Natural enrichment of arsenic in Loch Lomond sediments

Natural enrichmentof arsenicin Loch Lomondsediments
J. C. FATI.{ERaDd M. A. LOVELL
Depannetrr of Fornsic Mcnicine and s.ietre, Univcsity ofcldsow. Glai8ow GI2 8QQ, &odand. U.K.
lRec?ired Janta4 20, l9A6i k . .d ih @ised frtn Jure lO- 19861
Absli ct {onanldiiotrs
of aeoic in su.fe o. n@Gslrfac. $dimcri in Il of ll o6 lrom the lhre
major b6ins ot rsh r-mond aE sub6lantially enbanctd. up to 675 ns"/kB compaftd wirh hqckgrcund
valu6 of l5 50 n&/rB, Srdioe.trty As pronk d lnnbu|ed ro post-deposilioral ericboent p.@s
sincelherearc no re.enrsignihcanl$uI6 ofenvircnnentalas conlaninalio., anthrcpoeenic
or naluFl,
in rhe Leh Lomood area,The enrichnen$ @n b€ inbmrctcd in tcrns of postiepositionaldiaseoelic
emob natiod processsin sdimenl rducing zones,fouo{edby upwaldmielaion of As lhrcueninG6lilial
sale6 aod oxidadon/adeaiion/p.ccipilarion@clions in ncaFsu.Lc.onditn8 laye6. conErn.rion ol
1bediagendic/adsrption htpodesis is prcvided dn€dly by rhe lialtsis ol As sleci6 ( ] 5 8l 4/l) in porc
wakr aDdiDdircrly r@ comparien wilh sedim€Dtaryphosphotus.
Washin$on. U.S.A. (PErERsoNand C^RPEN'rER,
INTRODUCTION
r9E6).
THE coNcENrRATroNoF aisenic in eits is Opic.Iy
0. l-40 ng,/kg bul catrb€gratly €l€lal€d in minemlizcd
areas(woolroN, l9E3). Irveh ofarsenic itr frBhwter
lake sedineds might b€ erp€ded to reflecl the Daturally occuEiDga.senicconr€f,lofthe sils ofthe co.responding calchmetrt areas except where therc bas
clearly been sisnificant input ftom nearby industrial
(4a smelrine. minirg) or agricultural (e& peslicideapplication) acrivities. Thus, cnriched surficial sedimentconcentrations
ofaFenic of up to 2 I 7 ng/kg for
tde washinston. 307 ms/ls for Browns l-ake. wis,
consin, 650 Dgr&g fo. Kelly l-ake, Cad.d.. and 1,500
mg,/kgfor lak6 in lhe Nonhw6t TeFilories, Canad4
havebeenattribured b rhe etreclsofrhe Tacoma cot>
per smelter,wdhinglon (CREcEuus. | 975), addilions
of arsenicalhe.bicides(KouAyasHtand LEE, 1978).
ahospheric deposilion from sfteheB near Sudbury,
Ontario (NRTAGU,
l9E3) and mine tailinss (WAGE,
MANNer da, l9?8). respectivcl].
In 1979,however,FARMER
and CRoss(1979)reponeda highh elevatedaFenicconcenlrationof474
mrkg. ir astociatioD
with an enhancediron coDteDt.
in the 0-l cm Krion of a sedimenr m.e from th€
southem basin of tah t-nond, Scodard- In lhe abs.Dceof any koo*a signifrcanrloc:l source of lBnlc
(lelalive
conumiDatioo,rh'5.d 25-foldcnhancemenl
ro a 'ba!€line" aMdc level at deplh ir the *diment
column of l8 15 m&/kg)and thc venical profil€of
aBenicwerelerladvelyattribuledto the combinedef,
fecrs of upsard miSration. lollowine diasencic re,
mobilizalionunder reducingconditions.aDd subse
qu€D1readso.plion on oxides and hydroxides of ircD
in aerobiclareB. Mo.e .ecendy.similar po{ln.pori
tional enrichmeDt mechanismshave b€€n invoked 10
ac.ounr for enhatrcedlevelsof arsenicin su.ficial laye6
of s€dimenrftom tike Biwa.Japan(TAKAM^rsu€l
dl, | 985).frcn I2le ohakuri in an acdveseo$emal.
high-aJsenic. d@ of New Zealand (Ac,cETr and
O'BruEN,1985)and. 1o a lcgr cxrcnt, fmm trte
Followingthe earli€rwort €nied our in this hbc
mlory. w€ decaded10 investigale the disdbution of
ars.nic in Loch Lomond sedimeolsin a more comprehensive
fashionvtuthe anallsisofa$€nic,non and
maneanese
in the sedimerlsand porewatersofa rcpresentadve
setofco.es from the lhree tnain basinsof
the loch.The resullsfor corescollectedb€tweenNovemb€. I98I and Novemter 1982are pres€ntcdand
MATERIAIS
Enrnon"tdtal
AND METIIODS
!.tinE of Inh
Intdd
lah tlnond. l0 tm ro 1hcnorlh-wcsl ofclaaow. is an
ihponatrr dni\rn8 Mrer rN^on. emrc lor Rr@lional
puRuusandrhc taisN fiF.hMr.r bod, rsE 7l kmr.lcnSrh
36.4 kn: F!xh. width 8 kn) in G@l BnBin (FiB. l). ll s
a slacial lch consisiin8oflwo drstncl majo! b.si.s, a "lowel'
and .n Jppci . spaEred b' a \mJlcr. cnftl hasino{ in
remediat chaader. The lower badn, lyinB ovq edineollly
dks ol rheCa.bo.ilerousand Delonian,is wide.elahv.l,
shallow{naxn. dcoth 3l n) and biolosi@lly motc p.oducliv€
rhan thc natros. dccpcr (mdm. deplh 200 m) oligolrophic
b6ic to $e no.th. cxcavaled in melanorphosn DaladBn
nio-shDh. shFtor grb aod ila6. lhe Ri'.r F,ll6h. ar
rb. nonh.d riD.dFins a @rcbmml aM of n.taho.Dhic
ultor.rlain b! pear.pmritr avaiLbl. nuhenti lhc main
inflow |o rh.lowd lch is rhe Endiick water. dFiring prG
ductiv. fambnd o. Hs ofbodd€r.lay and dacial and m!nnc dcposiB Ourno* '( ria rbe turcr L.'.n E\.D dunrc
Fnodt of rhemal {Elilielion, ooR prcnourc.d in rh. iotemcdiale and uppcr r€Bion.whcE bonom tmpcdlures arc
loP lll year, dissolled oxygenleveli renain high (>72% s1u6rioi) lhrou$oul the ldh (MAUrooDa.d DoNEy,1980).
Botbm *dincnlsEosc irom brcwn mud5,wilh ! lhin nearsu.lacerust-Edlayer,inrnesouth,to black.ni$ccousoozes,
overlainby thia dalt-brownnnconslidaEd naterial,in lhc
nonh. Porosiliesaehigir,80 98%and 90 99{ ov.. th.lop
20 cn in rhc $urh and nonh, .6oec1ively. Suricid organ'c
mrbon conr.lr is g@ler in lne lorth (- l0?) than i. lhc
surh (- 5%) and de.ltas DoE sl@ly sith dcplh 6 a co.acidity od lovd tcmp.Et!rc of
squenc of th. imusd
northdn bouon sale. a *ell 6 ofrhe gr€rer proFnion oa
peiy allchthonoE maidial in rbe noni conpaEd wi& lhe
moe aul@hthonous pLottotri. debris itr lbc sllh (SL^cx.
2I\59
2060
J. G. Fme.
add M. A. tovell
verc frltced tblousli a 0.45ro CelnarcelluloF 6lte. (GA
6) 10renole paniculatcs and slored al 4'c h polyDropylere
conlaine6 for prcmp1 araltsis.
Plantlon enpls *erc coll$rcd througloul rhc lch, be
uecn Alsun md Novcmb.r 1982,by lEwling a 0.1 mm
m6h nd. The phyloplanhon dd dpldhon
ee epqnlcd
by si.vi.& ao oq€d by vacuuh flrEtiotr ..d fdzejryiDg
Monthly smpl6 of aimGphedc panicnlal6 BF collcael
fiherpapes,usineaSBplex
oD lE x 23 cm Gdnar acroDore
high-volumeai! enplcr at |he UniveBilyField Sotion.
Sr@n $.dimebrqmples *cF muded ar 27 lodlions
aroundtnh l-nond in June1981.driedai 30'C andeenily
g.ound and sievedfircueh a 2 mm m.sh.
Sub-smphs (0. I B) of loch edim€.t *dions $rclm s€d'
iments aDd atmospheric parliculatc mat€rial were dislved
usiir ai aqua .egia/hydronuoric acid/,bonc acid prcceduE
which .nabled dereminarion ot lolal Nnic by grapnit tur.ae ltomic abe.ptioa sp..rromelry (PE-106/HGA-74/A9
| ) (LovErL dd FAnMER,| 98la) and najor elcmcnr!, silicor.
aluminium.nosar*
aDdiron. by flme {N?O/CIH:)a.a.r
I F^iMERaDdCIMN, 198| ). Th* netho& wec validarcd
by a(lrale anallsis of $.ndard ref@ne oatcdalr lor e
and sdimenl and.in tn. qs of mnic, via addniondcorloboradon b, inslrum.ntal nellron aciivation anal'sis
Fla. L Leh tnnond, showinBmain inllos, frcm rheldnn
(FaRMER
and CRo6s,l9?9) aDdthe hydridescn.Rriona.a.s
and eurhs$, and oudow, io th€ $uih ard i.dimenl oe
nerhod of PAnuv^NpouR s/ al { 1984).
-5,
(
colletjon sir6 I
elrhem bosini l-9. centEl bsin: l0
Additional aliquols of lah sedinent w efaccd at 20qC
13, noinem t6in). NovemtE l98l-July 1982.Corc (t).
usinsta) 0.1 M hldmryknmoniun cdond./o.o1 M njlnc
collcct€dr i/ l2l81, watcrdeplh2l n; (2),l/ I 2/8l. 20 d: (l),
aid (0.5 hr) b rcled manlan* and Miarcd
adelb.d
4 / 3 1 8 2 , 3 tn , ( 4 \ . 3 / t 2 l E t , 2 4 m ; ( 5 ) , l 5 1 1 2 l 8 11. 9n r { 6 ) , clcm.nls frcm auriiBcnic maman* onde fEcrions ((}uo,
(7).
(8),
l9/l I/81, l8 n:
l8/2/82, l7 n;
lE/2/E2,55ni (9), l9?2)riln minin.l altacl on scordary anorDhousoxids
4 / 3 / 8 2 , 6 0 n i ( 1 0 )l,9 l 5 / E 2 , 6 0 m : ( l l ) . 9 / ? / 8 2l 4, 0 d i ( 1 2 ) , and hydrciids oi iron. whichweEsolubilizedusin8(b)I M
216182.t75 nt (13),2/6/82.55 mhydrorrldDoniln
chloride/25%aelic acid (4 hr) (CHEsr€R
and Huarfs. 1967:GrBsoNatrd FARMR, 1986).Manebe,
ircD. ldd and zinc wcE m6ued drE ny in fte l€.hard
by fl.me (aiy'C,tu a..-r The cidu€s mlal€d on whatnan
No. 4 I asbl* 6ller p6p.r. w.r loially drslvd ard anallscd
1954;bvEL, l9E5).Indusrrialactiviryand cidenl hunm
fo.aE
ic. enabliu slcularior of thc .trric errEdcd itr (a)
in
rbe
inhediar€
vici.iry
of
L6h
Looond
m
Dopularion
a.d lbl by subtmcrior fron rhc 101.1dnic con4nrFrion.
voy l@. esrdially whcn omp3rEd wirh 1hemNive indlstrial
Readilyoridtable orlanic carbonwa detmined in F
conuftdion ofclydBide, cenlEd on Clasgos,to the s!1h.
lectedloch sdine.t snDl$ by $e nethod of WALTjY
(1947).asmodincdby LoRiNaand RnM h(197?), while
lotal phosphoru and "irorBlnic phosphorus wcr deteF
A[ sedim.nr co6, l6h wls sld biological empl6 werc m'ncd.pon- aod pErgnito. ad concnlnred hyddhlonc
acid dig6rio., spcarcphobm€hcally uing ih. phosphe
col€ct€d fton thc Gldigow Uniye6ily Fi.ld Starion €la,
oolybdatc n€ftod @B..ritr8 lor lny @nic inerfcEne
men, Ffia, ba*d al Roe.rdernan on ftc casl rhoE ol
(JolrN.1970:JoHNsoNatrdPlrs()N.1972)L@h lrnond (LovELL.t985).
L@h eder and porc waren wcE aDalysd lor rRnic by
Thirlftn edinenr coresweE @llcred ber{ccn Novenb€r
l98l ald Jnly 1982frcm rhe lower(co6 l -6; lenslh l1 19 graphhelumacea.r.s. usingn(lel r{mte mrlnx modifi.rcn), middle (6res 7-9i lenglh ? l8 cm) and uppe. (co.€s ton, and lor disolved ilon rnd nansa.€F by fldmea.a-s.
S.ledcn pore wts s€ d$ anal}zed 6ine an ion<xchang€
l0-l3i lcn8lh 23-.44cm) bsiB of r.ch kmond (Fg- l),
chromaloenphy^ydridc B.nemlio. r.-s. mctbod for the
using the CFib colitr8 lehoique (id 5.? cn: CRATB,t965)
sF.iation ofNnic (GRABrNsxr.198l: tovELL a I-^RMF&
to eIfu Et .rioo of inlacr, u inurb.d, topm6( lay6 ot
1983b).
sdiDenl fBdrrR f, a/. laBla,. AiIe' rmov.l of ovrtyins
Nnnc/$lphuric/perhbnc lcid (62.5:22.5:15)
die6rs of
@rci sch coF s"r eirudcd srepwie and slic€dwirh a Frplanhor mR aortyyd bt h\dndegfldtion a.a.a.
for ffiic
sp€x bladc inro lrm thick Kdo6 wli.h. affo noEse n
polypop)leneja6. rerc seighedborh wcr hd pondrlins
al30qC. Eacbsectionwasgentlyg.oundwirh ! dorld a.d
penk pnor lo analysis.An Eckmang.ab wasalso us€dlo
RESULTS
enple sufaa sdim.nt al wiou lmrjos in the low6leh.
A fudbe. mE Ms colletd bervrn sit€s t .nd 5 in NG
I olal d'tr4c. oatrsanes..i@n rrd imo/alumiiium Bti6
vemb.r 1982 lor lhc crhciion of poE sllo lsing a nethod
in ech of rhe 13 co6 ar plotGd in Fgs- 2, 4. 5 .nd 6.
adJpled lrom D{ r EoN.r al ( ra82l aod baldl on lhe rqinging
Es!€.ri$lv The BUll! ofrhe *leflive chcmical. dclion
of n-dimed frcE a prctr.il€d. tap.d-up. plastc C6ib coE
p.e.durae
\ummanredtor mesr'tr*. imn and Nnic
!ube, fll€tio. rhrough a 0,45 llo MinipoE frllcr qnn (MHWP
i. Fi8. 8. Lead, zinc and aMnic protl6 for 6es | . 5 .nd I I
03? AO) inro a s.cond syringeunderi.en condilionsand aF show in Fie. 3, phosphotusand Ndi
profiles lor cor€s
injston in|o nitrogcn-frlledelf-sding lials, prior lo malyss
1,5 and l0.n I iB. l0 Porcs arermdn8,ne\e,rrcndndoMUc
tich water Nd collcded at vriou depths al rhe cous
.lar! lid Miated sclional *dimenl sulls lo. ihc addilional
sit s usiDga 6lnE pblic vatr Dom shpler Suuenples
corc arc plofied in Fig. s.
As in Loch Lomond sedinents
2061
o f e l e \ a r e ad G e n r tcu n h e rd F n n 8 u i . h erdd i T e r r a r senicprofilesin the northemfrom thok oflhe soulherD
There does nor appear10 have been any recent
sourceof envirormentalasenicpollulionwhicbcould
haveproducedthe ob*ned subslantial
effichmentof
arsenicin lhe top few cm of Loch Lomond sedimenl.
SmalllocalironsmeheBhadcloseddoM by 1beftid'
l81h century.Funher afield,industrialClydcsidc1o
' h e \ o J r h h r \ c e n r n l ) . o n r i l ' u r e dr , t r c r m o s p h ec
?
i.anspon and deposilionof paniculalcs)to thc approximalelylen'fold increasein thc lcvclsoflcad and
zinc in Loch Lomond sedimenlssincethe 1a1e-l8th
.E
! e n l J 4 L l - A R v l R . {J / l q l o \ T h e J l n ^ \ n h e r i .d r seniclelel of<0.1 ng/mr at LochLonond, hoeevef,
is in linc qith lypical ffal valuesof <2 ng/n' and
considerabl! beloF the representativcufban and
''smelter-enllronmenl valuesof 20 and 200 ns/mr.
3
quotcdby woolsoN(1981).
fcspccdvely.
I ilcrcd Lo(h Lomond$rrrrr dredl! lo$ i.r Jrienic
{<0.2/sn) $ hencomparedwith the 8 I 00 pg,/lreponed
for NewZealandthemalsalen (ACGE
rr andASPELL.
1979)and levelsof 190 1:60 /s,/l found in slreahs
and lakes near minins opentions (w[soN and
HAwKrNs.1978iBRoox,\er dl. l9E2).Thereare no
recordsofsodiuh aisenitebeingukd i! Loch Lomond
Frc.2. Prcfilcsoflotal asenic concertration(ns/ks dr)
q I r n h d e p r ho. v e '. o u n . d o - . l . n b r h \ u r r o 0 c r ' .
to confol rbe g.oelh of roolcd planrs-a5 has been
I3 sedimenr
coreslron Loch Lono.d: I 6 (sltheft basin). pfactiBl eheFhere(RuruERT
e/ 41, 197,1:
KOB^Y^$I
7-9 (ceDl.albain). l0 ll (nonhembsin).
and LEE.1978),and no indicalionlhal any arknical
herbicideswhich. unbeknownto us. may havebecn
uscd on the farmlandsof the Endrick barin. at the
Filictod loch sater al aI tnes and dcprhs w6 foud to
southeastcomcr olrhe loch.haveslgnilicanllrinflu'
conlainIc$ than 0 2 /M a6enic.Ahosphcri. a6cni. Nd
Arknic cor
cnccdwatero. sedimell concenlration!.
nol detededabore0.t ns.hr over 2+hour penods.The av,
ln planktonaretlpical of uncontamiDaled
era8casenicconcenlrations
of phrloplanhonandzooplank, centradons
fresh$aterenvironnenls(FowLER,1983).
lon in the loch $erc 3.8 :! 1.3ms/kg and 2.9 t 0.6 mvks,
respectirel,v.
,\Mnic lcvchin stEamedinedts weE lBs dran
20 mrkg excepl lor the 62 mglkg ecord€d for one nream
hearihc Ri\er Fallochallhe northerntip.
O r a " l l " n l l L r i . J l r e o r o d J o o l t ri J' . d . R S D r r ' 1 A c dj p
icallyfron 12-5% for najor ctcmenldeleminalionsro15l0% for lncc clemenlmeasuremerb
DISCUSSION
S e d i m e ncro r es e c r i o n(.i g n i l i L a n rel )l c \ c r c dI n J r
senicwerelbund at all silesexceprcore 13 (Fis.2).
.E
Maxinum Fctiolal concenlralions(ns/ks) of 526
(core1),173(2),42,1(3).
480(a).6?5(5).177(6)(southern basin).288(7).306(8).155(9)(cenlralbasin)and
204(10),200(ll) and 174(12)(nonhetubsin) contrast
i
with typical 'baclground values(to 20 or 30 cm
depth)in the range15-50ms/kg,cohpanble with 1be
basclinefigureof 18 1 5 ms/kg quoredby |_ARMER
and CRoss(1979)for the 76-cm core collectednEar
,sile L Thcs aMnic peal6 $ erelocatcdin i {ft s€clions
betweenI and 3 cm in rhesouthembasin.z and 5 cm
in the centmland 6 aDd9 cm in the northcrn(Fig.2).
Flc. L lroliles oflead and zinc (ng/ke dry N1.:I M hl
Abovc tbe peaksin most coreswcre sectionrwhich
droxrlamnoni!m chlonde/25cx
aceti.acidcxl.acrable)
and
had arsenicconcenlrations(<50 ms^s) similar to ol totalanenic{ng/k dJ-'B1.)virh deplhin Loch Lomond
thosefound at deprh.A grealerthicknessofrbc zone sedinenlcores1. 5 and 11.
I
2062
J. G, Fumer and M. A. Lovell
(Fig.4). Manganese
peaksusuallyoccunedin the top
: cm bul could be asdeepas 3-4 cm in the nodh (core
l 0 r . l h e r b i c l o e so f l h e/ o n eo f h i S h l \e l e v e d m a n gaoe\ereDdedro beseJrer ourwirl'rhe\ourhernbasin
(e.9.cores9 and l0) bll was nomally <5 cm. Tbe
high manganes€
concenl.ational9 l0 cm in core 12
m d \ r e f e c rd c o m b r n J r o o
DI r $ o p r o f i l $ .p o $ i b l ra r ributable to receDrslumpilg of sedimenl.assuggcsted
by adhcontinuityin the porosiiy,organiccarbooaDd
siliconconren$for seclion.between7 and 9 cmAs wilh ftanganese.there are sedjment secrlonscl
evaledin iron within eetrcralzonesofenbancemcnt
(Fis. 5). The latter, however.are les wel-defined,
€d
e\pccidll)in corerfi om lhe nonh. becrL\eol rhecomparativelylow levelofenhancementi! total iron. relative 10 averaeecore concentnlionsof 6.5 97o.As
mucb ofthis backgiound"ifotr is prcseDtiD lbe consriluerr mineralsof rbe non-orsanicfraction oi the
sedinenl.rends in iron proiles can be mote readily
ideDtificdif eachsectionaliron levelis "corccted" by
n o m d l i / ' n gr o r h e! o n e \ p o i d i b gs c c U o n caol n c e n r 6 lion ofaluninium, a major elemcDlwhich jncreass
dosDward io the *dimert asorBanic6bon dccrelses.
PronlesofFe/Al arc shorn in Fi8. 6.ln the sulhem
and centralbditrs, the zonesofenhancednon scnerally
occurwiihin the rop 5 cm. ln the nonh, the peaksc(d.JFrc.4. Irolilesof totd nansan* coDc€nlralion
further down the coresrn
M . )w i r ld- e ph o ! . r , o l t r r c d i o m
cneh\,upro
u r n . I n lions are seneraly found
I 3 sedinerl corcsfron LochLomond:l -6 Gouth*n bdin), eloncatedenhancedzonesallhoughthe pictureis less
7-9 (ccntnlbdin), 10 l3 (nonhembain).
clea!in the dual proile ofcorc 12.The non parrem
Streamsedimentdataconfrm theapparenlabsence
oflocalizedinputsofanenic to the loch from anlhro
o o B e n (s o J r c e i.n r h cc a L c h m e n
d re a . T h e c o n c e n r 2 t i o n !d r e\ i m i l a rr o b J c l s r o r b d\ d rd e p r hvr r l u e \l o r
Loch Lonond sedinents(FARTERand CRoss,1979r
MACKENZTI
cr d/. 198]),allhouehir is wonh noting
rhdr.Nnic le\el(in sconFh\orl. dcn\cd ftom qulrv.
mica{chists (which oulcrop in fie northem catchmenl
d r c ao f I o c h I o m o b d 'd e d o u b . er h eo \ e d l l a \ e ' J s e
for Sconishsoils(wEsr, 1979).
A . s a \ o b \ e ^ e di n r h eo r i g i . ] aIl o c h L o m o n d{ d .
imctrtco.eLLRPM I (FARMERcI
al, 1980).theoDset
of si8nificanlinoede in levelsoflhe hear1,melalcon
taminanlsleadand zinc @cu6 much lowerdosn the
coresand the upwardsrisc in concentrationis mucb
nore Sradual.,ones of enhancementoccupyiry at lest
14 crn (core l) 10 more than 30 cm (core I l) ofthe
sedimenlcolurnn, in markcdcortrastto rbe relatively
narow and rvell{elined scctionsof senic enrichmenl
(Fis. 3). This conlrdt slronglysuggests
that tbe influ
enccsafli{ting the levelsand distribulionofamcnicn
lhe Loch Lomondsedibentcolurnn areditrerentlrom
lhoscconlrollingleadand zinc and confims that ex,
remalarseDic
contamimlionis nol a signifrcan!
facto..
All kdiment profilesof mansaneselbllored tbe
samcupwardstrend bwards geatly clcvatedLelels,ol
up1o9.1%.in the upperfewco ofthc k-dimcnlcoiumn
t9\
.E
.E
l
wirb
Fra. 5. Profrles
olrolalilon conceninrion(% dry
"t.)
d€plh. oler coll€red corc lens rs.up ro 20 cm, i. I I Fdimenr
coresftom Lmh LonoDd: l-6 Goulhembasin),?9 (ccnlml
bsin). l0 13(no.thefr bain).
2063
As ih Lmh Lonond edinenls
Frc. 6. Prohlesofiron/allminium (Fe/Al)wirhdeprh,ov*
collected
cor€lencths.
up1020cn. in 13edimenlcores
fron
I o !h I o n o n d 1
: . 6( \ o r r h e m
b d \ i D7J-. o( . e n r r J\ L i n / , 1 . ,
6 divalen ions to bc reoxidisedand frxedin aerobc
layersof wdiment. As a conkquenccof thcrmodynamic and kinetic faclors,the resullantmangancse
peak in oxic surface layers of sediment is displaccd
upwards relative 10 that of iron (BERNER.1980:
FARMER
and Lo\.ELL,1984).
Secondary
enrichmeDlprocesses
in the carchment,
leadiDg1o larse enrichments prior ro fte suspendcd
load enleringlhe loch,can be ruledoul asa plausible
isolaledexplanationin view of the findingsthat (i)
many peaksof mansanes(aDdoi iron) in the loch
coresarc sub-surfaceand (ii) totrl manganek in sliqm
sedimenls irom the calchment arca w6 tlpically less
than 0.15%and nol more thatr 0.47.,valuescoDsidsedierablybelos the en.ichedlevelsof near-surface
ftent, It ; significani,however.thal the eledive
cheftical ertractant (a) releasedaboul 90L of the
m a n g a n e \ fet o m r h e \ e d r m e Drtc r i o n s h r c h e s irn
manganese
in eachcore.irdicatile of the secondary
(authigenic)nalure oflhe bulk oflhc clcvatcdmanganese
in uppersedions.Whilc ody an averasel.6E
o l r o r a l. r o nI n r h em J L m u m c o n c r n r m r i ornc r i o n \
of the 13 coreswas removedby {a), a corcspotrdirg
36%was solubilizedby (b). slill reflecliDs,relativcto
mangaDcse,
the comparatilelymodestexlent of the
secondary nature of thc less dramaiically enhanced
Reldln tshipsbeheenarsenic,manganese
for corel3 i! moreakin to that ofsouthcrnand central
The deDthprolilesof marcaneseand iron. chamcLcried b) :urlaceor nedr+urfdce
cnhrDcemenr'o\eF
Mns lairly unifom concenlrations,arc Opical ofpostdepositional
diaBenec remobilization.After bu.ia-lof
surfacekdimenl, ftanganeseand iron de solubilized
u.der reducingcondilionsal depth in the scdimcDt
column and mieEte upwardthroughthe pore ealer
Figure 7 is a diagrammatic represenhrionoflhe secr i o n a lp e d l . o . d r i o r \a n d / o r e \ o f e t h d d c e m e ni or r
thesethreeelements.The crilerialor inclusionin thc
zoneshav€beenchosn some*hatarbitrarilybut do
in the caseof
corespond10siSnilicantenhancements
(>1.1%)and of medc (>90 melkg) and
manganes€
lcpresenl a! anempt to delincare rhe zones for the
m o d e E r e le' n h d D c ct dr o nr n r c m . o I l e A l
1 . 0i r
Elem€nt
obc
o6c
obc
obc
o6.
obc
obc
ffi
tl]l
n
ilt
ll
i
.E
iL
2
8
I
IO
LIL]
13
Co.e No.
Frc. 7. strtional peaklocations(.) and zon$ olenhancenenr(E) for nanganee (a). non/rluniniun
(Fe/Al) (b) and dFnic (c),to a dcpthof 17 cn, in I I sedinentcoresfron l-och I onond: 1 6 ($utheh
bdin), 7 9 (cent6lb6in). l0- I I (Donnenbain). Cnlcdafor inclusionin zons o" cnhanencnt naneanc$
(a) >l l%i Fc/Al (b) >l 0 (coes | 10),>1.: (coB I l-13)i affnic (c) >90 ne./kc.
2064
J. G. FMd..d
it
I
M. A. LoEU
concentralions
of aBnic. of wbich J5-??% wa also
solubilized.
Diagenetic/odsotptia| contol oJarcdi.
in Loth Lonond sedinen8
In oidc surfacesedime.ls,aBeric is stroDglyassociat€d with iron. presumably in the form of arsenarc
adsorbed
on lenic oxrdesand b)d'o{ide' or ofprecipand
nabd FeAso4 (KaNAMor.l 1965; FERGUSoN
l9?5i PRrcE.1976).under
Gavrs.l972:CREcELrus.
reducingconditions accompmyDe the nicrobiologicat
deomposiion ofo.eadc mafls. lo$er in the *dimcnt
column. feric oxides and h,vdroiides are solubilied,
releasingaderbcd aMnate, $hich *ould undcrgo rcon pE and thc
ductionlo aerite andAsst depending
acririry oi HS . Upward miSxationof aEenic ib rcducedfom As(lll) o. as As{r,1,Eondado. ro As{v)
and readsorptiotr
on Fe{lll) oridesand hydroxidesor
precipiiationas FeAsO. would yield diageretically
producedzonesof enhancement
for ars€nicsimilarlo
Frc.8.Meanamolnrsotnesa€s, nonandNnic (cx- lhoseof manFneseaod iron.
prcsd 4 percent4esoflhe roBl) Flas€d sucesivelyfrom
Thc upward displacemenl of the mansanesepeak
Lch Lodond s.dim€nlscliotrs by 0.I M hydroxylanmonium chlo.ide/0.01
M nitic acid(tr) md I M hydrcxylan- rcla1ileto the ars€f,icandiron peaksin l2 cores(Fi8s.
monrumchlondc2r@acet(rc.d(8,for*\erclroLJsFerr 2. 4-6) refleclsthe precipilatiotr ofthc authisenicoxides
c o . c e n l l a t i o n b d n d s (lal 9i 9n0& & C r b1: 2 0 - 1 4 9 n s / t g r c o
; f up$ards-mremum
n sa n s a o e \act h i s n e rt h ( i ? .
150-199mg/kgid 200-399mg^g: e: 400odks: t peak moreoxic condiiont thanfor the oxidesand hydrorjn
aent s.lions coEsl-12).FromutMlcd origioal
dded
idcsofiroD, with whicha6cdc, predominanllyin thc
sdrm.nt.lhe*condchemcalerrd.fur Iemo!A(tr) (8)
Thc proponion
(r)
Enajnirs
is.ot ele&.d underlhe ex- iom of a$nare (As(v)). ; Nocialed. rhe no.thwards
iEciioncondidons
employed.
incr€asc.boft in the lengthofthe displaccmcnlbetw€en
l'.
[r
t"
cotEsl-l0and >1.2 incoB I I 11.Thc maiDfstuc
(i) iron and aMdc G clNly alsialed. mosr notably where ftc ma\imum sdioml Fe/Al Elio co,
incideswnh the a*dic peakin fiveofthe six$uthem
coresand in two oflh.lbree edlEl coEs.
(ii) the mangan€s€
peakis displacedupwdds rclative to $e a.senicpeak. the disphcementbetween
manganes€and ars€nic(and, therefore,;on) increasing
in a nonhe.lydirecdon.
(iii) lhe lhicknessofthe zoneofenhancement
tends
to increascon going fron the southem to ccnlral ro
lt
E
Th. assocraoon
betweeniron and aJsenicin It is
supponed by the resulb of the selectivechenical cxtmction proc€dures(Fi& 8). Ofthe 58 sedinenl $ctions
of arseniccontent > 90 mg,/tg for which chenical
I.aching datl arc available. the fBr elulion, fo. rhe
s€lrctivedissolutioooioxids aod hldro\ide( otmanganese,exr.crcd atr ayenge l2'r ofloul arsenicwhile
the s€cond,for s€endary mo.phous iron compounds,
rcmovcda funhe' 2q%.SrDllal!, for lnesrional ar9enicp€aksin coresl-12. rhe compondiD8 ngures
were I l% a.d l4%. i a 45%oftotal asnic wa sol
ubilizedby I M hyd.oxylamrnoniurncNoridc/25%
aceticacid.ln cores2, 3, 7. 8 aDd I l, unusuallyhigh
Fra.9 Protuesofedibenlary andporesater nangans.
iron leveh of 3.3-5.5%.some 36 54% of total iro!, non and aRnic in a Loch Lomondediocor corccolhcled
werereleasedby this solutionlrom wctioosof pcak betwen siresI and 5 on 26ll l/82.
"l
.,t
As in L@h Lonond edimenls
2065
for which supponingevidene, botn
sorption proc€ss€s.
dnect and indirect, is gived below.
{:.=.
PAs
na. 10.ProEls oflolal phosphorubd oaloial @nic
(ms/k dry R1.)wilh deDthin LocbLonond ediment co6
the manganes€and the irotr,affnic peaksand in tbe
thicknessofthe zonesofeDnatrceEentfo. eacheleftent
(FiB.r). ( cobsi\tebrwirh a no4 {dJuol rm0\[to1
ftom surfaceoxic to deeper aDorjc conditiotr! iD the
nofthem basin sediments, as sussestedby tbe geographical liends in th€ relative Etes of decline of ots
ganic cebon with depth in the sedimenls.In southern
Loch Lomond sedime.ls, organic carbon drclines
markedlyfrom -5% al the surfaceto -2.570 a1 15
cm: in the Donh it is ashigh as l09oand faily coDstant
over the top 20 40 cm, reflecting sorne inhibitioD of
orSinjc maner drcooposirion.allribulablero a sienificant allochibonous compoienl less slsc€ptible to
biodegradationand 10the increasd acidity and lower
temperaturesof the nortbern basin. The resultant redoxclineshouldthusb€ les proDouncd in the nonh,
leading to the obsewed ereater epdation between
manganeseand aJsenic-ironpeaks and to the thicke!
(and, ror deDic ed aon. lesswell-defined) zones of
Pore Fater concertrations for the core collecled b€twe€nsitesI and 5 in the suthem bain wereenhdc€d
by faclorsof L7-1300(Mn),6-2000(Fe)and 20 1100
(As) relative to levels in the overblns wal€r column.
Althoud lhe total amount ol a^enic in the pore water
roadeprhof l5 (n wasonly abouL0.2%of LolalNoic
in rhir legnent ofthe rdimebr columD.tbc rreDdrin
porewarerprofrles(Frs.9) $rongly suppon the conc€pt
of diaseDetic/adsorptionconirol of aJsenic.The pore
water trends are consislenl with upward difftsion of
the tbree elementsftoD a reduction zone, followed by
a suddeDdrop in concentmtion due to otjdalion/pre
cipitationin the oxidationzone.Again,the clos cor'
respondencebelween iion and asnic and the din-erencesb€tweenmanganes€and iron-arsenic are apparenr in lhe detailedsrrudure of rhe concenEalioD
changes
in the oxidationzone.
Descnption ofthe pore water proiles solelyin lems
of oxidation/reduction reactio.s i! oveBimplified
(ANDR!A!, 1979:LEMMosr aL, l98l). For erdplq
dissolvednancanes€rnay well be cont oled, esp€oally
lower doM the core, by chemical equilibrium wilh
precipiraredMncor (BEru\ER,l98l; JAQUETer 41.,
1982).Unfortunately,no informatioDis availableon
the alkaliDity or on th€ levels of nilrale, sulphate,
phosphareand thei reduced products in pore wate.
from this core.In additio! to thermodynamic conlrol.
kinetic faciors can be of importatrce, 4& in th€ precipitation/adsorption reaclionsof arsenicspeciesuth
ondes ofnon, the oxidized form. anenale, is adsorbed
more rapidly than the rcduced fom. aJserite(PIERCE
add MooRE. 1982).This, despitethe extremesensilivitr of the As(IlI)/As(v) ralio 1o slielt changesin pE
(PETERSoN
and CARpENIER,1986). hay help to explain the obseded consislenl distributiod betweeDoxidation slatesofpore water ars€nicwilh depth: As(I[)
averaged65 I 9% and As(V) 35 :r 9% ofthe suD oi
the two iDorganicspeciesover five pore waler lamples
ftom 3-4 cln 1o 14-15cm (Lo!'ErL, 1985).Thus,althoud chemicalondadon ofAs(II). p€rhapscaalysed
by mansanes(osc,aRsoNer 41, l98la.b; HUANGe/
at, 1982),may w€[ b€ tatins plac€to*ards rhe surfac€,
the relative proportion of the prcduct A(V) d@s not
incre6e, becauseof its gr€ter affitrity for amorphous
oude\ dd bydrobdesof;oD. Brolosilelin(e^enrion
c.a io tbe melhylarioDoidissolvedinoBanic aBenic
species,could also produce deviations lron themodynamicalypredictedequilibria(HorM e/ d/., 1979)
but Do evideDcew6 found for the presenc€of methylated speciesmonomethylarsonic acid ud dimetnylaninic acid in specialedpore wateG(LovELL, 1985)-
The lowe! mte of compaclion, as reflecled in the
porosily profrles,id the northem basin will also conribute to the obkned tmearing' and dilution (iD
concenimtion) of the aBedc-ircn peaksin the nonb.
Thi! is in spile ofcomparable sedime.arion rates(20l0 m&/cm'4,) for rhe oonberDabd \ourhem basin5
asdelerminedby'roPb datils @AxrERp/ al. l98lb;
Lo\.Elr, 1985). Biological mixins does mr app€ lo
be oisrious consequercein Loch Lomond sedimeDts
(FARMER
er al., 1980;BAXTERer al. t9Elb). ID atry
case,the effec1sof any potential mtjng have cledly
beeDiDsuficient 10homogenizesurfae laye6 and obscur€the well-marked zones of maDganffi, iloD aDd
In the rh.e€ Loch LomoDd coes analysedfor phosaJsenic enhancement, atlributable to diasnetic/ad- phorus, there was a stroDg resemblancebetween 1be
2066
J. G. FamersndM. A. Lnleu
profiles of 6enic aDd its Grcup
neigbbour and
chemical analoeue.phosphoru, p€ak s€dimert concentrations coincidiDc iD all tbree 6es (Fis. l0). Of
considerablerelevaDc€.o this filditrs is the work by
CaRlc:'raNand FLETr( l98l ) oDthc posinepositional
mobiliry ofphosphorus in *dimenb from lake MeDphremagos or the Quebec-Vemorl border. Nonh
Amedca. They shosrd thai the upward movement of
phosphorui sugSestedby solid phas€ and inleBtitial
phosphoruslrends. iDcluditrg sutrsurface maxima at
s€dimenldepthsof2 5 cn ad - l0 cm .especrivcly,
wasconrolled by a dislutioD misratioD-p6ipitarion
cycle of manganeseor non, eith phosphorus co-precipilalin8 o. co-dissolving*ith nangane!€ or iron or
In the threeLoch Lomond s€dinentcores3, 5 and
10,lbe appaEnt degre€of€nhancementofphosphorus
is clearlylessrhanthat of affnic- This isprobablydue,
asin theca* ofiron, to a relativelygrealerproponion
of lhe phosphorusresidingin lhe primary mineral
fraclion, i.p. inea + apalite-bound phosphorus. The
chemicalpretreatmentused he.e in the analysi!of
phospho.usdoes not di$inguish betw€en aparirebound inorganicphosphorusand Don apatitc-bound
(i. c la.8elyiror hydroxide-bound)phospborusbut does
providc a crude estiEate ofoBanic phosphorus,which
En8es, .5 a p€.cenhge of total phosphoru, from I 5l0% in core3,9-2?% in core5 and 9 2$]. in corc I0.
Elevatftt levelsofarsenic ard phosphoru haveaho
been measuredin 'causb" and 'coatings" collected
f.om lo*er L@h LomoDd.h shallowwaler( I I m) io
lhe $esl of site 4. a stiff 4rm thick crun ovcdyirg a
0.25knr baren :lM ofeleial clay \6 found ro corsst
ofa 2-cm thick upper manganese-rich( | l%) layer and
a2<m lhick loweronnge iron-rich(22%)layerwhich
conlained l.ra phosphorusand 980 mg,/ftgarsenic. Xny ditr actior of this layer identilied ;on phosphare
hydro des, bul Do mimral speciesof iron or manErne* could be $ ideftmed in this daterial or in uppe.
layec of Loch Lomond sediment.whereit is presumed
that amorpboushydrousoiides ofmansans aDdiron
coNclusloNs
lluences. Prediction oflhe fate of aenic in freshwater
consyslefts io the light of chaDsitrs envnonnenkr
ditions (s.& euirophjcation. acid pEipitatiotr, €1c.)will
thcrefor€ need to tak€ into accourt the effec1sof such
modificarions on the p.()l:eIs whicb led to arsenic
enrichrnenr atrd otr rbe mrure aid stability ofthe authiSenic mineral sp€cies and complexes ofenha.c€d
Acktu^ledgdeitewe
lliak P R. O. Bametroalnescotdsh
Main. Bioloriql Asriadon. Oban. for l@ ora chib @8,
R. S. Tipperl and R. McMaih ofth€ GlasspwUniyeor-v Ficld
$alior, L@b Looood. for con$demble Nist !c wnb rhe
enpling pro8nmme. A. B. Mact€Die, SURRC, Eat Kilbnde,lor :roPbJnJ! ss. theCrclosy DtparrmeorL n iveRiry
of Glasgos, lor X-6y ditrraction facilitid and lhe Natudl
Environdcnt Rsdch couDcil lor posr4raduate fu.drns of
M,A.L, Tabl.s containirg sclional Esdts of atrnic, nan8en*, ircn. porcsiry.o43ric €rton, phosphorui sfion and
aluninilo for e6chsdident coE andofaenic, 6aash*
lnd ilon in rhc o!€rlyine l@h wate. and poE warer for $e
sddhio.dl coe have b€ed deporited wilb the Nalional Auxiliary PublicarionS{vice.'
l:dilotial hahdline G. Michtd
RNFERnNGS
Ac,cEm J. EndAspELLA. C. (19?9)Rel@ of Nnic from
gcorb.mal rcurcs in rhe Waitato €lcbrmr
ln rfa.e
Sftttanet in Enti.unental Eealt (ed D. D. HFMI,I ),
vol, ll. p0.84-92. Univesit! of Misui P6.
Ac,oErr J. and O Bsh- G. A- { 1985)Detailed nodet for th.
mobility of aEnic in lacustitre sdiments ba.d on [email protected] in lite oh,lui. E vnon. s.i. Tdhnol 19,2i '2lE.
ANDRE^EM. O. ( 1979) Alsic sF.iation in swalg and
rrreBtit'rl Mte6:Tnc in0uetreof holoer€l<benic,l inredcrions on the chemisFy of a tne eiemenr. ttu,,t
O.@nos. 24, 440452.
B^xr€R M. S., F^RMIR J. G., McKtriLEy I- G,, SwN D. s.
andJ^cxw. (1981.,Lvidocorlb. Niubilir.v of goqry
conng for coll(rins sdinenr in polurion and edim€ntation nte nudics. tzvirdr. Sci- Trhnol 15, 843-446.
a^xrER M, S,,C&a*FoRDR. w., swN D. s. dd FARMER
J. G. (l9Elb) ?10Pb
darinBot a Lch Lonond scdiment
coE by conlenliof,.l and particle tEck nethods and em.
Eal h Planet. S.i. Lat 53,4348€o.hedical obs(ado6
aERNER
R, A, ( 1980)Eddv DrnE.,.rr. Princlon Unile6ity
R. A, ( 198I ) Authige.icnine.al lormaliotrBulling
This work has showo that asnic in the lacu$rine BERNER
fiom olganic ma11erdccomposilior i! mod€m sdimcn$.
sedimentcolumn is subjectto control by diagenetic f.nvht Minet 59,tt7 t35.
proces*s and adsorplion mftha.isft s. Consequently, BRooxs R, R,. FERaUssoN
J. E.. HoEECER J., RYAN
B. ( I982)
D. E.. ZfiANCH. F., DALEJ- M. AAdFRIEDMAX
ii is posible that someofthe publkhedliteratureon
S.oti!.
Pollution
by
arnic
in
a
drslrict
in
Nova
sold-oining
arscniciD *dimenls may haveerooeously inierpreted
Enrnon, Pollut.,Sq R 4, r09-rt1.
venical ars€Dic proiles by cofteDtEtirg slcly on
nG
C^RroN^NR, and FLEr R. J. (1981)Po$ deposjtional
temporal\ariadoa io local pouuuob rDpu|saDd inbility ofphosphoru in lake sdid.ars Lidnol- O.eNsr.
' Se NAPS dauDetrl .o. 0,141?for 14 pag6 of supplc,
menll!. nalerial. Order from NAPS % Micro6cne Publicdtions. PO. Box 3513- Gnnd CenlEl Srarion.New YorL N.Y.
10163.Remirin adEne in U.S. fu t otrly $7.75lo. phe
lmpi6 or $4.0) for niaonche. Oursidefie U.S. and Cana.la,
add p6t!€e of S4.50for 1he66t 20 pags and $ I -00 for ea.h
ol l0 pas6 ofmaErial the@fie.. t L50 for micronchcpGrnsc.
26. J6l-366_
CHAo T. T. ( l9?2) S.lcctivc dislulron of manean* ond6
frco eil! ..d *dimenrs with acidifredhydrcrylan,ne hydrochloride. .toil .t i. Str,,tza. Pte.36.164 168.
CH[srER R. add Huc6
M. J. ( 1967)A chemic2l tabniqu€
mineEls, €rbonat
lor the spaFrion of fedcMeatrF
min.Els and adsorbcdtie elenenll lrem D.!4rc sedim.nrs.Chert. [email protected],199 2r2.
CR^rBJ. S. { 1965) A eopl€r for l,Iins short udinurbed
m!nn. co6. ./ (-om Psu. 1,t. E\plo. nIs. il,34-39.
A5 rn Loch Lomonll *diments
t067
nenrs of Loch Lomond and sone anal)iicalspeciadon
cpccElus E. A. (1975)The eeocheniralclcle ol aNni rn
sludiesofaenic netabolisn- Pb.D. distuiion. Univesity
tjte Wdhinsloh and its Elarion io oih.r clcmc.is. rt,,ol
O..anqr. 20, 44 t-150.
DA\4soNw.- wooF C. and TUR\rRD. R. (198:) Handling l o \ r r I V c a n dF { p u r p J C L l a a l t r ) T h e d r r e r i n r i o D
and mcsuremenrtcchniques
of enic in soilandFdineni diseslsbr grapbitefumace
foranoxiciire6liiial walen.
,\ld/ue 2tl,582 583.
atonic absorption spedlonetr] . lntetn. J Enrnar. .lkal
FAfuER J. G. and CRossJ.D. (1979)Tlredeieminationof
L o r r | | V . A .a 0 df A e r p J . C . ( L c 8 l b ) T h e d e l e m i n d . o f
Nnjc in lrch Lonond *dinent by idtrumental neut.o.
aclilaiion anarlsis. RadD./'e- Radioanol t,e1l 39,429olaEnic s!si$ in walerand human urine by ion3xchanEe
.bromdrogrrh).\)dridc g"nc_arion.rom; .b{rrtjoD
faRv F I.G.a1dG.B\o\M r ( s8 )DiNrdc.minbr on
speclromeq (abstr.),4{41Prr. 20, 174.
olcadnium, chroniun. copperandleadin siliceous
sian- MAC(ENZIFA,B., Scon R, D., MCKIME' I. G. and WEST
J. M. (1983)A studyof loDgtem (10'-10" y) elenenlal
da.d referencenateri.ls lrcm a luoboric acid nalrix bv
migndon in erudled claJ_s
and sdiments. Rep. Fluid
Bmpn'tc fuftace atonic absorllion spectronetrl. .,1r.t ?.ProcesssUnii lffl. Geol. Sci. FLPU 83-6. Instnule of
F^RMFRJ.C and LovEL[ M. A. (198,1)
GeologicalSclences,
N.E.R.C.48 p.
Ma$ive diagenclic
enha.cemenlofmansaneF in Loch Lonond scdimc.rs. MAULooDK. and BoNEyA. D. (1980)A sond and ccolqical srud,vof the phltoplanklonof Loch Lomond..tI
Enrnan. Trhnol. Lex 5,251 262,
FARMERJ.
G., SwaND. S.andBAXER M. S.(1980)Records
dtahiol 7t.239 2t9.
and sources
of freal pollutantsin a daredLoch Lomond Nucu l. O. (1981)AMDic ennchDentin lates rear lhe
rdinenl corc.S.,: irntdllirvrro|.16,l3l 141.
snelredar Sudbury,Ontario.Gethin aaeflo.hnfl.A.1a
47,l52l 1526.
f r F u . . o \ J . F . c o dC \ q \ J . ( l a ' : ) a r e " i " u o f r h a N n n
OSCARSoN
D. W., HUANG!. M. aDdLa! W. IC (1981a)
cyclein naoral $ates. t'drern.r 6. 1259-1274.
FoNTERB. A. (1981)Atrnic nerabolismand toxicirr-ro
Rolc of mangans in the oxi&lron of aNnne b-vfrshwaler
freshwarerand nanne species.ln Bialosi.aland Entnoh
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hentu!Elicts olA6atn \ed.B. A. FoMrR). chap.4, pp. oscARsoND. w. Hri!\c P. M., DEFossE
C. and HERBI
LoN A (1981b)Oxidarile poNcr of Mn(lV) and Fc(rlll
GrBsoNM. J. andFARNGR
J. C. (r986) Murli,stcpfqucntal
oiideswith Esp(l ro A(III) in tedestnaland aqutic cnvronnen$ l?nire 291.50 51.
chedical ertncrion of hearl meralsfrom urban soih. t rnon PollltL.,
PAHLAIANPoUR
8., WEATT,EY
M, andI.HoM6oN M. (I984)
Sn. B 1l.l11-135.
T h c d e l e m . n a r i oor i a F c l i c .d l i m o r t d n d \ . T L r h i o
GRABNSKT
A. A. (1981)Deteminadon of 6enic(lli). rrndv), mononelhylasnaF a dineth,\'l6imle by n.in rhoscconlaininsnuch orsanicmatler.
soilsespecially
erchanBe
cbronbrosDphJwirhnrmol.\"roni. ab.orpr'on
]n Enriron,tmtal Contatninati,t,pp. 816 820.CEP.
soectromedcdetection.,{dl Cr.z 53, 966 968.
PrrERsoNM. L. and c.ar"ENrERR. (1986)AMnic distriHOLMT. R.. ANDESONNt. }\.. IVERSON
D, C AN<t
butio.s in porcNarc6andsedimenBof Pus€lSound,bke
S'IAN
FoRr R. S. (1979)HeErogeneous
washjnBon,thewahington co6tandS@nichlnlc1,B.c.
Eadions of aRnic rn
aquarics!-srems.
In Clr,e,rnzli1dl.,1i,s in |rry.o1LsS \tctrr,
Geothnn.caidD.hih ,.!crd50. l5l 169.
-,lCSSr,,? .ter.rrl(ed. E.A. JENNE).Chap.
3l,pp.?,,?rERcEM.L. andMooRi C. B. ( 1982) Adso4irionofaffniie
7:16.Ane.'can ChcmicalSociety.
and aBenaleon anorphous iron h,vdroxide.ttttel Ret 16,
HuANGl. M.. OrARsoN D, w, LrAww. K. and}ldMER
1 2 4 71 2 5 1
) J d a t o i Na o d m q h " n \ T \ o l r F e l . r ' o \ i U T rl'182D
PtucE N. B. {1976) Cbenical diagenens1n $diment' ln
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322.
vol.6.2ndedn., Ch!p. l. p!. l-58. AcadenicPIs.
JAOUET
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CRowLEyD. (1974)AMd. concerrrarions
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JoHNM. K. ( 1970)Colonmelric detemitudon of phosphorus
23.159-169.
in soilandplanrnarenah wilh acorbic acid.5ol/ n.t t09, Shc( H D. (195,1)The botion deposirsofloch Lonond.
2t+220,
Prd.. -4.Jr .S,. tdtn 865,2ll 238.
Joh.'soN D. L. a.d PrroN M. (1972)Spectrophoromclric TakM^TU T.. KawAsHrM M. and KoYAMAM. (1985)
deteminaiion of mnite, a$ra& md phosphateh natnral
The roleof Mn.-nch hydrousnanganc* oxidcin lhc acvarers.)nal Chnr ..lda 58.289-299.
cunulatiod ot asnic in lake edimcnt' ttArcr RaJ 19.
KINAMoRTS.(1965)Geochenical
r029 i03r.
sludyofa$nic in.atunl
wales. lll. The stnincance of ferric hldroxide precipitaF
D. M and LTNZ .
WAGEMANN
R.. SNOW
N. 8.. ROSEBERC
(1978)Asedicin sdiments.walcrand aquaricbiotafron
in slEtfr€tion andsdinenurion of Nnic i.lakc Mrc^.
J. Earth Sci, l\aEara L:n.r 13,46 51
l r l c , i . r h c\ n i n r r lo l Y r o L l d e . \ o n h r d I e m l u n e .
K o B a \ { \ H . S . a 1 d IC
r . F \ ' q - 8 )A ( u m u h t i o d o ' N d r
C^n^d^. Arch Erynor Cotam nrril.l. 7, 169-191.
in Fdinenrs of laIB tr@lcd wiih ediun aenile. t friur.
wArcy A. (1947)A cnticaleianination ofa raoidmethod
.t i le.rrdl 12, 1195-1200.
lor dereminineo4anic carbonin soil.,to/&i.63,2i1LEMMoN. V., FAUST
S.D, BELToN
T. andTL(KERR. (I983)
261.
A$6smert of lhe chcmic.l and biolosicalsignifr!:nceof wFsl T. S. (1979)BiosisniGcance
and analrsisoflracc clcaBenicalcompoundsraaheavilyconlaminatcdwateshed. menlsin aericulluralsoils.Tbe fi61Ton MilerMemonal
Par I Tte lak cnJ ,pecidlioool"Mni.J
omrcdndr i.
Lecture. The Nonh of Scodand Co[ege of AsriculluE.
a q u a ner n \ i r o n n e n E q l i r e r a r L r c r e ! i . { . IF , , ' a a L r
1 3p .
Hcalth 418,3)5 387.
wllso\ F. H. and HAWKNSD.B. (l97lj)Anenicconrenlol
LoeNG D. H. and RnM^rA R. T T. (1977)ceochemical
l r c J m ! r r c a n f d i m . n b r 1 d s r o r n d s d F ro - . f c F r i r analyes ol manne sdinenls and suspendcd
paniculaF
bants uea. Alasl€.t,firo,. drol 2. 195 202.
man r.Iihetiesard Mdtiip Seflirc T?tltninlRepartjin
u ooro\ L A i lqE rr I mrs.on.crcl ng1ndplT(a o'cNni.
70, Envnonnenl Calada. 58 p.
in soil ecos,vstems.
ln Bt,losi.aI and Enri nDiata! Efed!
Lo!EL M. A. (1985)ANniccyclins i. the frcshsale.edi
,/,l^e,'i kd. B. A. FowrFR).Chap.2, pp. 5l l19.