeschkc rt uf Altitude 4 k'"Gem""y (1978)

0.11 J..«hk~., at. Ahi,OOe 2 k,~

(1978)0,14_0,37 Joc«hkc " "I. "hilu<lc I k,,,

(1978)0.47-1.04 JIICs<hkc cr "I S",!...." I"y~r

(197~)

Norlocrn >e. """" II ,.~ OJl'J_036 J..,>ehkc" at(1979)

Urha~ N~w y",k It,s 1.7-~.4 JO<:oO>" uI. (l9~7) D',,""I "",",u",me""Ind"wi.1 ..gion ..... ". 1.4_85 Smith rl ai, (1961)

"ecl mill. and rok~

ind,,"ryW,,",k aln~"rOC" So",h and «,"ral COS 0,73 ± 0.09 To"C'", "I, (I9XO) D'",,, "lCa,,""""""',

I'.drl<. we>lcrn Vmr""" d"lri,~""",

"'~~'" "f N".,h wilh .11" ...10 up 10A"",,,,,,, I"'" ""'~'I""'"

I'hil.<lclph,", USA COS IU6± 0.04 TOorCH' ai, (1\1811)Philadclph,a. US" eo, 0,62 ± 0.0ll Mamuh. " at. (1977)Wy"",i"l!. USA COS 0,6S ± 0.04 Mam"li."at (1977)Oklahom •. USA "'" 0.7J ± O.OS Mare"l" " "'. (1977)En~ano.1 eo, 057-080 073 Sand.lI, .no.1 l'cnlw

(1977)Sua'""""".. ,we, ,he eo, O,)7-0,H I"" <I ,d, (11'7\1) AII" ...10 15,2 ,.,

USA COS IU.s lUll Inne/"I (1\17'1) Altilude 21,.1 k'"COS 0.02_0.025 In" ri al. (1\179) "1", ...10 ~1.2 l",

1 "8k".1 CS, 0,10-0,5,' o,n $0",0.1011. 000 I'<nkell( 1977)

'0.", the ''I'''n o«.n ror>ccn".'iof.. moy be O!'f"'>'''''''''y 11>.11 'h~ "I.. (G,aetkl. 1919)

'"0.05 :>: 0.03 /<& m-'. and IIIe <:oncentration of dimethyl sulphide and Olherreduced compounds with short fesid.nct time is 004:: 0.03 jigS m- l , ma~.ing a 10tal of 0.09:!: 0,06 "gS m-'. For wnes of a high bioproductivily ""esugge't a tOlal CQnctnlra,ion of 0.3:>: 0.2 !'gS m '. e,'en if there are 00mea,urement, 10 support this .,limate

Practically nothing i~ kno....n aooui llle ,·.rtiral distribution of hydrogensulphide. dimethyl sulphide. and oilier reduced sulphur compounds wilh .honresidence lime in the almosJlbe'" over the ocean. Based on in'..,,,,ion heightdala. Ryabmhapko.1 1'1. (1978) assumed their distribution \0 be uniform lDthe llyN up to 2 km. Jae"'hke .1 ai, (1978) '!lowed Ihal hydrogen sulphide isfound mainly in the lower 2 km layer, Model <.kulation. of Om'led! andRodhe (1978) suggest lh31 the height of this laye, sl>ould not ucced 1500 mand mO'i' likel}" is probably aboul I km (al ,he mos' probable h~'drogen

sulphide residen<x lime in ,he atmosphere). We assume the average mi~ing

heigh' of reduced sulphur compounds in the allno.phere O,'er oceans is1.5::: 0.5 km. We recall ,ha, the mixing heigh' of a subs'ance in the a,mos­phere is defined as

f,(It) dlt

H • ~'---;:-

",,'here ,(It) and ca are ,he roncenlra,ion. at alti'ude It and directly at thesurface. respttti'-el)',

l1Ie hydrogen .ulphide conttn"a,ion o"er continenlS has been measuredfrequemly; Ito",e"e,. the accuracy of me'hods employed i. no, high. and the"alues Obtained may be highly erroneOuS (Cadle 1975b). Recemly a TCliableme,hod has been deYeloped Oae",hke and Haunold, 1977) which makes i'pos-.ible to de'ermine hydrogen sulphide concen'rations "'ithin the ppb range.Measurement. made by Na,u",he' al. (1972) and Breedinge' Ill. (1973) inthe unpolluted atmosphere of <xntral USA sOO"'ed " rela,ively small varia·b~ily wi'h ....lue. in the range ofa fe"',en,hsof "1'&5 m-'. Smithet aJ. (1961)giYe hydrogen sulphide concentration values of 0.1 '00.5 I'gS m-' for indus­trially developed region, of England and Wales. Concenlrations in the surfaceair layer over land measured by Georgii (1978) appeared to be high(ll'gm '); Ito"'evu, even in 'hIS ca.. " rapid deerea.. in co""en,ration to0.2 I'g m ,j at I km alti,ude and a funher slovo' decrease to 0.11'8 m ' at3 km were o~,,·ed. Based on 'hese da'a. Georg;; (1978) find. it impO'iSible'0 negle<:t anthropogenic hydrogen .ulphide emission.

Values gi"en in Table 4.1 susseSl that ,he Spll«' di'tribution of redL>ce<l.ulphur compounds "'ith slto.. residence time in ,he atmosphere o'-cr conti·nen,S is quite irregular, All measurements "ere made in the ,emperatela'i'ude. during warm seascm. when an intensi"e hydrogen sulphide emissionfrom biological prooe!S"s may be expttled. As shown by Georgii (1978), ,he

T~ AtmQsp~ric Sulphur Cyck 2"

h)"drogen sulphide concentralions over marshe, and linornl, decrease sharpl)"with a decrease in temperalUre. Thi, wa, vividl)" demonstrated bJlthe sea­5()Oal dala of 1aeschke., al. (1978) who showed that lhe near-,unaa h}'d­rogen .ulpltide concentrations over f\ood(:d :rones in ,ummer were higherthan aulumn ones bJI an order of magnilude. Nothing is kllOwn .bout theconcenlralions of reduo::ed sulphur compounds such as dimelh)"1 sulphide anddimelh)"1 di,ulphide OVer cominenls. though Francis n ill, (1975) ha,.. shoownlhal soils emit.heil' gases inlO the atmosphere.

Summ.nzing. we aSSume lhal lhe a"erage concenlra.ion of sulphur in lheform of reduo::ed compounds wilh shon residence time in lhe atmosphere overcominents is 0.2 :!: 0.1 pgS m ". and (as for .he oceanic almosphere) lhe scaleheight is U :!: 0.5 km.

There are "ery few regular observalions of hydrogen sulphide concentra­lions in the urban almosphere o,.. r exlended periods of lime. We cannot uil'lhe resulls of occasional measurement< since lhe concentralion of pollutantsin .he urban a.mospl><re can "ary with time Over a wide range. The dala ofJacobs., 01. (1957) sUgg<'St an a,'erage concentralion of reduced sulphur withsbon residence time;" the urban atmosphere of 3 :!: 1.5 /<g m-'. (Any errorin this eSlimate will nol substanlially affecllhe cakulation of the tOlal conlenlof reduo::ed sulphur in lhe atmosphere.) For the urban almosphere. a mixingheighl for reduced .ulphur compounds with shoon residence lime is assumed10 he 0.5:!: 0.3 km.

Dala oblained bJI Torrese' al. (l980). Maroulis.' al. (1977). and Sandall.and Penkett (1977) allow uS to make a reliable e<timate for the mean tropo­spheric ooncentration of carbon}'] sulphide. Torres e' oJ. (1980) measured thecarbonyl.ulphide concenlralion from an aircraft O'.. r the PacifIC ekean in lheSoulhern Hemisphere to latitude 57"S and over the PacifIC ekean and NonhAmerica in lhe Nonhem Hemisphere 10 lalitude 70'N, al different heigh"from the near-surface la)"er 10 the lropopause. The meaSurementS sl\oVl'ed lheconslaney of concenlralion. bolh v.-ith latitude and height in lhe tropoophere.Inn eI al. (1979) oblained similar result. 10 .hose of Torreie' oJ. (1980) in lhevicinity of lhe lropopause. Earlier anal}"se. of samples laken in differentregions of the USA (MarouHs <I al.. 1977) and England (Sandells and Penk­eu. 1977) are in good agreement "'ith the dala of Torres e' al. (1980). Thesedata Indicale a mean carbon)"1 sulphide concentralion of 0.7:!: O.I"gS m '.

Less informalion i. available on the carbon di,ulphide concentralion of lhe.lmosphere. From the dala of Sandal" and Penken (1977) and Co. andSheppard (1980) it is assumed lhat lhe mean carbon disulpltide concentralionis 0.2:!: 0,1 "gS 01-'.

Carbonl'l sulphide and carbon disulphide are belieycd to haYe a long rcsi­dencc time and direCl mcasurememS 'ugge'llh.lthe ,"olume concentralion oftbese compounds in the tropospherc i. COnSlant. Thu>, t.king into acwunlthemean heighl of the tropopause (14 km) and ....nations in pressure with height.

we obtain a mi:<ing height lor carbonyl sulphide and carbon disulphide of6,5~ I km.

4.2.2 Concentration of Sulphur Dioxldf>

Since sulphur dio'ide emissions into the atmosphere are IlXali~ed in space(thermal power plants. "oleanoes), rather high sulphur dio'ide concentrations(up to sevtral lOgS 10-'1 can be detected near the emj.;sion SOurceS. Con­centration' mea,ured lar from lhe SOurCeS are ""nal orders of magnitudelower and make up a tenth or even a hundredth of I ~gS 10-', Also. sulphurdio'ide concentrations vary with time. i.e, daily. ",asonally and annuall)'.Table 4.2 ,ummarize, data on the ooncent,"tion of sulphur dioxide in theatmosphere of polluted and unpolluted regions.

II the data summariud in Table 4,2 are oonsidered in chronological order.there appears to be a decrea'" with time in the measured background ooocen­trations. Thi' may be due to the development of more reliable techniques forthe analysis of ,ulphur dio'ide and to the measurement of background le>'elsin the 'pure' region, of the world.

In the early measurements (1950-60), the detection limit "'as often higherthan the measured sulphur dioxide ooncentrJlion, As sho"'n by Granat n 01.(1976). during a series of 37 measuremenls oonduc.ed by FiSher el 01. (196&).concentrations in 21 of the ,amples were lower than Ihe detection limit(-0.5 ~gS m-'). Relati"ely high concentrations were obsorwd by Lodgerl al.(1974) in the air over the Panama mast and Balbados IslandS. This might bee'plained by the emiSSion of reduced sulphur compound, and their subse_quent oxidation in the atmosphere 0'0' the coastal ~one, The possibilit)' 01such an effect wa, noted by a number of authors. for e,ample Ngu)'en el 01.(1974) and Georgii (1978) (see below),

Exten,ive investigations on the content of ,ulphur-oomaining compound'in the atmosphere o-'C, the Atlantic Oce.n were carried out by researchersfrom the Federal Republic of Germany On board the research vessel Meleor.~orgii (1970) employed a highly sensit,ve method to obtain the distributionwith latitude along 30'W and showed that ma,imum sulphur dioxide concen·trations lXcurred ne.r 40"N (a'..,rage 2 ~gS m-'. ,'",)'mg up to 3,5 "gS m-').Fanher south. concentrations fell to 0.25~0.5 ~gS m-J at latitude 10-20"Nand weTC be)'ond the deteetion limit of the method in the TCglon of theequator. Georgi amibuted this distribution to the latitudinal transport ofpolluted air masses from the USA. ~orgii (1978) estimated the averageconcentration over the North Atlantic Ocean to be 0.5 ~gS m-', over IheCentral Atlantic 10 be 0.25-0.5 "gS m-'. and o"u the tropical zone of theAtlantic Ocean to be 0.15 ~gS m-'. We con'ider it r.ther risky to as>Ume aninfluence of anthropogenic sulphur dioxide emi"ions over the "hole of theNorth Atlantic Ocean. On board the MmM. Buchen and Georgii (1971)

COOCO"",,,;.,,, (nS '" ')

Coolinon,.1

Ibw,ii"" 1,1,,,,1,f'.df", Oce,nAn'ore'ic."'nl.rctic.F"""", 1.,lan,1<

Ca,ihOC"n Se.looJi"" .",1 I'"..,f.., 0';''''''Su~,,,,,,,,~,ic "-'go,,,,h,c",~ Islan<l,N""h A,I.",ic

Co"".1 AlI,n,,,,Atl,,,tic, tropic.1 roll<

p""if;,;, <'<nl,.1 I"',t

P,orifi.,' "n<l llcflng So",

,~"H""" I""(;"'0"1",,,1North AtlanticSoo'ocrn Pac'fic. I.ye' "vcr

wa'e, 'u,l"""Sou'hern pac,fic, f,ee

troposphereranamaII,a,i1Af,'" (""pic'll)

R"n~" Mc<'" Rcforeoct'

", Junge (1957)

" LOOgc <r "I. (1960)0.5-1.6 Cadlc~l"l, (1%~)0.5-2,0 Fi,he, .. dr. (1968)0()()-025 0.12 Buchen and Geo'gi;

(197' )0,6-1.~ f.l 1,~lgo",,1 (1~74)

0,(l2--{1,45"~ N~uyo" " "I. (I ~741

0.025 11.25 o.t~J Nguye" ~l "I. (I Y74)tI. 10 ' O,OS P,.h", ~, "I, (1976)

", e;.,'lfgi' (I ~7~)

0.2S_0.S Geo,gii (1978)0,15 Gwrgj; (I97~)

0,02-0,06 0.035 lI.y,ho:><h.pko~' "I.(1978)

0,On-0,3~ 0,12 T~" report

,un 1.0 0.21 flYb"'" ,,/ 0<>76)0.02S_I.5 0.3 I~ygc' <r "I, (1916)

O.O~I e 0,026 M"'o"ri, ~l "I, (1980)

0.12" 0.04 M"",,,I;,,, ,,/, (1980)

0,4~-1.6 Lodge~'dl. (1974)0.45 Lodge" .1. ( I(74):l.0~ !)Clm"H' .1 (1978\

e'M,,'.nt "'flOCn,,",;,,","·ith r",ig~1

"'1T<'I"fl ....''''''''11.''''A;re~,tt ,,,,,,,,•• t.,,,,22 "''''1'''''. ""oralt

,>11"""'10'1>IOU "''''I>Ie,. a,rel.1t

oI:»e"".t"n>

'"

Table 4.2 co"Io"Lled

Ref",ence ('.omOlon"

(;010"'00, USA 0.25_1.1JNorth A""""". w","em I"'rt.

,u,b"e I.ye'Norln A"",ric_, ,..,,,tern p<lr1.

f",e 1101><>'1'1><'"No'll><'n Europe O,07---{l.ll

USSR. """he,,, C.,"'.'u' 0.17---{l.31

USSR. I~",m", K",,,~~,"," O,lS-OAIlvrrs,,,y, T",",·IJ.nul>e I"',t 50-100hgbnd

ce"I,,1 EumpeCentral EumpcC"n".1 Europe S_lOC"ntral E",ope

0.16 ± 0,11

0,23 '- 0.14

0.12

0.09.\

(12

'",,

Georg,i (1970)M"lOuli,,,,,1 (lY~O)

Maro"li, "",, (1980)

Geo,gi; (lY78)

ICM (1973)

Ro.in,ky " al. (I YOO)VUTkollyi (1974)GatlaO<J ""d H,"n","

(1976)Georgii (1978)('...,o'gi (1978)los' (1970)OECD (1977)

Ai"".f, "I=,.at'nn,A ;",,,,ft ob;c, "'lion >.

20 "'mplesAi",,,,rt ol=rv.t1On~.

S9 ..mplesAI!;II.><I< 6-13 km

Ai",,,,,O obscl"atOon,Al'itudc 2.4 km

Moun,.i",AIt,I<"'" 2 km

M""n',,,,,Summ", ti"",Autornobik ,urv"y

In winte'

In 'V"",""Ai"''''ft ob>crvatio,'sA""age ".1"" for

north,w"'«1l EU'''l'e(-J ~ 11I"m') 1).",.1

orr """'>IIren","" 197J-4

U~.

m._ 0.\1-20 • 1lIolo "'......'

l~,h...n..~ SSII 0.25-1 0 !*>fI'Ou.u. n ., (197~1

W.,tt•••od t."km EItfOll" , EMEP(I'l801

USS .... 11.1,,, Sc. "'." U.02_~ 7 O,6~ ('""I,.,,,. (l~N)USA. 5:"", I~,u" ,es;"'n 0.0)\) .1~,? 7,~ Brc.·,hnSClnl.II~76)

USA, ,,,,"ro' I"" U7-67 " B,"",I",~ CI <II. ( I "7')U~A......h .,••,"," , AU,I,,,U,,. (1'111)

.'''"e'US.... ""rlh UliOC,n " A,1I",,,11<. (1\17)1

USA. wnl<rJI ...... " .01."",",,11<. (I97Jl

O"e. of 11", USA " CAPIT" (1971)

,.... A"llri<' 1>.2 Ihd,. ... (1\111)- ,-",\ ZI ~ 11"""'" (19711)c-..... of J_ " ."" (I.n4'

nos ('....... (1'118)

Avc~ ..h.. 10, ,,,,,,h......c.n •...., Cenn,,!En"",", ... ",0 ,,., mo"rme",nrcme,," 1'171_19

1~1 ""mr"" IlIn-?/>

A""f'~C .. I"" 1><,,,,0 un"",,",,,,,,,,,,,,,1<., 4"",n..

Ave,"" fu< 148 col'" "",...-""",.eo fo< 60 al ... fo<,-A..,•• _ ...~..

'r.o'""".1'04lbu fo>r I\ll.·nlblo 10< l'1H·n

214 ~ Global BiagrocMmical Sulphur C}'(k

obtai""d an a'"<,ra~ sulphur dio'ide concentration of 0.12 ~sSm-' in theregion of the Faeroe Islands, while Prahm ~l 01. (1976) reponed0,035 "gS m-' for the same region. Evidently. the area measurably aff..tedby anthropogenic emissions oeeupies onll the "'estern part of the I'onhAtlantic (probably 1000 km from the Nonh American coast) and a minorstrip west of Great Britain, Under certain meteorologic-al conditions, how',e'-er, a plume of sulphur dioxide can be episodically observed at more COn­.iderable distances. Th" was confinned bJ-' numerous (about 200) observa­tions in the region of Japan (Korole" and Ryaboshapko, 1979). Thcl' sho"-edthat at distances of 100-200 km from the Japanese coast, sulphur dioxideooacentrations in the plume from industrial regions can amount to 5 ~gS m-',At about 500 km, they drop to 0.5-1 "gS m ',and at distances of more thanJOOO km the contribution of anthropogenic SUlphur dio'ide in the plumetransported from Japan is only 0.1 pgS m-'.

Flyge. ~, 01. (1976) found almost tile same sulphur dio'ide concentrationsO""r the North Atlantic and Greenland using the i~tope dilutionmethod. No relation "'as obse ...'ed between concentratIOn andheight (up to 5 km),

Ngyen ~l 01. (1974) measured the oonccnlTations of sulphur--containingcompounds in the atmosphere of the Southem Hemisphere. They sbo"'edthat sulphur dioxide concentrations varied o"er the range 0,02-0,45 "gS m-'.No signiflCllnt difference was observed between the atmosphere in the regionof .fO·S and that of the sul>-Antam>c wne. Most measuremenll fell "'ithin therange 0,02-0,1 "gS m '. and only in a few cases"",re higher concentrations,up to 0.45 pgS m-'. detected. These authors suggested that the sulphur dio,_ide came from natural emissin'" of reduced sulphur in Klme oceanic areaS. In197.f investigations were conducted from the So"iet research vessel A, f.V<><,j.l:ov in the "a<!e_"'lnd w"" of the PacifIC (20--30"N latitude) and near theAleutian ridge (Ryaboshapko ~l al., 1978). In both regions tbe concentrationsWeTC essentially ,lie same. with the a""rage ,'alue: from 12 samples being0.035 :: 0.02 pgS m-', The trajectory analysis show'ed that in all 12 caseS theair masses did not comact land in the fi.'e days before sampling. During thejomt Soviet_Amertcan expedition on board the Soviet re ..arch vessel Volnam 1977, sulphur dio,i<!e concentration' of 0,025-0,35 >lgS m-', with an aver_age "alue of 0.12 "gS m-', ,,'ere detennined in the northern part of the PacifIC(>50·N) and in ,be Bering Sca.

Maroul;s n al. (1980) detennined the sulphur dio,ide ooncemration O'"<'rthe PacifIC Ocean in the Southern Hemi,phere. and ov~. the PacifIC Oceanand westem pan of Nonh America in the Sonhem Hemisphere. i.e, from57'S to 70·N and from the boundary layer to the tropopaU\(. They showedthat the concentratoon ,n the Northem Hemisphere was Klmewhat higherthan in the Southem Hemisphere, and that the sulphur dioxide OOncen­trations in the free 'ropospheTC ,,-ere e"~ry" here higher than in the boundaryla)'er.

The Atmospkric SlJphur Cyde

Summarizing, in tM atm0'5pMre N'er the open oceanic region~ character·ized b}' low biological producti,-ity. tM sulphur dioxide concentration is about0.10'" 0.03 pgS m-'. In up"'elling zone., in the ocean region~ of high hio­logical productivity, a concentrat,on of 0.2 '" 0,1 pg m ' can be taken a,a,-erage.

The profile of the ,ulphur dioxide concentr.tion m lhe oceanic atmosphere(.tudied by Flyger et ai, !976, Gr.wnhoTht !975. and lo-larouli, n al. 1980from aircraft) should be detennmed by its sources and ,inks, Since the oceansurface cannot be a diTeet <;Qurce of sulphur dioxide und se""" only a, a 'ink.it is reasonable ro assume that there should he some increase in concentrat;(mwith height in the lower atmosphere 11 the p1eCUT50Th of sulphur dioxide arehydrogen sulphide, dimethyl sulphide, and other reduced sulphur com­pounds. then tM source should be in the Io,'.-er troposphere: after a smallincrease in concentration in this layer, there should be a decrease in thesulphur dioxide concentration higher up. Maroulis et al (1980) believed th.tcarbonyl sulphide is the precuThm of sulphur dioxide: if thi' is the case. thereshould be a unifonn di'tribution of sulphur dioxide throughout the tropo­sphere. The problem of the 'ulphur dioxide preeursot in the free troposphere.till needs to he resolved (Rodhe 1981). Howner. from the data available.and if we assume that the mixing tatio of .ulphur dioxide (tM ratio betweensulphur dioxide and air volume,) is ronstant throughout the troposphere.tMn, we ha"e a mixing height of 6.S :!o 1 km. The increased sulphur dioxideconcentration, in zones of higher biological producti"it}, should ha'''' a smal­ler mixing height, which we assume 10 be 4.S :!o 1 km.

We ha"e less infonnation on sulphur dioxide concentrations in unpolluted(clean) continental atmospheres than in the atmosphere o"er the isolatedregions of tM ocean and Antarctica, The majority of continental ob:servationscarried out in Europe and the USA do not characterize a clean continentalatmosphere hecause of the considerable contribution from anthropogenicSOurces, We have no data on the sulphur dioxide concentration in the atmOS­phere over large regions of Asia and Australia. Meszaros (1978b) gi"es avalue of 3,05 pgS m-' for Central Africa. This is not in line with data on,ulphur dioxide concentrations in tM continental atmosphere summarized inTable 4,2. Lodge el al. (1974) give "alue. in the range 0.5-U /lgS m-' forthe atmospheTe of tropical forests in Panama and Brazil. Georgii', (1970)data obtained during aircraft observations in the clean atmosphere in thewestern region of the USA are somewhat lower. In 1973 in the Caucasu, acomparison of method' wa, made for the analysi, of pollutants in backgroundair; the value of 0,12 /lgS m- 1 gi'",n in Table 4.2 i' the average of all the"alue, obtained by various techniques during one week of comparison,.Extremely intereSling routine data were obtained in the Borovoe region ofEura~i~ (Ro\'i~\k\,ft al.. 1980) from 1976 to 1978, Tni, region is churamr­ized by the absence of local induWial sources of sulphur dioxide (at leastduring summer). We belie"e that the average summer concentration of

Th~ Global Bio~och~m~al Sulphur Cyd~

0.2 !'gS m-} represents the dean continental atmos~here. Maroulis~1 aI. 198Qpresent data on the sulphur dioxide concentrallon in the boundary layer ofthe atmosphere and in the free troposphere over lhe weSlem part of NonhAmerica. As in the ca", 01 the oceanic atmosphere. lhe aUlhors noted SOmeincrease in the sulphur dioxide concentration with height, This agrees withGeorgii', (1978) data Obtained in the upper troposphere Over Europe,

Thus the average sulphur dioxide concenlration for lhe clean continentalalmo,pher<: i, assumed 10 he 0.2 ='= 0.1 ",gS m-' and the mixing height6,5:;: I km.

The areas of regional atmospheric pollution COver considerable parts ofEurope and Norlh America. Furthermore. praclically lhe whole of Japan. lhedensely populated regions of China, India. the South African Republic. etc,can also be characterized as regionally pollut~d areaS. Owing to a numher ofintemalional and natIOnal programmes on regional monitoring of atmos­pheric pollulanls. much information has been published recentl}' on lheatmospheric dislribution of sulphur dio.ide "ilh space and lime in industrialregions and 'urrounding areas. MeasuremenlS made episodically o"er anational reserve in Lilhuania. with nO SOurces of anthropo~nic emIssion ofany imlXlrtance in lhe radius of ...verallen, of kilometres (Shopauskas~1 al.1974) suggesl that lhe ralher low concentration of 0,25-1.0!,gS m ' mo,tlikely characterizes the continental European hackground. Similar resull.were oblained by Godrailis (1979) from routine measurements in the ",meregion. Much higher concenlrations obtained b}' Varkonyi (1974), from anautomobile ,un-'ey in an induslrialized r<:sion of Hungary. were characteristicof a high ..tent of urbanizalion. When assessing average values of sulphurdioxide concenlralions in the atmosphere of induslrial regions (Table 4.2).one has to <Ietermine whelher the results are repre... ntalive of the region. Le.the duralion of Obse,,'alions has to he taken inlO aCCOunt. In lhis regard. thedala from the long-lerm programmes of OECD (1977), EMEP (l9SQ). andAltshuller (1973) should be representati"e of lhe regions studied, Al1theother values of regional sulphur dioxide concentralions summariled in Table4.2 fan within a narrow range. From these dala we assume the average sulphurdioxide concentralion in the almosphere of induslrial regions to beS=,=2!'gSm-'.

The ven;cal distribution of sulphur dioxid~ in the atmosphere of industrialregions was studied b}' a number of authors. Meszaros (1978b), referring toinvesligalions by Varllel}'i. giv~s a value of 0,6 km for Hungarian conditions,Special invt'stigations aimed allhe estimation of an average mixing height forsulphur dioxide in Europe we,e conducled within lhe OECD (1977) prog­ramme, From 23 profiles an average scate height of Ino m "'as oblained.The ..me ,'alue was measured by Garland and Branson (1976) and a similarvalue (1100 m) was obtained by Smilh and Jeffrey (1975) in observation'made over England during aircrafl su,,'eys. We consider llle value

TIt~ Atmosplt~rit: Sulphur C}'de 217

H ~ 600 m to be an undereslimate, since il was obtained for urban almo..­pheric conditions rather than regional. In our calculations we shall assume amixing heighl of 1.2:!: 0.2 km for lhe regional almosphere.

The sulphur dioxide concentration in urban almospheres is measured con­tinuously in many of the large elt~s of the world. The resulb of three reviewssummarizing such data are gi'..n in Table 4.2. Concentrations vary with lime.and over a wide range from se"eral ~gS m-' 10 several mgS m '. One eandistinguish shon·'errn variations caused mainly by meteorological conditionsand seasonal varia lions connected "..ith lhe increase In emission. in cenainseasons. Since the late 196&, average annual concentralions in many to"'nshave decreased as a result of the centrahzalion of healing syslems, conslrue­lion of high Slacks, and use of e:eaner fuels. A,uage concentralions varyconsiderabl}' from IOwn to lown depending on lheir size. level of industrializa·tion, lype of fuel used. etc, There is considerable uneenainlY in estimate' ofthe average concentration in lhe urban atmosphere for a specifIC country andespecially for lhe world as a ",·hole. In our e.,imales we assume the a"erageconcentration to be 20:!: 10 ~gS m-'.

In various countries bolh episodic and systematic investigations of the ver­lical dislribulion of .ulphur dioxide in the urban atmosphere have been per·formed using helicopters, aircraft, towers, and ma>!s. From lhe data ofGoroshkoel al. (1968) W'e assume the a,.. rage <cale height of sulphur dioxideover lowns 10 be 0.6:!: 0,2 km.

Investigators from lhe Federal Republic of G<:rrnany measured lhe sulphurdioxide concentration in II!<: lower stralosphere (Georgii, 1978) and found itto be 0.05 ~gS m '. So far lhi' is lhe only measurement in this region and wecannol judge bow representalive it is for lhe whole stratosphere, especially asGeorgii noted lhat intensive exchange belween the SlTatrn;phere and lropo­sphere was occurring during hi' observalion,.

4.2.) Co~nl,..,tlonof Sulphatr

Sulphate can be added 10 lhe almosphere by various mechanisms: seaspra}'" oxidalion of sulphur dioxide in the atmosphere. aeolian soil weather­ing. el' .• (Junge. 1963a). Differences in these mechanisms lead 10 ,'aryingphysical and chemical characteristics of the sulphates in the atmosphere. Inregions of intensive anthropogenic ,ulphur dio,ide emissions. sulphal" areformed mainly a. a result of sulphur dioxide o,idalion, and according toWhitby (1978), Friedlander (1978), and Ollie ... practically all of lhese sui·phates are airborne particles from 0.1 to I pm in size. s.ea-water sulphalesenler the atmosphere in sea 'pray. Gravenhorst (1975) showed thaI thesesulphat.. are predominantly panides ranging from 0.5 to 10 11m in diameler,althQugh most are within the range Z 10 5 ~m, Sim~ar data were oblained byLevkov er al. (1975) from Cuba. H appears that sulphales from aeolian

TM Global Biogux:/umk:al Sulphu, Cyd~

w~atheTingoccur in laTgN parti<les; Andre~v and Lavrin~nko (19158) showedthat in a dusty almosphere. especially during dust-storms, the majoTity of lhesulphale w'as found On large aerosol partides,

The chemical composilion of lhe sulphate<ontaining suhstances dependson lheir origin. If the sulphales are formed in the almospher<: due 10 lhe o,i­dation 01 sulphur d'o'ide. Ihe most probable species formed ar<: ammoniumsulphate (NHJ,SO, and 'IS acid forms-{KH,),H(SO.)" NH,HSO, (Brossel,1978). Sulphale can also Ottu, in the atmosphNe in the form of sulphuric acid(OECD. 1977). Sea sulphate, are associaled with th~ basic sea-salt calion"Na, Ca, Mg. elc, According 10 Khusano, ~t ai, (1974), Caso, i$ lhe mostprobable form in aeolian dusts sampled N-er Cent,,1 Asia.

Dala on $ulphale roneentTation. in the atmosphere 01 diff~rent regions arepresented in Table 4.3, Her~ we separate the marine .ulphale contribution bythe sulpbale : sodium ralio, as was done pre\'iously by Granal el al.. 1976,Nguyenel al, (1974) determined the sulphale rontent in th~ almosphNe O"ervarious region. of lhe wOTld's ocean from Antarctica 10 50 0 N in lbe AllanlicOcean. The >'alue oblained by lhem o>'er the Mediterranean Sea (Table 4,3)appea" to boo anomalously high compared with th~ir Olher Observations, It i.difficult to hypothesize any specific distinguishing ChaTaClen.lic of lhe Medi·l~rranean Sea from th~ world ocean. except fo' th~ possible anlhropog~nic

sulphate concentration in lhis region. Th~ r<:SI of Ihe dala do nol >'ary signifi­cantly from the a"erage value of 0,56 ~gS m-'. Gra>enhom (1975, 1978)showed lh.l excess sulphate accounted for 70-8~ ollhe 100ai .ulphale, theconcenlrations of which varied around the mean value 010,35 I'gS m-'. BothBuchen and Georgii (1971) and G'a>'enhorst (1978) obse,.>ed increased sul­ph.t~ ooncenlrations in air masse. from the Sahar•. The same r<:sult wasobse"'ed by Winkl~r (1975) who studied lhe sulphur content in submkronparticles. According to Winkler (1975) and Gra"enho"t (1975), sman par­licles are predominantly exce...ulphur. Prahm n al, (1976) analysed foursample$ from clean air of the North Atlantic O""an which ga"e an averageconcentration of 0.25 ~gS m-' and an execss sulphur contribution of 56%,w'hich is in agreement wilh the above results.

In>'estigations performed by Gillette and Blifford (1971) and F1yger ~t al.(1976) show thaI sulphate is found predominantly in lhe 10w.r atmosphere,I.e. up 10 2-3 km abo". the ocean.

Summarizing. W'. a5Sum~ that lh. a"erag. eoncentr.tion of .ulphate overthe oce.n is 0,5'" 0.15 !'gS m-'. which include. 0.35'" 0.15 ~gS m-' ofexec...ulphur. The mi,ing height of sulphale 0>'.' the oce.n is assumed to boo2,5 '" 0,5 km.

Dir~Cl m~"UremenIS of sulphate in the surfa"" continental almosphere areIe.. numerous than in the oceanic almospher•. GWen. and Blifford (1971)found Ihe sulph.te concentration. in the surfac. laye' of th. atmosphere over

T"hk4.3 S"lph",c CODOC"'''';'''''';'' ,IIC """,-"pi", re

,,,,,,,,.,, .. " '.....'·~I ...... "r"" '" "'_"' '"- ,.~ A".... '- Am"" ~,..,,~~o....~ ..., """ A"'.....~ """" "" ~..,...... (I"'''_...,.",

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• ~,.~ ,..""'"",,,,,,,,.. "" , , ," ,"' ~••,...... 11""1<',..... , A,t..", CO.\-O., ,,"''''. -' ,~'"..m,'1c,,,,'" A1I_., 'CO_, J H"''''• ..., ,"'.,.

I ,." I"'.'0 AU.."", O,l_J.V V.1.' ".1_>.9 OH (j".",".~0"1)e..,,,, AtI_., O.J? 0.» G,..,""",,,, I'''')e..,,~ Att..,,,, ,. OJ, ".07 G ...,.,",,~ ("")lO.,,,, AtI••,,,, co.•., 0." G"...~.~ (1"')

_'.A''''''~O. IS_,n, o l' ".OJ u.l\ ".J< "'_,,".("'H....,... AlI_.· ".l .". CO." '" ,~'''"'.... (19M

"".~ Oo.~.. """•., .. " " ".....'" -, ,.,,~

"J'" ( '''''''A' ...'•. '.... n.' "'w..,,..(,,,,,

All...", lJ«"" ,," "-.....~",.,. 0-" ", 'HH.',...,., ,","""""").....~ """" 0' ".. ""~'" """ B",.....(11171)

I'acifi< ""'" OM "" """,,, """ kW'",d(1"711

" ..... ~'"',.' IOl"..

r·"N'·' '""" """"w"", ,"',..., .....'A...... l , ..

""•T_Ut""_l

T_I,.s. 'I "--u.s ..-'),~. , • - - --. - -- - ,--- ..J .....' fill _ .... ll~~ ..._...

,- .......1: .- ............ U""', .._....,- M_ ." '_""'J ,-..- " ........ (1"'•• "-- ." ." -..... u.m ..._J.''''- " ~ _ ... ""'I ..._ ....1 ..- ". " e:-.,,(l9f7' Alo.... '..1 ..._A__f."' ,--,,--.... - '-1'01'1) i'c...,.....""" 01-0 .. ""_.... ,I'''')- ". ......,,, .. uoN, T'...... ,""" ....... 0- ", ",.0"".." 1""" r'_.. 1'"....... S

"~"" II~,,- M., " "., 11_ ........<'.It.., ......... ""'."..""_....- [(""') •w,~ ('","", ""'-I. " l_I'''') ,.

'· ... ' ......b "" "",.('ON) ,....... ....,...IUSA,_.. """ " ••• c...,.. _"_ ""........'

(0'71)~. ....... .- .. 0.17 G*no -' """'" A'''''' ...

0"1)l."A-_.. _ •• •• ......__. .._ .... ,.•I'''') ~--- ..... 0011 ........"01"_' ~ ..._-~-- ',J, •.." I~_I"" (19101

-~-,-_......-.- ...,..." "_"_,- ••.... ('-' •>'~

~,T__.. _ ..~ ,_.._.-- ,-- ,,- "'1!OSIl. .._ A_ '" -_.- "---.--- }4'_'.-.,,_ ..- •• -_.- """'"--_ .. ".. ,

"...~

msa. .._ ..... ., K_.... I"'" ~ ...-l'\A.......~ ........

__ ..m w ' .....' ... 1191'9'•• >,'....' _....,... "'..- ,/S" ,_" ••" " M'-"""'J ""'.-.1"," po_, ,L""'..... >:~. -"'" """ ,", 111,,-,,,.,,, ,""........ ""-'.,,,"'- ~

UM ._...."" H "PAl"'" (1o>n<o<,,"'" d ....ll. to".'USA._.. _ U El"A 0"'" ~"""'..-_B. Ie".'uJA.__.. _ ,)-'~ " ...., .... U1J1'O, -...U5A._" .- ,~. H .w, .... 41_' .,J-'..........

~--H c.."... ('""1 ....-, . .(- ._. H

~ll'''' .....--,..,---'- '" OIcnn-m .._..._, ....'.',.,...». • ,•..- " '-""41_ .._..._..... : ...C_,_ ,~.- --- ,~. orA (I"", ................

USA. __ ..... UU'A "'"'"

.........-.-- u _II"" n.-..,..""'I- .. ..-.l,l'.....' ''''3-''-- H -" ...., ,,,__>0.- H ........ (1'"1) .........-.,...~

~

222

California to ~ 0.3 ;<gS m-'. A, in tM oce.nic atmosphere. concentrationsfell .....tth height to 0,2 ",gS m- J at an altitude of 1 km and to O.O~ ;<gS m-1ataltitudes over 5 ~m. Thi' agrees well ....ith the data obtained by Ll:l~rgel al.(1979) at the l"'el of tM tropopau$C. Recently. Bouere' et <>1. (1977) andAdam' el "I. (1977) ..ported ,ulphate concenlrations at an altitude of5200 m over South America. l1te$C data al1o.. us to estimate a mean ~ight

for the distribution of ,ulphate in the continental atmospMre. but un­fortunately t~y gi,.. no idea of in concentration di..ctly o'-er the SouthAmerican continent. Guzman (1977) found concentrations of 0,55 ;<gS m-'for Central America (Sal"ador) at an altitude of 1900 m, In tMoe instances,the contribution of ..a-"'ater sulphur "'as no more than I~. Meszaros(1978b) reported measurement, in the surface atmosphere o'-er Africa per­formed by Delmasel <>1. (1978) of 0,5-0.6 ;<g m-', There is a good agreement~t"'",n the values obtained by Rahn and McCaffrey (1979). Chung (1978).and Sha,,' (1979) for I'onh America. For South America.. La"-mn and Win­cM"er (1978) reported a ,-alue ,,'hich ....as Io".. r by an oruer of magnitude.but tMy anal)'oed the fine fnction of aerosol only. From the limited dataavailable at the time. Junge (1965) inferred the ."enge concentration ofsulph.te in the atmosphere Over continents to be 0,17 I'gS m ' ..... hile friend(1973) ellimated it to be 1.5 ",gS m-',

Observations in du't)' regions should be considered separately, l1te Sovietin'-estigators And..ev and Lavrinen~o (1968) and Khusanovel <>1. (1974)m.de measurement, in Middle A'ia in a region characterized b)' intensiveaeolian ....ealhering. In lhal region lbe soils are mainly sands. serozems. andsaline soils. Saline soils .... ith sulphate concentrations of up to 5~ are ~oo.... n toh,,'e a loose struetu.. and are capable of producing dust al wind speeds of3-4 m $Cc·' (Za~haro'-. 1965). l1te average sulphate concentration of tMatmosphere ""ar Tash~ent is 11.21'gS m-' a<:c<>rding to Andreev andLa,Tinen~o (1968), and IOl'gSm-' according to Khusanov el <>1, (1974)Both group' noticed that. during dust·storms. concentrations increase d..sti_ean)' and rea<:b atmoSt 30 I'gS m " This confirms the aeolian origin of ,ul­phate in the atmosphere of this region.

These measurement, "'ere made during a warm seaSOn. During rainy sea­son~, or wben the wil is co"ered with snow there i' practically 00 aeolianweathering. l1terefore. the dala of Andren and Lavrin~n~o (l968) andKhusanov e, ~1. (1974) do not renect the ",-erage annual condilions of Iberegion. We can. oowO\'er. single oul specifIC regions of imensi,.. aeolianweathering wMre sulpha,. concentrations are much higher than the ",'eragecont'Tl(ntal value.

The data obtained in olher arid zones of the world differ greatl}' from Ihere,ull, .Ix".. , Pen~c" e' al. (1979) ,~port~d values of 1 ~gS m-' lor EastAlrica. Still lo"'er concentralions "'ere found by Hoffer tl ~I. (1979) for

TItl' Almo.pltl'ric Sulphur Cyd~ m

de.em in the south_we,tem USA. Increased sulphate concentrations wereobserved more than once in the atmosphere during 1M transpon of aerosolsfrom Sahara to the Atlanlic (Gra"enbom, 1918; Buchen and Georgii. 1911;Winkler. 1915). and abnormally high depo<ilion of ,ulphate from lhe almos­phere was observed in lhe arid zone. of Australia (Hingston and Gailili..1976).

From a consideration of the above data we can assume lhal lhe a"eragesulphate concentralion o,'er eonhnento i. 0.6'" 0.2 ugS m '. and the mixingheighl of the la}'er is 2.5 '" 0.5 km, Taking inlo account ",asonal variations.we may assume an average annual value for regions wilh inten.ive aeolianwealhering of sulphate-containing so~s to he 4'" 21'gS m-'. Since theaeolian dust consists mainly of large particles. it would be expected lhat theywould not ri"" high into lhe almosphere. Observalions by the aUlhor. madefrom an aircrafl in Middle Asia. showed that lhe uppermost boundary of thedusty air wa. u,ually at an altitude of 1-1.5 km. During dUlt.storm,. how·ever. aeolian panicles may ri.e 10 heighu grealer than 6 km, ~t us assumelhe mixing height of aeolian sulphate. to be 1.5 '" 0.5 km.

11Ie increased sulphale concentralion, in lhe atmo,phere of industrial re­gion, come from anthropogenic emission' and subsequent oxidation ofsulphurdioxide. ~"e1. of sulphate sulphur depend on the extent of industrializationand the sulphur content of the fuel. used. For instance. in Europe. lhe centralregions of England. Gennan;. and Poland are distingui,hed b}' bigh sulphaleconcentralion•. Altshuller. (1973) and Perhae (1918) .bowed a clear-cut dif·ference in concenlrations between the western and eastern regions of theUSA. Concenlralions of 1-1.31'gS m" over the we,tern stalos are approxi·matel}' lhe same as lhose of a clean cOntinenlal atmosphere. Over the eastern.more industrialized, ,tates lhe average concentration was 3.3-5,0 ugS m '.According to OECD (1971), the a"erage concentralion of sulphale over all ofwestern Europe was 1,7 ugS m-'. Based on the data in Table 4.3. we 'hallassume 3 '" 0.5 "gS m-' as an a"crage concentration of sulphale in industrialregrons,

Our eSlimale of the .ulphale mixing height in lhe regional atmosphereba.ed Oll the dala of DECO (1971). Rodhe (1972b). Jost (1914), Bolin andPernon (1915). MeSUlros (1978a), and Georg;; (1918) is 1.5 ~ 0,3 km.

Since the transfonnation of anthropogenic sulphur dioxide to sulphaleslakes ",veral hours or even days. mosl of lhe sulphale is fonned at distancesremote from the SOurce, Therefore. the urban concentration' of<ulphate (Le.near the oou=, of sulphur dioxide emissions) do not differ subslantially fromlhe regional a"erage. From the dala given in Table 4.3 W'e can assume anaverage concentralion of sulphale;n the urban atmosphere of 4 '" lugS m-'.11Ie mixing heighl of sulphate in the urban atmosphere is taken to be

1.5 '" 0.3 km.

TN Global Biogroclremit:al Sulphur Cyd~

4.2.4 Total S~lphur ConI..., of t'" AlIDOSpbtre

In p...vious seclion' ""e eSlimated "'erage concentration' and mixinghl:ights of vario~, ,~Iph~r compo~nds in the atmosphe ... of ,ix diffe...ntzones, oceanic withoutthl: influence of marine biota. oceanic ...ith high bie­productivity. clean continental. du,ty industrial and urban ...gion" The a",aof each of thl:se zone" i' re<jui...d for Iht del"mma,ion of lhe ,ulphur conten,in each.

A high bioproductivily is characteristic of rarher .mall region, of lhe...orld·s ocean; Ihl:se aro lhe areas ...here organic maner. phosphorus. nilrt>­g.n. and olhtr nutr;ent, are available in sufficienl amounts, Thi' situalionoccurs in regions of up.... lllng and along thl: continental shl:lf. ThI: area of the...orld·s ocean ... ith a high bioproduetivil)' comprise. 1510 olthe entire oceanicsurface. Or 55" 10" m' (Slepanov. 1974). The olher JOS x 10" m' i. ref.r_red 10 as the zone ",-iloout marine bio,a Or open ocean.

Regional atmospheric pollulion is characteristic of almost lhe ... hole ofEurope and lhe major pan of lhe USA. In Japan. lhe zone of regionalpollution COvers the ... hole lerrilory and spread, rar over the ocean, Olher""unrrie. of Asia. Africa. and South America are characterized by insignifi·cant areas of regional pollulion. Detailed estimate. of areas of regional pollu­tion are gi"en in Table 4.4.

The aru characterized by urban level. of atmospheric ponulion is assumedIn be I " 10" m', Therefo.... thoe area of ...gional pollution aCCQun" forII '" 10' m'. The area of all the desen. and semi-deserts in the worl<l ;,50 " 10" m'. and 9.S x 10" m' are occupied by areal in which Iht upper soilhorizon is salinized (Ko-'da and Sabolsz. 1980). More Ihan half of thi. salin­ualion i. the chloride-Iulphale type. From thi, we a...ume the area with ahigh content of aeolian ,ulphate, in Iht alm05phere is 5 " IOU m'_ Therefore.lht clean continenlal atmosphere """"untS for an area of 133 '" 10" m'.

Table 4.S ,ummarize. data On sulphur concentration. for reduced com­pounds ",-ith ,hon and long residence lime•. sulphur dioxide, total and excess

Tablr 4,4 Areas of indu",ialcounlri.. and ronline"1S

Counlry or ronline"t

region. in vario",

A,.a (l0" m'l

Europe ond AsiOJl 1'"" ot USSRUSA .r><! Soutl>--e.., Can>daJal'"nCbinaInd,aA"maliaAfrica$ou,b Am.,;ca

Total

",.,.•",.""OJ S

IUS

T""4.5 C....".'flll_ nom,. be"""__ of ""..... _ "' ........... ,be .,........'"('Ollie... rrp) ~

Mu.. lot,p.,

A~ ('_ral_ >Tyl'" '" ..........'" (10" _') - ,..... , ,~) - ..- ,Ooea.oc, ",,,-..,. _ dl«l "" • 0.09 - 0,06 I.S'O,~ 001---tl09 .0< •

~010"'0.03 6,S-10 O.12-OJO .~ •- 0.5 '" 0. IS 2,5 '" 0.5 021-060 .~ •

"" ,- 035±O'5 2.5 - 0.5 0.12-0.46 .", •Oou.oc......_ -.. ~nea " • 03'" 0.2 1..'! , o,~ 0005-0-'155 0,0"..5 "•~1

0.2'" 0,1 u· .. 001-009 'M ,•

• ~. 0'1-0''1 2.5_0'1 004_010 .m>-'iC)l ,~. on·O,I5 B' O~ 002-008 'M

0",,_..,.01 <k"" '",. 0,2 - 0,1 ',5 • o,~ 001-0011 ,0< •'iO, 0,2-01 (>-5 • .. Otl7---t1 '" 0,17

>0' 0.6'02 2.5 '" 0.5 O,IHJ'2 ,~

IIId""" ..1"'P'" " • 0.2 • 0.1 1.5",0.5 o (l(H).01 ,00>>0. 5,0 .. 2.0 1.2'" 0.2 O.O)---tlil 0,07

"" 3.0'" 0.5 1.5 '" 0_3 0,03-0,07 005Con'_n,.1 dU"1 , • 0,2 • 0,1 1,5 '" 0.5 o OO-O.OO~ 0.002

"'. 0.2' 0.1 6.5 •"

1l,OO-O,lH O.OO~

sol 4,0 ' " I ,\ ' 11,'1 'l.()I-O,06 0,0,'U,t"", ,. '.0 ' " 111'11.' lI,m-1I.1U IUl()~

so, 200 ' 10,0 1).6 " 11,2 O,tIOS-O,02 0.111~ol 4,0 •

"1,'1'" 0' IJ.(~I 0 °I O,OO'!

'1'",.1 • .,1""", ..,oth ""'" ""I<lc",-e Ii".. O.M-2,24 US51""lwon. <'''''.. wlJ'ba'"' 0,14-0.54 0.32'-- "" CO~ 0.1 ± 0.1 6.5 '"

"IU_J()6 2,32

"'. 02 ± 0.1 6,'1 • .. 028 115 'MToUI ...I""u, """h ....." ""Ide""" 'ome 1%"'.21 ,~

T,,,.I ...lphu, 1ft '"'f'O'4'I>e''' 2.1.4 6.45 4.J.l5 NN•

.~ """*- ........~ ,...,

T.h'" 4,6 Solphu, ",,,'cnl> (TgS) of ,he ''''I''''l'h'''', ...,,,,ding 'u dlHe"'''' ."'Iou",

I(e,h.c.,d solphu, To'al Mllphu, I(cd"""d 'olrho'~'ith ,I>orr with >I>o,t .,i,h "'"g""Kk".:c time W To,.1 sol "'CO" SOl ,.."Ie""" 'i"'" "'''''Ie'''''' time,

II,S]

(l,W 0.52 O,2~ U,(),()~-o.n 11.45 (UIU , 2.11O. , , U.511 0.74 IU2 , 35 2.uH

(l.O1 o,n 0.2S 0,g1 ,.• ,.. 0.14-11.54 0.68 2.24 1.\16-4.21

(;"."", " ",, ( I\>7(1)1',,,,.-..1 ( I 'n,)Me"",,,, (Iu7~t,)1'",,,,,,, ...."k

""•

TIt~ AtmOsphtri..- Sulpltur CJd~ 227

~ulphat~~ in individual part. of the .tmO'iphere. mixing hejghl~ and .re•• ofwne•. It .Iso gives the sulphur rontent of differem compound~ in sep.r.tepans of lhe almosphere and the troJlO'lphere ., a ,,-hole,

Table 4.6 show< tnatlhe e.timale, of lhe amount of .ulphur in lhe tropo­~phe.. agree reasonably well ....ith those ofother .uthol'<. Onl)' the estimales ofFriend (1973) for sulphur "'jth .hon re.idence time and .ulphate ,ulphurseem to be oul of line.

4.2.5 Strat",~rk: Sulpbate Lay'er

The exi.lence of an aerosolla~'er in lhe malO.phere was .usi><rled allheend of the last cenlury on the basi' of a lighHCal1ering effect In lhe last 20years... '-eral allempt. ha"e been made to meaSn" di"clly the OOnttnlla­lions of str.tospherior airborne part;cles and to detrrmine lheir chem;calcomposition. Studie. conducted by Junge and Manson (1961) and Rosen(1964) showed Ihat in romraStlO Ihe regularly der..aslng proflle~ of Aitkennuclei. Ihe profile of larger pankle~ (, :> 0.1 urn) .ho"s a maximum concen·tration III Ihe 10"'''' stratosphere. Beginning at the tropopause. Ihe concen­tration of pankles increase. '" ith heighl. reaches a maximum al an altitude of20 km, and then drops quickly: lhe maximum concentration is approximatelyfour time. higl>er than Ihat al the lropopause le,-el, Data oblained from anumber of aircraft and batloon~ ~ho"'"ed a 10.... range in concentration of ~uchpankles over most of lhe globe. from 70'N 10 6O'S (Junge. 1965),

Sampling ",'ith an impactor. Junge (1963b) sho".-ed thallhe mean radius ofparticle~ i~ approximalely 0, I 5 urn and lhe distribution of parlicles by siu hasa clear upper limit of I -2 urn. The concentration of ~malterparticles incl"easesrapidly as lhe radius decreases and ils change may be expre...d by lhe rela­tion'

dN/d(log r) _ a-u

....here c is a constam and' varies o'-er the range 0.1-2 ..,m,From analyse~ of lhe chemical comJlO'lition of panicles 5-"mp1ed in this

layer. Junge ~I al. (1961) found that the ~ulpnate in them amounts to about90%. Thus it is called the ~ulphate layer (or sollIelime~ Ihe Junge layer).Friend (1966) found Ihat the'" particles may contain persulphate. in addition10 sulphate•. 11 has been shown recemly (Farlower aI,. 1978) thatlhe sulphurd'em,stry in lhe stratosphere is closely connected ....ith the nitrogc:n cl>emiW)'and that compound. such as 1'0HSO" NOHS,D,. (NH.).SO. and(NH.),S,O. are formed in the Junge layer, b'en in the first chemical analr>i~

of stratospheric aerosol. it wa~ found thaI the number of cation. dete<:led ....a'insufflC;en, 10 neutralize an .ulphate ion,. Th;~ impl;es the presence of free.ulphuric add in the ~lfatosphere,

CallIe (1973a) Used filters of high effICiency to collect panicle, up to .iusof Ailken nuclei in aircraft f1ighlS al an altitude of aboul18 km over the USA

Tm Glo/xJ1 Biog~ocmmkal Sulphur Cycl~

and the tropical area~ of Cent""! Amuica. H~ found thaI the conc~ntration.

of sulphur varied from 0.025 to 0.1 2 tlgS I'll '.

At pr~sent il is lhoughllhallhe formation of the sulphat~ lay~r is go,'~m~dby Iwo mechaniim>: (I) the diffusion of sulphur-<:ontaining gascs to thewatosphere follo"'ed b}' their oxidation to sulphat~s (Junge, l%)b; Lazrus e,al,. 1971); and (2) the release of volcanic gases and sulphate, during po"'ertuleruptions directly into the stratosphere. The existence of the fim mechanismis <u",,"~d by the absence "f suffICient calions to neutralize all of the ,ul­phates. Fr~e sulphuric Reid can form only ill si,u as a result of the oxidation ofsulphur-<:ontaining ,ases. According to Junge. Cadle. and Lazrus~' aI., th~

sulphur cycle in the 'trRtospherc can he des<:ril>cd as follows: gaseous sulphurcompounds diffuse from tht troposphtre into the kw.'er 'tratosphere and areoxidized there to sulphur trioxide by atomic oxygen in a tnmolecular r.action.Th~ molecule is hydrat.d and transform~d into sulphuric add. The proc~s< ofcoagulation thtn cause. droplets to gro": by the time they ar~ of radius1-2 I'm. the panicles are ,,'ithdra"'n from the stratosphtre

There has been unc~rtainly for a long tim~ about which gaseous sulphurcompounds could ~xi" for long ~nough in the troposphere to penetratethrough the tropopause to the matospherc in appreciabl~ quantity. The par­ticipat;on of sulphur dioxid~, hydrogen wlphid., dim~thyl ,ulphide, anddimethyl disulphid< is q""stionahl~ because of thoe short residence tim. ofthese compounds in the lroposphere and the long period of tropo­sphtre-stratospheroc ~xchange (~il~r. 1975). CrulUn (1976) sug,g~".d car·bonl'l sulphide and carbon disulphide., pos,ible c.ndidates. According to hiscalculations; the carbonyl sulph;d~ flux to the stratosphere amounts toIJOS TgS year-1,

The role of carbon}'l sulphide in the formal;on of stratospherk sulphat~s isconfirm~d hy the data of Inn ~I Ill, (1979) "ho measured a r.pid deer.... inthe mixing ratio with height in the stratospher~, indicating rapid oxidation otcarbonyl sulphid~.

The validity of the second l'Il~dUln;sm for StralOSpherk sulph.at~ formationis based on the incrocase in sulphate cone:<:ntrar;on in the s"atosphere af'.r 'hoe~fUption of Agung in 196), A comparison of the d.ta ob'ain~d by Jungebefore the ~ruption with 'ha' of Cadle ~I al. (1975a) oblained in the period1%9-70 indicat.s a )().fold increase: in the concentration, According '0Junge (1%3b). ,he roc'idene:<: time of particl~s in lhe sulphat~ lay~r of tltt'tratosph~re i. 0.5 year, Cadle's (1975a) .,timat~. ar. I mon,h althe tropo·pause and 1-2 years at an altitooe of 20 ~m. Russell tl aI. (1976) consid<rocdit to he 8 month. based on lidar m~a>ur<:menlS of ,he optical thic~ness of thtnratospheric a.rosollay~r formed after the Fu.go ~ruplion. E~n If ..... ta~e

the maximum ,'al ... to be 2 lears, 'hen bv the time of Cadle's flight in 1%9.only 5,," of the stral~pheric sulphate. r.sult~d from the Agung eruptionshould r<:main. The most reasonahl~ explan.tion for the di",repancy bet"."en

Tal>Ie 4.7 ~"Irh"te in the ",,'mphere

Jun"" (I%S)Odle ,,,,,I (;"'''', (197.')C..I'" anJ G"m, (197.1)L."u,,' 01, (197 I )1.''''''<101, (1971)Ca'lleman,,,,I, (1974)Ca""'man <I 01, (1974)La""HI .1. (1979)

Concenl,at;"n(~gS m 'j"

IUlOl OJI04'0.06O. I UO.QlO.OSO,08-O.ISU.OS001 S-O.I

GI..,,.I di",;I"'I~'"No"I"'", lI~,,,,,pl,,,,~, II )oONN.."he,,, Ilcmi,phc,c. JO-4goNN.."he,,, Ilcmi'l'hc'c, U-JO"NNo,then, Ilcmi,poo '0_3SoNNonhe", Il<n,;'phe ...Southern Hemi'phereGk>I>.1 di,tr;hul~:'"

SIom['li"&heigh' (km)

'"17_IH17 IH17_1917-IH15-19I S_19lO-lS

Ye.. 01 "",,,,,, ... ",,,nt

1'160,%,1%')1'170_711970-711%2-711%2_711916

°lb ",H' ...."nle 01 ""t",I'hc''''"''·u.... "·.,;,,,'", I~"CO..."~'",,..."d" "'I'I';"~ cll~;'""1

""o

230

the cona:nlnllioM measured in 1960 and 1969 "',.< JiVl:n b:' Cadle (1975.)",1>0 poin~ oul the d,ffuence in c!fic;"1X} of samphn, drYicfi~ byJWI(ll' (;m~Of) and Cadle (filter). We do not ~jC'Ct the p:.>Mibk inJco;tiool ofla1tc' quamit;'" of wlphur into tho ",,"'losphe~ durin! intclllolVl: crupcion'l.but ptIIttally IlOl111111 ~mauK in the OIntospbe", from the Aruna crupcioon.From 1963 to tile pnlKm. It lew W:'~D cruptiom ho.'"e lICCUm:d .Iuo;b hI.,-.:been aa:ompanied ~ the l'dcue of volc2nic prod...-t. mto !be Rn~",(CIOI1IJI. 1971; fcdolO'" III" 1976). CIdk (1975.). lOr mstIIK'C. cwm&ted1M .....alI volc:an'" cmmion 10 1Ill: S1ntospbe", 10 be -0.14 Tp )'nr

Table 4 7 AUDm.rilfi lilt daUl on ",Ipbate conccntntions with hei&h1 IIIlbe J""lll' ~'tr 00Um«I by diffen:1I1 IUt!I<Irs dlltDll the jaR 20 )'urs. "''henJWlge". data. .. lacb an: conUdercd 10 be UD<Iere'itimaln. are 001 Wen InIOacc:own. die dauo of !Ill: other aU-than \-arin ..ilhin an order of macnitude,

11 is diffin,lt 10 dn'" any drrmnc (OftCIltSIOfIS on the sulphUI _lent of theS1n11ospben: Junac reponed • value of 0.01-0.03 T& of sulphu., WI hich isba"",, on undercStimaied tona:nlr1l1iom. Gran.t "<11. (1976). 1ISin,Iht dataof Castleman CI. (19-4), CSI......t«!'be sulphur conICn! in the .m,lOSpheuof the Northern Hcmlsp/le~ 10 ~ 0.2 Tg and llult in the Soullxm Hemi­sphe~ 10 be 0.1 T,. Lunno aI. (1919) g;,." an e~hm,~ of -0.6 TgS for thespring of 1975 ,fter the eruJllion of fueJO. l1'Ic.., eOlim,te. Soeem ""iOn.blebut. to obt,in mo", KCunte dll,. one should ~""" tM ""rt~,l cono<ntnt;onprofil"" at VInoUS l,tilU!kS. This is e5pttilll~' 50 in ";ew of!he influena= of theallnudc of the tropoj».use on the chemical wm]X>'lition and tOl,l amount ofsulphate•. If the une~pectedly hilh comem of sulphur dio~ide in lhe lowerstratosplterc of 0.18 jigS m '(Jatschke e, Ill,. 1976) is represemat"'e. then weshould assume that the total sulphur content in the stratosphere can reach0.5 Tg. This wn5ti!utes an appreciable amount in relation to the sulphurcontent in lhe troposphere. However. tlte sulphur flux throulh the trOJl!>"pause .. ratMr small C\lmpared to the tropospheric fluxes of 0,5-1 T,S ~ear .,if the .""nge rcsiden« time of sulphur in the stnlospllere is 0,5-1 )'Ur.

l1'Ic sm.ll V1I1ue for Ihis n.lunl nu~ IS indic.t;"." of i~ Soellsi!ivil) 10 chanae";thanlhropogen~facwrs(CrulZCo. 19i6). Hofmann and Roten(1980) 1uI.'emea",rcd a slulrp increue '0 the ronccntntion of "",rmol panicle$ in 1MJunge layer, l1'Ic) poinl Out that durio& m:cnt ~."an the OOlItent of paniclesluis incnued .nnual!)· by 9 =2'1'. "They COll5ider anthro~nlC emlSSIOlIS ofcarbon)l w1phode and arbon disulpbidc 10 be the p>Uibie Q,* of lhiaplle""""Cnon. ThIS SuggeIU thai "'dUttd sulphur compounds. illI 1on& "'sl­dena: limes a1u1d .ffec1 dlmalC

4J SOCRCES or ADIOSPHERlC SU1.PHUR

Sulphur colen 1Il10 1M alrrlOlfJbcrc from other gcoo.pberes via a n"",be, ofhoollC and abiollC PfOCCs.se-s. Some of lhese Duxe-s arc (:ormnllO\lS Illume. e.l-

The Armosphtric SuJph~, Cyd~

sulplull~ flux from ",a salls, ,,'hil~ othe... are of a ,poradic character. e.g,emi,sion, of .ulphur compounds during ~olc.anic eruptions. The rale of sui.phur input by biological processes depends on the temperatur~ of theen~ironment and. therefore. for temperate and high latitude' it undergoes"'asonal ~ariation" The'" f1uxe. are unaffe<:led by human a<:ti"ity and there·fore their "alae. may be regarded a, being oonstant dunng hundreds tothousands ofy~a.... During the la.t century, man's actiYity ha' mad~ a con.id·~rable impact on the global g~ochemi.try of .ulphur and on its atmosphericcycle in particular.Man·mad~ ~ffeClS on the ~n~ironment are di,...,ified and therefore it i,

often difflCUll to draw a distincrion betw..,n natural and anthropogenicemi..ion,. For uample. as a result of agricultural acti"';ty. man ha.dra,tically chang~d the eoology of "~getation which in tum ha. affe<:t~d therates of .ulphur input into the atmo,phere by decomposition oforganic matl~r

on land.As a result of natural and anthropogenic p""""""'. Yanou, oompound,

of ,ulphur can ~nt~r the atmosphere, Biogenic sulphur is repre",nt~d

usually by its reduced compounds from "'bich w~ singl~ out hydrogen sui.phide. dim~thyl ,ulphid~. carbony'l ,ulphid~. and carbon disulphide. A great~ariety of sulphur compounds. e.g. r~duced compounds. sulphur dio,ide. and,ulphates originate from anthropogenic acti~ity. Here we oonsider the mainf1ux~. infl""ncing the global atmospheric sulphur balance.

4.3.1 lIio#nic Emi..ion rrom Coastal Rtgions and tho Open ~an

Ga",ou, reduced sulphur compounds can he formed by microbiologicalreduction of sulphate. and 'lIrious organic maltor decomposition proeu",s.Estimate. of the oceanic and continental biogenic .ulphur flux into theatmosphere ~ary from 34 TgS year·' (Granat er a/. > 1976) to 267 TgS y..r-'(Eriksson. 1963). This large disc:repancy in e.,imate, is allributed to the factthat none of the autoors had factual material on emi..ions of hydrogen sul­phide, Nor did tl>ey consider data On the intensity of microbial prottS5e' indifk",nt erosystem. ""bich may ass;,t in the estimation of the possible upperlimit of emission

As can be ",en from Tables 6.11 and 6.17. the most a<:li,.. reduction ofsulphate occurs in periodically flooded and shallow pam of sea basin•. es­pecially in parts with oonsiderable organic mailer. Many in ....stigators ha"ecomm~nted On the odour of hy'drogen sulphide O'.. r shallow parts of marin~

bay. and roasts of sali"" lakes (Kumetso~ and Romanenko. 1968; ChukhroYer aI,. 1975; J0rgensen el a/.• 1978),

Howe~er. the emission of hydrogen sulphide into the atmosphere dependsnOt only on the ,ate of in production but also on the rat~ of ih ",,,,,,,'31 byoxidation and pyrite formation. Hydrogen sulphide emission was compre·

m 1M GIoIHU Biogroc~mk..I Sulph~r eyrie

hens;"ely studied by Danish cCQlog;'M in Jutland on shallow sediments(J0rgensen n a/ '. 1~78~ Hansen ~I ai, 1978), who used plexiglas boxn equip­ped wilh measuring dc,';"', to es(imate the emiMion, Sulphale reduc­tion occurs in 1he sediments ulKkr study; in the daytime. part of the hydrogensulphide fOTlIled is oxidized by photooynthetic bacteria in the surfatt sludgefilm and pan is oxidized by oxygen emined during poot05ynthesis by grunplants in the "'ater. Toward the end of the day. the activity of both groups ofphotosymhetic organism. falb and hydrogen sulphide increa..,. ;n co~n·

{ralion. firsd)';n the Waler and then;n the atmosphere c1"", 10 the waler. 1bemaximum em,";"n into the atmosphere i. o~",'ed at night. After soo,-is(,the photosymhetic processes resume, the pH of the "'aler increases, f"'.oxygen appears in the waler. and emissions 10 the atmosphere ""a...

For tho sandy lediments of Limfjorden containing 0.5-1.0'0 oforganoc mat·ter in \ho fonn of 20,le.a mariJIa detrilus. \ho annUli emission of hydrogensulphide was estimated as 18 gS m- l In ..,diments of the small lagoon.Kano Vi8. to tho north of Aarhus. rich in tho organic maner of decomposingalgae, this "alue amOunts to 450 gS m ' (Hanlen tI ai" 19711).

!be question ari... as to whether the.., individual data can fonn the basisfor calculating tho emission of biogenic hydrogen sulphide into lhe atmos­pho.e. We belie"e thai the)" oan be used 10 estimato the upjXr limit of the nu,of biogenio sulphur, si""" the data obtained by Jprgen..,n er al. (1978) andHan..,n el aI. (1978) On the intens;ty of sulphate redoction agree well ,,-ith theresulls of other in"esligators obtained on the coa,l' of the Bahk. Caspian,and Awv ..,as (lee Table. 6.11 and 6,17).

Asswning, IS did Karo (1956), that tho length of the "'orld's coastline is oflhe order of S x 10' km, and that the mean ,,-idth of the littoral ZOne is 100m,"'e obtain a "all>O for the area of shallow' ..,dimenrs of 50 x 10' km'.

Assum;ng that 50'0 of those ..diments are sands and 50'0 are h;ghlyenriched with organic malter or decaying algae, lhen the maximwn totalemis.ion of hydrogen .ulphide from such sediments i, about 10 TgS )'ear"_

Aneja er ai, (1979a.b) detennined ujXrimemally lho magnitude of thoemission of reduced sulphur comjXlunds (dimethyl sulphide. hydrogen sui·phide. carbonyl sulphide. and carbon disulphide) from gra5S-CO'.. red saHnemarshes. l1>e sulphur flux was mainly in tho form of dimelhyl sulphide andamounted 10 -0.66 gS m-' yur".

As the tOlal area of marshes is 3.8 x 10' km' (Aneja el aI. 1979b) lhoglobal emission from marshe' may be of the order of 0.25 TgS year".

To obtain more reliable information On biogenic sulphur emissions into theatmosphere. it will be necessary to detenlline lhe flux;n diffe.ent geographicwnes. It ..ems rea..,nable at pre..nt to ",sume I .'alue for lhe nux of redu""dsulphur in liuoral (coastal) zones of the ,,-orld's ocean of 5 '" TgS )'Ur" .

In ..ction 4.2,1, the Imount of sulphur in tbe form of its reduced com·jXlunds;n the dean maritime regions was estimated to be equal to 0.04 Tg. ff

Th~ Armmpherk Sulphur Crd~

"..~ a"um~ an av~rag~ ,..,sid~n"" rim~ of redu""d sulphur compounds in theatmo,phere 10 be 0"" day (>ection 4.4,1) then the flu, 01 these compound,from th~ open OCean "'ill be -15 TgS y~ar-I.1n v;cw ofthc un""rtain con""n­tration of r~duc~d suiphur in [he atmospherc o""r """,ans, thi' flux is assum~dto be 15 o!o 15 TgS r~ar-j.

Thus, the total flux of r~duced ,ulphur from th~ """,ans is20 o!o 20 TgS y'ear- t

, The great un""nainry of this e'timate reflects the in­adequacy of our knowledge. Nguyen ~r al. (1978). using the dim~thy'l sul­phide con""nlration in thc ,unace lay'cr of >ea-watcr. cstimated this cmissionto the atmosphere 10 be 27 TgS ycar-'. Marouli. and Bandy (1977). fromdirect mcasuremCnts of dimcthyl sulphidc on thc Atlantic coast. concludedthat its emission from the world's ""eans should nor exceed 2 TgS year-toGracdc! (1979) rev;cwing lhis "ork estimalcd lr..: total emission of hydrogcnsulphide and dimethyl sulphide by th~ "'orld', """,an, to be 30 TgS y~ar-"

and Hitchcock (1975) reponed the dimethy'l oulphidc emission by' algae to be0.05 TgS y~ar '. The range of these valucs indicales thc uncerlainly of ourkno"'ledge and this is reflect~d in our error estimat~

4.3.2 B~nic Emission rrom Land

FOrmalion of "olatile .ulphur compounds occur<; mainly under lheanacrobic condilion' found in marshe' (Bremner and Steele. 1978) andmicroorganism, play a I~ading rol~ in ,hi, pr""",ss. Emissions are likely 10vary, lh~refore. wi'h lhe temperature and moi.ture status of th~ environmentand wilh the availability of nutri~n"

The direct e'timalion of the biog~nic flux from land is rather diffocuh sin""its value may vary in ,pace and time by >everal orders of magnitude. Emis.ionof reduced sulphur se~ms 10 be very low in arid regions, but in tropicaimarshland. it mar be rather high, Field in'..stigalion, 01 the emission ofreduced .ulphur by Fal'\,,~t1'1 al. (1979) sho"'ed that soil emined mainlyh,'drogen suiphide along with caroon disulphidc and cartxmyl sulphide andnegligible amountS of dimethy'i ,ulphide, dim~lhyl di,ulphid~, and m~lhyl

mercaptan. Bremner and Steel~ (1978), howe"", found that more wa, emil­ted as dimethyi suiphide, dimethy1 disu!phidc, and methyi mercaptan: hyd­rogen sulphide was completely absorbed in the soil and transformed 10 melalsulphide, (predominanlly' FeS). It also seemed like I" that soil "'as the sourceof caroon)'! sulphide,

We shall alt~mPI (0 eSlimate the biogenic flux indirectiy. As se~n fromTable 4,5 the content of sulphur with ,hon residence time in the atmosphereO\'t! continents (except for the urban atmosphcre) is estimated 10 be aoout0.045 Tg.

If reduced suiphur with shorr residence time is a<sum~d to have a lifetimeof one day (>ee section 4.4.1), I[S flux inlo the atmosphere of continents

'"should be 16T,S ye.. -'. Comideringlhc unttrtainly of the e$tlmate ofl'tcillCtd sulphur "';lh $horl n:~,," ';Im in Ibis re••"""i,. \~ flwc may be,,;;!hin the flIngt: 3.5-30 TIS year"'. Hitchcock (1975) estimated the thlll ofreduced 5I.IIphur mto lIlie continental umosplwol't to be 2-5,4 Tp year-',",-hic:h qree....ilh the Jooo.-cI linu, 01 OUr~tc. Rod"" and lsa~n (1980)esrimalC the Il>UJ non of redUl:ed sulphur "'ilh >bon =i<k""" tune onto therontincouJ and ocean".~n: lO be. al lII05l. 40 TaS Jur

In oondusoon ..~ ilIall _nl>Oa the al:unalC of Adamo ... fII.. (1979) of I,""cmissire of<;;arl)onll wlpilldc from soil; 0.23 TgS )ur~'. It is aho DOIC..-onbythat <:a1bonyllU1pbode (aDd sulphur dioxide) m2) be fofmcd dlilOll& fom:!­fit«, but ac ba>c made DO eslJCMlC of the lII<Ignitude of !has nux.

4.J-J MollalI \\ tatbrrlolt 01 Soalpbalcs from the C...l1......tal Souf-...

Ahnost alllll'~"'10rsof the pobaI atmOSpheric: sulphur cydc IJ"O"' lhillDUll (ErikSllOll. 1963: Jun~. 1965; Kellogg ... /Ill.. 1\172: friend. 1973) orCO<ISider il to be iM'l"ifant (GBrulU' QL 1976).~ eakulalion of Granat... «l. (1976) ,,-u bued OIllhe Ullmale of BUlcbcr and Q>arbon (1972) lor thetoUtI emISSion of toll dust intO tbe almOSphcn: (200 Tg )U1 '). (irana, ... aI.(1976) ~med that only one·third of this amount is submlCl'(>n partICle.<""hicb a.., Tran.f~rred o,'~r ronsidcrabl<: d'Slan«s. and 1M>' funMI .16umcdthat lhie sulphur ronl~nT of dust approximaTel Thai of ""ellMted lOCh(0.33";'). Thul Gran'l II aI. (1976) estimated lhe aeolian sulphur ~mission

into Th~ annospM'" 10 be 0.2 TIS year '. ,,'hich il a negligibl<: qu.mit)' wh~ncompared with The anthropogenic ~mission. Al 1M """" lime lMy underlinelh~ po..ibilily of 8 consi~rable contribution by wind ~rosion 101M sulphurnux into tM almospMre 81 region.1 and local Ie"ds. Th~re ar~ dimcultl~s inthe ~>l,malion of I~oli.n sulphur emission .imilar 10 those found "'MneSlimaling "okamc em'sslORS. In bolh ca~s lhe emission vlrieS signlflClnllywith ",ace and "me we "templTo re-<:Sl'mal~the amounl of Ioeoliln sulphuremission ba""d On obse1'V1lTions of d"" n""es mto 1M alltlo",he",. lhe sul­phur conlent m tilt dust!lyer of soil and in tilt d"'t proper. and from lhe dustdepo!oilion in .rid zones. elc.

T'hoe d"" prodUCC'd by "lnd ~rosion rises 10 lhie 'lInOSpMre III 1M arid""Dtl of CQfIlInents. The anntlll ~>"" for .aoo mm roil'lCidts reasonably "..,ll",jlh lhie boundl'1' of lormalion of d""-.w..... (Zatharov. 1965). The lollllrea of IheS/: lOllt'S IItlOUIlI5 10 mo.., tlLan 37 x Io"tm', of "bd115.2 x 100tm' G III Ell..... 13.7 x 100km' III Afnca. .12 x 10'km.'in AII.nalia, J6 x 10' km' l1\ North AIMrn. .ad 0.2 x 10' tm' In

Soul.ll Amem. ".turally, IS dUSl:...orm. are oa:asioDaI ~''''nts. lhe dll5ty>llIDC occupie1 substanTl.lly Ins area at ctrtlm min. There IS no de&r<Vl

definition of a dlQol~. and Tilt< un~ tJl", l1\tel"pRIIUOft of "'pons ondusl-swrm. in dUkrenl reJions of the "mid. DUSl:-UOlm'S rna)' occupy IfCIS

TM AtmmpMric Sulphur Cycle

from several tenS to millions of >quare kilomet"'•. They "at)' al'" with time,local dust-storms last for less than an oour, but ",metimes they m.y continuefor twO days and mOre. Berg (1947) ""ted that in Middle A,ia in the Oshregion there "-as only one day witbout dust during the "'bole §ummer of 1913.Depending On the colour of lhe weathered soil. we recognize black. "'d(brown. yellow). and white SlOnoS (Nalivkin. 1969). In lhe first c..... cher­""zem "'ii' a", eroded; in the ...cond. the ",ils are charaCleri>lically colour.dloams. sands and day; and in the third case "'hen salin. ",Us are .roded. thesahs colour the dust panicles white, Usu.lly sahli from saline ",ii, containconsiderable quantities of sulphateli.

E'timate' of dust f1uxe, into the atmosphere vary o"er a wide range and thesituation is impeded by the fact that there is nO dear agreement of the upperlimit of the size' of dust panicle,.

Table 4.8 summarizes the d.ta On global rales of dust emissions into theatmosphere. We think thaI the majoriry of these estimates are not in accordwith observed f1uxe. for aeolian material on to the e.nh·s surface. Forexample. Kra."henko (1959) pointed oUlthat 200 Tg of dust faU annually inthe Volgograd and Saratov ",gions of the USSR (total area 0.2 x 1ft km').Howe>'cr. il sbould he nOled that experimental melhods for measuring dustd.position are inaccurat•.

If ,,'e assume that such rale. of deposition of aeolian material apply in theminimum case to one_third of the arid zoMS and in t!>e maximum case to the"'oole area of the arid zones (37 " 1ft km'). t!>en ""e Obtain a rate of aeolianweathering of 12 ()(l(l to 37 ()(l(l Tg ~'ear-I. It is possible that a substantialfraction of this flux is of. local char.eter, and is therefore not quite compar­able to ",me of the olher estimate,. A<:<:ording to Mat>'eev.r al. (1976). ana>..rage >..loe for deposition of dry dust on the territories of Sta'o'TOpol andKT1I>no<!ar regions and Kalmyk ASSR is 7S km-' year-I. This i,. minimum"aloe ,ina: the wash-out of dust with precipitation has not heen laken intoaccount. Using this rate and a..uming the area of the global arid zone to he

Table •.8 Flux of aeolian du", into ttl< atmo<ptl< ...

'"'00'00

7-365200" 100-15-75

"""001000-3000

Comm.nt'

All .....,<~ I'm

<20,,01Only in sub-Aral ...gionOnly in Ukraine. t928Only from S-ahara

R.t.......,

Buu:hef and CtlartliOl1 (1972)P.terson &Jid Jung< (1971)P.t.""n and luna< (1971)Hid~' and Brock (1971)Joseph" al. (1973)Pet ...nchok (1979)Grigorie. and K<>n<i...tiev (1979)Da,loeh &Jid Tru,hkovs.ky (1%3)Mon!.s (1979)Pr<>cnl "..,rk

'" T~ Global Biog~ochtmi<:(/ISulphur Cycl~

12-37 x IO'km'. ,he rate of aeolian "'eal~ring ;5 estimated to be1000-3000 19 year-t. The hightrestimale {compared to olMn in Table ~.g)

is reinforced by the data of Origon., and Kond,al~v (1979) on dustemissions in the sub-Aralll'gion which mak., up no more than 1~ of the auaof arK! ZOne. of!!It' globe. ""trenchuk (1979) ••timated the dusl.mission intothe atmo,phere Illhe globalle,-.I from the terrigenous material in precipitation(panicle, <20 I'm) to be 8000 Tg ycar-'. In ,ubsequem work "'C will usc thevalue obtained from the data of Mat,'et'., oJ. (1976) of 1000-3000 Tgj'ur '. We find it unreuonable to con,Kk, only ,ubmll'ron fJ1lction. of du.t.a, was done 1».' Granatel al. (1976) 'ince larger panicle. are also lrano;fe,,,,dto distance. of lOOO km Or more,

Table 4.9 summa"",,, the data on the .ulphur coment in lhe dust layer 01soil and in lhe aerosols ofarw'! :rones, The (tala showlhat saline soils ..n make• major contribution to the sulphur content of aerosols. These 5Oil' aro abun­dam in arid ZOnes (Gcrasimov. 1959; Capot-Rey. 1953) and. according to lhe,,'ork of KO"da and Sabol" (1980). lhey co"er 9,5 x 1(1 km'. Hero a clear_cut fractionalion of sulphur with depth 'sobserved. This i,due 10 lhe facllhalunderground "'ater.; rise to lhe surface. e"aporale. and enrich the upperm<>stlayer of '0,1 with sail> conlain,ng 'Ulphale,. A ronservah"e e,tlmate i' lhatlhe sulphur conlenl of dusl is within lhe range 0.3-0,7,,", (The min'mum,'alne coincides "'ith lhe estimale 01 Granat ., al. (1976) for lhe a"erage,ulphur oontent of ....ealhered rocks,) Consider;ng the possible IOtal emission01 aeolian du,t and u, sulphur ronlenl. we ",,,mate lhe """han em,ssion 10 be3-21 TgS year-'.

Zverev (1968) ..kulated lhe average deposition of sulphate in arW,! zonesof lhe USSR, He singled oul an arid zone with less than 377 mm of precipila­tion per year (aro. 3 x 10' km') and a df)- :rone wilh Ie.. than 149 mm 01precipitalion per year (area 2.45 x 10' km'), The rate of dry deposilion ofsulphale "'M I.~ gS m-' )'ear-' in the first ZOne and 1.8 gS m-' )'ear-' in lhesecond.

The major part of thiS sulphur i, of aeolian origin, Even if we aSSume thatonly hall is due 10 aeolian emission "'e obla;n a value for the .ulphur flux inlhe USSR of 4.7 TgS ,-ear-'. If the rale of sulphale deposition in arid zone, oflhe USSR i, characlerishc of all arid zone, of the ,,'orld. we estimate theglobal aeolian emi..ion 10 be 32 TgS year

The significance of aeolian emission in the inpul of sulphur ;nto the atmos­phere is illustrated bj' Iwo while du,Htorm.s in the region of the Caspian Seaon April 11- 12 and 18-n. 1955 (Kravchenko. 1959), Routes of transfer andzonesof du51fall are ,ho,,'n in Fig. 4.2. During Apri111~12 lhe du,,·hatt waSaccompanied by lhe formation of an ash-grey film -0.1 mm lhick o'-.r theterritories of Kalm)'k ASSR and 50Ulh of lhe Amakhan region, Analyses ofthe sedimented material showed that ...'ater-'Oluble salt. accounted for ~1.4"".and consisted mainly of sulphale. (90.6""). About 25 kg of sodium 'Ulphale

Krnd.. nk<> (1959)M.,,,,.... ,,, (1976)M,,,,,,.. " III. (1'176)M;'h·".'" ul (W76)"1.,""•• ",,1, (1976)C.lcul".,d tn"" d.,. of (Ow••nho," (197H)

A~~ -a l -..~o (1968)An<Iree¥ _ 0 (1\11\3)"''''''tc:.. -' k.. 11_)Andrn~-' I " ( __)G<ra>I..... ('"W)Gc:.-_ll"W)Gc-",_ '1m)c.. rHim<w (l9S'1)Khu!ilMlOY'" til. (1'74)

1l.S0.1'7

'M4.<\1I ,~()

""

.­,.,,~.,0.120.23

"S.61

'"

-~-~Sal_ mil,-1I.n! .- CO""'''.<1.- ......C"".... If>'Y"I p.b<.D<n.. ul' <TU>l.

St>iI ..mpIc:........A."""" durinl whll< "I......,,,..'"

('",,,,,,,,,'ed from An.-etiplllndc:pn:"ion)

SCd;,,,,,,,,,,,, dry d""Scdin",nted ,Iry din'Scdi,,,,,nted ,1'1 ,I""Soc,I""",,'." ,hy ,I."Aom,,,1

le""",oJ.,N"..",,,,,, ••,,~S"l>l0, ••"~'"s..,h",,,

.,.,.""","",-I).G<>I>o 0..."......Urld SSItlC.n,_ ASSII.

n. Tm Global 8iogtocmmkal Sulphur Cycle

fell on each ~cla.. ncar Elista in 35 h. A' ,,"en from Fig. 4.2, Eli'la "'M atlIIe leT)' edge Oll/x zone of dust f~lI-oUl dunng April 11-12 Undoubtedly,ncar l~ I'<'gion of du,! formation. 1M ;n{cn';t~· of lail-oul might Ix higher byan order of magnitude. let us ."ume an Iv.rag. lail-oul of 100 kg of sodium,ulphate on a M<:tare or 2.25 gS m·'. Assuming tbe area of sedimentation to

be: _4 X lO" m'. then {be amount of ,alphar entering the .tmosphe.. wilhaeolian dust during thi, ,torm ....a. 1 Tg.

llIe white dU'l-SlOrm durmg April 18-22 "'a, larger. In thi' OR'" the ...It·haze covered the Astrakhan. Volgograd. Voronezh, and Saratov regions andtl\<, zor>< of du'tlall extended me", Ihan 1500 km from thoe place offormation(Fig. 4,2). In the Volga region. the thickM" of s.a!! Soedim<:nt ,,-as 1-2 mm,and over the ..maindl:r of the territory;t wa. 0.5 mm. In ""me region, there,,·ere sediment' 2-4 mm in thickness. The upper limit for tbe distribution ofthe du't-<:Ioud "a, 3-4 km. As.uming an a"erage thickness of sediment ofI mm. then at a sediment density of 0.3 g cm-' "·C obtain a total du'tfall of0.3 kgm-'. Since this is the same region as that of the dUlt·Storm duringApril 1I-12. "'·C may assume that the chemical comJlO'ition of the dust is

.•.••.•.•. 9....""" 0' ...,*_,t,on.~.'" "·U "'S5

____ 9"""""', of ...." \*__.A..-. '8--22 "','.....'.......'oo .. oo" ....t

r---

,~".

FI" 4.2 Are•• of duSf deposition during ,be ,.-hot. dUSf·Sform, in April 1955

T~ Atmosp~ric Sulphur Cycle

identical 10 lhal discussod previously, The area of fall-ouI, acrording toFig. 4.2. amounts to -8 X 10" m' T~re10re (after allowing for c~mical

compositIOn). on April 18-22 1955. more than 30 Tg sulphur enteredlhe almosp~re and were transferred a considerable di'lance,

Similar e,'ents happ<:ned in 1933 in lhe USA w~n huge amount, of sui.phur were lransferred mOre Ihan 1000 ~m from lhe region belween lhe S,erraNe"ada and Ihe Roc~y Mounlains (Fen, 1961), and in 1950 in lhe LowerVolga (Zamors~y, 1952). Unfor1unalely. in t~se cases no data are availableon lhe chemical composilion of the ,ulphur-rich du't or lhe denslly of t~sedimenls,

Undoubtedly ,~se events are rare. Their singularit\ consists nO! in lheamount of saIl dust entering lhe atm",phere bUI in the unusual slability of theatmospheric transport process which carried the ,,,It·hale into regions w~reil does not usually occur, Local dusl-Storms wilh high!>att conlenlS very oftenoccur in Ihe Aralo-Caspian depression (Grigoriev and Kondratiev, 1979;Romanov, 1961), We condude Ihal atl~ globalle"el, the previously esri.maled m..imal value for lhe aeolian emission of sulphur (21 Tgyear- L

) isdoser to t~ true value Ihan the minimal one (3 Tg \'ear-').

In conclusion we eSlimale ,he sulphur I1U1 "'i'h dusl from Ihe Sahara. Anumber of invesligalors (Blichen and Georgii, 1971; GravenOOrst. 1975,1978) noled the inereasod concentralions of sulphale in air masse, from lheSahara. Gra"enOOrs! (1978) found lhal Ihe sulphur conlenl in lhese is-0.5 J<g m -, higher than in dean Atlantic air. Assuming lhal lhe widlh of IhedU'I·la)'er is 1000 ~m, lhal lhe a'erage altilude of lhe layer is 2,5 km, andlhalthe mean wind sp<:ed is 5 m sec L. and laking into account Ihat half of liletime the wind bill"" from lhe Sahara lowards th¢ Allanllc. the annuall1LIX ofsulphur from ,he Sahara 10 the A,lan'ic sllQuld be -0,1 TgS year-'. This isIe"lhan half of the eSlimale of Granat tI al. (1976) for the global aeolianemission of sulphur. II should be nOled lhat "e did not eSlimate the emissionbutlhe l1ux of mlphur carried al a large dislance lrom lhe 5OUrce. Therefore.the (Slimale of Granal er ai, (1976) is undoubtedly too low. Glaccum andPro,pem (198ll) presenl a h\'polhesis ,,'hich conflicts ,,'ilh our condu,ions.They suggesl lhal gypsum is formed during the lran'port of Saharan dUlt byreaction of sea-!>all cakile with sulphur dioxide, HIS possible to improve t~estimate of global aeolian emission by generalization of the experimental dalafor all arid zones of lhe globe, For lhe present we assume lhalthe aeoliansulphur flux in'o ,he almosphere ;1 20;!: III Tg year'.

4,3.4 Emission of Sea salt Sulphate from lhe ~an

Significan, amounts of sea!>att conlaining sulphate enler t~ atmosphere assea 'prays, There are several quile conlradiclory eSlimate' of lhi' emission.Eriks50n'. (1960) estimale of 44 TgS year-I i. the most commonly cited

"" T~ Global BicgHXNmktll Swplw, Cycle

figUTl:. whern. ,he lowest estimate from the data of Bruevich ond Ivancnkov(1971) h DOlg j"car- 1 and from GralXlv~t.y"i (l9~6) u:ork it It700 Tgyear-'. Recalculation of Selezneva', data (1977) gives a value of300Tgyear-1

•

ErikS1lOn', (1960) .'limat. was I»sed on lhe aSSumplKm [hal the ralio of.ulphate. in sea salls «:dtp::rsiu.d into the ocean and transfern:d to continentsis the same as that in moisture .vaporated O'"e' the """an (i.e. 9 , I). In ouropinion, such an approach undc«:,lim3lu the magnitude of marine sulphateemi,,;,,n, since il is un",a1iOflable to belie'-. that the'" ratios should be thesame fOT waler .'apouf and aerosol" This become. evident if we take intoaccounllhe rac, th.l rhe Jl:sidtna: time of WateT vapour in the atmosphere is-10 days (Junge. 1972). whereas that of aerosol panicle. containing sea s.altis undoubtedly less. Of great imponance in tl!;' case ;. the assumed upperlimit for lhe sizes of salt panicles,

Tho size of panicles corresponding to lhe ~position",te in lhe atmosphereof -10 em sec-I is asswned as a conditional limit, Tho re.idence time of .uchpanicles appears to he se>'erall>ours; tltis is suffICient for their transpon o'ercon.iderable di.tances, and in panicular, for their transfer to the continentalatmo.phere, Large panicle. differ from small one. not only in atmo.phericresidence time but al'" in composition (see below).

At present there are two ,ie",'. on the contribution of sea salt to the com­po.ition of atmospheric .ulphates o'er both the ocean and land. Tho firststems from lhoe kno".-n welghl ralio between callons and anions in sea·",'ater.",'hicl! i' prncticaU}' in>ariable in any region oflhe world'. ocean. It i. assumedIhal Ihi' ralio doe. not change during lhe transler of sail. from thoe ocean 10lhe atm05phere. The contribulion of sea·""aler ,ulphale. in any sample can becalculated from the relations (SOj-)/(O-), SOj-)/(Na'), and (SO;-)/(Mg").in sea water via the fonnulae:

(50;-)" - (SO;-) .. - 0.14 (0 )

(SO;-)•• - (SOn.. -,0.25 (1"a')(SO;-).. - (SOj·)... - 1,89 (Mg")

where (SO;-)" is Ihe quanlity of 'excess' sulphate formed in lhe sample fromnon-marine ",u=, and (SO;-) .. i. the 10lal ,ulphale in lhe sample. Accord­ing 10 Junge (1%5). the use of lhe ratio (SOl-)/(Na') - 0.25 ;. preferable.inee aero",l products may lack chloride due to it, volatility. Many in"ertigators use lhe ralio of magnesium 10 sulphur in sea·...aler. Such calculation.presume the absence of any fraclionation bel"'..en lhe basic ions of sea sah onformalion of sea·salt aerosols and assume thaI Chloride, sodium, and mag­nesium ions are ..du",-ely of manne ongm,

Exce.. sulphate, are found e'.'Y"'bere in 'he atmo,phoere ...hoen theserelationships are used, According 10 ,h. first >'iew the .xce.. ,ulphateformalion over the ocean is USUJllly e.plained by biogenic processes and

'"cmMion of pscous su/plIUI oompoWKIs hom lIx ocnn mlO Ille am\O!.pMRfolJo.,-ed b) ,he ... Ollid:alion 10 ...lpbotel. Gra~"horsI (1975) uplam the'>1libbWty of U~Sli Sl.lIpha<c:s in the ~an Ott...... a1rnospbtR by the.. IiDr_lD.J.tion In p-JIl- ructioM rather than II) frlclionatiou of chlol'1llC andmlpbale ions. To SU9JIOI1llis ide. he .sd1lCa 1I~ filet Iltal 'ucns' sulpha•..,art pn~m as smalk. wfO$Ols (0.1-1 Jtlll) INn aU sulpha,.., (0.5-10 ,11m),

lbe >eOOlld 'leW IlO N>ed 01\ the mecban...., of lOCI fr.CUOlUOl>On

durin!! IramScfofsal15 into the atmosplle'R. Bnoe.idt.1Id Kulik (1%7) nowdWI d"nIlI dill: evaporation of ~'_""'Cf and ,he IraMler 01 .unospbencprecipitation from the ocun to land .nd their funher tran.fomunion. 1Iw:ooncenlnl1ion of sulph.oles ,""'u.... c:omPlrtd to chloruw:. AQ;OrdLOI to\..l\mgstone (1963) the me.n (50;-)/(0-) ratIO f". ""N runoff 1101 upoKd10 .mhroposenic inl1\1tlltt is 0.82. In rain·...·.lcr 0\'('1 the PacifIC and Indian«<'nS it i, within the ran,.. 0.39-0.63. in AntarctIC >now;t is 0.80. and In

rain.wate. over the Black ~a it i. cqlLllllo 0.42, All of the.., ratios c~ceed theval"" of 0.14 characterisTic of "'.· ...'.ler. From an analysis of the aboo.e data,Bruc.ich and Kuli~ (1967) oon<:luded that sulphales are lransfemd prt'.dominanlly 10 .cr<»ols while ehlondes rt'main in Ka·" alef, Conlinenlal ri'-cfrunoff Os nc:h in sulphale and oompeMllle$ for lhOs prcferentia.lloss from lilt

~."Chan,es m lhe IOfl ratIO on lransnion from lhe oa:an to ll>e aunosphert'

art' also eharaclerisUc of ll>e otber axnponcnl$ of Ka,"-alef. To npla,n thefractionanon. h)l'Olhncs ha,-c b«n pul fororo"l.fd ~d on difkrcnccs inalDmic ,,'e'lbQ.. ionic eDC~, ion h)"dntlOlll'lldu. and ddfert'ncn In surlXlrIDd YDfumc eoncentnlliom of KB WI$. Hooo.,.... , ll>erc is uiIl no Sl.t~'ap!aJutlOfl fol the mechanism of frxtionItion. From anat,Yi of many ionsin KI sa.l~ Korzh (1976) ohowo"Cd WI the frII:tlOlUluon 0ttUn ,,'hile passmlthe occao-aunosphcrc iDt..rtaa aod lhe tatOO of ions "., the atmDSJl/lere ISmnntttcd "'ub tbe" ralio in K","'alef by the follo'."ng empcncal rt'llt»n:

"'here C A and C" arc molar conccntrahons of any ion lksignaled A and tbechloTlne ion. lespeeli"e1y. Accordini to Korzh (1976), the contribution ofsea sail sulphate! to lhe compoSItion of almospherlc: aerosol' should be ClIlcu·laled from the formulae:

(so;-).. • (SO;')... - 0.38 (0 )

(SO; l•• - (SO;').. - 0.67 (Na")(SO~-).. - (soj')... - 2.71 (M,")

It shouJd be no~ that dICK formulae a.R _ llIu'-crsal smcc they con­ttadlO many UpcrimellW rt'5UIts. lbe corul'lldicUon rt'.idc, mll>e fact thaI

'" ~ Global Biog~ochemkal Sulphur Cyd~

the calculated contribution of sea ,ulphate, may exceed the experimentallydetennined quantity of sulphate!: i.e. the coefficient, 01 0.39, 0.67. and 2.71are overestimated, This is observed when aerosol, predpilation, and drydeposition are sampled clo"" to the coasl. DiscuSSion of these me<ohan'sms hascontinued for many years and the problem is still far from solution (GranatelaI.• 1976).

Changes in the composition of atmospheric moisture 0"'" oontinents andfurther changes in 1M contpoJ;ition of ri""r runoff are indicative of tM exlent01 continental participation. Konh (1971) estimates that 15.9'0 of the sul­phate in precipitation over the USSR is ofoceanic origin. based on the a'SIump­lions that 100% of 1m: chloride in pre<:ipitation Over the USSR come, fromthe """,an and that It>. sulphate of <>aan;" origin can b<: calculated using the,ulphate to chloride ratio ob<erved in Ihe ocean. Korzh (1971) also calculates,using identical assumptions about the chloride. that 16'0 of the sulphate inworld ri"er runoff is of <>aan;" origin. He further cakulates that 28.1" of ansalt, in world river runoff are of oceanic origin, Other workers ha"e e'timaledlhis lalter comJXInenl to b<: 14'0 (Sugavara 1964), 10'0 (Poldervaan 1957),and 6" (Clarke 1924). After ronsidering these figures. we sugge't thatKonh's (1971) eStirnale of 16" may he an upper limit for the pe=ntage ofsulphur of oceanic origin in "'orld ri,,<,r runoff

II seems reasonable to assume that oceanic sulphate, form 10'0 of lhe tOlalsulphates of river_waler. Then, taking into aCCOunt lhe Sulphur COntent ofri''<'r runoff (60 Tg year-'), the amount of oceank sulphur in river runoffreturning to the o«an amounts to 6 Tg }'ear-'.

4.3.5 AnthrollOllenic Emission

The main human activities resulting in sulphur emissions 10 rhe atmosphereare lhe combustion of fossil fuels for the production of energy, smelting offerrous and non-ferrous ore'. oil processing. and producrion of sulphuric add,Sulphur occurs in all f""il fuel" but its content "aries widely. The 'pure,t'fuel with regard to sulphur is natural gas: on a"erage the ,ulphur concentra­lion IS 0.05" S {b}' weight). although lhere are sources. for example, inAlbena, Canada ",hich conlain almost 81}% of hydrogen sulphide in ga,. InAfrican oil' (Algeria and Nigeria) the .ulphur conceutration i' u.ually0,3-0.5" by woight. whereas in Venezuelan oils it exceeds 5'0 (Santa_Olalla,1973). The .ulphur rontent of coal. average, 2,2'll> (by weight) throughoutthe world (BhatIa. 19i8) and may ,aI)' from fractions of One percent to 5"for ",me coals from DonbaSS and Ruhr deJXISlts. and reach 8'0 or more inKizclov,k coal,. USSR.

In nalural gases and oils. Sulphur e,im as hydrogen sulphide and organ;"comJXIund, whereas in coals il is presenl a, organ;" rom,.ounds, pyrites. and'ulphate, The sulphate concentration in roals is nOl high. mually within

Th~ Atmojphuic Sulphur Cyd~

0.1..(1.2% by weight. On combustion. organic $ulphur and pyrite are o,idi'!edI<> sulphur dioxide (and partially I<> mlphur trioxide) and IOgether with fluegases are released imo the atmosphere. It is generally accepted that 95'" ofthe 'ulphur in luel is released imo the atJll<>$phere on combustion (Kellogg ~I

al.• 1972). and 96'" of this is in the lorm 01 sulphur dioxide. the remaining 4'"being ,ulphur trioxide (Kiyoura <1111 .• 1970).

In ore, of non-ferrous metalS. sulphur exists in the ,ulphide form (pyrites),The sulphur concentration in OOme pyri\e$ reaches 45'" (dry weight). Duringsmelting. predominantly of copper. zinc. lead. and nickel. mlphide sulphur i'(",di~ed to sulphur dioxide, If it is not utilized for other processes, it isemined into the atmosphere.

The contributions of various industries I<> ,ulphur dioxide emissions differdepending on the country. reflecting the general extent of industrialization.the development of indi"idual industries, the pr~dominance 01 some types offuel balances. etc. For example. Canada i' characterized by' a high level ofemission from smelting of non·ferrous metal' (65'" of total emission; Brown.1973). The sulphur emissions from large industrialized countrie' arecharacterized by a predominam contribution from energy production basedon coal and o~ as fuels. Table 4.10 sho".., the sourceS of anthropogenicsulphur emission~ lor the USA. England. the Fede'al Republic of Gennany'.and the USSR. from which it is e"identthat the emissions COme mainly fromenergy production and metallurgical processe$ in each 01 these countrie"

Anthropogenic emission is not constam with time, Its ehan~s are mainlyconditioned by the une"en consumption of fuels for heat and electricalenergy'. Three type' of periodic fluctuations can be singled oUl: daily. weekly.and seasonal. The daily fluctuation' 01 emission in the USA a", ahout 20'l0(Lavery ~r al,. 1980). Weekly fluctuations are characterized by the markeddecline in emission on Saturdays and SundaY". due to the decrease in theload of thenn""lectric power stations. The "'asonal "ariations are ellaraCler­i'tic 01 Europe. "..ith maximum emission in wimer due to the heating ofbuildings and the prolonged u'" of electricity for illumination during the longhour; 01 darkness. According 10 Barne' (1976). the ratio between winter andSummer sulphur emissions is 1,6: I in England and Wales; DECO (1977)estimated this ratio from maXImum winter and minimum summer eraissionsfor western Europe as -2. An inte",sting cllange has been observed in theUSA where ma~imum winter emissions occurred in the 1950s. Since 1%0.the summer emission. have mereased annually by 5.8'10 and winter emissionsby 2.8%. Tllis is due to the increase in energy consumption for air-wndition.ing during summer and it lias resul<cd in maximum summer emissions in anumber of regions 01 the USA (CAPITA, 1978).

Estimate' 01 the global anthropogenic sulphur emission have been made bya number of ~uthors, e,g. RobInson and Robbins (1968) and Cullis andHirschler (1980). These e'timates ,,"'ere based on statistical data for ooal

Typo: of r'tXhoc,;"n

USA

E"vlTo"nocntul Qoality (1971):EPA (197S); RO<Icrid (197S)

G,,,.. Il,i,.",

Fjeld and Otta,(191S); Rc.y(1973)

Fjeld."d 0,,",(1975)

USSR

B'od'ky (1977);Solo",.,in. (1977)

(no)(6,9)Ox)

(I 7~1

Io"c,~y 10.65I'ctrvlc",,' !o'c"lmcnl lI"d ",r.""'Y I,MI'clfoo, "",,,.Bo,y I 4.0SN""·krn",, "",'allu,l'J' .hld",,,,.II"o,;,,,',,, I

"W('0.,1 rn""''''''~Otll<" 1.1To,"1 19.3S

OF'S",,,", ",,,,,",1><,.,, d,,,.,,,, ...

(SS, 1)"(8.6)

nO.x)

LH0.'0.15Iu.S I

0.10 (JIl)0.3 (ILS)1.9 (100)

I1..1S (SKS)o IS (S.8)01.~ flO.~)

O.SS fN 9)

2.3 (100)

""'U1.2S

IU,5

0.5'A

B.6

(SI8)(1.1 )(9,7)

fl~.5)

(U)

('.1)(lOA)

(100)

The Atmo,pherk: Sulphur Cycle

production. petroleum production and procC$$ing. mctal smclting, and oncmi$$ion factors per production unit, Rodhc (personal communication) hasr~vicwed tM independcnt estimatc' of emi"ion and has prepared a diagramshowing tM increa.. in sulphur cmission on a global "'alc during the last 120yca" (Fig, 4.3), "The global anthropogcnic emi$$ion of sulphur in 1980 " ...cstimatcd to be 110 TgS (Cullis and Hirschler. 1980). During combustion offuels part of thc wlphur may b<: cmilled in the form of sulphatc; thc pe=n·tage depend, on the a,h content of thc fuel and rna)' vary from 2% for liquidfuels to 5~ for lignite. and shale. with high a.h content (Danil0va andDcrgach)'ov. 1977). From the data of Culli' and Hirschler (1980) andDanilo-'a and Dergachyov (1977) it may b<: assumcd that the anthropogenicflux of sulphur dioxide is 98 TgS ,'car-' and that of sulphate i' 12 TgS ycar-'.givin8 a total of 110 TgS year-I. We consider lhal an uncertainty of ~ 15,.should be assigned to these cstimatcs.

•m

~

-.!\,~ TO

I~0,.•,j" :toI" • •

•" •" •

•••

•

•• •o '-;~l.r.~",r.~",r"_,,,~"~",~_...,-'-_...,--Fill,4,3 Cb,ng. "'i'h tlme;o ,he glob.1 emi",;"n of ,ul·

phu, from ,n'hropoaen;c SOuroe•.• Culli, ond Hirshler,1980; 0 Katz. 1956; .. Robin>on ond RobIlio,. 1968

2" The Global Bwgtoclumiclll Sulphur C)'dt

It is difficult 10 estimate the emissions of hydrogen sulphide and other""du""d sulphur compound, into the atmosphere. ~"" is one opinion thatthis emission is insignificant, because the range of hydrogen sulphide concen­trations is even in space and has 00 time fluctuations. However. Georgi;(1978). in considering measurements of hydrogen sulphide concentrationsovu the Federal Republic of Gennan)', concluded lhal the contribution 01anthropogenic hydrogen sulphide to the total anthropogenic sulphur emissionmay be signifICant in certa,n regions. This condusion waS supported byJoes<:hkeet al. (1978) and Smither al. (1961). In his comprehensive workdevoted to the emission of organic sulphide' from industrial ""Ufees, Bhatia(1978) singles out the following basic <;ouree, of reduced sulphur: gasificationand cnri<:hment of coal. wood working. oil processing. some synlhelic materialproduclion, krafl-paper production. eiC. Unfortunately. Bhatia (1978) proo",nts no estimates of emis>ions except for the emissions of hydrogen Sulphidefrom paper·mills which vary "'lthin the range 0.64-4.1 kgH,S per t of drypulp. More concrete estimations ""ere made by Sitting (1975) (",e Table 4.11).The data of Kalyuzhnyl (1961) and Jarzebski 01 al. (1971) on hydrogensulphide emission Irom the ferrous industry and coke firing were u",d In thepreparation of the'" estimates. a< was the data of Komel (1980) on paperproduction.

The -.lue gi"en in Table 4.11 " probably an underc>timate of the totalamount of anthropogenIc emission of reduced sulphur into the atmosphere,Several proce''''' have not been laken inlo account which must make a con­Iribulion 10 this flux. for example, production of plastics and ,ynlhelic fibresand oil processing, The pos>ibilily of significant eml"ion, of hydrogen sui·phide from fuel combustion has been po,nted out by Sitting (1975). bul noattempl has been made to quanlify Ihi, flux, For global estimates, we shallassume the amount of anthropogenic flu, of reduced sulphur wilh short resi­dence time 10 be 3::: 2 TgS \'ea,-I which is in aiXord with lhe eSlimale ofRasmus",n eI al. (1975),

Anthropogenic emissions of carbonyl sulphide and carbon di,ulphide poss­ibly occur in a number of induslrial proce'ses. but Ihere are no reliable

Tabk4,11 AnthropogenIC emi..",n of ,hon·Ii,·ed ..doad,ulphur in 1980

Indu""

Paper.mills

Cokin~

PI~-Iro" "",ltingCement production

Total

Compound

Mere,plan,li,5. D\ISHe'H~

H,S

EmISSIOn (TgS ~.... -I)

Ol---OM

0.07-0,70.1---0,5

"U-3.0S

247

estimates. According to Crutzen rl Ill. 1979. carbon,'1 sulphide emission dur­mg biomau combustion. including naturally occurring fire'. amountS to0.24 TgS year-' on a global scale, Hoffman and Roscn (1980) estimated theamhropogcnic emission of carbon disulphide in the USA in 1973 to be0.085 TgS year". By 1980 this "al"" may reach 0,1 TgS fear '. Assumingthat the carbon disulphide em's<ion in the USA accounts for one-third of theglobal eminion. "·e obtain a ,·alue of 0.3 TgS )'ear as a global estimate, fn,·iew of the paucit)· of data no attempl has been made to estimate the globalamhropogenic emission. of reduced sulphur compounds with long atmos­pheric residentt times.

4.4 PROCESSES OF SULPHUR RE~10VAL rRO~l THE ATMOSPHf;RE

In this seclion "'e include all processes resulting in the elimination of agiven sulphur species from the atmosphere. even if sulphur is not remo'edfrom the almosphere in the process. Therefore. chemical transformations of.ulphur dioxide and reduced sulphur compounds in the atmosphere areincluded. Where possible .....e r.lt.1l generaliu obse,,·ational data roncemingthe intensil) of lhe various processes.

4.4.1 OxIdation ot Rfdoctd Sulphu< Co-mpounds in tM AtJnOSlll>ere

TIle atmosphere is a sy·stem "ith oxidative propenie,.•nd therefore allreactions in,'o],·ing ,'.Iem:e change. lead 10 the formatlOn of sulpha" O"da.lion of reduced sulphur compounds may o«ur In ga•. phase reactions. on thesurface of solid panicle .. and in lhe liquid phase of cloud drops, The chemis­Iry of these re:Ktions has been described in detail b) Heicklen (1976). D,,·;-'and Klauherg (1975). and Harrison el Ill. (1976). Here we Shall oonttmrateOn lhe estimation of rate. of Ihe most imponant chemical reaclions ofreduced .ulphur resulling in its removal from the atmosphere,

TIle most imponant reactions for lhe gas-phase oxidation of red"""d sui·phur oompounds appear 10 be those involving the h)·droxj'l (OH) radical.Measurements of these reaClion raleS from the work of Cox and Sheppard(l980) are presemed in Table 4.12. We aSSume thaI the 24 h ,,'crageconcentration of OH in the Jov,er troposphere is of the order of 10' molecuksem-I. We use this to rnkul'le the residence time. d"" to gas-phase oxidationfor lhe reduced .ulphur oom!X>unds in the Jov,er atmosphere and suggest thatan a'·erage residence lime of the order of one dB)' is appropriate for the,oon-li'ed reduced sulphur compounds.

This is consistent ....ilh model estimates by Junge (1972) and Rodhe andIsaksen (1980). Some"'hat une~peC'le<l in this connection ore the results ofHitchcock er Ill. (1980) ,,'110 found indications of a rapid formation of aerosolsulphuric acid near a natural SOurce of reduced sulphur, This might possibly

248 TM Globol 8iiJg«x:Mmical SLdphu, Cy.:k

Tobie 4.12 Reac,ion r"e, of redllC¢<\ ,ulphlll compound' .. ilb OHradical< in t'" ,,,,posphere (Co>: and S"'ppord. 1980)

Sulphur compound

m·lDSMSm·tS

"''"OC<

Reaction rate con'lan' (cm' molecule L se" L)

(1.33 :!: 0.8) x 10-"(9.04:!: 0.85) x 1O-11

(9.1'" 1.4) x 10-"('.0=0.3) x 10-"(0.43;: 0.16) x 10-"4,,10-"

he explained by lhe fact lhal lhe ,ulphurie acid pree",<or in this ca.. wasdimethyl disulphide or melhyl mercaptan ,,'ilh residence lime less than a day(Cox and Sheppard, 1980) (Table 4.12).

In a<:cordan<:e with lhe model <u&ie<led by Maroulis.1 af. (1980) ooncem­ing carbon di<ulphide o<idation. the final product< may be .ulphur dioxideand carbon)'l .ulphide. Carbonyl sulphide in tum is o~idized 10 sulphur diox­ide. ut uS assume ,,·..age residence time. for carbon di,ulphide of 70 days(Cox and Sheppard. 1980) and for carbonyl sulphide of 500 days (KuT)'Io.1978). From lhe concentration. and residence tim.. we can calculale lheamOun' of sulphur dioxide formed by oxidation. This amounts 10 1.5 TgS\'ear-' O\..,r land and 3.5 TgS year' over lhe ocean. giving a lotal productionof 5 TgS year '.

4.4.2 Sulphur Dioxide Oxidalioo in tM At""",pbeTe

Sulphur dioxide may be oxidized in the atmo.phere in the gas phase. on thesurface of <od panicle•• and in the liquid phase of drop/cIS in clouds and fog.h is diffleul! to say "hich of the.. mechan;<mS ma~es lhe greatest conlribution10 lhe chemicallransformalion of ,ulphur dioxide at lhe global leveL tboughlhe majority of in"eSligators are no'" tilting lhe balance in favour of gas­phase oxidation. The kinelic a<pects of .ulphur dioxide oxidalion in theatmo,plle", "'ere discussed by M6Uer (1980).

The rates of various gas-pha.. oxidation reactions (Cox and Sheppard1980) along with the hkely atmospheric concentrations of Ihe reaclanls, l..dsuS 10 .ugg<'.t lhal lhe reaclion with OH ;s the primary one and reactions"'ith HO, and CH,O, arc !COOndary. (The ratc COnMant for the reaction ofSO, "'ith OH i' 0,72;: 0.16 x 10-" em' moleeules l S(£l, Cox and Shep­pard 1980). It should be appreciated lhat the atmospheric OH con«nltationprobably varies b\' orde", of magnitude "'ilh cloudiness, lime of day...a~>n,and lalilude (Le. inlen,ity of <olar radiation). Direct measurement. of OHha,.., nol been made On any ulen,;"c basis in the Io....cr lropospllere. butmodel calculalions are re.dil\· available (c.g. Allohuller, 1979). As a oon..­quencc of this OH varialion. "'e can expecl the rate of .ulphur dioxide oxida­tion to "ary greally depending on cloudiness. lime of day...a<on. and lat;tude.

TIre Almospheric SuJphUT Cyde

Direct observations ha>'. shown that tho rate of chcmicaltransformation ofsulphur dioxide depends on the length of lime that the polluted air ma,sesh,>'e been prese'" in the atmosphere. In a smoh plume near a source. therate of sulphur dioxide chemical tran'formation is high and it deereases as thepolluted air is earried awa~' and diluted. In the plume. oxidation reaclions onthe surfaces of panicles and catalytic and ",-,n<atalytic oxidalion in the liquidphase of droplets are of importance,

Table ... 13 summarize, the rale, of chemical transformation of Sulphurdioxide under different conditions, These are expressed "" rale constants.assuming first-order ~inetics. The data are separaled inlo three groupsdepending on the les-el of atmosphelic pollution, bac~ground. regional.urban. When considering Table ... 13. propu allo"'ance musl be made forchange in rat.. of sulphur dioxide oxidation to sulphates with time of day'(Husar er at.. 1978) and seaSCn (Cal"ert el at, 1978). In this connection oneshould be careful "'hen using experimenlal results obtained mainly in the daytime and during warm ",ascn, to e'timale average re,ults. 11>e rale 01 chemi·cal tran'formation' in plume, mal depend on the r,.'pe of f""l burnt. Accord·ing to Homolya and Fortune (1978) oxidation of sulphur dioxide to sulphateoccurs 5-10 times faster during the combustion of oil than during coal burn­ing, The authors suggt'st that thi' i' caused by the catal~'tic action of vanadiumand nic~el. the content of which is substantially higher ,n oil than in coal.These data contradict those of mugi and Jordan (1979) ,,'ho obser"ed anextremely high rate of sulphate formation on lhe surfaces of coal·ash panicles.Thel estimated the abiht~' of ash panicles to remo>'e sulphur dioxide to be0.07 and 0.095 mgSO, mg , ash at 30% and 6O'lo relat;"e humidity. r..pec·li"ely, This process could be of importance in the immediate vicinity of com·bustion sources. In the liquid phase of water drops. the oxidalion of sulphur·ous acid to sulphuric acid occurs rather quic~ly. and the reaction therein maybe of a catalytic (Pen~e!l el al.. 1919) or ",-,n<atalltic (Hegg and Hobbs.1979) character, In the laner case H,O, and 0, may be the dominant o,id·ants. a.'idation of sulphur dioxide usuaHy yields ,ulphuric acid. 11>e averagerate of ,ulphur dio'ide oxidation in the liquid phase is determined nOt only by'the droplet chemimy and the rale at which fulphur dioxide can diffuse intothe droplet. but 01"" b)' the tim~ taken for the fulphur dio'ide molecuk. afterrelease into the atn>ofp~re. to reach a cloud.

After conSldenng the date of )'1cMahon el al. (1976) ond Calvert et al.(1978) we aSSume that the a'-erage oxidation rate of SO, in the """anic andclean cominental atm""ph~re is -0.0033 h '. Liquid·phase oxidalion was notcon~idered; therefore this estimate must be regarded as an u!'P"r limit. Theoxidation rat~ increa"f substantially' under conditions of regional atmo5­pheric pollution. From a conSIderation of the rewllS of McMahon er al.(1976), Eliassen (1978), Rodhe (I 978). and Hidy el at. (1978). w~ assum~

the a"~rage oxidation rate of sulphur dioxide in the regional polluled aUn",,·phore is 0.015 h I

I)"" "I 1'''11'''.,,'

Keg;',,,al

t'le;," "'''''''f'l'''''' ""C' ",,,h,,en,,A vcr_!>'" ""1"'1'1"""" "".101.""

hn".')'July

(fie, ""',,"N""_u,oo,, "'g.''''A'''''''~ Emo!","" "omhli""'Avcr_"" I;"",,,,,,,,, co••I""""A.",,,~" I ,or"I""'" "",.1".""A>'Or-,!l" I ""'I"'"" ,"",,,1,,.,,,,N""h.....,"·'" USAT,an,fe' "I I~u"" ,,, 4'KI l",

in ,loy'"''''at nigh'

Tn""lc, of I~umc to 300 kmT,,,,,'fe' "I 1><>lIu,«1 ai, maM'" J <:, <: 4(j h1.I>o,~.,a"gc """1''''' 01 pl"me fm'" eTee"",

1"""" '.....n'

lUll

0.0010.0020.0))0020.007IUlI2O.O'H6O.llIlS0,01 ~

0.01-0.040.0050.132-0.03(4 + 091)

0.074

~k\blx,,' ..' "I (1'J7~)

Cal","" ".1, (197H)C"I",,, .., 01, (197H)"l">","lg.i (1971)McM.hoo n aI. (1976)Eli;"",o ",><I S"I,b<>"". (1975)1'II"~,,,u (197H)Fhhc, (19n)R,oJhc(197H)Ilidy 0' at. (I '17K)

Rc~",oal

u,oo"

A""'age cooo;,ioo. of ;ndu,,,"1 '"~lOn'

I'i", day of ph,"" I"nsbSreooo d.y of plume Ira.,fc<18 h 'rnn'l"'r1lrom Gre.' fl",,'.Tran,f" of plum< I", 24 h (a'"

(., ",ght)A' U·C/.. 20·CI'oll"'cd ""'~"I'hc",...", "',u, of ".,,,,,,,,,I~", 2_4 h "f lra,,,I"'"0-10 m,n 01 "'"'I'''''D; .. ,,>«: from >ourCC _20 kmLoo Angeles: p""'""hem"" ""''&Ihgh homi<1'ty. k,w ph<>t""ocmicalacti,;'y'~"n>c "I electrie 1"""" plan'. SO k",

( .... 'UI 11M' n'", "f """'1""')I~"n>c "I <lee',ie 1"""" I"""'. ,n h~h' " ''''''''

A,cr,~.., f'" 24 h",;"",,,,,, lro,,, rlly Ju"n~ 8 hI'm"'I"''' of poll"'e,1 ai, m"""" fm'" e"~'T",n,I"'" of ,",lIolCd ajr .,",s,,, from nudal"'"

0.02-0.080.14 '.0,040.10" 0.02Max. 0.010.002S0.000.020.04n,01-0,11.83'.00.18_3.70.067---0.10.'OM

0.02U.ln0.01M"., 0.040.042IJ.I

Miller (1978)Alkezwee"y .nd l'nwcl (1977)Alkcz;wccny .nd Powel (1977)Smi'h aoo Jeffrey (1915)R'>bc'l< .",1 Willi."" (1979)

Ro""".o and Sn"I'flC-)",,>t> ( 1978)R'""",,m """ S"""...·.J,.,,h ( In~)Co, (\'114)FI,'ge' ""d 1'"''11''' (1971,)Fly!:"r" aI. (1976)M,M,lIon " ./. (1976)MeM ....""'./ (1976)Ile.I)'."d Hkly(1979)Ile"I)' and lIi<1y (1979)

1'0"""""1. (1979.)l>a,;", 0/. (1979)I),,,·;S""/ (1979~

';)In,,' ""/. (1'11910)('b",,! (1"7,,)11"".,h .n,1 lion,' (IYW)

252 TM Global Biogwcht<miJ::al SuJphUT C}"Cle

4.4.3 Remo.'al of Sulphur Compound, by Prfclpil.ation

It is (u,toma,') to di"ide the rem(,..al of sulphur compound' from theatmosphe:re by precipitation into two processes: uptake into raindrops "'ithincloud' (in..c1oud sca"enging) and uptake intO raindrops as they are falling tothe ground beneath the clouds (sub-cloud sca"enging).

It is diffICult to distingui'h betw""n in-<:Ioud and .ub-cloud scavenging.Sulphur removal from the atmosphe:re hy sub-cloud scavenging is greater inregions of ;nten,i"e atmosphe:ric pollution ,,'he:re mo>t of the: sulphur is foundbe""ath the: cloud layer of the: ato>osphe:re. Unfonuna.. ly. information onrates of in-<:Ioud scavcnging and the content of sulphur comlX'unds in cloud·watCr and fog is meagre. The most extcnsi.'e in"estigations of the (he:micalcomposition of cloud..water ha'" been made in tl>o S<,..iet Union h)'Petrenchuk (1979). He showed that. in the: eastern region of the Europeanpan of tl>o USSR. the concentration of sulphate sulphur in ,ub-in,..r<ionclouds reached 15 lOgS litre-'. The sulphate concentration in precipitation inthi, region was 3 mgS htre-'. ThissuggestS that rain drops ha.'e a high absorb­ing capacity and that ,ulpha.., may be concentrated in (loud..water duringpanial evaporation of cloud-<lrops, Rather high concentrations (1.5 mgSiitre- ') were obsc ....·ed on c1oud·water 01 the: clean marine atmosphere by Lazrus., 01. (1970). thoreb)' indicating a high dflCienc:. of in-<:Ioud sc..'enging,Junge (1965) commented on tl>o ' ..ry h,gh (up to 17 mgS litre-I) con~ntra­tions of sulphate, in log_water, \he" data arc confirmed by Kirkaite el 01.(1974) "'00 summari,ed a great deal of data on the: chemical composition offog ..water and showed that a high concentration of ,ulphates in log''''ater is a"'idespread phenomenon, For example. they sho"ed that in Lithuania. con­centration, of sulphate in log..water varied o'er the: ranll<' 10-27 lOgS htre L."'hile in rain·water the:y "'ere 0,2-5 109 litre'. When mountain peaks arewith'n clouds the dclX'snion of sulphur in fog droplets may be rather high.

There arc many studics of scavenging of sulphur dioxide and sulph.atesfrom the ,ub-cloud layer. Mech.ani'm' of sc3\'enging of sulphur dioxide andsulphate, differ from each other: concentration and surface area of drops arcdeci,ive factors for ,ulphates: for sulphur dioxide. they also include the pH ofrain- or cloud·"'at.. (Hill and Adamowicz. 1977). Sulphur dioxide sca"engingand o,idation in the: Water phase have been de>Clibed in detail by Adamowia(1979) and a,'erton.1 at. (1979). "'ho ,tudied the: offcet of drop ,izcpH of solulion. ammonia. carbon dioxide. and orone concentration in air. andthe time taken for drop. to fall to the: ground. on sulphur dioxide oxidation inthe: liquid phase,

We may assume that the quantity of ,ut»lancc sca,..nged depend. OfItheinten,ity of precipitation and ,ts con'en, ,n the sub-cloud la)"er. and that therate of >ca"eng,ng obcy, first-<1rder kinetics. where m is sulphate 0' .ulphurdioxide mass in an air column 01 the: sub-cloud la)'er. and I i. a proportionalit)·

TM A,,,,mpMrlc Sulphur C)'d~ m

dm._ mr. '

facto, (often called tM Langmui, factor) which depends on precipItationinten,i,),. Naturally. as far as a'-erge oonditions of any region are ooncemed,ItQt only tM intensity of rains bUI tM freq""ncy of occurren"" of precipitation~uld be laken into a<:coun'. tn 'his case. 1M a"CTage residence ,ime "."hregard '0 ",a'-enging or irs reCIprocal ~aJue. 'hoe sea"enging facto' K_. ISgi"en by , ,

------'"K.... f· 1

wMre f is tile f'artion of ,ime wilen p,~cipillllion is occurring and '. is tiletime from an arbitrary moment during a dry period to thoe start of precipi_tation. Here. to and f are dependen, on tile climatological characteristics ofeach region (Rodhe and Grandel!. 1972),

Tables 4.14 and 4,15 summa,ize puhlished data on 1 and <~, for sulphatuand ,ulphur dioxide. "They .110" that the uncertainty of our knowledge of thisfarto, isquite high. When the precipitation intensit), is I mm h-1,he estimatesof 1"" ~ary from 10 't" more than 2.5 • 10-<. An e--en w'ide' range i' foundfor .ulphate,. from 4 x 10-0 to lO < If we take f· 0.1 fO! Central Europe.then l)picall ,'alue. w'illiead to a"erage re,idence times for sulphur dioxide

Lallim"ir foetor Mean residenceCondit;';'n. (oec- I) time (h) Ref".n«

Euro"". ,wn""" 100-)00 Root>< .nd Orar><tell (1972)Europ<. v,in'er ,,,., Rodhe OfId O"'ndell (t972)

3xI0·'1 MoMa""" ... m. (t 976)I" • 1 3 ~ 10-' Cbamberl.in (l9SS)S ~m panicle. 1.6 x 10-' I·' Engleman" (19M)O.S ~m panic... 10-" Slinn .nd Hale. (1970)

4 )( 10-0 Ewen (19n)8 )( 10-' Ma'hon·ko (1%7)

E",ope. a"<Jage 10-< Fi.he,(l97S}rondition.

Europe.•,'era~< 10-0 G.rl.nd (1978)rorxlition.

Euro"". a"(f'ge " Roobe (1978)rorxlltion.

Europe.•"crag< lO- o,i Seri"en and Fi>hc:, (19H)rond'"on.

254

ToNe 4, I~ Lanpn"" foem" 4IId IIlUft rniclo_ ,....... fa< Mdph", dooule ...."""'-.:1._-E..........-..- 10-' , " ~B...:I "'...... fJ9~S)....- 10- • \W.....·to{l96~)f' • I 1I>-6~1 ~ 10 ot.... (1972)f • 10 (~.~_.u) ~ 10" Okiul (1972)I • O.~Z 2.5J~10· H6J'l_(197~)

LS! ~ 10-' E....' Ind HopI_ (1979)I • 1S 7.4~1O· Ileilke (1969)

HI ~ 10 ., \te.\-f.""" ., '" (1976),. , 10-' Clulmbcrllin (1960)I· 10 3.S ~ 10 Clulmbc"I,n (1960)Europe!......ge • x 10 Eli....n (1978)

condition.Europ<. a..erl~e HI- , Glrland (1978)

eooo,tioo>EUn)pt.•'erare to-· ",.w, (1978)

1X>rld",o...E"",pt...e..,. ~ x 10 '00 Ilodbe (1978)..,.,.,,,.....,.- J ~ .0- , \10011 (197 )

".~al'po l_k' "

and sulpbale~ .. iih~ to sca'.ngul&. of 6O-ilO and iG-200 II. respec.Il,e])

A number of autho.. ~,~ atlelllpte<110 de:lermine tbe .belllni form ofsulpll'" m .....~. fallen "''''. Table 4.16 surnmanzc. tbe n:$Ultsot Ibex npon­~.~

From TlbIe 4 16 il folJmr.~ 1~llboul 80"0> of the sulphu, in pm:ipna,ion ispr.~m a. !I<llpha,••. Ho.. e'..". IhlS doe. nol mean 'hat .ulplulles Ind .ulpbu,dio"de: are .....bed Out b) pre.ip'lltion in Ihi-; Tllio. since dunng lbe tim.taken (0' drops to fall part of the sulphur dioxide: is oxidized to sulphat.s.

Table 4,16 PrOponlOn of ,ulphlte and .ulphi,e in , ..ndn)p$ ruehlni 'Il<!n)"nd

87_100...." O-llIO-!O

""-::: 4

Hof'"''''' (197<1)Hale' and D.... (1979)O..... /19·9).........,'al)_ *"""" froao en...Gra'e_ n •. (19S0)

255T~ A'm(Jsphuic Sulphur Cyd~

4.4.4 Sulphur Co~ntntioo iu !'r«ipitalion

Traditionally, Ih~ sulphur content 01 pr~cipitation is d~termi""d by sam·piing the rain-wal~r and suboequ~nt laboratory analysis. although somealt~mpts ha,"~ been made to uoe instrum~nts based on ion-sel~ctiv~ ~Ie<:trodes

to determine sulpha/e concentrations during rainy period,. The proceduresuoed for sampiing and analysis are of ..Ireme imponance for a rorrectinterpretation of results. More than 10 }'earS ago il ...a, widespread practice touoe permanently open funnel" though in some case, ,amplers were open onlyduring the rollection of predpita/ion. Later. sample" with automaticallyopening caps w~re wid~ly used. Collectors which arc permanently open col.lect not only precipitation but also dry aerosol maller, According to Maninand Barber (1978) in East England. the amoum of sulphate in precipitation i,2.4 times that collected during d'} "..eather. In arid zones "'Ith int~nsive dUllformation, dry deposition is ,utJ.tamially higher (Mat"eev ~I ai" 1976), Whengeneralizing ..polimemal data we shall use information gathered with bothconstantly open and aUlomaticall) opening samplers. However. the sulphurCOment in precipitation e'timated bl' the first technIque will be taken as anupper limit.

In the presem section, a, in section 4,2.3, we shall attempt to distingui,hthe contribution by panicle, 01 oea sail u,ing the ,ulphur; sodium and ,ul·phur, chloride ratios characteristic of sea-water. This is valid for sample,taken O\'~r the ocean or in coastal zones. In continemal conditions such acalculation rna}' yield erroneous estimates due to possible {errigenous COn­tribution of sodium and increased volatility of chlorine (Junge. 1965). In aridzone, this technique is absolute I}' unsuitable .ince the soil' may contain largequanlities of sodium 'and chlorine.

We shall now summarize data on sulphur in precipitation and e'timate thesulphur was!>out from the atmosphere on a global scale. Table 4.17 present'pubii'hed data on the sulphur COntent in precipitation 01 polar and Alpineregions. As expected, the concentration of sulphur in the predpita/ion ofpolar region, i' '''''y low. In Antarrtica, no appre<:iable increase in Concen·tration is observed in ice layers chronologically associated with the industrialepoch (last 40 years). In Greenland, how~ver. ttle roncentration ha'increased signifICantly during recent years. According to Koid. and Goldberg(1971), the ice formed before 1940 contained 0.027 mgS htre- L

, while theoeasonal snow (determined in ttle mid 196Os) contain~d 0.063 mgS litre-'.Delma' (1979) found that during recent decade' the concentration inGreenland ice increaoed from 0.03 10 O,OS mgS litre . The ,ulphur concen.tration in Amarrtic ice and snow is of the same order of magnitude as that inGreenland, va'}'ing from 0.02 to 0.12 mg litre~l. From a consideration oftheAntarClic and pre·industrial Gre.nland data, we may aSSume that the minimalooncentration of non_anthropogenic ~ulphur in precipitation i< -0.05 mgSlitre-' in these regions. In allttle other regions of the world. sulphur concen­tration, in predpitation ,,'ill be higher.

The Global Bidgro<:hemicaJ Sulphur Cydt

Inlere>!ing daw ha,e been presented b}' Vilensk,i and Korole"a (1973) onIhe inten,ily of ,ulphur def\Osilion on lhe !uria~ of the ice·shield of Antar,"tica. The)' showed lhat nUr the coast the deposition amount, to0.04 g m-' y.ar-' and lhal it decrease' .igniflCantly with distana inland. dueto the decrease in .ulphur concentration in precipitation and the amount ofprecipitation in the hun of the cominent. At a distan~ of 10Cl0 km from thecoa.t, the intensity of .ulphur deposition was only 0,003 gS m ' year '.The authors consider that the major part of thi' Ilux is dry deposition, In allGre.nland and AntarctIC data. the sulphur cont.nt rellects both fall-out withprecipitation and d.y deposition. When considering the global atmosphericwlphur <),<1•. the .ulphur deposited in precipitation in polar region. may beneglected be<:ause of the low sulphur con,enlrations in precipitation and theinsignificant amounl of precipilation, .specially in the continental region. ofAnlarctica.

In Table 4.17 we included data from Ihe Caoca,u. glaciers (ahitum,2.5-3,5 km). Matveev's data (I %4) on Elbrus give substantially Io"'er value.than the later data, Mat"eev n 01. (1976) obtained concentration. an order ofmagnilum, higller (0.6 mg lltre-') for Mt Cheget (-10 km from the samplingsite on Elbrus and -700 m lower) from routine samples taken b}' automatj,csamplers. The data of other authors are in good agreemenl (0.3---OA7 mglitre-') with the Mt Clleg.1 conant.ation. These concentl'3tions, an order ofmagnitude higher than tbose in polar regions. rellectthe con'iderable impactof anthropogenic and natural con,tituent. on lhe .ulphur rontent of precipi­tation in thiol region.

Few data have been Obtained routi""I)' on the ,ulphur content of preclpi·latian in oceanic regions far enough from land to exclude the possible ad·mixlure of dry deposition in the samples, The a,'ailable infonnation is sum·marized in Table 4,18, The data of Chukhrov el al. (1977) and Andreev andRozhkova (1971) are not enlirel)' of oceanic origin since the sampling sitesare located on contin.ntal 003sts and rhe pr.cipitation chemistry iol un·doubtedly affected b}' some land trajectories. In addition, And.eev andROlhkova's (1971) samples were taken using constantly opened samplers;th.refore their data refl.ct the maximum possible value. for concentrationand fall-out "ith precipitation in oceanic regions. The data of Eriksson(1957), Tsunogai el ai, (1972, 1975), and Junge (1965) were obtained fromepisodic obseryations and cannot characterize a"erage annual conditions insampling regions. Ho"'ever, episodic sampling of individual precipitationminimi""s the impact of dry d.position, and thus these results g,ve mo'~

repr.sentali~ values for sulphur concentration ill precipitalion,From the abo,,,,. "e find that the rang. of possible value. for total sulphur

ill precipitation at sea·)e,·el iol from 0.3 10 1.0 mgS litre"' and for exceSSsulphur, 0.1---0.5 mgS hl'e-'. We assume an a"erag' value for total sulphur inprecipitation o'·.r oceans of 0.5 -= 0.15 mgS liue ' and for excess sulphur,

IkfcfcfK'C

lleh"., "",I Ik,,,lmn (Ing)IJelma, (1,,7,,)Delm., (1979)I}us<:ooc'g.nd I..og..·.y (1 ,,79)B,,"'nbc,~ and Longw.y (107\1)

Dn",nm (II>H)Vilen,'" a"d Ko",leva (I\l7l)

hlal"",,v(I961)

J"ng<: (1%0)Koidc .nd G"ldoc.~ (1971)K"idc and Goldoc.g (1971)K"i<lc and G"ldhe'~ (1971)C.ag'''" "I (1'174)

C ••~inn ..III"74)

Ma'""e.".1 (1,,76)Sop'H.,h,ili (1970)I'~hal'gav. (1%1)

Co",,,,,,n"

h" la" HKlU ye."Old ".,.... 2 11I7" ~m on

,h"",k, "I !"c-i,u'","ul pc,io><lIcc 01 pre.;,kI,,"'ial pc,.kIIcc of pre.indom;al PC'ooIcc"t 1,,74-1S

Il.CCCI\I ',"l'"

Icc "r ]uIS-S7. a""••1"Old <rIO... d""og 1\l60-6SIcc 01 1300_19400 __

I'm I." !lOO yea"

l'n"h prc<ip;t""'ns.::.soo.1 __F""h l""";p;I.,.,n

A""".,I p"",;p;I.''''''Old "",...

01,1 .."""

aaa

1'.1""",,,, I","ale.l.,"",01 e,oc" S

,,,"Na. CI1"•. 0

1'"-';.''''''Ipho'(ong I"", ')

0,0610.0240,023

(W270.047oms0039

0.010Ollt»0.0270.0260.1127

'h~ol

""Iph'"(mg Iil,e 'J

0,0.1O,OS0,016 ± 0.0020,040 ± 0,009

OM012

'Ul66

0.06

0.0

"0.47

Orecnl."dO"",nl.OOGre.:ol.ndO"'enlandAnla,.,!""'. V"''''~

.""io"An'.re'ic m."Anla«'''''' Monl'

V'''IO~ "",t<Ca...."'. hit. hlh,,,,

3700 mC....." ... MI. CII<:I""

JUOO n,C ~Iac"' ...C 'o,. glacie ...

T"I>lc4,11

O",enla.dGreenlandGreenl.ndAnl.,.,hc.GreenlandA,,'arCh<o, Ijnd

,'a'.",An",,,,'.:.

Aoo"-",v,,,KI R",h'ov" (197 I)

Ch"kh,ov ~I .1. (1 u77)Aoo"",...00 K"'.hk"va (197 I)

I rih"",(lu~7,

J,,"gC (l1'6J»J"nll" (1963.)Junge (19630)Junge (1963.)Koy."'. rI aI. (11'65)Ny",,'g(1977)

I).", "f 1946Sampling on hoo'd ,hip>S,'"'I>I<. wi, h hiJ;h ",II ""'len,

,,,... 'h"'" ",1.'10<1 lu 1"""1"'"r""" i"'I","",1 'eg""" "IN. Anoe,,,,".n: ..eluded

M,,,,Y'" "'1>1<' "" "'''' ,toy,111 m .I"vc "".-le"d

One ".'''>n, 01'" d"y gO m000'" >ea-le",'

1:.""'-'<Jic.1 ,""w ..",p1;"3Ro"'ine ,.mpling of dry 000

I<C' depos;'ionR,,"ttne ..mpling of d'y ",w'

wei ,lepo ... '.'"II"",,,,,, """p1"'g "f ,lty ",,,I

we' <lepo""""R"",,,,,, '""'I~i,,~ "I ,loy ."d

we' ,lepo,,;'.,nI>"'g.l<,m """''v.,.""

"

IOle"'"'" f",<.",ul.,.",

"I .'oc"'"' ~ C""''''''''''

1.4.'

1.71

0.47

1.6~

O,gl

11.1 )0,22".M0.)10.41

"'

1.4J

I 'I~

l.56

o.ss

T"',,I E"""",,,Iphu, ,ull~'U'

(,"g I"te 'I ("'3 It"e 'J

H64 Ulu

0.231.8g

lUI0.'31.130,720.4S"..

I'd,,,p,.'~,,,,k

K.",d..".yVI,.Ii"",I"k

Sakh'''nSakh.lln

IIe,moo. hJan,hUSA, Flo,.... coastUSA, weSler" eu.,tNe I< f",,,,,ll.,,dbran coastNo"",,,n A,I,,,"<.

cenl,,,1 ra,l

TN! Armmphtric Sulphur Cycle

0,2:: 0.1 mgS litre-'. The inlensity 01 precipimion (Korzun ef al.. 1974)varies o"er an order of magnilude. The val". of 1280 mm year-' i. taken asan average. From these .... calculale the loral sulphur flux ...ith preeipilatioonfrom the atmosphere o'"tr oceans (area 3.6 " 10" m') to be 230:l; 70 TgSyear '. and lhe .x<Otss sulphur to be 9O:l; 45 TgS )"ear".

To eStimale the sulphur flux ...ith pucipitation to ,r.. ,urface in cleanconlinenlal r.gion'....e use- European data from the pre-industrial period andmodern data obtained in isolated regions of olher continents. Table 4.19summarizes the concemrations and depositioon for different continents. It ise"idem thaI. in Eurasia. concenlrations ...ary ...idel)' from 0.3 10 4.7 mgSlitre -'. Thc high value. are characteristic of zone. of inten,;,,, dust fonnation(Malveev 01 al. 1976; Khasaoo" and Rakhmatullina. 1969). The data ofMa"'eev <t ai, (1976) are especially interesting sinc. tr..;- w.re oblained on aroutine ba'is using automalic samplers wbich exdude dry deposition. Thcdata of Drozdova or w. (1964). Andreev and Rozhko"a (1971). and PGO(1970) were obtained by pennanently opened sampiers and therefore gi"etr.. ,um of dry deposition and precipitation. We consider that they provide anupper limit of possible concentrations. viz. 1,3 mgS hlte". Data of Vit}1I(1911). Vorintsev (1954). and Granat or al. (1976) var} o'"r the range0,3-0.7 milS litre-'. The e'limated sulphur concentration for Eurasia Can betaken as 0.7:!: 0,2 mg litre . Using this value and an a,'erage rate of pre·cipitation o,'er all continents of 400 mm year '. we calculate the intensit) offall-<lut 10 be 0.28 :: 0.08 gS m ., year-'.

In Table 4.19 tr.. data of Wr..lpdale (1978b) and Junge (1965) for NonhAmerica presenl a range of ,'alues similar to those o".r Eurasia. Thus for lhiscontinent "'e assume thallr.. conc.ntration is 0.7:: 0.2 mgS litre" and "'etdeposition is 0.28:: 0.08 gS m-, )ear", Unfonunalely. "'e ha'"t no infonna­tion On the chemical composition of precipilation in South America,

The daUl On Aumalia and Africa are quile variable. O"erall. ,,,l,,.s of "'eldeposition for lhese contn>ents arc Iow"tr than t""'" for Eura'ia and I'onhAmerica. It is notewonh)'. howe"er. lhat arid zones in Australia and to alesser exlent in Africa occup}' consid.rable areas,

Based on Table 4.19 and the above analysis. we IhallllSSUme that theaverage sulphur concentralion in precipitalion 0'''' the clean regions of con­tinents ;. 0.7:1; 0.2 mgS litre and the inlensit)' of w'et deposition is0.28 :: 0.08 gS m-, }'ear -'. Taking into account tr.. ar.a of 'c1ean' regions ofcontinents (133 x 10" m') this estimate gi"es the sulphur flux wilh precipi­tation over 'dean' reg;,,:msas31 '" 10 TgS)"tar-'. For arid wncs. we assume ana"erage concentration of 3.0:1; 1.5 mgS liae". With an average intensity ofpucipitation of 200 mm year" and an area of 5 x 10" m'. we cakulate ll1csulphur flux with precipitation for arid zoneS to be 3.0 ~ 1.5 TgS )'ear".

The chemical eornposition of precipitation in industrial regions has beenstudied quite ,ntonsively in ncarl)' all de'"tloped countries. Ho...ever. in many

CO''''-''''''''MM'(mf\.~ 1I11e ')

A"M)"'" del"",,«J(f\.~ III 'ye", ') Coo"',,,-,,,,

f.~,,,,i,,

S"M>k",k "'IlionK"it.y,,,,·v ,.~......1",.n.. II.,••1"'8M'"Komi ASSRKhaba",.,. ",,,il<)'Y

Irk""k ro~io<>('~",r,1 y"kull'K"I"'yk ASsK~1"v"'I..1'"''''o'y~b""":r,, '"I'MMlT,,,,,,·II,"k.1 rc~j,o"

K"I',kh""nA",' So. <"."Fe,~"", volley

0,3.~

0,35032

""II,~J

"D22,Ll(I.~1

1.241.01.,

0.220.19

o.n(U1(11on

0.49

0.76

0.90

I)"," 1",1909-10

1957-621%3-671'}I>2~6J1'162~~

I '16i>-1IJDry ,1<,""'.'" e,ol",""tl'I'",,,dfO "M)W ",,1>75 ·7(,1':1"..,.)10 .now ill 1'I7J_74Ep;",>d1O "'lOw ;n 1'169-70

D'y ..'" "'" ,lorn"'M'" i" 1%3

Vi'yn(1911)Vi'y'''(1I>11)Vo,ints'" (1954)[)ro,d(""~I"', (1%4)1\00=' ,,,,, R",hk""" ( 1971)1'(',0 ( 1'170)1'(;0 {l<J70)M",.wvrl.1 (1'176)M"'''''"'r/,,111(176)Cllo'IIm. "' "I. (1977)Cb"I:II",. " "I. (1977)Ch".t"o_ " "I. (1977)KII...".,. .,Id R,kh",.",lIi,,,,

(1%9)KII"",IIO' a"d Ihkllmatulli,,"

(1969)KII""".,,, ""d K"kh,,,,,,,,lIi,,,,

(I ')(+I)

N"r,hem S""e'lc"Oroa' Unta",

,j,....,l<uNOrlh·""".,", USAClcan n:g;"'" of

N,,"h Amcr~'a

AJ,.;,'uN,~'Crb

lJg,,,d,,. K""'p.,I"biroK;l'"hoEqoatorial ea;t.,,,

AtTic.

Au.llmliuMA","',li"A,,,'m"',We",'m A,,"ralo.,W",'cr" A""",I;.,Wc<lcr" A",,,.I ..

0,41.0

02~-lU

10_2.0

0."

"'1125

O.lh0.'

11.1 IO.XO.2X0.'

0.2lUI

'"(U~J0,6

C.Ic"latod valLI<Ex",,. ",Irh.'c calcol.lcd.

IHH1-g7

19S5_S61·..·0« ",Irh."· 031c,,1"'cd

b«", ."11'10;,,. o."'.I,'cd10.«...."Ipha", 03lcal"'odMonthly ..mpl;ng at N I"'i"..

1974-78, bee... <"'rh""<.Ic"I.,<:<I

h,'C>s ,,,lphHlc oa~·"I"IC"

he<" ""'~"". o"",,,I""dOff,h<"" ,e~.""

l 'Ie"" ,~,n,i".,,"al TC~'''''

I)""y rog''''''

G"""" r' "I (1976)M'lIe' (1905)

J""I:<' (1965)W""'I~I.1c ( I91Nh)

1l",,,,r,,,I" (1~74)

V"",. (19611I,rib,.,,, (1%61l1e.", (1957)1'(,'<1"" <r ,,1, (19X I )

I r;k;"", (196111II",.,,, (l'i60J11o"g."'~' a,,,1 l;",hl" (1'171»11o"~t,,n ""J n.,I"" (1~76)(;,.",,,, ,', 0/. (1976)

A"HH"" '"']>''''',,<1(gS tn I )'Cu, ') Com"",,,"

Sl.. ,p....l..,,, "I 11"'7,,)Chul.h",.... <II. (1~77)~Om,.,,·. <>I. (1\077)

Rele",,,,,,

Dtw<h'a ... ,., (196<1)

PGO(1970)1'GO(1970)'OIIIIlY _ R.- (19721'Ian.. _ llarl>t. (1~711)

OtTO (I on7)

I-.M"-' (1'J'llO)

1Ac:........_(1'7~)

Ju_,. (1965)

Whelp<l>l< ( 1971:1.)K.".......... oJ (19M)

na'. I", 1976I,.," k>r 195'"

Sum "I d'y ,,,1<1 """ ,lei""".'"J I"......h"..,., """~'''I....... of df)' a wei ,I<i""", .....C.....,"'.-_........... 1%8-76Sum of dl)' _ """ dep<»"""'.,,~

Sum of Ill)' -.I """ de_,_Oa'a foo 1%1 1965

lbo..... 1\016lbo>foo I'J'H-7~._..,.

II ,..,...0aIa foo l'J'n_19. __---0aIa 10.- 19M-7J

"",.•U,.•,~

"I.7~

IS

"

C,,"''' III '''' "'",,,,~S III,e ')

""Ul_~

"

"07_10

11)..1,7

"

,.

"><ok'" _ cu,ral,-USA......."...........

~"USA, """Ma>I<'"

~"Soulh..,.....,." e_N""". "'ion, hI"'"

USSR. ern,,,,1ElOfUI'Can .-.

M...... ..,~SorIoIc...... "'"...(·~...."I~1.-0'" t"l:l-l"'.nb.....-.... t .....,...:

I "~U,'"'''" SSRM,,,,""" ,<~ ..'"I-t.N:<_ "'V><J

T~ A,mo.p~ric Sulphur C}'d~

cases separate "alues for dry and wet dep:>sirion are not ava~able. fn thisconnection. the most "'liable of all tM data p",sented In Table 4,20 are thoseofOECD (1977) and EMEP(l980). Value. forconcentmion and dep:>sitionobtained in 1M USSR may t>. considered to be the upper limits, Assuming tMprecipitation in industrial regions to t>. 600 mm year- L and the averag<' sui·phur con""ntration in precipitation to be 1.5;: 0.3 mgS litre- L

, we calculatethe intensity of sulphur dep:>sition as 0.9 ~ 0.2 gS m-' ,'ear-'. We have esti.mated tM a"a of industrial regions, including cities. to t>. 12 x 10" m'. andthu< the sulphur nux with precipitation on industrial "'gions is 11 ~"TgSyear 'L.

4.4.5 Upta~ or Sulphur DIn"kIt by Underl~mg Surlaces

Dry dep:>sition cannot be measu",d in a depo>it gauge. It is, therefore.customary to infer dep:>sition from other types of measurements. l1le mostwidel)' used and fundamental a"umption about gas uptake at theearth's 'urface is 'hat the rate of uptake per unit area of surface, Uw,. is pro­p:>nional to the gas concentration in contact with the surface, The constantof p1Op:>rtionality i< the in"erse of a surface resistance. ',. This resistan"" isassumed to t>. constant for a given >urfa"" in a given condition, but variesaccording to the physical. chemical. and biological propenies of ,he 'urface,e.g, from water to bare soil to fo",sl. When the gas ooncentration, Cso, ;Smeasured some distan"" abo"e tM ,urface (as it alw'ays is). then there ti anadditional resistan"" to gas uptake due to the air between the level of thecon""ntrat;on measurement and the 'urface. r" This resistance varie' accord·ing to the intensity of turbulent mixing in the atmosphe" and can be veryhigh when turbulence is low, e.g, during a nocturnal in"ersion, l1lese tworesistances can be added. The in,-erse of their sum ;, called the dep:>sitionvelocity. Voo, which relates the uptake at the surfa"" to tbe concentration at afixed height for a specifIC rate of atmospherie mixing acootdtng to the expre.·

"'"U~~Cv::d(,,+r,) ~V"""xC"""

In practice SOme ill·defined 'average' condition' are assumed (see GalbalJ)'1974), As mentioned above, the phySIcal, chemical, and bIOlogical propertiesof the absorbing surfa"" are imp:>rtant in determining uptake rates. l1le acidnature of sulphur dioxide and its high solubility lead to extremely rapidab"lrption by humid surfaces and lurfaces with alkaline propertie<. Forexample. calcareous surfaces (under the same conditions) will absorb sulphurdioxide mo", rapidly than acidic surface•• and moist foliage is a bellerabsorber than dry foliage, etc. Brimbleoombe (1978) p:>inted out that dewe<wering the foliage may ",rye 10 increa'" the uptake of sulphur dioxide,

0 ....... 0.1 m !Up.Slwubo., I '" h'IJIT=.. 10 m ~'IJI

C......rcuoo> ""I .""o<l", ..".. 01..,l\cIdo; ...... _ ...

'>,­U._.,,, __N"_"~1Jr_'_1 •

'0-Modc",1<Iy~_P-D,y tn_S,,,f..,. of • """KIeotft

UIW"kc ",'e(e'" >C" ')

"""OJ_tO...."""""011

'",.,""

Ilclcre'",c

~"'tIN!l_, S,...,.,.._.... s.Jp1u<..... A-..polw".. 5<........,•19n. l)ubnwaik. V........

loot...... (191'\1)

Gall>o.I,. .... (191'\1)

16'Shepherd (1914) lias oWn'ed!iC'asonaI """"biti!) in de~liun ...loe1ll"

at OM SIIC. and both HuYl tf III. (l1l78) and .... ~.• n._ (1918) reponeddiurnal >'ariatoOns 1ft dl:posuiun 'dOOllltS ....111 n1ues In or<kr of mapfl>Ck100.(. I' nlJbt 1!wI in t'" d1~lime llIe5e Ialler mull< art in k~""'I ..uh tile,\11),,·1_~ of uomata and the decTUsoe 1ft lI,trbuknce thaI mq..enl~0CC\lB ncar IhI: unll's surf~.~ fKtor1. bodI "'inORlII and rllllflW.obouJd be raken mlO 1ttOUI11 .. ben n!l/lllun, n."n~ upukc taln,~field delCnnmauom of aMMption nICS Ire usual~ performed for limitedpeno<b and WLlJly during the <bylime. and the re""lt. do nol "'fIe<:l mean""asonal and diurnal oonrlnions.

Recent da,a. including til<, "','.,,, of all data lip 10 1977 ma<.k I' theDubra."nik meclln&. are pre>entcd III Table 4.21 Considering the factors";l'5CIIs""d SO flf....·c assume v10, - 0,8:! 0.2 em $Cc" for "-"'.' surfltts.

It i, more diffICult \0 dClcrmi~ on .~crll' vall>l: for cont;nent.1 rondllions"jIll variouS I)'PCS of underlying >urface. ranging from <no'" to humid tfOpicalforests. Possible V!IOl value. lies witllin the range 0.1-2 cm ",c- t

• For nanh.ern regions wnh lasting "inter. and arid zones, the value witt be 10"',0.1--<l.3 em $CC t For !Outhem regions, especially "ith humid climale," thevalues a", l\lih. 1-2 em "'c COlIscquenlly, "C ll>Sumc Voo:·0.6::: 0.2 em Me"' 2$ an a'"eI"3.~ value lor <:ontU>l:ntal rondnions.IndUSlrial ",pons a", main1llocalCd in moOerile IatinJdc. and a", ctlllrxter­ittd b)' .....,., III "''''lcr. n..,d,,",. 10, m,h'slnal and urban ""ions. "'"e ~Iassu.mc a V.... equal 10 0_5 ::: 0.2 em sec

In Table ~.22 lhe sulphur f111Xe'S from Ille atm<l5fl/lere d"" 10 ouJpllur dioJ­ide aMorplJool by urdcl1ling surf~ _ F"en,~:u of !be '"II!'J0U'5 "'ponsand sulpbw cbo.o.ide concenrn.tioaas ia the atmospbc",. of tile'" ",pons IlrC

lateR from Tabk ~.5. "The C2ku1ation shows Wl 11 ::: 6 TSS lur IS lakeRup 1»" tile ...rfaoe of tile ocean and 17 ::: 10 Tp l"ear is !Orbed '" !be land,,-TabIc 4_"2 Sulphu, lIu' from ,he a<moopII<'" d... 10 ...Iphur di<Jrik uptake .. the--

'"' Conoenull"", Ul'uke ".,~O< (10" m') (~~Sm') (cm sec-') (TJS~u, ')

Ocnnic zone "nbcu' bion,.e!fcc' '" 0.1,.0.03 0,8", 0,2 8",4

Oceanic ,.,.,. .. iii! bir>tl,"= " 02'" 01 0.8"'0.2 ,. ,C<>n'tnenlal B' 0.2,.01 0.6 "'0.2 '''' 3lnd....nal-"',.,.w " '''' 2

O,j",OIS '"U.... , 20", 1O 0,j",01' 3,. 2

,- 28'" 16

266 Tiu Global Biog~<x""mi<:al Sulphur Cyd~

4.4.6 Dry Oepo.>sllJon of Sulphat"

As nOled above in seclion 4.2.3. sulph31cs occur in parlicles of differenlsize depending on Iheir origin; 0.1-1 I'm for sulphales fonned in gas-phasereactions. 0,5-10 I'm for sulphales of sea salts. and 1-100 "m for sulphates ofaeolian origin. For panicles of .ubmicron size•. sedimentalion may be neg­lect.d and llle rale of dT)' deposilion is delennin.d b)' lhe lurbulence of lhealmo.plle ... and the properties of underl~'ingsurfaces. For large particles. e.g.paniel.s of a aeolian origin. sedimentalion is lhe dominaling faclor.

Where lbe partIcles are ,uffldently small so Ihat lheir sedimentalion rale isnegligibly small compa...d wilh lhe raleS of lurbulenl mOlion oflhe almos­ph.... lhe IheoT)' of uplake of particles b~' underlying .urfaces is similar 10

gases (discussed in seC\IOn 4.4.5). Thele a... , of course. differences in lhetransfer processe' in lhe immedial. "iein;ly of the surface and lhere areconflicting experimental data which suggest thaI we do not fully underslandIhese processe,. For the presenl. a simple approach using a"erage deposilion"elocilie. i. the besl a,'ailahle.

The dry deposition of .ulphate, present as suhmicron partieles in a layer ofunifonn distribulion and constant heighl can he descrlhed by the exponentiallaw

(v.,- ")c(1) - c(O)exp H - c(O}exp(-K",j- x I)

where c(O) and C(I) are sulphale concentralions al lime 0 and I. r.specti"ely;Vsoi- i. lhe lin.ar rate of dT)' deposilion of sulphaIe and H i' Ihe height of lheuniform distribution. For large particles. the picture is more complex, bUI inour ralher rough calculalion. we shall use comtant values of lhe dry deposi­tion velocil~', V~..

Table 4.23 summarizes the estimates of lhe rate of dry deposition of sui·phales given by differenl aUlhors. AU estimates refer 10 sulphates fonnedfrom gas_phase oxidalion of sulphur dioxide. From ll,is dala "'e assume a raleof dry depo,ition of sulphale. of 0.2 em sec·1 (range 0.1-0,5 em seC') inclean continenlal regions,

Sulphates existing in the marine almosphere are represenled by a mixlUreof particle sizes including larger particles than lhose fonned o,'er contin.nls ingas-phase reaclions, Nalurally, lhe average ral. of dry deposilion of sea sui.phale, 'hould he higher than lhe value of 0.2 cm sec-'. OUf estimale of lheV sci' value for sulphate, of sea 'ails is 0.5 :!: 0,2 em SO<' " and lhat for .xcesssulphale. ov.r lhe ocean is 0.2cm sec ' (rang<' 0.I---{I.5 em sec"),

When evaluating lhe deposilion ral.s of ,ulphales of aeolian origin, w'eused an averag<' residence lime of dUSl-elouds in dry weather of one 10lWOdays (zakharov, I%5). Thus lhe coefflcienl of dry deposition of aeoliansulphal• ., defined", Ihe inver~ magnitude of Ihe a"erage residence lime ofdust particlc$ in a cloud, isK..;,- - (0,6-1.2) x 10-' $C<O-I.

T~ Atmosp~rit: Sulphur Cyd~

Tabl.4.B Dry deposition rat., for .ulpbate .ulphur

RateSIze ,)f t;]'" of panick. (em 5Ce- ') Commen" Reference

AnthropogenIC 'alphal' 0.2"'0.16 Depo<J"on on "aler,urf"""

Anthropogenic ,ulpha" 1.4'" 0.• Depo<ition on I.nd.urfocc ncorSt. L:>ui'. USA

Anthropogenic .ulphate 0,47 Hunglry. ",'e'"gecondition,

Anthropogenic ,ulph.te 0' Un;led Kingdom.",'.,age condition'

Anthropog.n", 'alphate 0.2-0.5 ""

0.05-0.1 ~m

0.1-1.0 ~m

0.5 ~m

0.1 1.00,010.'

We.. lytlal,(1917)Clougll (1973)Esmen .nd Corn

(1971)Sinering" al. (1979)

h.,.tt " 01, (I979)

M."""" andVarhelyi (I9H)

Garland (1978)

Rodhe (1978)

In section 4,2.3 we eSlimaled the a>'erage altilude of lhe mixed layer ofaeolian ,ulphal" 10 be 1500;:; 500 m. Henee, for aeo!ian ,ulphate. the calc,,_IatedvalueofV""" i'L5;:;O.9cm\l:C ' .

Table 4.24 pre~n.. dalO on the ,ulphur nux from the atmo>pheTC via dl)'deposilion of ,ulphates. Area' of differem zone. and concentration' for thesezone, ar. taken from Table 4.5.

The calculation ,how, that 17 TgS }'ear-1 (range 3-48) is depo.iled dl)'into the ocean. The tolal dry deposilion of ,ulphate on land amounts to 16 TgSyear-I (range 5-47); half of this i' depoxiled in zone, of imensive aeolianweathering,

Table '.24 Reom"aT of 'ulphnr from the Olmo<phere by dry <kpo,ition of "ulphate

Sulphur n",Rate of (TgS year-')

Zone Ofea Concentralion <kpo<ilion.

"'"' (10" mZj (~gS m-') (em ...,-') A'erage Range

<Xe.ni<:e'ce.. ,ulphate ;~ 035"'0.15 0,2 (0,1-0.5) • 2-28marine .ulphole ,~ 0.15'" 0,10 0.' (0,3_07) • 1-20

C1e.n conlinental m 0.6'" 0.2 0.2 (0.1--05) , 2-17Du"y continental ,

~.O '" 2.0 U (0,6-24) • 2-23Indu"ri.l region" " 3.0" 0.5 0.2 (0.1--0,5) l , I,-,U,ban , 4.0" 1.0 0.' (O,l-O,S)

Tot.1 " '-"

,os TM Glob'" BiognJ<:Mmi<:al SuJplrli' Cyd~

4.5 ATMOSPHERIC BALfu,"CE OF SULPHUR

In lhis~lion we collale ,he eSlimate. of sulphur ill the various regionsoflbea,mospbere. ,he fluxes. and the rates of individual proce~' obtained in 'hoejnt'vious sections. The NIlan« i. based on kinetic's of tl>e fim order and timechange. are neglected, This enables us 10 determine the mi",ing ,'.lues fQrfluxes or rate•. lbe balancc is compiled for each of the different region, of theatmosphere bUI. to facilitate the 'lfll<'tur<. 1I'" reservoil'$ of ..roon and indus­trial atmosphere, are combined.

4.5.1 Sulphur Bal~ in the AtlMSphen or Industrial Rtgions

In this section the atmospheTl:s of all indumial regions are treated collec­tively. but it musl be realized that many regions. spatially disconnected. exist.lbe balance for jodi>'idull regions may differ in many r<:spcctS from thegeneralized SlrUC!"'" presented het<', see for example thoSt: constructed forNorth Europe (Rodhc. 1972a), Europe (Me"a=~,al_,1978).lIOrth..,astemUSA, and SQuth..,a,!em Canada (CAPITA. 1978; Gallo...·ay and Whelpdale.1980) and for the Donba.. indumial complex in the USSR (L~'sak. andRyaboshapko. 1978).

Figure 4.4 iIIu,trates tlte atmospheric sulphur balance for SOme major

98183-''-'' '21'0_'41 'I'·~l

h-I~", !'" iiI• 1• d .. =~

• ,H I

i "•·co·'I"

"19-Ul 21'-11 '21~-"')

FiJ.4.4 Glot>al ...lphur bal.nce in the atmosphere of indu,"ulregion, (TJS lear")

The Atmospheric Sulphur Cycle '"induslrial regions of the world, The input of sulphur is emirely amhropogenicand con,i'l' of sulphur dioxide and reduced sulphur compound. with shortre.idence tim. (113TgS )'ear~'; rangc 94-132). Removal processes ...scavenging by precipilalion, dry deposition of sulphales. and >ulphur dioxideabsorplion by underlying surface (25 TgS year-'; rang. 15-39), The un­certaim)' of lhe values for removal processes is 5ll'O. rrom the balance ,Ifollows Ihal horizonlal ad"eclion from Ihe resen-'o;r is 88 TgS lear' (uncer.laim}' 25%), Thi. sulphur enlers hoth lhe cont;nenlal and oceanic almos­phere" Let us assume Ihe fluxe, of anthropogenic sulphur to cominental andoceanlC atmospheres are each 44" 10 TgS year-'. The sulphur conlenl,n lheindustrial regional atmosphere i' 0.145 Tg (Table 4.5); given lhe lotal flux weobtain the ,,'erage residence time for Ihi' r.sen-'oir of -12 h.

4.5.2 Sulphur Balance in lhe Dust)' Contlnenlal Atmosphere

Figure 4,5 dep;cts lhe sulphur balance lor a dusty com;nemal almosphere,The only inpul here is lhe aeolian weathering of sulphur (20:!: 10 TgS}'ear-'). Removal processes are scavenging by precipilation and dry deposi.tion of sulphate (12 TgS year- L

; range 3.5-27.5), The uncertainty of removalrales is >65'1lo. To maintam a balanced condilion it foU"",'s thallhe sulphurflux from lhe gi,'en reservoir is 8 TgS year-'. This f1ux;s directed loward.thedean conrinemal atmosphere The residence t;me in thi' ,"..rvoir is -14 h.

!•! ,,

~! ,'0_' 003~ T~S To to" cleO'

_n<o r,,,. 0.6"'" ,~-

","""Ph""

! ! i., ••II i ~;

~Il~"" 912-23)

Fig. 4.5 S"lp~ur balaf\Ce in the du"y eonnnentil atm<»­ph<re (TgS year-')

270 TM Global Biog~<XMmu:aJSuJphUT Cycle

4.5.3 Sulphur~ fo. tbe Cifan Continental Atmospbert

Figure 4.6 show, the sulphur budget for the dean cominental atmosphere.[nputs are >'Oksnic emi"ions, natural f1uxe, of sulphur with shorr re'idencetime. sulphur dioxide fonnation (or H,s) or oxidation of reduced sulphur withlong residence lime: emissions from indumiaJ-regional and dusty cominen­tal sources and sulphur flux from the """an atmosphere. The last item isestimated in Ihe following way. Aerosols are transfe=d into the continentalatmosphere with lhe proponion of sea'S<lh sulphur 10 exce.. sulphur of 3 : 7(see Table 4.5), 11le flux of ,ulphate, of marine origin amOunts 10 6:!: 3 TgSand, from {hi.. lhe flUll of ex","", sulphates from oceanic 10 continental atmos­pheres is calculated to be 14:!: 7 TgS }'ear-1

• Therefore, the total flux ofsulphate sulphur from the oceanic atffio>phere amOuntS tu 20:!: 10 TgS}'ear-'. Volcanic emi>sion was estimated in Chapter 2 to be 28:!: 14 TgSyear-I. It should be noted that rone. of volcanic activity are grouped alongthe edges of continental .hield•. Hence, it is reasonable to a>Sume that onehalf oflhe volcani<: emi>sion (l4:!: 7 TgS year ') will be directed to....ards theclean conti,-;'enta1 atmo,phere. and the olher hal/to....ard. the oceanic one.The flUA resulting from oxidation of reducod lulphur i. calculated from theIOtal ,ulphur in the form of <:aroonyl .ulphide and caroon di,ulphide in theatmo.phere over continents and the residence times of these compound,. andamounts to 1.5:!: 0.5 TgS year- t

,

•.1II • ll'

JIII......,,,1--.. co, on<I cs, .....- 04' T,S "-_t~"'" ._-,-,,-, _.-",,,,,.on, _'_',''''''' -,

"-'" '_M .-,,,,,_.1._.II

!• iI !,• is'

lOIIO-'O)

"Ill-'" ~Il·m 'I".'

Fig,4.6 Global sulphur b.l"""" for the deon ron';nent.1 """"phere (TgSye..-')

·w< n<~«l lh.. ~"' in til< re><rvoir of in<l"'lrial roJion' and d""y ",,,,o.:n..1atmooph<ro,and I1tn""«d it 10 ,II< ro",,',,;, of tI>e <""n """0.:,,,1 111110,_'11"•.

The ArmO$p~riL: Sulphur Cycle mThe sum of 1"- inpul' is 103.5 TgS year' {59~150} with an uncenainty

of 45~. Remo"al processes are as follows; scavenging of sulphur by precipi­tation, ,ulphur dio~ide absorption. and dry deposilion of sulphate. The sum 01the'" outputs;' 47 TgS year" (range 31-72, uncenainty 45~), From balancecalculations the flux to oceanic atmosphere should he 56,5 TgS year" {range31~g2. uncenaint}' 45'110),

The residence time for sulphur in the clean oontincntal atmo,phere can becalculated from lhe total sulphur pre",nt (OA1 Tg, Table 4.5) and lhe fluxvalue (103.5 TgS year·') to be 1.5 days {(OAI x 365)/103,5 - 1.5 da}',),

4.5.4 Sulphur Bala~;n the Duank Atmosphere

Figure 4.7 'oow, the e~ce.. ,ulphur budger in Ihe oceanic almosphere. Inoompiling this budget u", w.s made of average (Le, the mo,t probable) valuesof inputs and outputs. Our aim was to see whether e~ce" ,ulphat.. over 1"­ocean, are the product, of ga•. pha", reactions or due to fr.ctionation of...·"'It ion' on transition from the dissolved ,tate in t"- hydrosphere to t"­aerosol state in the atmosphe'e, InpUI item' here are Ihe estim.ted volcanicem;'sion. the natural emi'sion of reduced sulphur w;lh shon re'idence time.and tran'fer of anthropogenic ,ulphur from tbe indultrial atmosphere.

The flux due to carbon)'l ,ulphide and carbon disulphide in oceanicatmosphere.. estimated from their contents and re,idence lime,. i'

" "

•,

~ IIi• ! •

II ' 0 ili- 1h ~ ~;

4 T"",••",t ~"" T".,,,,,,,, o! ,"...,..,' ........ '«en""""",'"a_p",," E«......,......... «,",.nl.O,32T95 <""'"•.,"',._.T,on, 1 "Om ,O<Inl,nenlQI

,ot"""""." , ,

• [•,, •,, , , , ~, I i ~'J,' ..

•

Fig. 4.7

~o • t1

E>.ce...ulph"' b.l.n<:e ;n the <>ce.ni<: >tm",p!ler< (TgS ye..")

Th~ Global Bwg~och~ml<:al Sulphur Cycl~

" J5 lO "0(1-l" IB-'~>I<HOlln:><>J1

. I JI I•, ipI ~ )!l II I I

T_'".",~,,,",- Coo!tn< 0'.","-" ..... ".,,, ,--T,,,,-,,, """' _. ''"'0 , 0'" -".,04..........-"'<11 ""00"'

IIII IiI. ;,'9,'

Olto-WI

no t? "".0"<>0> 1"'" (,·m

Fig.4,8 Global ,ulphur b.la",e '" (he C>Ce.nic otmospbere (TgS ~~"-')

3.5 ± 1 TllS year-'. Therefore. the mosl probabl~ input ilem. amount 10138 TllS year-L.R~moval processes are sulphur dioxid~ absorption by lhe ocean surface,

sca,'enllinll and d" deposition of exce.. sulphates. and the flux of ~'ce..sulphur from lhe oceanIC to the continental almosphere, These tOlal 123 TgSyear-I.

The above calculation cannol prcwe unambiguously the absence or pres­ence of macro-ion fractionation on tran~;lion through the ocean-atmosphereboundary. HO"'e"er, it ",ems that th~r~ is nO need to invoke any such lheOryto ~xpla", the origin of the'" fluxes.

Figure 4.8 'howsthe sulphur balance in the Ottanic atmosphere, The fluxof sea-!-Illt sulphur is delennined by balance calculalions. The sum of all otherinput items amounts 10 138 TgS year- L(range 63-213) and the sum ofremoval items i' 278 TgS year- l (rang~ 178-395). Therefore the flux of seasulphate$ neceS!-llry 10 balance lhe 'Y"'tem is 140 '" 63 TgS year-I. Knowledgeof lhe ,ulphur content in the oce.nic atmolphere and the tOlal flu, allows uS10 estimat~ an average residence time for sulphur in this reservoir ofone day.

·U.5 Global AllllOspbork Sulphur Bud~t

TIle basic sulphur fluxes inlo and out of lhe atmospMre ar~ ~ummarized inthis seclion after combining lhe regions inlO two areas; cOntin~Olal andOttanic.

mTN ArmospMric SWph.., Cyd~

From F'I- 4.9. il (01"""'"$ IMIIlIt' IOlal n"", of ~pbur into lIlie IUI1OSpbI:re0-.,,1 I&nd il; 164.5 Tp)'C"ar aDd the eM"", is 84 Tp ynr-' .... hiJe ~r liltocean. the ClDlWon is 77_~ TIS ~ur 'and relllO\-allotak 2S& T&S AllhoIlmOIphere "" ...boIe obouId be: • balanc\od S)"Sltm. if ..c il55uml: lhal thesulphur nUl< from OCCarlll: 10 rolI"llCntal'I~'" iI 20Tp year-'. tb:n

f •••!, ,

•

I,••• •• ,I ii•• 8• •g g

•,8•

••~••~•

.~,

•.51

IIlI

N•~,

..~'

1'·_ 121"'~

-- MIU-

-."• , .''''-- 310·'1........ _tedloa...____ 011

"'\1-21

• ,.____ alSO.20110-•

__01 ......'· '4iC4-30-,._....-__of""- ...

l'll-21".5"- COS.tId CS,p,to9""'... o<:c".'f"~ $1131.5-

C><, ""l>OO" .... of 50:- I6IS'~7

u~.... <II so IT(1-27)

k""..-.............t- ....u 20CO-",~-VOI<Otu< _._ 01 so. 1<0(7-20

s.c ......__ '" so.... UOIT1·

r -'_atso. .. "'2.5·HrS _ cos _ C5.I'oK I : ___""'l

~,~-- 1l1S-11l

Or,,,,,, 4_oISOf" "C}-'I)

T... .,n Map f1owoo 01 'he P>bol .....- <)'do

Robon_~nd ~..... 0_I ,,~_,.~ ~ •• .....nd •• ,-,."'. (l\llil.l) (I%~) (1%8) (1972) ( 1913) (19710) ~.,

Anlb""",,"n.. _..- ~ ~ ro " " " onVolcan.. eM'.......

", ,

""'eoh~n eM",,,,,, 'r "II"",... ",,,,,,,, ""land " ro M

1 " ""'

fl ..."' ......'" f'om hll"..1 <elli<>o< uf """.n'l ,~ I'" l~ ~ j", ,

11".,,,,..,••,, fro... "pe" oceo'" " " ~I' """.,,, 01 "''' ..I, " ~ " " " .. '"I" m",.", "I 1,,,\~·I,ved ",dL"-"d 'ulpho, , [1\1"""1••>" "I SO, h~ 1,,,,1 " " ", " " '" "W.,h·"ul ".,,, I.,K! } " ro ~ ~

.," •"

,",' 'I<f">'i'lo.m or I"nd " '" '" '" " 'i• •SO, ''''''lfpl;,m by oceo" ro " " I" " '" "W.......,,,, ''''''' 0«"" I,.. '" j" I" " '" •SOl <lefl"'l'''''' """, """.n " ,,.

•"0aIJ__ " ....,.,., '" ....- .. _mI -"",-,ale 1',n1u.r......... %>•,.-~

The AlmospilRric Sulphur Cyde

the reverse flux Irom the continental to ()Cunic atmosphere must equal100.5 TgS year-',

Earlier. in Stttion 4.2.4, we estimJled the 10Iai amount 01 sulphur wilhshort "'sidence time to be 1.35 TgS. Now, given the value of the total sulphurflux or efflux as 342 Tg year-'. we may estimate the a"erage residen"" lim. ofsulphur in th. atmosph.re 10 be • 1,5 days.

In conclusion .... compare the calculated global sulphur budget in Ihealmosphe", with budll"ts obtained by the oth.r authoN (Tabl. 4,25). Thistabl. shows that our budget agrees well wilh toose 01 olher amoors, Themajor difl.renC<'s are the fluxes of volcanic activit), .••olian "'eathering, .nd.mission of sea salts, In our opinion. vokanic .mission ".... und.reSlimated byother authoN, Usually the volcanic emission estimated was associaled v.-ilhperiodical .ruptions. while the constant emission .ssocialed with fumaroleson drift lields and crateN of resting volcanos wl\5 disregarded.

The ignoring of aeolian emi'sion b)' other autho... is reasonable since thetransfer of .eolian sulphates is n01 global in nalUre. For this reason Granat eral, (1976) considered only the submicron fraclion 01 aeolian dust. and esti­mated this flux to be only 0.2 TgS year '. For large regions. !towever. aeolian",·..thering is lhe major source of sulphur into lhe atmosphere and. therefor.,we included it in lhe general scheme,

In our v....ion of the atmospheric sulphur cyde. ,ulphur .mission Irom theocean together with sea sahs is gre.tly enhanC<'d compared 10 the values giv'enby our prede""ssors. Almost all earlier workers used Eriksson's estim.tewithoul crilical evaluation, The e'timale of 140 TgS year-' seems to uS moreprobable tlum 44 TgS year '. This is eV'ident from a comparison with the,,'ell..,Slablished value lor sulphur ",..hout over lhe oceans of 230 TgS year-'.

4.5.6 The Global Sulphur B.allllltt In lhe ~.Industrial Eno

As experimental data on sulphur conC<'ntrations and sulphur depositionlevels pertaining to lhe last century are not available. some assumptions mustbe made to estimate the pre-industrial sulphur balanC<'. The anthropog.nicnuxes of sulphur dioxide. sulphate and hydrogen sulphide should be neglig_ible and are nol considered in the balanC<'. The volcanic emission should beunchang.d and so we can use the estimate of 14 TgS )'ear" for the emissionto atmosphere over land and 14 TgS )'ear-' lor that Over the ocean. Aeolianemission mal' have undergone some changes during the la't cenlUry. a viewwhich is supported by an increased innux of salts 10 lhe atmosphe", in lbe AmiSea r.gion due to increased agricultural and other human activities. However,quantilative estimates 01 any such change are not available and thus the Duxof aeolian sulphates is considered to be unchanged (20 TgS year-'). The sameargument is used for lh. natural nux of short·lived reduced sulphur com­pounds: as no informalion is available 10 sugg.st thatthi' nux was different

'" 1M Glo/xli Bio~ht:mical Sulphur Cycle

prioT 10 the ,ndustrial period its ~5¢nl val... is IKed in the bal.ntt; ~16TgS year-'. The intensity of .ulphur dio~idc (or H,s) form.tion fromClIrtJonyl sulp/1ode and carbon disulphide durinS the ~-itldU$lrial periodshoWd ht~ ""port.nl l/wlll IS _!xca"", """'" of the c;arbonyl sulphlCkand carbon m.wphide: emouoon IS of an~nicorigin. We &;;swne 111.11thi:§ flUl[ in the pre·mdumw period ..... I T~S ~nr '0'0'(:< land. and J Tp~"U-l oYer lIlle Ott.n. BioFnIC emmoon of .aon·1tved redllted fIllphw <:om.pound< and the em;".ion of Ilea-JaII ""ph.... """"uId be ....chanIN. and Ih...the respectM: f1.....n of 20TgS ye.r~l and I40TSS )'C:ar-' are used III the~n« <:aIcubllOftJ. In od<!'lJ(lII tho~" fila from the oceanIC 10 mecnntmental.trIOmpherc sbouId be unchanged.t lOrIS year"-01 of dll: ,..narion 11'1 nmoff~appea~ 10 be mon: d,'·

ficuh. One _y assume thai the w1p/1ur dioxide ~DlrlUOn bas not

dwIgni """ the dl:an COIlllllCOlal rcpons "'hich ......... UQlI w1pbUf Iboudc:uptake by UDderlyll11 .urllCft may bie lOSS"-.:I a'I 3 TgS year-' (Table 4.22).Dry deposilion of JUlph3«: III duoty rcpms(9 TgS year") should renlaU11hcsa..... <ina ....., ha,,, no cnlScru lor. oignific.an. chan., in lleOIian em_.Willi ,"" usumpllon lhat ""nhoul anlhropoJCnic ""..ra. IhI: ronttntration of..,]pllate in the conllMnl.1 .lmosJ'hc'rc "'''' OA IS III -'''1: tin calculate ,""intensity of sulphate l'(!rlO"al by dry do:po5i1ion from rl>( dun rom'Mmalalll1OSpl>(l'( as 4 TgS ~'ur '. Thus lhe: 100ai t'(mo",,1 of sulphale by dry do:po­sition o""r land amoun,s '0 13 TgS ynr-'. To a""<S rhe: magnirl>de of sulphur~a~engingby pteeipiralion from lhe dean atmo<phen: .....e make use of rhefacts rhat tl>( anrhropogenic ~omponent is ""'" 43' of tl>( total input(Fig. 4,6). and in the pre-industrial period the regions with dean rominentalatmosphere ro"ered 143 lC 10" m' (Table 4.3). Thus the magnillide of sul­phur ....a'h-oul o,'cr unpolluted regions;" the pa5t w." probably of the orderof 23 TgS yur-'. The intensity of sulphur ~avengina in areas with dustyatm05phel'(S ,""uld remain unchanged. i.e. 3 TgS y..,ar-'. Therefore lhe nuxof ",Iphur rO land ;n II>( pte-induslrilll period obould ha"e been 26 TIS~..,u-'_

In summaf}'. il may be oonctuded rhar;" rhe ptt:_n1dUUrial period lhe IOralinnUll of ",Iphur rO rhe armosplw:re ~r land ..... 71 TIS yur and lheOUlpul .... 44 TIS y..,ar-', Thcrdote. rbt a'h=tive f1Ull of sulphur from lheo;onrincntallO rhe oceanic IllJlOliphere obould have been 27 TIS year ,Asthe rota! supply of sulphur from the oceilll amounts to 177 TCS ~~ar lhe:toW nUll from lhe: atmOSphete 10 lhe: o«an must havoc been 184 T,S year ;.

SulpbllT dio~ide uptake by rbt OlltillllC..mace obouId hlvoc tematMcl o;on­0WI1 al II TIS y",ar ,and 11 io.....mro WI rbt n:lauorMtp betw.-eeo the:"'te"",rlCS of sulphur dioxide uptake_ ~' do:poytinrl, and wastHlur of sui­pbalei in the' p""-md\lSloal and I""""nl~! periods rernamed the same, If 10,then ....,1 do:POSIIIOfl O'",r rhe Olltilll"'" 161 TIS y-ca, and dry depllSllion......, 12 TgS lur m lhe: p""-IfIdU51nal period_

TM AmwSpMric Sulphur Cyd~ m

Figure 4.10 presents the global sulphur balance for lhe atmosphere in lhepre-industrial era, A romparison of Figs. 4.9 and 4.10 sbows lhe markedchanges Ihat have laken place in the !/,Iobal almospheric sulphur cycle underthe impacl of man. In lhe pre-industrial era lhe lotal flux of sulphur to theatmosphere appears to ba,-e been of lhe wokr of 228 TgS year '; (he present"alue i~ 5'"' grealer. Abo in the fonner period lhe <:onlinental and ocean",<:omponenl~of the aUt>C>5phere were approximately b.alanoffi, whereas al lhepresent lime lhe ad,..ct;on of sulphur from <:omincnlal 10 oceanic al""",­pheres is fi"e lime. the flux in lhe re,.."" direclion.

The changes which ha"e occurred are especially marked in the atmosphere

, ,> >• •• •• ,, ,• ,I ••,~

••; I,• •i l,

, J

, J

"113 I ::

"1" oo

, en", '0"""'. ° ,,-

Aoe"•••m'..' .... 01 SO.

N.""". .m'....".! , .."_,,...

r'".". ,.1,.,,,, 'Ofmelien of So. oM ><,s•• trom COs ."" CS,0

SC.""9'''i I>y pr,,,p,!OMn of

scf.-, SO,Orj <!fpo"',,,,, 01 50:-

UpIO" ~y ••'!oco o! 50

AMOI .m"..on 01 .~o,t-I< •• ~r.d"".. ...lfII1. r

Velee"'" 'm'iS,on efSO

,-Soo IIOlt.m"..." el SO.

'o'mo'i"" ef SO . <.I'em COS ,n" CS,s.co..ng," bj p""o,lo',on ofS~-, SO, ,-£)0-. "PO"'''" of SO.

UPI'" by ...d.ce 01 so"

"Fig.4.10 Global atm<>spoheric bala",," for the pre,indu'lfial or' (TgS)'U' 'J

~ Global Biogeochemical Sulphur Cycle

o,,<,r land: anthropogenic emission "'p""...nt' about?~ of the lotal emissionover land, and may account ior mO'" than 95~ of the ~ulphur emilled into lheannmphe", of industrial region~, Mmt of the anthropogenic emis~ion is "'P'"'sented by sulphur dioxide which can be oxidized 10 sulphuric add. A' the'"t,,·o compounds a", extremely ",acti.'e they h3''<' a g",ater impact on theenvironment compa",d to natural compound~ such a~ sulphate~ of marine Oraeolian origin.

4.6 THE ISOTOPIC CO...IPOSITION Of SULPHUR L'Io: THEATMOSPHERE

The isolOpic composition of sulphur has been used with some ~uccess 10delermine the source, of sulphur emissions to the atmmphe",. Two of theearly studies (Ostlund. 1959; Jensen and Na~ai. 1961) were de"Cled 10 the<;ource of sulphate in rain and snow. and later papers (e.g. Cortecd andLonginelli, 1970; Dequa,i and Grey. 1970; Rabinovich, 19?1; Holl eI al..1972; G"'y and Jensen. 1972; Ca'tleman el al., 1974; Ludwig, I976; Chu~h·roVel 01.. 197]) gi\'e examples which sho" how sulphur i<;otopic analy.i, canbe applied 10 determine local source, of emission, These slUdies (some ofwhich a", summariud in Table 4.26) show thaI tbe J"S value' of atmmphericprecipilation and aerosols "arr 0"" a wide range. and it has been concludedlhal rain-water sulphate is depleled in ''S wnh respect 10 ",a_waler sulphale.This effect is mo", pronounced in industrial are.. (compa", the reiults forindustrial versu, non-induslrial ",gions; Jensen and Na~ai. 1961).

It i' evident that se.'eral sources may affecr the isotopic composition andthus several examples are discussed in detail I<> 'how how this technique canbe u",d in source idenlification.

Sy,lematic invesligalions of sulphur dioxide concentration and isotopiccomposilion in the air near sour-gas pro«~sing planls in Alb<:rla, Canada.have been carried out by Krou... (1974). The sour-gas "'ells of Alb<:rta a",used to produce elemental sulphur; pan of lhe hydrogen sulphide i~ oxidizedto sulphur dioxide which is reacted with more hydrogen sulphide to yieldelemental sulphur, During lhe process mo", lhan 1,2 X 10' gS day-I. mostlyas sulphur dioxide. are discharged into the atmmphere (Krouse. 19?7). Dataobtained since 1971 show that tbe sulphur oxides in the atmmphe'" have ,s''Svalues which range from +5 to +30"1... "hleh is in the ,arne range as thehydrogen ,ulphide processed (Krouse. 19?7). Krouse (1974) concluded thatemissions from different plants do nol mix well o\'er a large area and that theisotopic composition of the sulphur dioxide in lhe air depend' On lhe I}'PC ofraw material proce,sed and the wind direction.

One e..mple of the "ariation in J"'S values and sulphur concentration inthe air of the Ram Ri.'er ",gion i' gi.'en in Fig. 4.11. The histogram of d"'Svalues. which are related to lhe sulphur dio~ide concentrations. ha, two

TM AmwspJuri<: Sulphur Cyd~

Table 4.26 lso'opic rom"",i"on of 'ulphu' in prttipitation from differen' repun'

Isotopic romJl"<i1lon(6"S, "1011)

-3.2to + 7,3 +6.0-12.3'0_15.6 + 14.0_4.2'0 +8.6 +6,9

+39 to +7,6 +5.8·3.010+21.6 +10.6

-2 1 to +3,7 +3.2·3.6to ... 4.6 +4.1-S.6to +~.6 "6.9-3.8to+12.9 +7.2_0.7 to -2.4 ·0.7

+ 10.0·3.8'0 -6.2 ·4,8·1.6 '0 +5.9 +4.0

·5.1 to ... 5,7 +5.4

·2.8'0+11.3 +7.1·32'0 +8.2

Region

Ital)

Japanindu'''iol region'oon·indu",i.1 region'

Sa~halln .nd V1odi.""okregIOn

Magadan "gionSiberiaKaukh".n

<tewe "gion'mountain 'qpon,

Kirgizia. mountain,Tadzhiki"an. mounTain,C.",,",u,. mount.in, TlCar

TIC" ElhrusKol. Penin,ul.Moscow aoo Novgorod

,e8lOn'Ural,

RoSlo>' "gionS,,'eden

Range

-I to +3

Mean

+2,0 Conecd and Long,nell;(1970)

Jensen and Nakai (1961)len..n and Nokoi (1961)Chukhro' " ai. (J 977)

Chukhro",' al (1977)Chukhro>' .. ai. (1977)

Chukhr"" .. ai. (1977)Chukh"" " ai. (1977)Chukhro,,, ai. (1977)Chukh""" ai. (1977)Chukh",'" ai. (1977)Chukhro'" ai. (1977)

G.v",h,n and R.bino>'ich(1971)

Rabin,wich (1971)lensen and Nakai (1961)

pe.k" For high ,ulphur dioxide concenlration. the predominanl J'''s 'alue isdo"" to + 20"/, which was t\ plCal of the emiss,ons from Ihe naturai·gas proces­.ing plants. Howe,«, during a period when atmospheric concentT3tion' werelow, J"S values differed. oflen consideT3bly. from tho"" of the indUStrialsource ,uggesting the existence 01 another source, The ""rond peak, withvalue + 10'/00. "'3'l con.idered to be due 10 a biological SOurce,

Significant anthropogenic ",Iphm i, oboerved in the almo,phere neaT Ore.prOttssing pl.nt', The results of 'uch a study lor Salt Lake City (Table 4.27;Dequa,i and Gre)'. 1970; G"'}' and Jen"'n. 1972) show a di'tinct differencein the isotopic composi'ion 01 1M almo,phere sampled belore and duting astrike by tM smelter pl.nt wotk~ts. Outing normal plant operation theisotopic composition of the sulphur In air wa••,milar to that in the "",~h~r

plume. Studies mad~ during {he strik~ ,bowed isotopIC values wilhin {he ran~01 biogenic sulphur. Howe''Cf. differ~nt valu~. Wefe obtained for the atm",.phe..s on different sides 01 the ,tud)' .re•. ResuIt~ from one silk ",,~m~d 10be due predominantly to bio~enic ,ulphur, but thoile On the Olher ,id~ .ug.

280 The Global Biogro<:kmi<ol Sulphur Cycle

•

•

••

• •

•

°O}-~~-~'O'OO,".:-~~~'o','o!~ ~,

m~ SO, 100 em OOj

Co"'en' and ;",'opic compo'ltoon of ,ulphur in .i,R,,'., region. Alben. (Krou",_ 1974)

.,

Fig. ~_11

""'" R.m

T.ble 4,27 bOlOP;'; compoSItion for ,""urce. of 'Im"'pOe';'; .utp""' in ,he Salt L.hCity are. (Orcy and )on""n. 1972)

Isotopic compo;ilion(6"s. ,,,,j

Sour"" Range .\l..n 51aodor<! de,'ial;""

Automobile exh.u"Crude oilOre.. Salt L.keStream<Biogen", ,olphu,Pre<:opl1.,.,n

I>O,m.1during "rikocontrol"

Air ""mpl.'normalduring .trike""n'ml'

Smeller em,,,ionCop""r Ore

"'10,310+17.0+4,3'0+11.1+O.Sto +8.7

-1.510 +~,3

+4.7'<> .6.5-8.010"10,2

-1.010 +3.1+~,OlO +7.5_8.0'0+10.0-3.8'0 +3.4-4310 +2.4

~ 15.1·16,6+l~,3

+9."+~,3

-L3-6.0_9.0+1.0

0.0

0.'

""U

'0

0'0'0 .•0'M

'C"""ol ",mple' ~ert roli«..d for from the 10<:11 "'",,:« oI,n'hr<>pot<ni< orism

The ArmospMrit: Sulphur Cycle

gested a mixture of biog~nic mlphur (-90'") "jth rrfinery ~ff1~nts andautomobile exhaustS (-1~).

As m~ntioned above, the precipitation from industrial regions of Japan had6''s val~s which a"eraged +6"/00 (Table 4.26; Jensen and Nakai 1961),Usually. tbe sulphur IX'llution of industrial countries is associated with theconsumption of coal. but the "'idely dilfering 6"s "alu~s of thoe precipitationand Japanese ooal (awrage -18 /",,) suggest anothoer ",u=. This ",u= maybe the large quantity of Persian Gulf oil (6"s - - 5'/~ ) used in Japan (Tbodtand Monster. 1970) "hich pr<wides marr than 60% of the total an·thropogenic emissions to the atmosphere (Ryaboshapko and Erdman. 1978).

The data presented suggest an intensi.'. local effect of anthropog~nic

",u=s on atmosphoeric sulphur, but an aerura," assessment of the an­thropogenic contribution can be made only if information On the i",topiccomposition of all IX'lIution ",urees and the amounts of sulphur emillW tothe atmosphere and d~po>ited in precipitation is a"ailable.

Sulphur emission by natural processes such as aeolian transpon. sea-saltspray. and biological acth'it\, has al", been studied to explain thoe "'idelydiffering 6"s values in precipitation, e.g. the "~'1'Io.... val~s found for theCauea,u, Mountain' ( ... 0.7 to +2.4) whicb cannot be amibuted solely toanthrolX'genic effects (Table 4.26),

Rabinovich (1971) analy~d 62 samples of rain and Snow from thoe Rostovregion and found that the 6"S ,'al..es for sulphate (_ ... 7°/<») did not dependon thoe type of precipitation. the time offall-out. or the direction of air mo''C'ment. He condud~d from the closeness of the 6"$ val..e' for precipitation andsoils that the ,ulphate in th~ lower layers of the atmosphe", "'a, principally ofaeolian origin. Chukhrovel aI. (1977) took the oppo,ite "Iew and suggestedthat tbe dosen~ss of the val~s was d~ to the fact that the ",il sulphur "'asden.'~d from the atmosphoef'C. ThIs vioewpoint would not explain thc diff~r·

ence in isotopic composition of the precipitation from Siberia (+ 10,5,,/00).Kuakhstan (+3.2'/00), Or th~ mountainous f'Cgions of th~ Caucasus and thePam~.

In an allempt to understand th~ processe. "'herebj marine aetmOls oftenhave a grea«:r sulphur: chlorine ratio than tMt found in sea-"'ater. Lud"'ig(1976) analy~d sampl-es of air taken frt>m the San Francisco Gulf region for.ulphur isotope composition. His results show that unpolluted marine air hadsulphur i'iOtope ratios that "lore significantly k""er than those for sample••ubjeot to urban pollution, The 10'" iSOlOpol: ratio of marine air could oot resultfrom a mixture of sea-"'atu sulphat~ and pollutan, sulphur beeauSt lheSthave higher isotope ratios (Fig. 4 12; Ludwig, 1976). and thus il is possiblethat the marine air aerosol material "'as of bacteriogenic origin. Ht>...ever,unlil more information i' available on the isotopic composition of biogenicsulphur ~mi!Sion these results cannot be used to determine the imponance ofthis source,

1M G/obQl BiogeocMmical S""ph", Cyclt

... ..• %0'"' ~,ool."$I,ot". 00,".1..Non_ .'ou~ O.'O.ot

•";':=~'='t;::-~:,_S'''''U'IfO'l OfoOI,,... ... ... ... ..$I,0Iu.1I0900"ocl••I. .. Non-.'ou~ 00'0'01

.. ... -(01 OeSER~W

• •l~l TYPICAL (S"",," O<Q"o.i oM GfOy, '970)

8oc'O';OQon;,

:~==:":':'=:~olton;, SO,

P,,,o","'"

NoT"rol 90' --:~:::::.. _Cool

500 ....0'.'-

_I' -'2 -fO -8 -6 _. -Z 0 2 • 6 8 '0 12 ,. '6 f8 20 Z2

&"5. '1••

Fig. 4.12 lsotopi< romposilion of ,ulphur in air 0'"'' the San Francis<:<> <:0.0."(af~r Ludwig. 1976)

Another oompkx problem ;s the determ;nation of the oontribution to theatmosphere of biogenic sulphur lrom continent'. At prescnt no data arc"'ailable on the isotopic composition of ,ulphur prodlJCed during sulphat."'duction in soils.. ~...-amps.. and f",shwalcr bodies,

ACKNOWLEOCDIL'TS

The anthor gratefully ac~nowlcdg.. the advitt and assistance of H. Rodhc,l. E. Galbally. and J. P. Friend during the preparation of lhis eh.apter. and lheli,erature scarch made by D. l. Grigo'}'an.

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Andre.y. B. G .• and RorlIko'-,." G, (1911) Slnd~' of cbem...1 rompo<ition ofp..ciplt.UOfI 0"" ,he Far E.". In: S,.""",i< M'rMro/Qv ""d Am,IoV'. \'01. 32.Hydmme'eoildat. leningrad.l'P. 213-227 [in Ru»i>nl·

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Anej" V. P" O".rton. J, H.. Cupm. L. T.. Durham. J. L. ••nd Wd""n. W. E, (l919b)C.rbon di.ulphide .nd carbonyl .ulpoi.de lrom biogenie <oum:' .nd tllei, """lri·bution> to t'" global wlpou, O)-ck. SalUre ILend),. 281. 493-496.

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Beilke, S. (1 %9) ~c Ergebni... liber dao Au.·.....,l><n otmr><phar""ber Spurenll'"und Aerosok, A , M~l<Orolol<it. ~o. 4. 122-125.

Be'll. L, S. (1947) ClimllH ~nJ Vit. G.ograpoizdat. M<>«<>w. 242 pp. [in Ru..ionl.Bna"a. S. P. (1978) Orpno<Ulln, emiMion. [rom indumial ,",urco>, In: Nriagu. J. 0.

(ed.\. Sulfur;" rh< &""·on....nt. 1'1, 1, Wiley. ~cw Yort. I'P. 51-83.Bolin. B.. ."d Pc""",. C. (1975) Region.1 disper>ion and <leposition of at""""""ric

poilu""''' "'itb particular applicatioo '0 .ulfur poIlutio<l o''Or u'.".m Europe. Te/·/w. P. 281-310.

8ouere•. L. C. S.. Adam•• F. Cn I'.incbe,tcr. J. W.. Onini. C. 0 .. Nel""n. J. W.•D.hill. T. A .. and La-o-·"'n. D. R. (1977) Sulphur 000 beo,)' metal' in South A",.ri­can urban and nonurban .tmOopl><re'. 5pt<:;,,/ En",ro","~ntal R~po". ~o, 10. P. II.WMO No. 460. Gen.va. pp. 102-108.

Breeding. R. J., Kloni•. H. B.. Lodge. J. P. Jr., Pat<. J. B.. Sbee.l.y. D, C.. Englert.T. 11,.. ond S<a~ D. R. (1976) Meum.men" of atmoopberi<: poilu,",," in tbe S'­Loui••rea. A"""•. E"';"'n" 10. 181-194.

Breed,,,.. R. J.. Lodt<, J. P. J,. Pot•. J. Bu S....oIe)', D C.. Klon,.. H. B" Fogle, B.T.• Anderoon. J. A .. E"glert. T. R.. H..,."",n. P. L.. ~I<Betb. R. B.. Mo,-,-u. A. L..Pout<. R.. and W.rtburg. A. F. (1973) s..:kground trace II" col>C<ntratioo. in tl><""",,,,I U"it«! Stote<, J. Grop""', Res.• n. 70S7-7064

Bremner. J...,\., and Ste.k, C, G. (1918) 1I,0le of microorpn'>m' in tl>< at"""l'!>erie,ulfur cy'Ole. Ad", M"""b. EroI,. 1. 155-201.

Brtmblecomt>c:. P, (1978) ·00"'· ••• ,;nk for ,ulfur d;",lde T~II,.,. JO. 151-157.Broc,!lkl. Yu. N. (1917) Sourer. of 'ulfur dio:"d••m,,,ion to ,''' ""'''"1'1><.. In:

ROlJOn;"s and C"",,01 ofInJ,.,rrltJJ £",Wio", to,~AI_'p~",H)-drometeowlat.Leningrad. pp. 34-36 {m R.......,,].

'" Tht Global Bk>gw<:~mic,,1 Sulphur Cyd~

B,omf..ld. A, R, (1974) TI>c dqlo>ition of ,ulphur in lbe rain",.t•• in ~ortbem

Nigeria T~IIUJ. Ui. 408-411,Brm..,. C. (1978) W".,-solubk ,ulphur <o"'pound' in .erosols. Almo'. En.iron,.

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world oceans. OktIUWWS'f"'~' No, 5. 835-841.B..u"kh. S. V", and Kulik. E. Z. (1967) V.na'lOn of the sail <ompooj,jon of """.nk

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Bud",". M..•n<! Gw'glt. H."W. (1971) Ein Ikitrng zum .tmo<phiri>d... n S<h"del.hau,h.1t iibe, dem A,lan";;. 'Motto, Fo=hung~rg<b.• Roih< 87. 71_77.

a_oberg, E..•nd Lrng....). Cli. C. Jr, (J 979) Lc"el' of .mmonium. ""Ira,.. chlodd<."kium. and sodium in <now and ice from sou,hem Greenland, I. Grophj'J. Res.. 84.170S~I709,

But'her. S. S nd Cha,lion. R, J, (1972) A" imroducoon '0 Ai, CIoi","")" AeodomicPress. Ne York. 241 Pr,

Codle, R. D, (l97~a) Volcanic emis.ion. 01 halide. and sulpour compound. to lhe,roposphere and sua",sphere. I. Grophy•. R,,-, 8(1, 16S0-16S2,

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Codle, R. D., ~,>her. W, H.• Frink. E, R.• and !.<>dge, J, P. (1%8) p.nicle. in th<Antare'ie atmo>pllere. I. A'"",s. xi" 25. 100-103.

Cadle, R. D., and Gram•. G, W. (1915) S'roto<pheric aerosol pani,de. and ,h<iropueol propertJe'. R..,. Spa« Ph)'J .. 13. 47S-501.

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CAPITA (1978) Bud~' 0fMon.",ad. Sui~hU1'. \'i'ro8"" on<! HJdro~" 0.,<,,10< E",,·<Tn US and SE C~n<WlAi"Md, Cen're lOr A" PoUuhOn ImplK"l and Trend Analysis(CAPITA). W"hm~ton lIni'·enity. St. Loui. N 63130. 38 pp,

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Chamberl.in. A. C (l9S5) A,pee,s of travel ond deposition of .."""I and .'opourcloud•. AERE. HP/R 1261.

Ch.mberl.in. A. C. (1%0) A,peets of the depo<ition of radioacti.'e and 011.,,, go",•• nd partiel... ), Ai' Pollul.. 3. 63-88,

Choni. T. Y. (1979) E,"m'le of 1I,e con"e"ion rate of 501- from ,he Do Vincifi'gJI1 da ... Almos, En'i'em.. lJ. 1663-1664

Chukhro>. F V., Churikov. V, S.. E,milo,·•• L. P...OO Nook. L. P. (1977) [SOlOpecompo<ition of atmo'pl>eri<: sulfu' .nd its p""ible e"olution in the hi>tory of theEonh. h>. Akad. -"auk SSSR. Suo Grol.. No.7. 5-13 [in Russiao].

Chukhrov. F. V.. Ermilo,·o. L. P.. Churikov. V. S...nd No'ik. L. P. (1975) Onbioge""hemi'1fy of 'u1fur i""ope•. Jw AW. ,Vauk SSSR, &,. G<OI.. So. 8. 32-48[in Ru"'ian].

Chung. y, S. (1978) Tile dl"ribulion of atmo.pheric ,ulf.,.. in C.n.do .nd it!ret.tion>hip to Iong.r.nge ,,.n,po't of oir pollu..n". A,mos. Environ.• n.1471_1480

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""mpound'. N"'urt: fLo>u!,). 28-1. 330-331,Cragin. l. H.. H."on. 1>-1 M.. L->.ni"'ay. C C Jr..•od KlolKla. G. (1974) In,.,­

h<mispllori<: rompo""", o/eh.ng.. in ,I>< ""ml""i'ion of a'mo<pb<ri<: p....ipi'.'ionduring tb< 101< C<nozoic .ra. rape' p,...ntod a' ICSV'SCOR/SCAR Conf.",,,,,,,on Polo, OCO..... Mont..al. ~la~' 1974.

Cronin. J. E. (1971) Recen' >oleani"" aDd 'h< OIrarospbo ... Sco,,,.. (WaUl. D.C).U2.847-849,

Cru'lOn. P. J, (1976) 1h< """,i\>l. 'mpo"a""" of COS fo' ,I>< .olfa,< 10)'<' of 'ho",a,ooph<'•. Groph)'l. Rn Un . J. 13-76.

Cru""n. P. J.. H.id'. L. E .. Kro.no<. J, P.. PoIlo<:k. W H...nd Soi~r. W. (1979)Biomass huminS"uo= ofa'''''''phon~CO.H~ "',0. 1"0. CH,O ...d COS.NMUrt: (Lend.). 281. 253-256,

Collis, C. F.. and Hinchi<,. M, ~l. (1980) A,mosph<ric .olfur: n01urol .nd m",,·madoSOurc.., A_I. En,'i"'n., la. 1263-1218,

D.n,I",·a. S. T. and O<rga<h)'o,'•. 1'1 F. (1977) A......,..n' of.",,,,,,,o '0 ,I>< atmo>­

ph<'. from ,ho"".1 I""'·.r , ..,ion., In: Rtut: Soiling ""d Control of I>u!WiIrWl Emu·lioM JO rIlL AllfWlpNr-t:. Hydromoteoinlat. Loning~. pp. 37_03.

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Davie•. T. D. (1979) Di_I,.d .ulfur dio,ide: and ",Ifa,< in u,ban and ,ural prccipi­ta'",n (Nonolk. U.K.), A,,,,,,•. En","'" .. U. 1275-128~.

D"i•. D. D...nd KI,ubo'g. G. (197~) Atmospl><ric ga.,p~a .. o'ida,ion mo,han"m,lor ,I>< mole<ule SO,. 1m. J, C/oom, Kin.,.. 7. 543-556, Oi.."""",: 641-652,

Da,i,. D. 0 .. Smith. G" ,nd Klaobelj. G. (1914) T""'" gas an.ly'" 01 1"""" pi.ntplume' via aircraft me ••oremen'" 0" NO, and SO, ,I><m;'uy. SCO'..... (W..... ,DC). 186, 733-736.

D"is. D, D" He.po.. W" Phi~n. D., acd MeG«. T. (1979) BoundOJ)' 10)'<' mea"'",·men" of 'Il< OH raJ...1in ,II< ';",nlty of ... ;"'lat<d 1""'.., plant plume: SO,.ndNO, <I><mical ""n.-.nion ,ime,. A_., En.iron.• 13. 1197_1203

Delma,. fl.. (1979) Sulp~.'e in pol.r "",y, and io<e, Pro<. Im<m, Sympo.ium onSulphu, Emi>.sion. and the En,'iroomon'. London. 8-10 M.y 1979. Soc;""" ofChemic.1 Ind""Tj' (UK). pp.72-76.

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Doqua,;, H l.. and Grey. D, C, (1970) Stabk i""ol"" .ppli<d '0 pollu'ion "lId;e •.Am<'F. LtJb. ~.. 19-27

Dlugi. R.. and Jord"". S. (1979) Forma'ion of "'Ifur;" acid "nd i" .olla,<. on ..m",1pan;,,~, l»' e.tall~ic rea<tio"'.i. Aerosol Sci.. 10. 190-191.

Dotonin. A. K (l97~) Chem..al rontpooi'ion of til< our/Oct: ""'..- '" 'bo ."'. ofVMlO~ "a'ion and along 'ho rout< M'my-Vootok. In!mn""ionny Bull. So..."koiA"wkficl",k"j EkJp.tdinii. 91. 61-68 {in R"'''''n].

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Dro"",. D, p, (1%0) Acc<:>,oon of .ullur in tho '"o".-aler at Perth and NedJ.nd,.W.".m Aus'rali•. l.R. Soc. Ww, A"",., 4.J. 81-82.

Drozdo... Y. M. Pe'reochuk. O. P.• 5<le...."o, E, $" and S,-j"ov. p, F, (1964)ClU'micol IAmpo,iliOn of'lI<! Atmillpl,uit: FolI-QUI 0"" 1M t"umptan Pa" of Ih<USSR. H)'dromeleoi>d.t. L<:ningrad. 242 pp. [in Ru....nJ-

EAJ (1974) Q""/i'y of 1M Environm<nt in Jopan. Envi",""",nt Ase""Y of 1'1"0_Tokyo. 269 pp,

EIi.,,,,n. A. (1978) 11>< OECD study of kong ..nge tramport of .i, pollutant>: long...ng< tr.n.port modelling. Almo.r. En'iron.• 12. 479_487.

Eli..",o. A" and S.l,bo"",. J. (1975) De<'J' and trtm'formation ,.,« of SO,_"estimated from emi''''n data. lraj<owrie' 'nd m.asured air eo"",ntrat;';'n;. Amw•.E.";"'n" ',425-429,

EMEP (l9~OJ COO{HTa'i," I''''g""",.e pT Mo.iro"ng and Evmuaoo. ofril< Long.,an&< Tromm"";,,n ofAi, poJlwo"",;a Europt. Swnmary ReI"'" Cb<m. Coordi...,·in~ Centre for Ihe Firs, Pha.. of EMEP. No",e~ian In". Air. Res, EMEP/ca::Report No.4, 45 W'

Enger. L".nd H6g.,,6m. U. (1979) Di,persion ,nd ~'e' depo,ition of ,.Ifu, from'p""'er pl'n' plume. AmwJ, Ea"iToa.. 13, 797-~1O.

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Esmen. N. A .. and Com. ),-/. (1971) Residence time of particle, in urban air. Amws.Enviroa.. 5. ~71_57g

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Farlow. N, H" Snol'ingeI. K, F" Hay... D, M.• Urn. H. Y...nd Topper. B. M, (1978)Nil"'~n-sulfu, rompound' in stralOSpberic .e",,,,I,. J. Geoph,-J. RtJ.. 83.6207-6211,

Farwell. S, 0 .. Sherrasd. A, E.. hck. M. R.. and Adam,. D. F, (1979) Sulfur oom·pound, vol.,ilized Irom ",il 01 different moi'lure oonlenl, SoU Bool. BUxil<"". II,411_41~,

FeoolOv. S. A.. Khreoo". A. P.. and Chirkov. A, .\1. (1976) G",al fi.,ure eruption 01the Tolbachin,ky vole.no in the Kamchatka in 197~. Dokl. Aklld. Nauk SSSR. 1:18.No.5, 1193-11%[In Ru,,,an).

1M ArmoJpMNC Sulpl"" C)'cI~

Fen, W. (1961) -,_;' ,_ 0-. l>1a. "'-'. ))6 pp. [ill R<miaaJ.F~r. 8. E. A- (1975IThr Ioac '*"I<" ltUIlopOftoioulphut d..."':k. A_. £,0....-..

t,I06J.\O'71l,F1OIIo<t. B. E. A (1971) n.e ........~ of """ IlOna AIpImr dr__ .. E_.."-u-.. U. 489-501.

Fioho•. '" H_1..odF.J P_ .... artbarJ. A. F."" """".J B (19611) F__01_••moopht""..- poe>" Antarno<::L £,00_ Sd. T«-'.l. 46-t~,

FJd:l B_ 0Ild Onar. D. (1975) Dnft ..pon... dot uP"""""'" piDe<I ill dnt..__01..,....,.. 01 SO, ..._, IN EEC. 0..:-... E" \lOP. I R.ll. Gaoe.... 1'9J..roat)'. 1975

Fl)l!t" H~ ud Fe J (1\1'6) eo..,,,.- of ouIph.... dIo.... t/If< .UIlOSpl>Il~

F""""", Z A a...... m. ~\I.-.lOO.

A)'F" H.• H..>dam. N z.. ttao"",. K•• M..S" W J. Wolter, E. G.••1Id liopa....W, (1916) The back""ur>d 1e'''1 of II>< mer lropoophon:: ..n>tOl. wlp/l\ll' d;o.-ide and ozone 0""' O....,nl."., aDd''''' Nonh A,Ian,., oc.,.".I. A.wn()i. $.:i.• 7.103-140.

Fornin. P. L Fom,nl. O. G .• and l...u.orova. R. p, (1977) Sulfur 11w< frnm 'bt .,_pb<.. in ,he Moseow Region. Khjm. Sd',k. /(/11)<" No.6. 29_31 [in Ru..ion].

For,..'. J.. O.rber. R.. and l',,,'m.n, L (1979.) Formamn of sulfa,e, .mlllCl"'''''ODd mira.. On an oil·fired po'O'" plant plum•. """"s. E",';"'''., IJ. 12~7_

1297.Fo".. L S<h'Ul'l. S. Eo> and ~...-.n.n. l- (19M) (;oo...1"!ion of .u1fu, diMicle 10

sulf duntl. 'Il< Do Vn:i flip". A_. E"._.. U. 1~7-167,

FtaDcio. A. L Du>bufy. J, M., *"" Alu,andot. M. (1975) Formohon of "OIotilootptIit pt<><luct, in ... llOdet __ II. MeIabolMl of ....--.ado. So<I&oL 1JiocIv.... , 7. 5l-~.

Fnod'ando•. S. K. (1918) A ..' .... of til< dyumaof ...Iph... <onlUlUl& ..roeob."-. £,0.-.-.. 12, I 7-195

Fti<ud. 1. P. f\966) """"..... of '100 stnlUlphtiK .......... T...... II. ;J6S47).fn<D<l J, P (1913) Tbt P>tW -... <)de, Uo~ S l (cd.). Olio "1~/*

~.u j \ '", P1en__ ""'" YOO't. PI'- In_ME.~. I E. (l9U) Gao ltanI06e. _ til< Eanh"..toot Ab,~.. I'"

329-339GahIr,l. E.G~ J A_""" w-. 'I J G. (19""9) Sulf\lr "lIUle tr- ,10<.u It .. by I;m-$r _ brmbnd.. ,_ (l.otr4.I••. 49-50.G21.....~. J ,,~ """ "'....Ipdak. D, .\.I. (1980) A.n"""""'l'kri<: IUlfut bCp'''''~'" "onh A_nco.. A..-, £,0.""",.. 14, 4(I9-oll8

Garhnd. J A (1918) Of) """ ...., ........-.1 of ...."".. ftom 'boo .tmoopbt: ... A_I£,0",I'0/Il.. 12, J..t9-362.

G4rllnd. 1, A .• ond 8 ...n"",. ,. R. (1976) The mil"" he,p, on<l ""'.. bol.""" of SO,.. ,he """",ph<", .bo... Gte., Bri.... , A,,",", t;;"",,o" .. 10. 353-362.

O..ri"i •. A 1.. and Robino"ith. A L. (19?l) Pooibili~' of u,. of ,,,Ifo•• 1"lfut;""ope compo."O)n i. n..ur.i ....,.,... """pectin, in<lex of ,be: I')'t". ore forma',"'. In ,he Middle Ural., CWkh""';'o. 7. g7)-g7S lIn RUSSIan].

God,,;,... B, t (1979) .\ko,u..menl of ,to: SO, lMckl"'un<l coDCOn'rotion, in 'Il<o,mt»pborie ait In ..........""',. from indusui.t "'"'" ... In: Prowe'_ olINAsmo""".. from Poll"""". Abd. ".uk Li.h. SSSR. lnlli,u'. of PlIyoa. M~",",.V~nl"" "0 S. PI' 7&-84lin R....w.!

G«qil. H..... (1970) (;oo'fillu,i<>n lO tlIo: o,..-pbe'" lUll'''''''' -1"" J, a.",..r.u.RD.. 75. 2365-2371.

GtorJii. H .... (l978)~ <010 opwaI ud lO",p:ont d'''l1b'''''''' of >uIf\Ir ........~"'-. &-..12.681--690,

Th~ Global Biogtodumk:al Su1ph~r Cycle

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Go""h\;o. B. B.. Zaiuev. A. S...nd N...",n\;o. V. Ya. (1%8) Me'OOdie probl<m'ofatmosphe,e pollution in''''<l;gation u,;ng helieoptn In: Almospilt,.;., D;ffwion ondAir P"lIwlOn. Hydrome,eoWl... Leo,"g:rad. pp, 85-92 [in Ru,,;an),

G'ahovsky. Fl., I (l9S6) A"'IO.piltric N"d'i of Cond~n<Olion. Hydrome'w;,d.,.Leningrad. 164 pp. [in Russi,n].

G.-aedel. T. E, (1979) Reduced 'ulfu, emission from ,he open oce .... G'''phy•. R,,­Lell. 6. 329-331.

Granat. L. Rod!l<. H,. and Hallberg, R. O. (1976) The glob.1 'ulphu, C)'de. In'S,.n""". B. Hand S6de,lu.d. R, (ed,). \';Irog,n. pluMpho'''' ond SuI­ph".---GI"bal Cycles. SCOPE Repon 7. Ero/. Bull. IStockho/.m). 22. 89_1 34,

Gra..... oors,. G. (1975) The ,ulphate component in aerosol >ample, over tile: NonhAtlan,ic. 'M'In>' Fom:hunl¥''I!eb.. Ser. 1:110. 22-31

G",·enho"t. G. (1978) .\lari'ime 'ullale Me, ,11<: Nonh A,lantlC. AlmoS, Env;",n,.12.707_713.

G'a"enho"t. G .. Beil\;e. S.. Be". M.. and Geof~i. H.·W. (1980) Sullu, dK>XIde.b>o,bcd in .. in ,,-.ter. In: Hutchin"'n, T. C .•nd HOI". M, (ed'). E~1S ofAcidpr«ipitolion on T"""rftJl Ero,ym"". f'lenum Pre". New Yo'k. pp. 41-5S.

Grey. D, C...nd J.n..,n. ~l, L. (1972) B"",..iogen;" ,ulphu, in .ir poilu' ion. xuna(Was~ Dc.), In. 1099-1100,

Grigo'ICV. A. A...nd Kondratiev. K. Ya, (1979) A'mo'p!l<,;" du',- Ob><""tion<from oute' <pa<:e, Sa"ko ZhI"". No, 6. 88-92 [in Ru"i.n).

Go:zman. G. T. L. (1977) E'1alion b.,b de conlOminocion .mb;"n"l en EI CerroVer<le·El Sal ••<!o,. prime'o' re,ult.do:!, Sp«iol En";",n_nlOl R'porr. No.1 O. Pl.lL pp. 70_77. WMO. "0, 460. Go..... ,

H.les. J. M.. 'od Dana..\1. T. (1979) ReglOnal.",.I. depoSl'ion of ,ulfu, dio'ide byp«cipita'ion ",a"enging. Arm",. En,';"," .. 13. 1121-1132

H,n", •• M, H. lng,oNn. K" ,nd Jorgen..n. B. B. (1978) Meeh.n"m, 01 hydrogen'ulfide «lea..: from coast.1 ma,i ... sednnent> '0 tile: a,rno'p~e,e Lim""l.OctoME'.. 2..1. 68-76

Harrison. H .• Larson. T. V__ .nd Hobbo. p, Y, (19761 (hid..ion of <ulfu, dioxide in U>e"mo'phere; 0 re"ie~ In: 1m. Con! En""'n. St"'ln~ond A".",.. vol. 2, La, Vega,.Ne' .. 1975. New Yo,\;, pp. 23.1/1-23·1/7.

He!>.". D, A.. and Hob!><. P. Y. (1979) T1>e homO\!eneou, oxidation of ,ulfu, dIOxide in"loud droplets. Alma•. En>iron.. 13. 981-987

He"'\;I.n. J. (1976)Almosphe,ic Ciltm;'rry'. A<.<!emie p",,,,, New YOl\;o XlV. 406 1'1',H.,OOm. K C, (1978) Sulfale .nd n;".,e in ,,,,al <u'pcndcd p.n;"ulat. in Ontario.

1. Air 1'01/",- Control As''''".. 28. 803-806.Hem,.. R. C. and Hid,. G. ~t. (1979) ~'"t,i",,,",. onol~"is of ponicula« ,ulf.,o 'nd

o,he, .i, ~uali". vOfiables by prin<;pal components. Pl, I. An"u.l dato from LosAngele''''d Now Yo,k. A'mo<. En";",". 13. /581-1596.

He''''. p, R, (19S7) Sulpliu, .nd ni'rogen chang.. in fore>1 soil. of Ea" Africa. PlamSoil. 9. 116-96,

H'dj'. G, M.. ond Brock. I p, (1971) An .,,,,,,menl oftbe global ",u=<ol 'lOP""'p!l<ric aerosol"~ 10. Pr","udittg, "f lhe 2nd I"trmononol CI.on Air Con~""

Ac.dem;" Pre,,- ",,' Yor\;. pp. 1088-1097.

rill! Armosplrnic SWplrur Cycle 28'H;dy. G, M,. MlIelle,. P. K.• Ind Ton$. E, Y. (1918) Spalilland ..mporll di<lribul;"""

01 .irbo"", .ullate in part. 01 lhe !.ini'ed Sl.l«, A/mOS. Environ,. 12. 735-152l!od)', G. M., .\luelle,. P, K" Lavel). T. F., and Warren, K. K (1919) A,..."meOiof

",sion.l oi, pollulion ,,..e, lhe .."em Unl1ea Stale<: ""ull. lrom lile 'ull.le ",.gion.1 «p<ri"",uI (SURE). In: 11'\10 S}'mpmium on til< Lon".",ngt T'<UI5PDn 0/PolluUln" and in Rdorion to &",.0/ CimJillicn Indud"'~ S""",spltt:rie/T""I'O'"Nrie Eulumge~., Solil. 1919. WMO. No, 538. Ge"" ...., pp.65-16

Hill. F, B.. ItId Adlm".' .... R. F, (1971) A model fo' roin rompo<ition ,Dd the,","shoul "f ",Iphu' dio'oOe. A"""•. En,·j"", .. II. 917_927.

Hlnpton. F. L lod Gai~t;,. \'. (197b) l1>e _"'pI.., ",-"It",n 01 SlIt pt'O<:lp,taled0'''' We.tem Au"'alio. Aus'. J. Scil R.... 14. 319-335

HitdlCOC•. D. R. (1915) Dime'h) I .ulfide em;";,o,,, to the globlll1mosphcre. 01<'''1<>­spire". 4. 131-138.

Hil<lIeock. D, R.. Spille'. L, l .. 'nd Wil..,n. W. E. (1980) Sulfuri< ocid a",,,,,,I. andHCI "'Ie.... '" """"tal almo'phc"," O"idct><e 01 rapid formltion 01 .ulfuri< acidpartlCUlat••. Arm<>s, Envimlt.. U. 165-182.

Hoff",. T.. Kh",..,. J" aDd Moyer. l. (1979) Sullat. """""n'ration. in thc Soutll·",."1<,,, Des<:n of thc United State•. A"""s. En"iron.. 13. 619~21.

Holm.nn. D. L and R""'n. 1. ~l. (1980) S,..to<pheri< ""Ifuri< acid II)"" .vidct><e foran on,lIroP"i<ni< compon."t. Sc...nc< ( ......h. DC) 208. 1368-1370.

H6gs1rom. U. (1914) Wet f.llout "f 'ulpllu,o,," pollu,"n" .mitt.d from Icily du,inSrain and ""''''. AtmoJ. Environ .. 8, 1291_1303.

HOlStrom. U, (1\119) Ini".1 dl) depo'itiorJ.Dd lype 01 ..,Ul« in 'ellliorJ '" "'"adi""""" ,ran,pon "f oi, poilu,""". Atm<». Environ,. 13. 29~-301 ,

Hoi,. B. D .. En~lk."",i,. A. G...nd Von,e", A. (1972) V"io'io","f sulfu, iontop<ra,,,,,, in sample. of ...",nnd a" "".. CIOCaI". En"iron. Sci, T«hnQi.. 6, 338_341.

Homoll'. J. B , oDd F""u"". C. R. (l918) Th< """.u",,,,,,n' of "'" .ulfuric "dd .nd',llIote coo... , of panicul.'e mlller ",.ultin. from 'hc combustion 01 """'I and o~.

A"""s. En.;ro~" U. 2511-H 14,Horvath. L...nd Bonis. K, (1980) An ....mpl to .stim... 'hc t8te «Inst.n, 01 sulfu,

dioxide .ulf..e oonve"ion in tbe "'ban plu"", 01 Budap<<l IdojQ"". 84. 1\10--195.Huebert. B. J.. and Luru,. A. L. (1980) Bull:: eomposition of .."""I. in lhc remole

tropo,phe",. J. Groplr}'•. Res.. 85. 7331-7344Hu,"'. R. B.. Pallo""n. D. E.. Hu,",. J. D .. Gillan;' N. V.. and Wiloon. W. E, Jr,

(1978) Sulfu, blJdll'" 01 • p""'" ptont pi""",. A"""s. En",rofI.• 12. 549-568.fC~' (1913) In........"""o/ Comp.>rls<>n 0/ .'ftthcds WId Insm"....n" 0/.11<' A""",pll<'r-ic

PoIlwion Con,ro! Qt SrQIIOIU 0/B""k(round ,If....""' ....."It, W~IO,GUGM5, SSSR.69pp.

Inn, E. C. V.. Vedde,. I F.. Tl'""n. 8. J.. aDd O·H.,•• D, (1919) COS In lhc "',,0­.plle,•. Grophys, Ros. un. 6. 191_193,

J...,bo. M. B.. Br,,·erman.~' \1.. and Hoellhc;",. S. (1957) Ul't8-micro­delOrm,,,al.,n of .ulphkle' in .i" AnQI. Cltt:m,. 29, 1349_13~ I.

J"..<II.e. W., 'nd H."""Id. W. (1977) I"e"" melbods oDd fi'" ""III" 01 ""'....nn•..""""beri< HoS .nd SO, in ,be ppb '''''8'· Sp«ud En"iron""nrol Report. No, 10.pp. 193-198. W.\IO, No. 460. Go"",,".

J..",II\::o. W.. Schmltl. R .• ond Geo,gii. H. W. (1916) Prelim,nal)' ""ul" 01 Sit"'<>­'f'beri< SO,.me.,u",,,,,,nts, Groph)'s, Rn Ut,.• J, 517_519

Jao"'lIl::e, W.. a.ude, H.. Henman". J.. and VOSIe'. D, (1919) ~1o..unR und "",.teiluns von ..h.... fel"......"'off in r<inor und ' .. run"'inigto' .,mo<phii",. SrQ";"Ro",hair. I.uft. l'. 114_171 [in G.rman].

Jacschk., W. GeoIKi'. H.' IV • Cloud<. H.. ltId Male....k,. H, (1978) Contri""""", ofH,s '0 lhe '''''''''pheri< 'ulfu, C)·ok. PutY Appl, Grophp,. 116. 465-115.

Jarzebski. S.. G,._...i. I . and K.pall. I, (1971) Prin<iple. of determin'lion 01 'hc

''''uh.J.u.. _. 01 harmflll >UbMl.nces "'10 .1mosphe.....or durint; ........ri.&I pn>­,;c:iM::>. ran IV. !be proeclol of toll wbnJ. I'ollloIJ ~IllY of SO:lICn.'" rodn!-I'. .......'. p. b6 [Ill f'I)lt>ll)

KD!oCD. M. L. ODd ".k.o&. -.:. (l%lISom=& ODd ....op;o .....po...J(lIloI'~""<tdpl>uf .'i<it>I<>' { .... uIo. DC). lJoi. 2102_11lUJ~ B B_ Haftlt... \l.. H. ODd J.Dron<"... K. (197 ) wta.. red"",_ ..

coauIltOuIleo.. ad lIoe "'leaK 01 H:S III lbe a,..,.p.e I., K"""be... \lo E,{ed.).u...-..l """'~do;:_Jry_~ I """ Albor s........,.. M""'" PI' 213-253,

JaicplL. I. M, M.-... A. """ AIlRL 0 (1913) ~n ........~ bl'tb .;..~_",",d-a.. o&<-u.J. AppI. Iii_., 11. 7'92·797.

lost. D. (197'0)~ of ........... "'......,. _'........~ _ P' 1

.",. ; tift.""'" AptII, CM.o.• 14.601~loot. D (lr4) At-"""'P<a!-.n "" tIIot 0lIll00pI0tn<~l*F~ T......

206-112Jm>p:. C E. (1957) ChoIllO<al ..tysoo 01.""'" putJ<k> _ of PI~ 000 tb<

_ of H.n>-. Ttihu. ,. 521-531.J",,!IO. C. E. (l960J S<o/pIl_ ...... M""'rc. i. Cift>po1Ip. Ra. 1lII. 227-237.Jm>p". C. E. (1961) \~...,.. profiIeoof <:cDd<mauc.Il\dei .. 11>0 ............. I

II...."",.. d. 501-S09J_, C. E. (1%)1) AUC~ .... ~ln"Ily__""" I"rc-.. -.:e... YOft.

381 1'1'-JUDge. C. E. (196)I» SIIIpl"" '" lIM:~ .._J_ GtopIIp_ lin.. iii. 3975-3976.JUliet. C, E. (1965) o-ur.I CtJmj1<nItO<HI fI>Ui R"di<>ot.....'10!tlwA~,. MIT.

Moscow. 414 pp.JW'lI!C. C. E. (1972) The cycle of Ilmospbenc P"''' ""'unlond m.....mO<k. OJ·R.

.w,rroroI, Soc" N. 711_'2~,

Junge. C. E.. ond \lan>Ol\. J. E, (1 %1) S"o'''''P''''ric aeroilOl "odie•.}. ~phYI. R<I.•66.2163_21$2,

Junge. C. E.. Ch'cnon. C, W...nd M.nton. J. E. (1%1) SlfOlO.p"""" aeT'OlOl>.J,Mnrorol., 18. 81~IO$

Kobel. R. L, 0'0<11. R. A" T.beri. M.. and D• ....:.. D. D. (1976) A hol""i"",., M",ulof C"""", PoUII!Qn/J Up'.k~ by V'8"'.'ion. n.. hnn<yl...n" S'olt Un'....nity.C~nl~' for Air En'uonmenl S'udie•. ""b1icatioll No. 4SS_76,

Kado..·.ki. S. (19;6) Sou distribu'ioo of """"'pb<ric total ""T'OlOIt.. iulphol•.amlllOftium."d nilratt ponlc.....u in ,I>< N.~,. o"".A"""•. £,,""0".. II. )9"').

Kolyuzlmyi. D N (1%1) s",,""'Y 1'roI«tioIt f)f w A.-1f>Mri< Ait fro... Em__f)f fmow In4"slI)'. Got.. Mod. I'" utr. SSSR. Kx:_. IB) pp. [Ill R_J.

Koto. H A, /1936) llIorid _lmo .......-moA'-l.... Hyd,. Rn.• lJ. 131~10(1

K.otz, M. (1936) ell) ploM,nl_ plam Io<alioa UId a.. polhn.... la, MociI.I' L.Hoiden. FR., and AckJty.C, l.(tdI.).Au~ H""db-" McGra...HiI.So-. Yori<. pp. H-~·SJ.

KclkJg. Will. cadle. R D, AI..... E. R_ l.aznto.. A. L ..... M.nd. E A {l9721n.. ......... C)'Ck.~ ( .... 0>Irl. 0 c.). 175. 587-391>.~. A s.. and RotlnDatlllbaa. R. Sll. (1969) 0<> lbo _","I """'P'""l- '"

lIIl: otm<><pk""~ ....., Uzt>o_. IJI, HJ<h",....",1MIi &c....,..,GtoIt/ryoJ. An4 Z- of* USSR Faa. TooIIUDl. PI'- 6S-7S ,_ R_l-

K_. G. KIL. I'I!m-' 0 r~ l>rwdcn-a. V. M. (1970) Ooomo<:al_~ol"". II' ,.., con- .._"'MJddIoAloa.Jro; I' 'ISof .4_,' ,,. Doflo- _..t "", Ilyd>_"-'" I cod.pp. 192 2011 r_ R_J.

Krl,""". A A. SI>Dpolllbt. K. K.• ODd Go<lr:utto.. B. L(1914) CIot......J """'_ol"""'....' la· ....,.,,_o(.Aa "...,,,...,,- Tr.llOM F'1Z-\l-.Abd. Nouk SSSR. I. pp l>4-SJ ,_ R_J

The Armosphnic Sulphur Cycle

KiyourIL R.. Kuronuma. H" U"'ani'hi. G, e, al. (l910) Som. npinion' nn ,ulphu,dio,idc a, 1m a'mo'pt>eri< pollutan<. Bull. Tokyo I"", T«ltnol,. 118. 111-120.

Koid<, M" and Goldbc'l!', E. D, (1911) A,n>osp""ric 'ulphu' and fossil f....1combu..tion, J, Geap";-'. R<J,. 16. 6S89-6596,

Komel. K. (l980) Avilog paplrlpat3 1918_bon, Popiripa.,::4. 22~26.

Korole,. S. M.. and RyabO'hopko. A. G. (1979) In"'''iga'ion of pa,amelt" of dilu­tion 'nd ,erno,'.1 01 ,ulfu' dio'ide .nd lead during 'mn.porl ,I>o'-c oce'n. In: W,lfOS;-mlX'sium on lite Limg_Ron$' T,.mlX''' of Pol/"'on" ona ilJ R,lolion 10 &"",.1Ci",ulotl'm JflClwfing St,olOspltericlTroposp/te';c Eulumgt pro<:e=s. Solio. WMO.No. 538, Geney•• pp. 117-124,

Konh. V, D, (1911) C.leul.,;"n of ratios of the o""mical components 01 00. "'"ortr.n,le'red from the ocean to the ormo'pl><re during O".por"ion, OkellllOlogiy.,11. No.5. 881-888 [in Ru..;'n)

Korzh. V. D. (1976) Cl><mic.1 exchanse of tl>< <><:c.n with tl>< atn>ospl><,.. as factor of..I, compo<ition fonn.,;"n in r;'-c, "'ote"', DoH ""ad. "ou, SSSR. ;UO, 432-43S[in Ru,';an).

Konun. V I.. SokoloY, A. A" BUI)·ne,'. M. I." aI. (1974) World Ware' 80lilnu ondWo'" Rowu",.. of1M Eonh Hydromcltoiz.d.t, leningrad. 638 pp. [in R""i"n).

Kovtla, V. A., and Sabobz, I, (1980) MO<hllmg ofSolmlza'ion {',ou_, in ~Iine SoilFOmlarion. N.uk>. M05CO"'. 262 1'1', [in Russi.n].

Koy.m •. T.. N.kai. N".ad K.m..., E. (1965) Possil>le discharge ra,e of hydrogen,ullick lrom pollu,ed coo".1 1><11, ,n Ja!='.J, unh ScI. Nagoya Unlv .• 13. l_ll.

Kro'''henko. l. V. (1959) S.hne du" >tonn'. {',iroda (Mosco"'). No, 8. 89-92 [inRlWian]

Krouoo. H. R. (1974) Sulphu, ""tope .l>und.~ "udle' of ,he envimnment. Pape'prcliCnted or C.n,d,an Sulphu, Symposium 30 May- J J~"e Unl"rnty 01 Calgary.

Kmuli<, H, R. (J977) Sulphu, i""op< .l>und.oce el""Kl.,. upt.ke 01 armo.pl><ric.ulphu, emissions l>y vegetation. No,"," (Lolld.). 265. 45_46.

Ku'yl<>. M. J. (1978) nash pl>otol~.is ,..",nonce n"",..scene< ,n","is"ion 01 tl><reaction olOH ,adical. "'i,h <XS.nd CS" Cite",. Pit,.•. Len.. SII. 238_242

Ku'ne,,,,v. S, L and Rom.nenko. V. l. (1968) Micron"", of Siva,h and eYapoTati".\>a,in. 01 solt_minins. !.tikrobiologf)'a. 37. No, 6. 1104-1108 1m Russian].

Uvel)". T, F,. Hidy. G. M., B""k,tt. R. L.,.ad Mnoelle,. P, K. (1980) 1ltc: fOrn1 ..>:>nand regional """umul.,ion 01 .ulfate coocentrolions on the northeastern UnitedState•. In: Smgh. J. J.••nd Deerak, A. (ed.). Proceedings of dr. S,.mpo.j"", onE"V1rom",",oI and Climare ImiX't' ofCoal Ullli<,,,,itm Aco.demior fu... New yo,k.6SS pp,

Lo"'son. D, R.. and WiJ>che<t... J. 1\ (1978) Sulfu,.nd trace element concentrationrel.bon<hlps in ""mwl, f'om the South Ameri<on continent. Geophy., Re>. Len,. 5.195_198

Laz,u•. A. L., l;I'ynton. H, W.• and Lodge. J, P. (1910) T",,,,, con""",n" In <><:c.ni<:"loud "'01cr and 'hei, oris'n. r.lI.w. 22. 106--113.

Lo.ms. A, L.. Gandmd. B. W...nd Cadle, R. D. (1971) Cl><mical composition of.ITfiltration sample' of ,I>< ,,"'tospl><ri< sulf.te laye, I Geophy•. Re'" 76.8083-8088.

Luru.. A. L.. Cadle. R. D., G.odrud. B, W,. Gr«nl><rg. J, P.• H",l><rt. B. L .ndRo«'. W, J, (1979) Sull., .nd IIalogen chemIStry of tl>< ""toSphe'" and of vole.nieeruption plumes. I. Gwphy. R".• 84. 7869_1815.

le"ko,', L.. M.rk.., A, G .. and Sonf;"l, R. P. (1975) M,.,urcment 01 sulfate oemwl,in ,I>< 'urfoce lay",r 01 the ","""phere O....r Cul>o. Hydr%gia i "',rw,r>io~ja, 24.15_77 [10 Bulgarian]

1.e.l><rg. E, A" HumenIk, f, M.. and Otle,wn. D A. (1979) Sulfate andnit'..e mo<ing ratio. on tile "iciUlt)' 01 ,I>< tropopau"" A,,,,"•. Environ .. 13.1299-1304,

1M Glob.21 Biogt'XMmiciJl SWph.., Cydt

Ukem., G. E.• and Bormann. F. H.41914) Acd r=, • ..,,..,.,. ..~iofIoI en"tooIIMnwprobIcm. Scion l\\uh OC). 1101. 1116-1179.u.~.D, A, (I'J63)CIlmrkMC~ofR,,~ .. tMJ LorA:n. USQeol Sur>'

Prof. Pop_ .uo-o. 601 pp~. J. P_ "b<Donold. A 1., and V'IlnwI. E. (1%0) A "1liiy of dIo <OIapololl>Oll of

III1l1Ile .lIIIOOflloo.... Ttihu. ll. 18-1_187W<IJe. J P_~. P A_ Po..J B.• SloeN<~. D.C._ ""onIN.... A. F. (1914)

Atmooploene u_ d ..-.y .. <I.. """'''''''' blllDid lropI<1 Tdb4. 1llO. 250-253L<-Iock. J E~ "'"tIl- R. L and ".,."tIl. R. A. (l91l) Aim' phne <bone<Jl)1

....pID<k _ "'",n ....... <yeIt \-. /u-L,. l-J7. 4H4H.l.D:looit- f L (1976) Self'" -.po""'" __ .,."..01 lloe...- and_

droI*ll .. Calitonlao >In''' Tdbd. lI. 4r433.ll...t.. A. V.1IIdR~o.A. C (I9~11 E..im.... of"'" ., ",.,.. odmm~

bIoul f... I..n- ......... 1L A .' ,oe ..._. _ c......oeM F..-.""'.39 Hl"""""'=om.. _. pp.114---122[iD R J.

..k ..!aII<>IL. T. A~De-.P J._Flt-. R.{l9~6IA p"""'-~ .....wI _poo......-Mboa, ...... <by de~ <OIa~"",A-. ClrnlUlL. II. 7<1_761

Mo._hoa'llo. K P (1967) SuolpJ"1Cd .........,.... __ of __,.m..On' ..__~ by~_ Inn dIo .,moopht... Tdlws. I'. 4674-6.

Marnu1J>.. P. J_ and Bandl. A. R. (1977) EItlmo... of _ """tnl>Io.- of boc>IcJp:alIyprt><1u<I<d d....'~'1 ...Ir"", to tloe JIobol ...Ifut CJde Sc...,.,.. (w..... DC.). 1t6.6017-648.

\I.",,~I;'" P. J '. T<KTfl, A L. and Bondy. A. R. (19~CI A''''''''''''''''''' _n,ra,_ ofearbonyt ....1ide 'n ,~ IO~''-e>tem and etile,n liMed Stole>. c."pr.yt. Rtf. /.nO..~. 51O--~12

\Iaro~h>. P. J.. To'res. A l.. Goldbe'8. A. B.. and Band~. A, R. (1980)AI_lplttrirS0, W••'u"'........ "" Pro~t GA.W£TAG. Repon. Cb<mi>lf)' D<panment.D.... I Uni"'''''l·. Pllilodcll'l"•• pp. 1081_1082,

\lani•. A .• and Sorbe,. f. R (1978) Som. ob>t,,·.IIOn< of lCidn~ lod ."ll'h~' inrain"'otCf from rural In•• ,n ""n".1 E.sl.nd and w.It•. AImOJ. E","to." IZ.1~81-1~87.

\I""",v, A, A. (1961) Cho:mic.l compooilion of ""'". in ,ho: An,.",,", """"nI,n, toob>e",.,ion. on tho: M,mj'-VO>!ok p«>filt In' H;-d<oclotmicoJ M."ri4JJ. ",,1. 34.Hl'd"''''c:tc<>ozdo'. Len,n.rld. pp, 3-11 {Ill Ru.>ionJ.

M"vuv. A. A. (1964) Cb<m..al compooition of """". ice and pn""p;II11on in ,be,Ia<uol .... of EI1>N•. In; H;-tbr><Itt.....oJ lI=rUJJ ...... , 37, Hl'd""""'te<>IZ<lI'.u"",~. pp. IG--22 I.. R......"j.

l>lo,vtn. A. A. o BMhmIkovI. 0 I.. na.:........ v. l.. ond Knipe","- L \I (1916)"--nt "'1"'t""'l'IlI'_ of "'bOOlODr:n In>m ,be a'..-pIICre ..-db d.... and r...o

foIlo. In: l'routdUl(J (Jfr/w." AII·U,,_ H.d~C"",ttal. IV_, 0*"" __ It S-J of 11_, ,.,,,.,._. !-fl'dmmc-.zd:o" un""",,,. pp. 261-270

'b.... P. R. (197S) Prel"""'''' "", teO 01_ .._ c:octlic:otn. lor tuIr.. diouk-. dIU Irotn all E.... MId1atId 1e',,1_, ...._. A_. CIr...""'-.11, 251'-HP~ A. (19~"') Cht ,bt .- and ..... <Iiouibuaon of •• m pMnc'"

fatt portJ<ln ..... norIl -. ArnM><. EJ,,-.. U. 2425-2~!l.l>1eIuso>. E, (19'SbIC"""""._ '" flIIpIo=-<OIa~ ...... _

__ ue....~. £Jo 12.699-~ ,_==l>1=aroo.. E.. _ VarIoel\ Q (l9H) Oe _ .......nn._ """~~

....:dc:_ 1_ of MIl""".. pomdn iD "'" """tr ttOflOII'bc:T< l~. l't. 267-27l.Mtszaroo.. E.. VarIoeh .. Q. _ ......... (l9~111 On 110: M. pMnc tuIr..~

.,..., Eatope "'-s, ClrnlUlL. U. 22'3-2r-

Mill<•. D. F. (1978) ""'cu'",' dfe<t. "" SO, "aid.."",. "',,,.,•. En_iron.. Il.273_280.

Milkr. S. H. J. (190~) T'h< alDO""!> of ni''''X''" .. amIDOn.. and ., n'tric aoid an<;l ofchlorine in "'" ";"·"31<' ooIkcrro at Ro,blom...d, J. A~ri... Sci,. 1, 280-299,

Milne. L W .. Roberts, D. B" and William•. D, I. (l979) 111<: dry deposition of ,ulphurdioxide_fiold m " with. '11,,,,<1 chambe', IIIIMS. E'n,-j,."n.. U. 373-319

Moller, D. (1980) Ki",,'ic model of ot"",>ph<ric SO, oaid.,.", bo~d on publishedd..... A"""•. E"0;"'0.• 14. 1067-1076.

Morak.. C.(19i9)S<JM"", 0 ....'. ,lIab,/"OIlO1I. T.""'POTl. Dtpo~, SCOPE Repon14. Wllo). Ch><be>ter. 320 "".

Nali,-k,", D, V. (1969) HunYoM>. Sto"",. Tornadots. Ned,., l.uLngrod. 472 PIl-t inRu..ia").

NuuICh. D. F" Kloni" H, B.. Axelrod. H. D." al. (1972) S<ns.iti~ method f'"meo,,".men, of ItmMfllleri<: hydrogen sulphide . .111021. eM",....... 2067-2070.

Ngu~.n. 8. C" Bo"..ng. 8n and Lomb<n. G. (1974)"The aunosphcric =0''''1Ionof sulpllu, dIOxide and sulpha,. ..,,,,,,,,b~, Ant.mic. ,ubantamic area••n<!o«an•. Tell",. U. 241_249.

Nguyen. B. C, Gaudry. A .• Bon"'n~, B.• and l..ambtrt. G. (1978) Rot',.lu..;"n of tilerok 01 dim<th)'1 .ulfJ<k in ,1'10 'ulfur bu<lgct. N"",.. (Lend.). 21!. 637-639.

~ybt... A. (1977) On .ir-bome tran,port 01 ..Ifur 0"" ,"onh Atlantic. QJ R,W>t<m>!, 50<',. Ill). 607-615

OECD (1977) T"" DECO f'rog,o_ "" Lont RsnSO T,onJp<m "/ AlT. P"'-/"·'""ts_.\I'<II"''''''''''' I/ltd Flltdlltgs. Organ'''''lOn for Ero<tQm", Coop<r.o'>On aud~"Iopm<nt, Pans. 326 PI'

Okita.. T. (l972) C.kulat;"n 01 rat< 01 abso.-ption <>I .ulphur d;"xide by rain .n<!doLJd-<lmple'" Bull. IIUI. Pub/", Htu/'h (T<>k.yo). 21. 9-13,

Om".dt. G" and Rodhe, H. (1978) Trotnsfonlt.t;"n .n<! 1<"""'"a1 procnse. for .ullurrompounds in the: Olrnosphc1< a. Je""ribe<l by a o...-<I'm<n""n.1 tim<-dcpeD<l<ntd'ffu""" mo<\el, A"",,s. En.;""',. 11. S03-509

O"lund. G. (1959) lsotop", ""mpo,n.,n 01 sulphur in p1<cipitation and ....,...,e.Tell",. II, 478--480.

O,·enon. J, H .. Antja. V. f ...nd Durh.m. L L (1979) Prod""'ion of ..If.,e ,n ""n.n<! r.indmp' in polluted atmosphere•. A"",,s. Endron .. 13. 33S_ 367,

Penken. S, A.. lone., B. M. R...nd Egslcton, A. E. 1. (1979) A .cudy of SO,oxi<l.tion in .to1<d rain",."" <amples, AImOJ. End""'.. 13, 133-147

Perha<. R. M. (1978) Sulphate 1<8IOn.' experiment in nonh..,a>1em United Sta,.s:'T1>e SURE Program·.A',""s. Envi"'n.• 12, 641-6-47,

Peterson. L T.. and Junge. C E. (1971) Sou~, of p''''",ula.. matt.. in the.1JrIO>­pbcr•. In' Matthe..... W. H.. KeUOA. w. W.• ond Robinson. G, (<0» •.II",,'. I",f'«'0fI1n. ClUltQU. MIT Pre... Cam\md,.. M..... pp. 310-320.

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Polde".n. A. (1957) Chern',,!) 01 ,he .anh',"",... In: D"'h', Crusr. I,,· I_t<. Lit.,M"""'.... pp, 130_IS7 [in Ru..ianJ

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Rahn, K. A..•cd ~kC.ff"y.R.l. (1979) Long.range tr.n.port of pollu'lo" aerosol tothe Arctic: a problem ,..i,lIoo' borde,,_ In: W,\lO S,'mpo,ium on III< Long.,angeT,ampon of Pollow", and its Rtl.,ion '" &,"'''' c;~"l4lion Including S'MI)­Jph",/Troposph.,. EJehl111g< I'roc.... Sof,•. WMO, No. 538, Gene"a, pp.n-35.

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Rca)', J S. S. (1973) lX"gn of environment.1 information .y"em•• Chap"T 5, Ai'Poll",..," M""iro'ing ill ,/I< Uniud KI1lgdom LonOOn, pp. 109-134

Reiler, E. R, (1975) SlIa'oopheric_tropo.ph<ric <"hange procc=,. Rm Grophy•.Sp«' Phy... 13, 459_474.

Roberts. D. B.. and Wilh.m>. D. I. (1979) The kine'ic. of oxid.,ion of.ulfur dio,id."ilhl. ,be plum. from ••ulphid< >TOcher in. remok region, Almoo, Eo,'iron ,13.1485-1499,

Rohln""n. L .nd Robbin•. R. C. (1 %8) Sou'Ce•• AbWUl'anu and Fa~ of Gi1MowAlmo,ph<,ic Pall.,an", Final Report, Project PR·6755. S'anford R...."h In"i·lUTe. Menlo Pork. California, 110 pp.

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Rndhe. H. (1972b) Mea'uremen" of ,ulfur In ,he free otrnosphe'e 0''''' S",,,,d.n.1969-1970. J. Groph..·'. Rn. 77. 4494_4499,

Rodhe. H. (1978) Budge" ,nd lum..,"., lime. of .,rnosphe'ic 'ulfu, compound•.A"'IO'. Environ .• U. 6714i80.

Rodhe. H. (1981) Curren' problem. rel.ted '0 Ih' ."""'phoric part of II>< .ulpbur9',10, In: Lik.n,. G. E, (ed.). 50_ Pmp«,lv" of lh, Major Biog_hemicll1eyck'. Scope R,po" /7, Witty. Oich..",. pp. 51-W.

Rndl><. H.• and GrondelL J. (1972) On lhe remo,,,llim. of ,",,<>sol partide. from 'I>ealmo'phere bj pre,ipi..'ion "'.....nVng. Tell.,. 24.- 442_454

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Rod.... , H .. Mukol""" E.. Ind SOderlund. R. (1981) Chemic.1 compo,ilion of I"'ecipl.la'",n in E." Afric' J Sri. Ttchnol. K'"ya. 2A. 3-11,

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Rosen. J. M. (I %4) The ,.rti",,1 d""'bu"on of duS! 10 30 km. J. Grophys, RtJ .• 6'1.4673-4676.

Rovin'ky. F. Y... Kolnskov.l, A.. Cherklla"">. Yu. P.. Voron'",,". A.I.. P"lukhnv.B, V.. 100 Ru.ina. E. N (1980) Mal.".I, on oompl" backgroWld mon,'o'mg ofpollution of n"ural .oo.y'le"", I.n: Compl<x G/ob.1 :'.foni"';IOj ofEny;ronmtn,aiPoIl",ino. Hydromelcoiz<!", l..enongr.d. pp, 83-91 [m Russ..n ,

Ru...U, P, B.. H,k•. R. D. Jr" and Vie .... Vi (1976) LUio' Me",.re"'.." of~p"".FUTSO S",,,o,p/I<.k A"owl. S,.nford R...."h In,"'u'e. Final R.port. MenloPork. Calif" 48 pp,

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Ryabo'hapko, A, G.• and Erdman. L K. (1978) Re"den"" time of SO, in the polluteda,mo'phere Mer the ocean. In: oilmo'ph"ic PolluMn '" an Ecologico' factor,'01,19. Tr. In't Prikl. Geofi... pp. 90-107 [in Rnssi••].

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Son"_OlaJla, M, (1973) TI>< European ,ulphur dioxide emission problem, 1'.,/'",oo""m. 1m., 13, 48-52. 83.

Scri"cn, R. A.. ,nd Pi.Ile,. B. E, A (1975) The long range Ir.n'port 01 olr_bornemale rial ond il' remo..1 by de]>O'ilion '"d ".,bout, A genc..1 con,ide..,ionAlmO<. En"iron. 9, 49-58

S<lezne,-.. E. S. (1977) Salt exchange be''''con ,he otm"'pherc..,d ocea" from rhedo,. on chemical comJ'O'ition oIatmospheri< prcoipitotion, In: A'mo'pM';C Diffu­'ion and Ai. PolI",,,,n TNdy GGO. 387, H,·drometeoizdot. l.eningud.pp, 110-]]5 lin Ru"ian]

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pp.lllll-l9J [ill ~~nlTb<>dc. H. G~ m:I \~r. J (1970) s..Jphw ilo<opc .'''''0IlO'O aDd .....tr~..

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Torre..... L. Ma"""'-. P J.• Goc*;llx~ .... B.. "'"" Baddy. A. R. (19 ) A 'molP'"'''''OCS _= '''''1lI$ 001 pro,.et GAMETAGJ G«>pIq.. Ro.• IS. 7357-1360.

T......,.ai.S.(1971) OuSalJOll rueof~ .......~,""" itllx......... meona;..oI."""** ill _ ....rIC p""~.GftI<-. J. 5. 17j..IM.T"""""Pi- s_ h1t1lCl.L It.• _ "ataya, S. A. (191S) A doota>c:ollll"'" of _ ""-

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T_ 5_ SUo. D.. V-.da. K_ """ "~'a.S. (1m) Cbnouo::aI_~010C1<2IIi< -"**1~ R4. 77, S28J.-S.?92

vod<layi. T (1'7~) I'.udIo<:d _~-.. ~!Upo~ • _ ... ~tn'il..EJrnr.~II .. n. '0. 1. 1~22I. "_I.

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Z""rr>". V. P. (19611) Role of~tIOII in the qd....ot tbe"".a1cl<_,,a lor........"tbe a'· pbe'" _ "'hoI-pW'" DoIcJ......bot..\_ SSR. III. So. J. 716-719 (.R_J.