Determination of Hg As a Pollutant in Marine Culture of Karachi's Coastal Waters by Cold Vapor Atomic Absorption Spectroscopy

Determination of Hg as a pollutant in Marine culture of Karachi's coastal waters by cold vapor atomic absorption spectroscopy

SHA||(H MoHtuDDtN M_ 5c

Disseiation submitted to the University of KaEchi for the award of degree of Doctor of Philosophy

Department of Chemistry University of Karac$i 2009 Dedicated to:- Anni, Abbu(My pdrents) fianls to All.h-eobh.nahut rh the mort nercltul, eto e.abled n. !o @mplele thls

t8L I k jun bs@ of Hlr klndns a.d .sn,A th.i | @uH 6ndud. thb nody.

I owe rpel.l Srattude to ny rupedisor Pbl Dr lftilh.. ham N.qvl, romer D.a

F.clltv of lclence .nd Chakm.n Depanment of Chehistry, unlv.Eliv of K.rachi. Hls

8uld..@, sg8lit-btr' sqpporl .nd Esdr mor. tta had h€.n th. m.jo. $urc. ot

inselr.rbn lofa.ds .cconplbhir€nt ot rh. t ft!t,

I am abo thanktul to Prot, 0r. Z.hld. T, Maqlood, Ch.lrper5on oep.rlnent of Chemistry

Uriv€r!|ry ol |(.r&hl for prcvldl.g me hcilhl.s .n.l lsurces. 'ftev In $. l.nt l(s ny pt|!11.8! to th{r my hmlly mnbs, @ll..8ss ..d niEndr

. p6y€d ior m.luslon of thls study thar I del.yed due to mv lau 1..33, I offer tpecr.l

Er.thod. to 8.rhe* bh.l io, l.Ddl.8 a helptul h.nd

l Total mercury (rcgadtess of irs foftn) is inv€srigaled as a polturanr in ihe marine system of coastal €gions ot Karachi for rhe pedod between 2006-2008. seawaler ssdiment, fish sea@d and ,itr€l Hers have bs€n focused tof rorat

mefcury c4ntent (THg). Seven sites wers setected for anatysss. Sires have b€6n

@t€onzed into polluted and eG aro6s. Po uled area haooens to be near tie city and safe area is beyond the civit activitiss. Manora is ide.tified 6s most pollll€d slalion. Industfial and domestio €fllu€nts havs b66n identiti€d to b€ a majo. sourc€ ofpollution. lndust,iatwast€ goi idenriied to b6 the majorpoltuiio. conlibutor in consequenc€ of cohpaBtjvs seawater anatyses of samptes

@llecled n weekdays and a€ek€nds. Bioaocumutation and bio-amltific:rion in ecosystem has also b€€n monito€d tnrcugh anatyses on ssdiment and tittsr ieeder (bamacles, oFter, and mlssets). For a pedod ot the years seasonal vanalons have also bee. marked. Monsoon 6nd non-monsoon metat load was specitically €corded and cornparcd. po ution toad is estimaled by anatysis of seawater n nalw channets having difeEnc€s jn tjdes. Anatvses ot sudace water s.mpl€s cottected trom d,stanes in d€ep sea estabtish that ihe polturion goes towards deep sea lrom Karachi's coaslal paramere.s. Furure THg ievets ale arso being pedicred as an ourcome p€d.qining to lhree yea6 data. In tish sampres THg va.ied with diftecnces in ags a.d size. Liver is noried to b€.r the highest THg load among various oqans ot the same tish. Seatood samptes arc also invesligaled tor THg and they arc found ro b€ wlhin Oo ,ecomdended limits. Selected samptes of seawe€d ano no Drominent i.ado||!tip of THg I rflh ned tEgbo, re.cl o. lotnon Ddf. Col n o. AAS b ltlpbFd €s a rflo. -atdcst boa thb bonq€ a .dntrrd b yriorrl anJyllc.t FE ralt a td * dst|&{ tfitasE dr b 9r€actca of !.*r!tcatio.B aE rlin . tibrr|6 nun Cl., CA, tg, Cut ]d bdtd. ftt F!.elce d MnO.) *r b.hg ,tporlod, Ar lnofter bd?€.rhrn .|brfc.l bdnhr t|. rnodtc .ttpi,rg vof€nm.ny (AaU war .rnpby.d b !!c.lbh h-. |! u|lt. ftytlcodbmhat panlrrb,r lbo .Wpm in€ TH! en.r|€! oulcoml.. s.vlrat.H.!cd poq bst !k AtErvA.nd hrv. b..i dnptoy€d ior compar.on and deta tlducuol! 'Wv'F Jr',!'JL'l d,'p,!- t,f 1t,.c J' ttt L ql tur' t( t li,!,)t V t i ilr,,t , l!tJ,,/ -+ s- r,y, " 1 -/L,tt it,,( firLa L* Ovt|J,fi/,ti,t +{.)e ..t /-w-v-t/tra i 664;,1G, zit ot rtj z elJl"nr.-tL -v,1,- ik,!, t Jtt'L J e' arv - )L j ;Fo d,!1 ! Ltit,t, ri 6 t a o' -{y i. I, t - ^tetv "' i { f .*-{!t "i,!t- y.Jvftil -4 z_g,.-,.tt /7ai L,tti4.q,rL i Ltd.r ,?4d, rl,i,,:arn \i!JL/ r'- z- a ii L& o;-4. Lf v.r,t M,-P,,,,.1,1,,t 4 ;, L gtt,.r 4t, i?4 1 L.i 4 hr ht.i t.t--t'.,r/ c|^t,jl t'at f 1)a. I 2, i ((Bic.nctfr.arioA)ivttt'"b/Ltlr!,ttLrvJV"tnltr,!,ti+,1(Bioe@murarion)

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Envircnh.m is mad€ up ofcondirions or circuNld.ca bt lhich hlman. animat. plnnl

or obl.ca e slmundcd, Living beinss e inn*'cd ad modiflcd h lhcn aro$d &d

d.vclopn nl by swundings. The $iotifi. vision of qvibmdl is th. conbiMrio. ol

layc& tocdia, aroms, ietopB. livinS and nonliving.orgdisn erc. snd combine ro fo,m a

perlccl placc for lifc ih $c unilee.

ln th. UniEse rh€ E nI is . ve., dny objel Dcdaps ir is titc a sd panicle in

cohp.risor with rhc whol. .anh cdst or pdhspG even snalld b ir Tle eanh i,

conposd of four €nvionmental sSnenB lirhosthee, hydrcsphere. biosph€F and

Pollulion is undesircd chmle in rhe physical, ch.nical or biotogicat checrc,islic oian. land ond water dut My hmful io hmdn or o$cr livinS orsmNm.

Pollurion ncd $@rhii8 odd. In siatific wy n is needcd lo cxploE how odd? How mNh? l;or whoft il is odd? tl6 be cl*itied s airyo ulion, watcr po urion od La

. Hdd lo humm healrh.

Hind@e of lEire drivirics ircludi.g fbhine.

Impaidcnr of the q@liry for th€ Ge of s.walo.

Tnc fcus tn.Ffoc on mMcd. F0!er $d mru6l inpurs !o tn€ s6- Tn connon 's sources for lhe D&ine pollution e irdlsrrisl, dohestic and agricultunl (lrotcd or utptcd) wa8., ships and 3pift Aon i! $lid Er. disFFd is !o neine sl.6 er.

1.3 Mcrcuryas an Environ m enr pollutant . Out of heavy n.tab melclry is on. of tn€ host toxic. Io Frdal cnviroMents h.r.uy is ccuinS in .l.m.ntal, bivaldt iror8&ic and or8&ic foms. lr! pc6itrenc in lhc nduEl envirment is de !o aifrnity towdds pardcullld &d organic D.tl*. Consunplioo oi ionic nercury in elual war€r by r.d@rion od m.0lylalion hs b€{ cponed ( I ).

A bivalenl ior of mmury al$ fom @dplexa sirh orEeic rnd iiorgeic lig&ds.

Melhylmocury (M€Hd is lhe nosl abundet of all orymic forms of mercury. h ca.

6ily accudulat d by agnatic or8eisc. A3 . Buh oi !rch bi@Mularion $ar coil bul6 aboul95% ofTHg in fish d$ue. Whilc it pmponion in Mt€r md s.dim.nl h far lower @mp.otive to IHg e).

1.4 Sou.ces ofmercurytn thc envirotrm€nt Sou@s oinercu'y in the aviomdt q be id.nrifi.d s natunl and anificial o' msn, nadc $urces. Natul swes include volcuh mptions, igncous &t5 &d vapodzation ofclchmtal mqcury v.pos nom m.rcury @nrainin8 bcls. M*ury is 6.d by hum& in vdi.ry ad hosl of rhe* us e thc posiblc $!rcc of rdspon'ns ncrcury to envircMcnbl obj€crs. Thc hojor nFs 4c rhe mininS, smcliing of neeury, conbustion of coal ed fossil frEl, banaics, eutic $da ptuduclio!! agicultuE, pdnE, dat l u.lrnents, nDsicide. indusrial .nd @nlrol isnlddrs, bb.dory us.1c, ln l9E4.bou i?9?.5ror Hg @ @tuMcd ir U.il.d Sbt6, cxcluding blmii8 o{ fo$il f!€1. The woddwidc consumpdon of He io thc da!d. oi

1980-89 ir 6liDal.d about 5000 ron y.'&d fNil tuet @6mprior is add.d funhcr

3OO0 ron r'r (3).

1,5 Chem i€ | speciation ofmercuryin environmetrt Gc.onllt the ndury an h..lsilicd 6lor.l n.Eury GHg), ino.e&ic rcory (tHs) ed [email protected] (M.Hs) in $c cnvimmat. THs @ve6 all ch.ni@l ed physicd loms of hceuly in systen, tHg includB €l.ncntal (Hc0), mercuroB (Hsi') @d mcrcuic (Hsr) ioro. No m.0lyladon is hrlFn.d by boln ckDoral ft.rclr, &d n rcuou foms. Bolh foms @ abl. to oxidiz! lo Hg?'-

Rcrciiviry of Hg:' is hicher the lll inoigeic iorN, il ce foms @nplex6 with s.v@l inorgdic ud orseic lisdd.. Thh fon is al$ . major @nniburor in ncrhyhtion or n.rclry. In hiShd pH ed Cl conceftations it forms Hgcllr'domimdy.

Olgeic nqcuy (oHg) @mpoundr e drivativs of Hg" with olgdic conpoun&. a slable C-Hg bond exisrs in hd of OHg @pourds. lHg is .orv4rible !o OH8 by m.thylatod and vice v€'e.

1.6 Mercury distribution in eDvironm€nl Mdcury dd it diffftnt fom e disuibut d in rhc cnvibifunr in edimdc, di$llcd or sspend.d in wd6 anl in *morph@ in gs@us or i! @sols. This disFiburion is factou in e@sysLem. Tx. distiburion is sunndired in Figw l-l i\*

1.6,1 Merctrry ir *dimcntr: lnorgoic n ruly (lHg) t n6t likely lo b! $uld and in €[email protected] ir asiates yirh p.niculat€ mnq (a) (5). whcn r.\e ertent of &rl.dcor and r&sportltion of p.flicular€ mud is hider $. THg in sude walq bdom$ low (6). Mercury in s.dih.nls is als sff€ded by Finfrll, patcm ofwrer circularion ed edimdt clamr.riirics-

MNury in *diftnrt 6oD faslE&:6r.6 .s@ie (dw b Binf,ll or drhe' urha

MorD &d sc$ d.$rb.d in @ns.qwM of inrc@don wilh salirc ni.B (ssatq).

This di$olved THE is onc ofthe facbrs for t nporsy incremenl ofTHg in liltlr fcsdea.

It w6 eviddced in lar.i studi6 $al in Biny s.en tcGt ial sediment incr.d.d THg in shrimps dd olhd or8&is (?). vhq fi€sh a fin. ediDar is innodwrt i! . sysrcn 0at6 crc.) it ddc.s lhe dissolved THs and als oppos uplake of mcrcufy by plsklon (8). Mellg incrces wilh 4 decrease in lHg of sedimenr. Il wd reponed eelier tnal when fesh $dihenrs a€ inlrcduc€d, nethrladon oftHg t fahRd_ Highd tHg in s€dimcnr is al$ Epon d in loq

1.6,2 Mercuryinseaw.ter: Bioavailabilily ol mclals &d m|ll @hplexs is a fietd of inr.6l for eneionnc.|al

ch.mis6. Modck for sp@iaioi &d disFibuion or uprak€ have been susceskd ii gen ral

o! sp.cinc ro paniculd nelat (10). Mostly oH8 is pr*nl in dislrcd fod i. wrd_

Son. of IHC is al$ pEql scFrt.d wnn low dcGiry p.nicutlt maner. Solubilily of dmedylm€rcury (DMeHs) is v€ry low. How.va a rae or (DMeHs) is prcsenr in sluble fom. It B .vid.ned ih.t th. panjcul c mlnd 6 c.B &.l!e jn THg of

$aEler if *nl.d by &y phy3iol, [email protected] or biolosical chdge (6). THg is cnhdc.d in ward ar low slinily d4 (4). A dcd€@ in TH8 of *awater k nodced aner sropFd

1,6.3 [4crcuryinatnosphere: Th. lwo mosl .bunddt foms in armospherc d. atoDic m.rcurt Gs5 od dimerhyl m.rclry (CHtr H8. Tle te chdic?rl spei6 d volatilc in n.l@. Borh roms d nor rcadily olailable for medylarion in lquaric sysremsdi@tly. h .tncphee $w$ elem€nral m.rcury is oridiad to meEnric (Hg!). The oxidadon is Epon.{t by w.ml oxidizirg !g.nr like O&n , HrO!, Chlmin., nydrcxide Edist md doud doprets. (l r),02), (13), (14), (lt.

Sekol dod€ls h.E bed sugg6rcd (16) &d sludi.d for tEspon of difeEnr foms of hctury frch an b aqutic envionm.ld s T.blc l-l. (t7). Atrnoiphcric m.rcury hs

& ihpond @nribution toMds cyclins m€rcury fron an to aqudc syilen 0 8). Pmipilalion nay sle b€ a rcuc for nftury cycl€ &d *vcEl nechaisft tor il hav.

e!.lbdlh.ric D.rcuP lntuDni (t7) ModeI Refererce ADOM

CMAQ Bullst..d Brl'n 2002 (21) DEHM Chdsren, cr al. 200a (22)

EMAP Sy'ako! 1095 (21)

GRAT|M Daloor and tmcqG 200a (r4) HYSPLTT

1.6,4 Mercuryin ha.ine organism.: Methyl mqclry (in aqu6s fom) n moe accuutaled in hdae orseis rh& rHg

{25). Mcrcury is inroduc.d ro di,I.@t org&hn b, difl.@t ways_ In fishcs nonty il e eis though gills, Mcrcury is ehulaled in risu6 ed dain d for long p.rio&, TH8 ir in difr.r.d rhc or8u of sinAt. n&irc Gatue irs @mposirion in orge5 of bo

1.7 Ch6misftyotHgir the Environment: Changcs in the meGury load e mosilt due !o ch.hislry of$c s!rcudin& Chcmical uclrons are oauriog ar diffeent cxte.t md spe€d dd tF* ,ea€dons e quite

@npliqr.d. Md of thc svioMcmd @don3 dcFnd upon orhq @dons. Il is qune ditl.ult 1o fix rhe chehislry accudl.ly,

1.7.1 ChehisFy in $seous phase: Mqcury ha d arincph.ric lifdim. of0.5-l ya6..nabting iB rlespon on s global 1.7.1. I Parti@late tffi anon; ln sascous ph* elcm€ntal mcEury @Hg) is rmfomed into psnicul.rc mstl( (PHs)

or Hs(p). Orcie b onc of lhe p.imary ag€nrs for seh rmforturioni rh. rare oi sucb

@crion is Eporr.d ro be 3-ox lo'"[email protected]. (ll).

HcL,+Ora) Hg\p)

In slralorphere (d.trnospheric layq ofeanh) thc @clio. h noE f€dibl. due b niebcr

abundance of oen.. Anothe! ag6t rhal is fa.ilitaling tusfomation of EHs to PH8 h

Hsh+H,O1\n+HE@)

Thc $ovc ca.tion is wll sludi.d dd i6 rrr. is d.p.n&d upon $vcnl physical

D onditions in al.'osphft. Th. Er. of sdion ir r€pon€d s 8.59 x tO cmr/mols-s (t2).

PHg i!.l$ fomcd b, hydoxidc rsdical (OH) *nh kinetic Rt ol3.7x I0ra chr/molec.

Hsit +' oHn, + Hs(p)

Oxid.tion of EHg is [email protected] tldioq s Gvid..ced by 0E obsqv.d seml cycl. oi EHg (28), But n h sdll ucLd which oxid.nt is donimling.

M.rcury is dined b rlE armsphce tuinly s .l@erl'l D4ury (EHs) ad ir oxidiad within rhe arnosph.€ ro ionic fom (H81, which hs good solubiliry dd n i5 rne @jor d.posirins fon of m.rcuy (29). Ir'. derGidon of nftuiy ro r,h. o@n is due 6 thc supply of Her' to dE ahcpncdc Dqift boud.ry tard (MBL) rhe tay.r dcnds abo(

L0 above kiloners $c oc@ surf.c. (lo), (3 I ).

Atnosphelic Chlorine oxidize EHB 6 fouows;

HgL,+Ct1\b + HsCt\*)

The rale ofrh. reetion is 4.0 x r0rr cnrhotcc{e (12). fte a6u6cy in obsenins above reaction is quire quesrionable, b4ausc.xirlence ofCl, in at nospberc is innu€nced by some compter iactos (31). So apptoximak anbuir ofavaihble ch is esihaled and

$e nodel of oxidaton is @osid.rcd. As phorolysis h happening in daytieht $ availabihy or Cl, is Io*!! ntuwhil.. li@sc in th. chto,onuoDcnrbo6 (CFc) atso favo6 tn chbnne availabiliry.

IIE ircEe in mdirc ga@u mftuly (RCM) @nenrarion wilh swis is dre !o a phobchcnical oxidat p'odued by photolysis of w*ly-bold nighuihc l€s@oi6. Br qn qnibn m

Availability of IHg of ionic mercury is iarc in ltmosphere or al MBL, lhercaore no c

1,7,2 Ch.nbtry lor cquilibriuh oI Httn aas.aqueous phJscs: Merc6 compohds e dishbukd in g&liquid phe rn m4me syst€ms, rf $is dhtribuion pEvails fien ch&8cs arc cxprct d in order b rctain equilib,ium. The distribuion Eio for EHg is cponed 0.1lM/ ,n. Lindqvist and Rodhe in l98j (16) r€poncd disribuiion rario 1.4x10'! dd 1.2x10'4 t4.rn, for HgCh md Hg(OH),

Gsp.clively. S.vdl olhcr m.chanim! ard hod.l rcE als eponed for derosnion of atnosphdic mercury (37)

1.7.3 Chemistry inaqucouspha*: ln aqu.ou phe a sHr wiely of @dioB wrc snldi.

HscL4"dI Hs?&) + 2cta^4)

Hs(oH),<.d) H sl:o + 2oHa"4)

Th.sc re&tioN ae siDply dis*cialion b @.lcErc o$er E.clioE dep€nding lpon

.vailability of IHg. Asiadve @lio6 wcE al$ Epoi.d by (t8), the @ton wilh SO: is principaly spoNibte fo. de following tw$oo'

soal"'d+ Hzo ) Hso-t +H+ fisot(r..){J0ii4)+li+

HslA) + so;?do ) Hssqtq.)

Hss'r@d+ s'ita ) Hs(so)ra4)

1,7,3,1 Otidation in aqueow phase: Oxidarion of EHs is r€toned by sderal ch.nicdl spej.s. Murhe, in I 992 { r 5) erDned

1 oxidation of EHg by rre6 of Or in aquic syst tu at 6le of4.7 x t 0'7 M.L-s(

Hsl"a.) + 0,<"a.) - Hsl&) Lin and PehlNno in 1998 (39) Eponcd oxidation by hrdloxidc Etticjl; |he nle of such

@tion is 2.0 x toa ttrr-sr.

Hst4 + oH

suggstcd by Lin rnd P€hkoncn in t998 (!9).

ct2GO - Hoc\4 + cll.o + Htq)

Hoc\ad ) actad/,+ Htca)

Hslcd ) Hoctldq) + Hslta,

Hst" - octa. + Hs?:a)

1,7.3.2 ReductionoJHg in dqteous phoee: v.rt few srudi* hdv. ben Fponcd d Edrction of Hg in hieha oxdlton sbt. Hsr, dc. vd r&n, Mad.r ad Scon in 2002 (40) .vidd.d cdGdon of HgSOr lo EHs; rh. tldion it slow dd d.lhds upon ldp.nlw. Egsoko) HsU)

Amds lery slor Eaction is at& .vide@di

Hs?&) + Hoa"d ) HsU) t.7.J 3 Metltytalion nJHs in oqueous t hose: Mcthylalion rcsu.ll con\e66n o Hs p;ncipduy Hg,i lo d.rhyh.rcu4 (a more rorrc fom), rhis p@e$ is qied oul in two ways, by micrcol8aijehl and chemi€l ddvir, (41). Midoo'coism cd do ne$ylarion in borh frcshwar., &d salrwab (42). Me$ylation th.r o€us threuei nic@rg&ism is tm.d $ biom€$yla1ion.

IO Thcr e rM foms of monGm.lhyhcd mcrcury, merhylmcEury chloidc &d

ne$ylncrcry hydroxid.- Mcthyl ndury chloridc is slabl€ in eawaler while ils

hydroxidc is slable in freshwar.r,

Anolb.r lom is dimerhyln.rcury thal is volaril. dd uualy oocs nor st.y o @l€, du€ lo

its hi8hd volarility. Bioh.lhylador FirciF,Iy d.pords upon Hgr' @nr.nr and hi@bial

aclivity. wnh he$tlarion, dc-ne$ylarion is .lso a ni€,obiat eacrion. p@ne of jpally rcthylbercury is pin dep€ndine !po. lstc ot me$yt.rion and de-ne$rtalion

(43). S.veol f&toB afcct h.oylatior like Hsr, corcmlFrion, disslv.d oxysa (Dor,

pH, SOr'z, Sulfid., (,14), sunny dc. (45). srsigty bonded H82' Oke HgS),@c slowty

in conpdison 10 HgCl: (46).

Dissolv.d oxy8€n (DO, conl butes ro nerhylation diferenlly in acobic rnd aMercbic

@iditiotr (a4. M.thylation k slow in @bic anl quit fasrd in e@bic syn6s

(4E).

X w6 sludied thar whcn sulfar is added !o lale *dinenr in oxyBcn defi€i€nt

enwonhent,t Dc!€es MeHs prcdEtion (49). Ir prcFnce ofsultidc h nisher.nounrs

ar hiSh pll and lov rcduclion poGn(ial, nccory h pEcipirar.d in tom ofinelublc HgS

&d inhibiG m.rhyl.tion (50). Undd ljs or neurd pH of wrer, thc nonomcthylhdury fomaioi is [email protected]. Vhile at higher pH to,marion of dimcthylnercury (DMeHe) is fevorabl€ (5r ). Usually at hisher pH $e cscapc otnercury frcn wat€6 is incls.d dE |o mor. fomadon ofvoladle DM.H8. pH slso conrots rh€ aumsphcric-watd disriburion of H&

In hi8h salinny, rhe ratc of biooe$ylarjon is to*, (45). Biomerhyta on is atso allded br bicalbonalc comcnr of scawaler (52),s!|idc (49) ahd chtoide conrcnl (51),

ll Huic &d tulvic mardds fom oDptqq wirt He!' (54). h tn* inrcr&rions MeHs

ion h hound ro sulfidic bi.ding sitc ol huni. sub$dc6 (55). ln acidic condirion MeHs

bn is releed od bio-.vailabl€ in aquadc sysiem,

OrSdic conrent llso incrcs6 $e oc of mdhyladon b, stimutlting micoorg&iss

{56). Minerals lik Fcr'(in highd @nc.nftdon) bindr sulirh blr has m rcmarbbte

cf.cl on mctnyhtun (5?). Selenim and me8&6e drc bind H8: sd afecr

M.rhyl ion @ at$ b. ard.d br see.al Ei.rion or lenp@rue (44). MeHs is

pmdud in larg.r mout5 in sllmcr tr whitc ahosphsic ImFdlc i3 hiCI (58)_

1,7.4 Chemistryfor equilibriun otHtinsedimenrwater phases: Dissolv.d btuury compounds @ contidowly dcpositins ed ag.in diselvins. This dissolulion pr@es h.s @n in cquilib.im. Th. s.dincnl-water inrcracton cSarding

|lfupon of m.rcury is su studicd (59), (60). tvbry fe|o^ intt@nc. chdi$ry or disdbution of Hg in $dih.nt-warr ph66 lik pH, DOr, distv.d or8snic c5tbon (I8).

A najo! deposnion b du. ro mcthylaion or biom.thytadon, EHs h 6lso disr'ibured in b.rwco liquid elid phe. This EHg is usuatt, poduct of Edrcrion @crion of tHe srlll lik. HgCl: elc. lI is r.mcd a H8X in folto*iig F.cr'o!.

HsxoJ) HgL)

Th.s salts d€ atso in equilibdm wi& disciarion in ro soluble iom like ionic Hsr.

2HsXG) - BsA)+ Hsi; + zxa&)

l2 Hgr' s6p.nd.d b edindt ud.rgcs b&tcdat mctrryl.{on dnd sinulr2.Nusty ill

sulfide is also fomed (49), (50).

tl gi; CH,H sr

Hsii - (cH')'usi,t

dsi,- + Hs5

Disolution of MeHg hd eqlilibrim wirhin iolid,liquid phe. lle DMeHg is votatit.

so ndncc t goes lo water od llnally lo arnosphcE (5 t ).

1,4 Bioaccunrulationof mcrcuryj Aqurjc tldts, invenebnrd, ,lsh.s" tu@ls, see€ds elc. bi@aunutat€ m.rc!ry. Il

Esuxs into bio-naeiifica on (inc6ine conccnmtion ofHe) in orsdisms. EH8 does nol b'oaccu6ula& di@tly, whil€ high redivny of IHg dd McHg with i,racelular ligdds rcsuhs inlo seI€r deerc of bi@cumulariotr. The.L8@ ofacumutarion or uptale is diftffil for difieMt lr?.s of hftury p6em. !r is rcpon€d thai ncltEl nercury spccies accuoulates hoG [email protected] rhan chdeed specics (61).

Out of lh6.lwo lypes of @uhulaled IHg and McH& IHe sp.ci.s e nol biona8niUcd

(26), (62). Ahhough, borh ncllEl md orsoic conpld6 havc sinile lipid sotubilily,

MeHg is elcclively accuhularcd duc ro horc abitily of rlnstq aod tov roh of eUmirarion.lt6ul|3bicmagninc ioniDhieh.thpicIevets(I), soll@ of lHg and McHg in bioacc@utariotr s wakr. sedinc ed f@d.

Accunularion al$ d€pends upon the life $yle of livin8 speies ed ils aE , sie, habibr

ll 1.8.1 Fa.torsaffecring btoa.cumuletjon: Facbrs affcctine bi@hulation 6 be ctsificd d physical ed biologiat. physiol ferc6 like tenFnnIq son, pH, elinily. @nduciivity. cdox pot nlial er e(Isr bioacclnulalion. THg in ldllifish h foud fi!€ fold hi8her in sl!m$ $an olhei edon

(9). Als @plekon mcrcuy vdq @ el.v.tcd id Jue in Swdbh lal6 (63). On iDccac in |mFatrc lhc M.Hg ed Illg uplrt. is incFded for enc sp€.ies tik phtloplanlbn, Bsropo&, and fish. (6a), (65). AXhough pH, @oductivity dd elinily arecr lHS in 6shcs but no posnivecoreladon isevide'@d. (66). (63). A conelation ot

THg upraL i. nsb w6 didenced 6 iDcdon of conducriviry oa fchware! lare (6?).

This corclalion sngg6r. rl|r rhc bufreling @p&ity of t.le h6 & impondl inflwne on eunuhtion of nscu.y.

Biololical factoA toay bc idcntified d ase, dicr, *ei8ht ex erc. Trb rcponcd jn m!$k lissu.s ofa nEsnwrer lish is SMlcr in f€sat6 rhd n 16 (68). A pGitive @ftlarior b.r@n THg wirh ase, sia wish is Epoded in nw@u srudis (69), (70), Or ) 02).

1,B.2 Bioac.umulation h firhes: h ns|Es rccumuhtion iom wcrcr @cuts thlugh gill hehb'ee' Aqu€ous Melg is moe radily tznsnon d thtorgh gill @mbtu. tha IHg (25). Ultinar.ly MCHS is eldnd in [email protected] of fish for long paiod {26). lHg rccmuld6 only in rhe d$G b lh. posterior inksline ofll3h, It h .ol easily ra.sfeftd rhou8h lhis orSan ro orhcr pa s of body (25). Il hd been PIopoFd thrr abod noe $d 80p/6 of IHe .icErc out within 15 days ol cxpsw, in f4 lish spei6. Livs &d kjdrcy of fish h.vc high{ @unl of lHs lhan thcir h6cl€s (26). Ir is eported lhar half lilcs for MeHs in nost fish.s is one lo $r€c or clen mor€ years .nd half life for IHe is f.r lower, lew dars ro donrhs (73).

(6e). T@ferinS of mcrcury fom adulr to esgs ir at$ Eponed (7l). ExposuP oa p.c.r population lo McHg in l.borarory Gulted 2mg/q in rhei! €mbry6 {63).

Food web is th. pridary exposw parhwy ol m.Eury in most or8eisms. Il wd noriced that inm@ in M.Hg of pry it€Ds 6ulc inb .mcicnr tnst* of M.Hg (64). Dicrary shiffs ar€ obFwcd in pEy ncms oasiDild rrcpic levcls but frcm differenr habilar and due to difi@nce i. siz, a8.. Stluctre of prcy .ho aiLcts THg i! lop level pcdsto6.

(61).

1.9 Toxicity of Mercury Ton@b8iel .ffcls of n Eury irclude n.@loSi@l damq.. F Fductiv. inpairenr dcvclopmcnl abnornaliies dd Srosrh iolibnion, Il B studid lh.l adull fishes expoed lo MeHs, caus u-oordination, dininished etFroivqe$, imbility to feed. incr.m.nr in s@irivity in slvth ed rwiv.l (74). Tn. nudy at$ comlud.d lhar rcuFloiicny ffi ro bc tlt. nost prcbabl€ chrc.i. etfel of Hg loxiciry-

R€production b a,Iect€d by H8 .xposw. Also inpair€d rcproduclion in sensilive aquatic orseisms h6 be. shom ro o@u ar aqu@6 THg conlenl bclwcen 0.01 &d 1.6!9/l

(75). kborstory sludics Gtablished th.t cpoduqlivc cndpoinri e CenfrUy noE seBnive lha. grofib or swival wnh embryos and lhe e&ly developoenral sus* b.ing

Toxicily of McHg is bieher the IHg, wml c4h rnicl6 wrc rcponed rhe toxiciry oflBs and Mctls in sawaid or freshwater on difldcnt organkms. exposure ofkillifish lo l0-40rg/l m.rhylm@ury in Mld for 48 day3 €u6 stelcril m.ifomadois .nd dcfe.tive caldiovelld syir@ dd edukd uis fomadon (?7). Exposurc ro

l5 ph.nylnercturic acelate wa $udied @d at 0,1.20 pgn THg in wter for 25 days si8nifirut d4rce in harhinS frcqqcy is nori@d (78)_

'Ioxicily ol lHS is weu studied in p6t when rnerculic chloride is sradually incrcsed in vakr dd n is noli@d that at 0,l2!g/l lHg in s.r.! fo. 5-8 days c.|s 40./e nonaliry in fenilized eggs ol Rainbow rour. lt tuflher b€6i6 l00qo ancr 8 .lays (79). Mctcuic chloride (l040pg/l) is inrrcduccd to wl.l at laboEtory rrisls resutrs skctctal mdtotmrioG dd andioveold.Lf*tirllB i! 4l dars exposw ro Falhad Mirnow fish (80).

In Bivalves or fihd feede4 th€ roxiciiy is quile low in coDpdison to fish species Linper w4 lbcus.d for lHg expow rhougn wler al di|I.6r conem6do6 of lHs. ancr 16 w.clG Cro*ih inpaiment is noric.

1.9.1 Ch.inisoy otHsToricity: Bolb abiolic dd biolic i&tou in0uqce thc chemi$ry of HB toxicn, lo aquaic or8dGm by ailhc of i@rgdh or orgdic m.Nury {81). Thc chchislry of loxiciry is also ail4ted by cnvircMar.l condniotu (e.8. ropc6tN, elinity and pH).

1 he moc toxk foms of Hg .ompounds @ n.thylncrcury (or irs derivariv.s) .nd H8:'.

M.ihyl n rcury G 6oc eurcl, roxic thm IH8 in sEler crc.llmi l*l or thc sm. fEshwatr specics *ith both lH8 ed MeHS 3hovcd lhal MeHg i5 lgain norc toxic rhan

IHg(75).

R.gdding lus. lhc divalsr im (HB,) h4 lnsh .reiry {ilh pDlci6. ll is epon d dar n binds with sulfhydryl or rhiol geups of Plolciis (84), ReMrkable chang.s in ploducrion &d syndEsis of Foreins w€rc ale noried by tlsz' ion (E5). l6 As fd d MeHg k conemed, n is cffcicnlly $luble in lipids- lt sllos lhe apid peherration of hcrcury denvalvca to blood ed bdin eic. Prot i.s ft mosl abund&t ol

$e .hcmisrry of brain (8O, (51).

accumulaled ne$ylnwury to the eebellum &d €Ebhl cort x bibds tiSllllv lo

sullhydryl grtrup ol csp..rive pot iN sd c.es d.@9. to $c coual neRoN svstem

(8?). Simildly McHg inhibils sy hcsis ofpoleit &d RNA insidc lhe ell

l.l0Guidelines formercury Thc guidclinc v.lu* have b.en tuggst€d in odct to fls!rc lcssr toxic onvibnmenl

Regarding limils or guidelin€ vllucs for wat r World Av.ra8. valu€ for scaMtet is

suggdied o.o5Fs, (88). U.S.EPA prehu!8ated AVQC (Ambi6t wda Qlllnv C.ileda)

$ar 6bblish$ guid&ce on fie €llcls of polluran$ thal cm be $cd to d€tivc regulations

ba$d o. wat r quliry impacc- Th. &ur€ suidclirct @rdins to AwQc arc 2 4FM for

li.shwater dd 2.lFM for n&in. oreeiss Thc cbonic AWQC suidclins ae

0.012!E,l for tEshsat.r Md 0.025r8/l for nahncoeanisns

U.S. food ed Dog Adminisltstion (U.s- FDA) enon kv.l lot n*ury is I ne/kg of

edibh nsb (89). Aiother older euideliie 5ons/l for dercurv in $awater was rcponed (l).

NEPA (e eovitomdt l pret4lior ascacy of Chim) auowd 0l msAs wct vr'l a

mdinb p.misible libil ed USEPA allowcd 0 6ne,/re $d *t for fth (90)

Ceddid walsQuahy Glidclin for Pot@tion oflquric Lif. is 0 Us/l (91) ASEAN

M&ine warer Quality Cnkna for pFlation oflquuc lif. is 0 16!e/l H& fot Fotction

ofhumnhealthftomssfoodconsumptionslid.lineis0.04Fg/lHgaodlbrplotecdodol

hmd health fton Brcalion l edvirie is 2IPAI Hg in wt.u C@bl Mtcr qulny

standdd in Tnaihd is0.lrtc,4 (8E). t7 Srdinenr guidclire is not€xac y dr.blished yel. ERL (Efecr.d Rrg€-r!w) O.15 hg/k8 dd ERM (Eficred Rangc-M.die) o.7lns/k8 valu6 for sdihenr wqe susgcsred b6ed on da(abde establbhed 4 a of cnviomenral monilori.s (92). (9j). The '€suh AET (AppaEnr EII€cs Th6hold) appb&h slggered by EPA S.i€ncc Advi$ry Board is 0.41 dd 2.I mg&g for ERL dd ERM, r€sFclircly (94).

World avqage value for ndi.e sedin ht h 0,3!9/8 dry vl. Scdident Qudny Shdard for rhe sb{. of wdhitrston 0.414/g dry ua. (88). Dnn tnt.nh Canani.n nsine s.dine.r q@hy guideline 0.l3Fg/8 dry vi Ssdimcnr Quaht Olidclines ior Ftorida is

0.I l-1).7A3/g dry *. ed in Alstalia ed New Zealud ir is 0,15-1.01lg/gdry M In ltone

Kong guidelinc val@ is 0-l- l.0 !g/8 dry }t. (EE).

1.11 History of mercury poisoningr Mercuy h hdmful aor health and historicauy it w6 used by huh.o beings in scverdl d.ily rcdincs. Il B idddlicd 6 a loxic substDe an r feq di$1.6, 6F.iatly in l95l dcte w5 a sMt dislcr nm.ly Mininata Bay disEter thal hapFned in Mihimata boy.

Kyushi Isldd, Jap&. Few of th. dislqs e bricl y eponed h.rc $ar w6 happ.ned

1,1 1,1 Mnrinr.u aay disaster: As m€htiansd .bove il happencd in lhe p€dod of 1950-1960, but gor horiced in.boul

1953. A imbcr ol€rs w€rc e6 ro drM in rh. lnatl fishins lillag.s alona MiniDar!

Bay, The cals wen [email protected] lo bc nad 6 thc, wcr ninging rh.n*lles inro 6c *a.

ThG unusual b€havior in cal3 eol inceGed by 1960 and other crcarurcs like btds, do8s,

&d fish wF also s@ doing llE ucual acdvniB [kc €ls (95).

Tnc 6r$ c@ Elaing lo hercury poisning !o hu@ w6 r.pon.d !o a clinic of hospilal

!l the shin NihoD Chisso Cohplny (A cheniql indutry nealby} M4. watanabe

t8 brcught her 6-ycd old daughts. Sh? wd disSiosed by lhc doctoG lhat her ncNous systn had becn aflecred. About wk larr on Mrh€r child of M6. War.nab. ws ad'liited with symplohs similsr to ho elder sjster lew horc paricnls wee diqnosed having sme dis.@. Atd dcn initiaUy 52 lstioG fmn about 40 f@ili6 ,4 loud viclin of di*a.. In rh. period of 195l-1960 h.dth &pann€nls Mognizd 12 I p.licnis out of theh 6E adults, 30 childrn dd 23 f.ral vicim. conscnir4l c6es wec also

EPoned wilhin f€q ycs.

In 1964 moths ircidenl 6 rpon.d in Nisarr (anodtd @sI!l viuaSe ot Kyushi bland)

30 viclim weft id€ntified &d 5 of then di€d v.ry $on. h 1973 at Ariakccho in

Anallw disuict(dolhqFgion ofKyushiIsl&d ndAriak Se.) snc victihs having sihil& sFplom! wcE als evid.@d,

By l9?3, owr 850 Minimata dhae victiis Me identified dd the quanliry wd dp.ded 1o incce ir tutG. Thc cvidqes of |hal rime indi..rc fial other m.Eu.y poienins c6cs may hav€ gone undiagnosed. Edli.r in 1946 sihihrly ddcins caG weE ob$ped at a fcw dbtanc* frch Mioimara but no humd c6@lti* wee noticed at that

For investigation lhe @use of such dislnq a @ndirtee qas imm.diately iomed i. lhe

Kummoto Univ.Eily in 1956. Thb@noin . qliclly shed th.irwork to uncover the culpri( ofrh6. incid.nti. Thc connine sweycd lh. rfroi€d vill.gca ad lri.d lo find oul lhe $urcc ofsuch dis6e, Thc, firsdy focu.d on lhe b&t rial aclivily byhov by unn dthy liying sryle of p@r villageF, Thc p@!lc wrc no3lly.aling fisncs od othcr

loods aucmol.d wiln *af@d which they gor fom wld orMinihab Bay (95). ln Nicala (aorhq locality of coaral vilascB of K,lDhi Isl.nd) me incid.ir w6 noticed an{.ighr 16 of Minitura's ituid4t th@ w a fl@d rhat ruin d de rie ficlds of poor Nigata villages dd very less rie was availabl. to theh ed rhus they b.gd to @t don fish. Vicdns ofNigdawcrc son individuah atc up !o onc pound fish daily (97).

As the fdilies of viclins arc Eoe isb, h.nce comnilc. focused loMds n. lunhemoe, fi3h wrc ale b.havins si6g. a.d show $hc lFprom lil. huge qwdly nsh osc lo lhe mld sutf.e of dE bat in niStus. Ulim.rcly fishi.s was b.nned in 1957, ad cohs.qu.hdy in f.w montns l6er ces of such viclims weE observed. lr confimed lhat toison w6 in th. ish or shcltfish. Furrhd llsmh mbled @eh6 tlEr lhc asenr thar is eusins lbis dis6e is som. chcmiql agenl inalead ofmicDbi.t or orhq snild agen$. Bur stillir w6 nor cl4 *hich cbeftiqt sp.cic w6rcspomibh.ln

1958, Kmato Eserch lern coDlircd thar ! nunbd of h@vy mcrals w* csponsible for il. Sev.ral .quaric orsaism! wcE rested Md ir I 969 a crysl.l of sulfur containins

McHs conpou& eG ielacd fotu sh.lliish. Th. nsh dd shcllfiih w epon d lo b€ conlaihing up ro 50ppn of TH8 {98). T61 in blood, urine and hlir aalyss ot hw& paienb aho confimed pEsence of neury.

'n eucs oi chcnical cont himrs we *dh.d and f.w ch.micat mdufactuiing indutries 9d idcntificd s ihc solre of dBining IHg in& watcr of MiniMta bay. Tbe ellccb persisted cver after rhc abandoni.g indusrrial actividcs. lr w6 due to rhe aauoulatcd Hg lnar is nade !v.ihbl. fd ehc pcdods. Dimcuty E thd lrE tHe s srcled by $esc indsFies bul $c cals weE lalcd for tHg poisonins md lt 8 lcvch were not fomd to be s &ute. Ir 4rablished rhe lsct of nelhylarion oi H8 in ldsc ponds

20 of wal$ in MiniEata bay. Watd in Mininah bay did not rcfrcsh likc *a or c@sral shors. This w.rer body is quir. i$laled fbm lh. oFn s and ddat chegcs had a Ery ninulc cff.cl on Ml€r qulily, thE HC Gumuh€d in hieh4 dounls (9t. FouowinS this incidenr only in Jape severat agencies dd orgdiations srueStcd for procnins liae being afTcctcd by Hg poi$ning. N.tional institutc otMininara dise{* (N|MD) is one or' tE s€eh b€$d o.gdizrior ririvinS for rl* c@ and sfay of tife fom Hg poienin!.

1,11,2 PoisoringinSweden: Abo anq a decads fron Minimar4 Sw.dish fmes found lhe bir& |o be flopping h€lplcssly on |he sroud aid rhey sdfrfr.d inlo i@gltd positios .rd dicd. Tte nuber of thc* wild birds in crsad in days. Als dc bid. \e tcjn8 {Fir habtu lit n6{ns in slch a wy rnar they d.srroy.d nsr b€foe hyjnS eggs or even rhey demolished thc n6ts having th.ir eggs in it. Most of rho* birds w.c $ed€alcq f€B of lhcm ate oddrs

.tc. rhar wG *edcal6. Thc iun* of biirts w! E rd sn r; ir s du. to 6ring sd gains ftlr.d *im ajkyl-mercury tungicidq (99).

In 1965 n we discoveed lhsr Swedish.g$ conrained fou tiDes high.r THg conrenr cont4a$v. ro othd Eeps couuiq *it cxaption of NoMly wh.rc ue of McH8 iagicidc 6 very conmon. Io @tuqudcq at rh.l iftc wml E@p@ dd o6er ou"ai.s r.fued to inpon S*dish.ges or orhcr poutry ilens, Finaly an atkytnercu,y sd lralm.nr wd b@ed &d aftd such edon th. wild bird popllations r€tumed ro

(99), (95). mmal b.h.vior wiu im s*dish $tcottr dd flvirom.nlat agdcics sor qsagcd in sv@l oviroM.nral nonibnns poje6 espe€iauy aor nsh. ( I 0o).

1,11,3 l,lystery in lraq: In 1956 ano&{ alkylmercury poi$nin8 gor d€rcci.d in lraq_ In 0F pdiod of I95tl96O thc l6qi Covemem disliiblt d t@red seds for cutrivalion in nodhco IBq in 1955 and

2l jn cdtral lnq 1959. in ln nonlFm I6q wnhii rhe period of Jduary_Apil t956 hoE hd 100 fmrs md rh€t imily ndbers wlrc admitrd 10 hospiLl &d od of th€m 14 died (l0l). Wnib in @nlr.t t6q aboul moc rhs 200 p.@N lm admiued lo hospjlats. 'nrc @in lEeN ol|his ircidctr gft iltircacy &d pov€rty. The iujr.6le rm€^

$e!€ mable ro poison @d thc lab€l on lh€ e.d I,ajn &d lhey consuhed ir s food d

mey wse poor peoplc ( 102).

r,11.4Poisonint ir New Mexico: In 1969, a 14 y6 otd Ci.l Anos Huckt.by s id€nli6.

sevdal rmily iembe^ vcrc als fomd ill of rhe s.m. dissc. Tle poiloning occued only to Hucklsby fMity, &d it b idendfi.d thal they rerc €aring pork in higher mounis. Nddbo6 did ior cosu. @nllniFr.d fod continuosly $ccforc no ce ofHS illns rcrDncd for &y ofdtrn_ Th. pigs we @ndnmuly f.d by orc hixrurc of

$!@l rhings wi$ d. seds rearcd wilh alt lmdury fungicide p&ogeno (95).

1.11,5 Lake ST. Cldi. incidenri ln 1969 ir found b He @daftinaled fish in w.rcMays of Onrdio lnd euebN pbvinces of Cdad4 wncre twGtird of C&adie cblor-alGli pldrs rcrc tocatcd. &rhornics -nre Ceadid rcntodily *bbtishcd O.tpph THg 6 acrjoi l*t in nsh (95)_ carch frcn |hc Litc Sl Ctair ed olns adj.ccDt sils Erc ats snsuDcd in U.S. An Joinr ConDision's Adviery '.t€mtioml Board m.t i! 1970 ed $e sou@ ofgg rcrc rnveslisated, In th. sahc ycd Ceadie aurhoiirhs bamcd $e cohnerciat an,l spon fishing in St. Clair lak. for a pdiod_ Thc datl.r ws atso inreroively supponed dd moniloEd bt u.s. Aurhoritig ( l0l).

22 1.11,6 Other ninorincidentr: S.vclal other incidclrs w€rc reton.d for Hs poi$nin8 glob.Iy bu no major disler is eponcd alls 19?0-1980. ScveEl lahoEbry H8 .xpow cei *!. rcponed tik. rhe adol6cenls wilh sevele hypenension due to heeury i oxicalion by shool bdom.rm is

ln 1996 Pol rscn Waterhalu iniliaEd D&rhouth,s Toxic Mcrnt pogrm, white p!.pding d experihcht lhar involves lhe uF ofdiheihylmercu.y she spilled t€w drops ofcoopound on ht x doB slt won Bfi $ar glow qs in d.qur. in pErntin8 bd from exposw. Within six monttu stu slip!€d inlo a @ma ed utrinately died ( I O5).

On Februaly 19, 2006, the UP-Narional Poisoro MeageDar ad Confiol C.nl€r (Up-

NPMcc) ar d. Philiprine ccrc.ll Hospir.l in Msila @ei€d a 14 yem otd boy *irh nrnrbness, r€dncss, andpain olextremitieswilb hisrory of cxposur. to clchcnhlncrcury in his sch@I. Thc roxicologisl rc infomcd rhar a F@u!y spitl o@uEd in rhe scio@ clas i. lbe moming dd eorher simild incid.nl hrppened in rh. anenoon in anodei cla$tun Tbe childen reporledly applied nercury on thenskin, bair md orh( pans of

$c body Some .vd brenghr $nc m.rcury spl6 ro rhen hom* d souvsiE. The

UFNPMCC al.ircd concem govemmenl agenci4 ed coodinared wirh th. sh@l au$oriries b elicit sddirio@l infomafion on rhe locidqt ( 106).

1.12 H istory of Mercury monitor'ng HlDan beinss took srock of poUutioi very larc lter induskiol €volulion in thc lsr ccntury. Regarding n.rcuy polludon, $iendst ed |tfuhd wr€ atmed.no oic of bi886t di*ler of m€rclrt va occuftd in l96t in Mioitula, Thc disl€r happcncd in

1963 bd ano fa yeds it w6 dploed thar lh. que of srch disNt€r is niercury toi$nins. No pronincnr Hs monibnnA wd Eponcd beforc th. d.adc of 1960.

.21 lh lhe decade of 1960-1969, scientht did some rcsch h6tly egadiig cheftnq ol m@ury- Somc tri€d to disrer ho{ nftnry is roxic. 11 wd quite dilficuh to g@lify lbe trace l€v.l m€rcury 6s al rhat tine ml),tical m.tnods for tEce le!€l an.lyrh wee not

ln 1970-19?9 int€nsiv€ rcsscn w.! ratoned egardine nonitorihg, toxicny, chenisrt dd Mlm.nl orn@!ry in difl.mt dvituM. d $gmcnls (*c T.bl. l-2). ll beuc posible duc lo developnent ofinpov.d ealtiic.l f&ilili.E w.rc availablc.

Ih rhe Friod of 1980-89 ed then 1990-1999 lnc .*er &d r@c level dekmiharion ol mcEury wd dqelop.d .nd it mde il posibl. r. nonilor Hg &d its oth$ speci6 in di,I*nt .rltoment.l ffp16. Al$ @dch6 hav€ suggatd sv.r.l modch for

.xpGn ard cyclinA of n.rcurt in dvireMcnl.

Now in nodem tihes f6l. effrcieni, p@ise dd ecurare ealtlic.l mcthods and

@pline m.rhods @ av.ilable rhll allow nonitorins of h*ury d llh hc. lev€lr.

This is $. era ofemersins sciaces {td diffo€ni di$iplircs ofludies @ doins t'ojeds in Emedidion, prediction, plading rhc us5, whing .lEmativ€ elc. Scidtisls aG locsins on ihis issu. .rpoldtiauy wilh ti6e G4 FiguE l -1,, Figure I-2: Compt.ilor of Btinrtcd numb.r ot rni.b ler adrum for nercur]

'120

100

0 196G69 r970-79 1980-Eg 19€0-99 2000-2008

25 A bri.f oa histo.y of nercury pollutun @nnoing ed c@ch in the d.cade of 1970,?9

(the pcriod in strich H8 G id€nlifi.d s hmful) is obrhcd in $e folo*ing Tablc t-2,

tbh l-1. s.tdr.d lir.nrun tdr ovimpn.ibr ncrcunti ib.d(.d.ofi97

l97l Toxiciry and .euDuldioi ol mcury @!ooM3 b .qdic orFlhr 1972 P.n.hrion oa M.Hg h blod.bnitr syn.m. Eff.cr or phe'ylm.rcuric .*tb on htGhini t972 in$.ebdfi,h, Kihkt'w .nd Hulth 1972 (78) l9f2 Toxialosr ol th. llkyl m.eri.l .mlodds M.Hg in ninbo* t913 rot lissuc upbtq dislriburion dd excErion. A@rnularidn in OHg.nd lHs in Osb, McNury{ra.nk matu.si{lhs in 6tu.nG s.dircnts dd incFlhiil v:rd. LindbsB dd H.rns laT4tlll) Oral.dminifttioi to 1975 ofM.Hg rainbo* rout finsdlins. t915 H.kinscr sd Ge. 1975 ( I l3) SchcM, Amstrcng .nd No*.k t975 ElIEs olmcKury conuminlkd dier ir FLh, 1975 (l t4) Hrll,Tcnylnd Oouglitz 1976 1916 M*ury in tuh ud shcllaBh fl t5) H.ll, Teny and Lrsis, .l !1. 1976 1976 MeEury in filh ?nd shcllfish 0t6) H.n. Llw rd McDonald 1976 EfieB oI harcur, .nd opp.r in ninbou hur (I|7) Efrdi ot McHs on t916 fie Cencd ons orb@k Compa.isn oi &6bic {d ea.rcbic t9?6 Olsn dd C6D.r 1976 (16) dhyldioi of m.sic dlod&, \916 A6unulrtion of orgei. mcrcury Sudivlland gowth of bivalv. t977 l(a. uidcr hary ddlr slra. t971 DFmi6 of hiolo8i.:llr r{ihbl. m*ury \977 ElTa ol M.H3 in Dor.rn iyn.h.is 1917 Elrsa of h*!t D.r!k ,n fish. M.Hs Inhibnion lnd inc@tion wnh r978 s[.iry md cldnium. Aoeu mu lal ion tnd bioblnsaom{ ion of r979 WindomandKctrdrll l97o(64)

l9?9 Mcury rd *l.rium 6nro' of @erd,. Arin. ud Nrg.lo6 l9?9 ( 120)

26 1.13 Preventiod fron mercury pollutton Thc a*@ns of mury poiening is ir@ins wirh rime in $e rcrld. Inr.marional

ellorti re udwy ro d6uge comunitis to hlvc e 6vibnn. sfe fren IIg

conpounds. The contnuous @ of m@ury in indusoiat ard other prcs,e to bc

.xchansed *idr lhe alleoar sysrm $ar e et r,.grdins Ha.mi$io.. Anoder way prelenling io! sviremmr fton H8 pouution ir !o pft-rreat the chission 6oh indusr,ies

ed o$er sources !o trdsfom rhe Hg inro anvircnmcnlgt f,iendly torm.

1,13,1 wastewarer treathetrrtor Hg: elhods w.rc suggcsrcd and eftDloyed by induslrics and @munni€s. Or of th€s thc weltestablilhcd ed wid.ty lsed or ,€poned lechniques of

mcrcury t€alrne.ts ae pEcipitotio! of Hg, coaSul,tion or co-prcipiradoh &d

ad$ryrron on e.vated Ebon (l2l) on difctur cr.rs (122). orher.dvdced Derhods

@ dcsiSn d in nod.d asc rEh d ion .x.h.ngc t@&n nr, ch.nical edErion, dd n.oblm sp,rarior Slnc ori6 a .n.,Bin8 l6hmtogi6 Uke @rc{ycl. 4borytion, biologi€al reaunor (123) qd h.Dble.rrlclion.

Prccipiladon of mercury in diIlcFnr fodr is eri.d our by pv@t ag. 5. Ineluble sllfid.s de one of slch chcmiel foms ot ioiic nccury rhat gel p@ipiialed. Sodim sulfide, sodiun hydosulfide, nasresium sllfid. .tc. @ used 6 asenb of sultde pr€cipnado. (124). Coasulmts like.luh (atuhiilF sulfale), ircn slrs md tihe arc hoslit employed for ioorgeic dd or8&ic mcrcury Emovat. rhe mechmim for mercury rchoval by d@ dd ircn js litc adso.plivc co-p@ipiiirion. Adsoplion l*hriqE is moE lopuls in srwrer a.arnol due to ils cost cfiedivend' Activakd cheost of wbon conraining ha a is cfecdvet, €Dplorrd by

5eEEl kys (125). Kinctics of Hg ad.o,ption dcpen6 upon @nenrarion of a

27 tucrial, ed rhe physical dd ch@icat ch@crenstics of th€ ad$rb€nl Aderprion atso

depends upon th€ pH of fie sasrcwarq and as p| is dcceGe

inc6e4 Mss resfer coeilicicnr, etf.dive dillqion .@ificicnt, acrivation enersy &d

edtopy of acivation contribuk in thc mechdin oi adsrPtion. Adsorprion occu6

lhrcurh a filn difusion necbmism ar tow conc.nudions ud panicte diffusion

mechdkn ai higher con@ntrarions (126). Tlc eurcc otsuch carbon is nauht tike bone

charcoal (127) as w€ll as synrh€tic (l2E), (129). powdercd and gtdutaled acivakd

@bon mostly dploy.d i. the aderpdon of pollubd in 's wdeules. Rehovalof elated cohpouds of Hg is at$ inv.siigar.d u6in8 rar!61 dd syn$etic conmerial

adsrbenrs (130). Al9 cmwnls rbm sp.cific irdurrics arc jnv*dgabd for Hs emoval

lion d€n @leqler ( I I I ). Advdend iD dE qulity of vst Mrd lrelse pldts

Dats lh* planrs steguards ir fton bcing ! $ue ot Hs aner Emoval. As $nedd€s

incin€mrion of sludSc froh lreincfi ptdr. b.@n6 {uE. of armo+h.ric Hs. Tne

mN balde stldi6 of such pldls h.lp |o fud oul rhal the emci.ncy of pl&l for

movrng nmnry. Ev€n lh. incii.Erion prsqs for sludgc of r,ealncnl ptan b.cohcs

safe !€sdding arhosphdic Hg lcv.ls ( I l2).

Acljvared sludge ed clays ac ale ued tor H8,snovat fmh w6€s (Bl), (Da)

P'ocesed quite clays ee emcient ii Hs(lr) Fnoval fiom wsr.warer ( I 22). w6te natrials like ussd paper, concrcto, ch.rcodt erc are lsed by nixing wilh linestone. eraone, nilrclile, edsitc erc. as adsorbenr. They are found efncienr aor reatnenl of Hg ed renovat ofothd pouuranrs iD small rcalnent dm6 ( 129). lon exchoSc nedods ft al$ ued in ucalocnl of wGwr.r for Hg enoval. principte m4hmis is the ata.tion of ionic Bg |o rhc prc-chd8ed ion excnmee eins. This

28 nelnod is iNnsitiv. ro vaiabilny in physiel condnios of *srMler ed an levcl

€muenr conrrnitul ce be achi.ved. A vdicly of qins re availabl€ for sp€cific polluranl chedial A disadv&rag. of ion-cxch.ngc systcn is thal it cmnot be usd for

wale.s wnh bigh diselved $lids, Coomonty usine conmercial mercuryjetccrive

chelare rcsins tre Duotile Es-466, Dowcx A-r, Nhe Atm-525, Diaion CRI o, mbcrhc

IRC-7 18, Unic€llex UR- t 0, Sumichelab Q-t O er.

A l6s populd n€lhod of H8 Moval is ch.niel Fduction usinS st,onge, Fducing

agerls. Chemicsl edlcing aeenr likc aluninuq zjn , ircn, hr.tr&ine, srdnou cbloride

fld sodiu borchydride e few such appljcc i. Th. rcdu@d H8 is inslubte in sysrm

ed cd be s@datcd by filtnlion or by othcr eud s.pdation lahniqles. Biologial

agen$ ae arso inBdsaicd for bio-..ducdd 023)or €E matic Gducrion ( I l5).

Exu&rion ofpouur.nl e be po$ibt. BjnS n.6baEs. Di{I.cfl fittrarion dd Evry osGis srsteB @ povd for abour ?9.9.9.2 rcmoeat of Hg ( | 24).

Sonc biological tlatnors e ate advis.d fo, Hg @oul. On of ir is bio-educrion usin8 mitubial cDlrue likc Preudw@ putida.t . \t23), At8.e e ate i"Btisat.d fbr Hg emoval in w6t w14, Th.F m.thods e mor enviomenrzt friendty ad qdle cost el1:ecdve subj*r to rh. avaitabitiry or such livins m6 (86). Us of enzyn. ats helps in efllcrenr rcducrron ofHS( r ro ct.m.nratfom (13j,

1.14 Lcgislation lor controlting mcrcufy po U u tion.

Conrrol on rhc usge and disposat offrc(ury conpounds cs bc torced itrhc lcsistadon

6 allo{ed by propc laws and acrs, pieen y such taws !c8a.din8 environnental pouurion qist ih alnost all coun[ics in lbc World. But in p6r nany devetopcd @unl,ies

29 EE awade! &d nade las for qviroMcild p,or@rion. k @ f@iliral€ $e adivnjes

of €nvironmmlal p.orecdon org&iationand.Sqci.r.

1,r 41 I'ritial re8ularions by communirics: Mercury 4 a dalg€ro6 tollula M i&riti.d by htc 1970, but lhee B a@s

about $e pollularts ed pollution wrld ov.r. p.rh.ps n.e!r, ws coNideBl indi@tly

bt ddsifying it 6 a netal pollulart. lo rhc wrkc of rhe othe, Minimata disl€r ed

subsequedt lamuirsj a Japd€sc judge rutcd rhdl compei.s rhat coutd not cte& up their

wasGs should not opeEtc. tn rh€ United Srarcs, howve,, federat asencies iBno€d lhc

ble dischdsd for yeds md then movcd vsry stowly ro find oul what was beine

dnch&sed &d ro fom policia not b hat rnc disheecs bul lo no.tror rhem.

The kgnhdon ovded lhc m|rd ofpotlution in rh. devctopcd @mlries lik€ U.S.A. Ir wa I E99 $,iro Amcdcd 6.gB p{sd rh. Riw6 &d Heboc Acr .lso identincd 6 lhe Retue Acl of li9- Erlid US @ngB dicrcd rh. Us Afty @rys oaendneG ro pohibn Ih€ dumping ofEni* inlo N.w yort H4bor,

F.deral laqs p6sd aft.r 1889 moE oncn ru$od4d lhe tEarn€ of wdMrer lhan prcvening turther conlanimlion. In l9l2 th. pubtic Heal$ SeNice w6 aurhoriad lo svcsr'gate the healtb effeds of pollurar! ii Dvig.ble lal6 dd slcms. rn 1948 lhe

Fedelal wate. Prctecrion dd Conlrot Acl galc the srai* the prindy .ishrs and respoN'bililies for the @ lol of warer pollurion. Cohequ€ndy rhe filn pmfle.r warer

@ntrol rcl b pa$ed in 1956, Fish dd Wildlif. C@rdinadon Act rhat suppons agmcics lhal enfoe pollutio! @.rrolpregms, b@ic law in 1958.

In 196l Ferteral wra qualiry rcr.xlcndcd,rd l|mgrhened fed@l adority over incdare &d cGlal DvigabL hLc. 'nr wE qlr]ily acr 1965 plaed all fede.al w.rcr pollurion otrlrol prcg|!@ Ddd rh. n*ly c@led F€dcral War* poltution l0 Control Adftinisn?tion (FweA). ftis FWeA sEs trcfcded ro Depaftre.r of $e

lnl{ior ard fi.ally 1970, in il @. bdd EpA, ntc d@ qEu esroBton er 1966.

8.ve stales noE inentivq ro adopr warc. quatily siand.rdr.

Ahd Walq Quality act of 1972, rlE t899 R.tu* Aq vs no bnger a s!@re oforcnor whicl.. The I9Z War.r eutiry Aci et sods of "rh. b6r p,ftri€bte" wa$e dischage reclboloey .,b. br l9?7 &d rh. availablc,,lechnolosy by 1983. To

'restoe nainrain rhe dd chmical, physisl md biotosical i,Geriry of rhe Na on,s Wac6, all discheges ' of wsle elflueor inro thc wareNays were decided to b€ halGd by

1985.

In l97l fileria E fomulaled b potccr work 6 fon ccupflonar qposure lo

This is a srory ofoie of&e brSs( indusrial @ury od n.nd h6 not b.cn qune difl@ in o$er ddeloped n doN in p.sr. Oth6 rhe devetop€d @urnq, no prcFr IcgBlalion qplored B allhond sI.rs th.t hrrc ben tutcd by oder natons (like

Brnish, Fen€h Ponuguese oi coloni.t_ Th6. colooial sllls had a tide allecl oa legislation eskblished by their rulin8.ouuy. j.14.2 LegislarioD itr the presenrera: In fi. nodeln rides the aqEness of.nvjrcmcnkt poltu on is aoout at, o\ er rhe Wortd and $erc e agencies srivinS for n. Llws re applied to contolsuch poblen. ln USA rbc laws, ordimcB ed EsolutioN freh difle@t govem€Dlat toms havc bd develoFd in pal. @nr Cl@ air acr E imptcmcnlcd rhal hd poGnrial tor onbouinS rhe qposw ofqg b amospheE. Somelim.s gov€@ents @ Siving pdonty to indurial deElopnenl or orhc, &n,cvcftsG oB dvircmo|.l po16lio! laq, by prcposing elqadon elc. h nalc ll rh. legislalion re€ler in eftciency, Iit. in USA. prcsidc Bush Admi.ishrion,s p@poFd Eldalion in .jr pouudon l.eistarion. Cl6 an aq cumoy cqurc Lp^ ro

isrc "Mdim@ Achidablc Conaol T@htuto&,', (MACT) slliards. Th* $.ndards

lold rh. Erli$n Eletric Inslitur. dEr rhc Clqn Ai. Ad s MACT standard @!td Educ. powcr plec hwlry €misios by 90 F@n! trcn 48bns ro onty 5 bE by 2O0s in wbol. USA. Bul io Bush Adhinblration', popGal h.lF

Rduclionslo20l0ddalloMng€ni$ionsof 34tonsin20lOe.l l5!oos jn20r8,

On fic olhf hmd in 2001abour horc rhd 40 sn|es in U,S, 6sh consumplion advies lbr h.rcury lmcd cnizns lo tinit how otco thcy.ar ccrujn ryp6 of fish, b€qus the tish rc @nlamimred with neeury. Thc U.S. Food sd Dtu8 Adninisration and EpA

Accifically $d pEemr wonc4 mh.n of childb*ing aee, nGirg holhersr dd toung children mt ro an shdh shdnsh, ldrg Drckftt, or ril.fish. Tne .dvie ate wos dE se popularion b linn dEir @nrunprion of alb.coE.wntu rua" or rwa sl6xs lo rx ou6 or l* Fr @h &d lsh ihlr havq toE tdels of n@ury, such 6 shnmp, .m.d lidl tu4 satnoq polloct dd q(ish, ro 12 ouc6 o, less pq rek. Six ounces of fisb is n awnge cooked m.al, about ih. sik ofa6 of r@.

J2 pdt In @ot ev€Dl sr.t€ laws @ b.iig ihplcmdr.d in dififfir srald of U.S. and als

in Cmda. The brief d*riprion is liscd in th. foltowing lrble:

I4!. r r: sbrc Ls in us^ r'dcrmd. Md

T'k h" bx, ri! n$!Id!6 $k ft dkLihri@ i'i trifi,'il,aT^*'**** rrh! eEhibtB d odury h qrhq moedi 4!@ (,icr!di3'h. Dinmnmffir 'r nrhmir5 dd or ioKdr hii'F tu coM

'dN$s.h!li.mfuls'$d@nn, rtu l6rry 206

se['@momd.Bh|yio|b.$|d hd'lui orhe|0'm felrt ri6 a ffi

r4n hr ht ftlk of ffi!ry ffiom;

ftirtubrhd!*or@rlqhmtr;6

@di''li6'onciatoo,f,6a'fulll.ei. hir b" dls d' rh"ry.itu d dt4 dr.ddlll@4idt''dJ6dftnhE'sn'FliibiG

nit !w eml'$ib ft ,h { didhlion o. ;ffi fu]!Nq!16fr0!'d!i6o.lofu|d!d 4*@4mD6ihlerei$ibi4idlbeF|yhs

r rdi! , ,tu !k or h*a ft,an-me; ,;T;;t

ft. h* hrr s. drcumjbiq -d.inid-;6:i*

1. tr* p"hru" ,i. eh d annhia; ;i-;G rhl tu h* eohibic s. sr. of d;;;affiaa

3J Lcal ordimG d lle imptm.nl.d wi0r timc in diFc@r st 16 thd bmed m.nulacturinB dd scllin8 ofsde.al irens $al dG d.nseous m.cury ,o[utams.

l.rbl. r !: shk hB tn us^ rid cr;rd. Rsrdi

od,Ie tui4*orlEq f.Gjr td !ffiB ftrua !.ri 4 Eulr dq trEqtu!4xa rFi|'rcd

odrue b.ii tr3 tu u of mddtt@;in@;cd 6br orE DE&E xc k or ruH oijb* b-irB dr; ;!andG;iG6i;'k ftiephrrr.dtuqi(€-bqdffi o!,8( btr'u 6i M;tuRr-A;-Ah;i '4 odii4! tsiirs rdr !r4 mr,;toE ndld;e of

odrmc b.iih! Eh sr, .eht@nd];F6h, or o,ni,lrebmilgft uirdqmffi l@-ffi ; tu;:;b----:.;;::=:- dbler.x4E|Hamd'luMrd-qfutr odirehibtddrne;i;@j,n;?;;;E

i. MlfkrlB nFi d ru | $t.r;hq i;;iE;;;;=;;-

o'.n& hhl nn6fr q irFnaaGiE;;i; fu'E4o6 od,re roiq MurrdE-;rd;;;il;;;7ffi oldrEu tur. tui * ;rnm{y?;, d-;; ;i

34 1,14,3 Efforts in Pakistan: Th. govemefl had Udned $cB in iG ellorls lo srd poUurion frcn shipping along lhe Kecni .o4di@. A. $arcd in rh. innod*rion, th. goverMst is rryitr8 lo find . niddl€ goud b.lwaD lDlici6 thar FoDorc irirlc wirhir a sBlaieble .nvibnncir

Th€ Ea$h fo! dis dis@mat srems from rh. eto;l sov€rMehrt bubtes in mc8ins the e.liroment ed economics in dre deision n.king poce$. Iollowins .rc fcw efons tnat havc b..n mad. in pan:

' Pakisbn har d*lopcd a d6n for N{iodl Action Pld (NAP) on Envircm.m fo! tnc poterion of Mdine enviom.nt fr.h led bed aclivities NatioMl

Acdon Plan or P.list n h6 been pEpaEd by a 1ed of lool expeds idciified by

fie Minisky of Enviroment lcal govcmnnt dd tu61 dcvclopdeit

covehncnt ofPskislan. The impo'rdt rcle of cnviroin€nlal Nqsdcnr (EA) in

inregFtcd @anal anc n@g@il is r@g!izd.

. I. 1994 thc govcmenr $1up 0E Mdio. Pollution Coflrol Board (MPCB) ro

supeoi* 4d inplemcnl pollulion @ntrol md prcvenion measurcs along

Pakhtd s @atline. A reU cooidinai.d natiolal poerm of EonilorinB Mrine

aosyst.m .nd biodivc6ity dsi€rEted pet@t d at6 E pmposed.

. Narioml lGrirulc of oc4oeBph, (Nlo) w 6rablished io l9El in K@hiby

Minislry of Sci6e ud Telhnology, covmeni of Palisiar. NIO also h6 a

rcparch s€lion ar Gawad& Blluchbtan c@sl, NIO in a relatively a shon t riod ofits cxkence hd madc oplinum u* of$.linned Fsdces, It ha inniard,

condet d and conplekd a nmb.r of pojats rclated ro @em rcsarch dd has

l5 efdjvely Bponded ro . widc vdicry of ts s rcquiencnq $nl is ndine

iidusrry and iarional iBtirurioE involvcd in rhc fiqld ofndirc caEh.

. Palisb.\ n&irimc *ctor is . vit6t coopon4t of our narionat €@ootoic md

milirary poB*. TIE Go!finm.nt of p*isld ha appbved Narionat Mditine

Policy of Patista! rhat aho co!€rs rhe polulion maner,

. h. Sidd wildliie Meas.nenr and wodd witdtife Fund fo, Naturc (wwF) bave

porecrion itutiar€d a and rcscarch program to consep€ rhc tuntes. rheir eggs and

harchinS d rh€n habilats.

. Th€ Nalional Oil ContirSdcy pld is bs.d on lh. esence lo prcvde vd€

intenado.al obligarions iicFatis rh. Inctutional Consndon oD Oil polu(on

Prcp*drc$, Rspos &d Co{p.r.rion, t990 (OPRC-90), lo which palisl& is

. Palist n L a sisBrory b a n@bcr ot @nEn{ons, poiocots ,nd i marioml

> Conre ior o. biologiql Diwuny, (CBD)

> MARPOL, (p@ ELia e hhrtu cdsb 6 illdm dtoeiq dln $s ) > convention on |mdc ofcnddsqcd Speciq (CITTES)

> Th€ Pakisirn Fisheries Odinan*.

> Int marioral Seabed Authoriry 0SBA)

> RAMSER Conrcniion.

> Kyolo Pol@ot etc. ( I t?)

l6 1,15 Analytical techniques in Environmefital mcrcury nroniroring A laricly of analyrical techniqu6 4 used lor cnvilonmehral Hg monnorins, each

lechniquc is fudhei modified in odcr io achiele bcrt€r r€sults. Soneioes coupted

techniqucs arc ued, or in soh€ ces ne$od of dnoving irlcrf@ne is also us.d whitc

ruMing smpla, in som€ studig spl6 (6p.ci.Uy like swateo ft pr€{onenlE!€d !o .mpliay d.ktion linils (138)- ln lhk srion a bricf dacriprior of fd popul&

tcchniquA, ued in he Hg dalysis dc givcn eith rcry f.w @ftslonding €xople'

1,15,1 Spectrophotomet!y: Analytical tehriques de the fluddent l rool for ay tr&e ealysn. h c6e of hercury

deEminations in the envilom6ral smptes sc ar rrace or llra trace levets Usual

elylical rcch'iqles like sp€cropholohetry eE dlstty ued in edrier times oi nodch

analtlsl nedods- SF.rr@hotom€try Bually i..ds b magnify de conco&dion bvct

by prc@[email protected] .hvircMalal smplB.

Dibio&nc is ued 4 @npldin8 agcil for H8(tl) in spl*. Thc chmcrc.inic wavclcogrh p@vides q@iratiE araltrist toot fo. rcminal d€kction linils ed tcsscr

Mic.lld medium is also ued in sp€clophoron.rric det mietions, Hg(rr) comphx.s dc used wilh ionh sufaclanh. Sha md Soomrc in 2005 (139) rcporred a mcrhod sinS

8.Hydroxyquinoline 6 acobplqinc a8.Di in dctcmioafion ofHcoD -irh *nsilivny of

1.1 5,2 Atomic Absorption Spe(rrophoromerry (AAS): AAS B $c mosl popular nedDd for rracc m.ral a$tysis. Us!.1 0m6 of AAS dc nol supposcd to be good in deremimtion of lra@ Hg in.nvirom€ al smpl.s. Ftdel.ss methods havc bceh reponed for tra@ Hg dcr.miradon, F6e aloniz.s ae ucd for

.17 bc. Hg dccniialion ed 6np.Ed ro onizd H8 in frme eirh aid of orh.,

chenisl ag.nB (140). Pl@@nlnrion on 86phhe rubes wid rhc suppon of flo*

sysreh .v.h improB de d.i.dioi lidir ro 0.09|1g/l THg (r40). cBphirc 'btecrron

funsce is aho rponed for quantiradve d.remioarion ofTHg &d MeHgspadcty using

@mplexins.sc s like 2,1-Dinerap(opropdcn3ulfotut€ ( t 4l ).

Oul of $s 0dd6 merhodr Cold Vapor Alomic Ab6orylion is mosl poput& in

q@tirariE H8 d.r€minador. Derdion li6it is cualt, about o.lFg, THg ad m.lhod

is cven usful for nftury sFcialion (142). Pcconc.nradon ed orhd inprev.h.nr.

€nhanccd the eilicicncyi *Nnivny dd d.t dion limi of CVAAS. (t43). (144).

Dekction limit h ihpmv€d Mifold by pre-concenrraring the Hg or its spcci4 b, analgmaijo. vnh gold. Very low dlGciion linir 0.0001!C/t 6 b. a(ained in dclmidtioN (145). Solwol exretion ndhodj @ ale Ntul for ltu. H8 del.mindion (146). Mdho<15 for dicr d.r.mi.arion of ditr@d spei.s of He ac d.v.lop.d as id.ndficd 6 di@r nercury eal'*c' ihprovendrs m al$ .chicv.d by using emci.nl m.thods of smple digcslioos lit. ni.owav€ dig6lion etc. wirh dirccr

L15.3 Aromic emission/nuor€scence rDcctromctrvl Enisrion .rd n@Gq* sp4b!sp' i; noE *Biijv. 08, AAs. uudty ebhic nblt*n* speEosopy (AIs) hls dctc.rio. timiis for Hs is abo( O.OO2,I3/ o..vcn b. .r (148), (149). A supled rysrcm of AFS wnh Hyddde sdcErion hs iftpovcd debnon linit of0.06ngn Hg (lt0).

Aron'c Ehision SpecrroDelry (AEs) is colpled with inducdvely oupted phsBa (tcp) speclrcscopy for d.r.minadon ol ulu! trs6 of n rcuy hdely ICPAES wiih d.rcrion linnof 2'5ps/l (l5l), (152).

]E Sderal AAS h.thods weE als ued N a derelor in chrcmatogBphic sysrcms. Mss

sDctron€r.r is al$ @upl.d with IcP 6 lcpMs is u!.d fo. H8 da.midtion liding wirh

s@l prconehrFrion sysL6 { 153),

1.15.4 Chrohatogr.phi. nethods: Several reversed phsc ljquid chronabgrrphic n thods werc sludied for t6c. t€vel

qua.tirative Hg dclcfrinarion. Il 6 mosrly prdtic.d by ioming a suilable conplex of

He(ll) wirh @npl.xins asent md by ncs of liquid chrc@osraphy (LC). Th€

ncrcuial @nplcx6 de $p6ded. S.v@t conptqing aSd|l m poptt& like 2-

mdaprobcmthi@lc (MBI). dilhio@bmar6, horyholin dirhio6bm& dqivarive

elc. ch@narogEphic nerhods de qune.ftcicnr in sepdaring differenl m.lcury spccies

(r54)t (155) Xiao"jing, €r al. ii 2000 (156) dcv?loped ion chrc@tosaphic nelhod for sinulran€ou dclmimdon of Hs0D wilh otlq mcr.l iotu. ftljs Belhod is Esrricred tor

{teLminjne ionic h.rcury with rr.,ret'on tinn of2o|ran Hg.

Hybnd tahniques likc LCICPMS is usd in H8 Md MeHs der€minadoD wirh daarion limit of 0.01-0.lFs/l (157); (158). Few Cas Chomarographic (cc) mcrhods mre .tso cxmi,rd and cflicicnt andly*s is reponcd by usiiS hcad sp&e CC-AES (159).

1.1 5.5 Elc

39 dlffeEndal pul* vol|amhcrry supported wnh sp.cial srccn prinred ct.cuodcs lh,r

G'rlting dekction limit l2pM H& Anolher study Eporr.d a rctiable Ddnod uirg squ@ Mve of sfuin8 pordtial tarm diffeMe ujng . moditie

method is appli.d by sv.hl ways with dcrccdon liftits of O.5nMHg (t62); (l6t). jn ,nprovemenl dcr.ction limils of 6-2JpM is obtained by sing gold nicoetccrrcdes (164)

lon *l4livc clctftd.s (ISE) @ ate u*d in Ftdtioncrry with dillcEnr m.hbrac of cletrod6. Qulily of ISE is quite poor in .ohp.lisn wirh orha rgdding dct crion limn ed ensiliviiy, bul rhis melhod is fsr ed good for rcutine o.tine nonnodng (l6r)i (166).

1,1s.6 Son€ othe. nErhods: Moded mcthods & at$ g.ning dd.lopcd fd H8 d.icroron N€ulrn Actiurion aal'5is (NAA) is on. of lh. Gfemc. r€chliqu. iowsdays ad used in H8 analysk d wU (167), (137) (l6E). Sev€€l techriqu* @ conpaEd foi THg d.r.rnin.tion with NAA. (169)

'fte oln&o-panicl.s e is al$ goinc io b. u..d ii ealysjs (l?0). Ncw ed cxremely s6il've m.tbodr .E dcv.loped for Hg ..allsi3. As H8 Edity fo@ and8m wnn gold, the gold @o-rcds or @o,tubcs e' b.ing .Dplo'€d for s.ruidvc Hg detsminadois. Manh.w. Ftorcicio ed CdpiStia in 2006 (l7r) devetoped a nc$od ultm-low Ievel Hg dercmimtion ui.8 eotd nuoods wirh 6.6 x loir g/t linit of detecdon. T!*e ectho.b e 6dEr @srt, ad rdiou oving 10 awil.bilily of neo- l.l6cold Vapor Atomic Abso rprion Spcctroscopy (CVAAs). roro vapor aromr.bsorprjon [email protected] (cvAAs) h. L;hrjquc n aromic

sp€cnsscopi |har is d.diard ro qMdbrivc elrsis ot mcrcury. r€rbaF rhis rGhniqk

wa develoFd by Hatch &d orl in 1968 {172). ti this r*hnique ionic or oHs is reduc.d

wirl rbe help of a srong reducing agenr inlo abmic Hg. The.lenenht Hg has d appreciable v.por prBsurc, il is volalile ad gdrfoms into g6ous vapors. Thes gar@us !aDo6 dc cdied ro rhc pealiSrcd eI in rh. paIh ofeletrorugn.iic ndi.tion coDine tom holtow popute carhode lmp of AAS. Educine agcnls @ N.BH., SiCI, e

1 r 6,r Techniques in CVAAS CVAAS can bc cldssified ilto rwo rr!€s, sr.tiomry and conlihuos. In slarioMry sysreh the vapo6 of EHg de coUaled irro a c.ll ed an , its sruaflo. ab$,bme ot Hs vapoB n*urcd. wl le in 's @nrinDs srsrch elt hs oFn €nG and il allows EHg valor lo ,low our of rhe .e[ on{nuouty dd aberb€nce is mesu.cd co.lir@usly.

D€t€tion limn for sraionary js syst m s@d bur .ondnuous srsteb Ms beuer prec6Dn hliovencnl in thc delecrion linil is ,rbined by riapping Hg; gold analgamaroA are sed 1o deposit or prc-.oncerlrat€ He. th.i lh.mat cnergy N ued ro G1..5. ths orarB@Ed Hg lo ob|jin absorbae of.ll H8 vapo6 tike simplc CVAAS. VdioN tns of oalgdatod u*d, 4 ki€r.d .lomic .b$rprioN sFchpr@&hd6 to, Hs e @@@idy aBitabt. .Diecl ndely ocrcury &at'26,_ ft.y employ gold raps to dcumulatc Hg. No ex[aordinary kple r.armcnr is required for such da]yzqsi th€elbre i! aho reduces ealysis 1ih€. Floq injedion sy$efts ued ro rnplove dc derection linil ad Dr.cisjon ftom sihple CVAAS. 1.17 Thc Coast ofKa.achi

1. r 7,1 GeoEraphical imPortance: P.tistan pc6id is lodred al the galday of rh. Cutf. tt is clos ro ttu, Ome, lndia and

lhc land-l@kcd eoral Asie counlriB. A corsiinc abour 990 Km lone c6 inc &d

adjac.nt coelal rcre of 240,000 Sq.-(n in Nonhm A,abie Sa is lhc @ known a\

Pakhhn codtline an. 11 conpris oflwo

$rorches ovcr 760 km. The Kalachi codrlinc sftrhcs over I35 kn. pakhtsh occupies a lery import3 position on rhc vitalr.ade md oilsupply outes fmnl Ihc Pclsian Pakislm Cult is nol fd fom rhe Rcd S., eirhcr. Thi! seosraphi€t toarion provldcs a oppoft4ny for Palist:! ro dohirare rh. ctuciat sterch€s bd vi1ot roules &rcss lhe Arabia Sa IEcfoE nud.os ich living &d nonliving ls@s d. prc$nr r lhc coaslal2onc ofPatisbn.

1,17.2 Ecotromie I importan.e aod.criviries: I h. b'sg$r pati$ar ^mcn h& &d eoronr enrcr of lls potu h&dte rh. najonlt of$e coulry\ sbom. rade whit. rh. sMoundins ciry of Kmchi accouils for half of rbe govemenlt rcvenu.s dd conrribur.s 20% ro pak6r3n\ cDp. The co.sral md pakiskn trdin€ ars of produc. .bour 5e6,98o meric tons ofmaine ljsh dd 25.000 netric tons ofshrinp. Funhq lo lhal ir cxporE about I :J I ,000 heric lons pK& of fish wonh 7.272 billion (pakistani cutr nc! Rup.€).

Paliarn is al@dy comifted lo povid. a suibbtc.d..p mreryDn ror rn€ lmdtcked coutris ofdre ECO (Ecomnic C@pdrion O.gdizdon), like anral Asio @uri6

42 Lla Ehvironmcntal Hg nronitoringitr (oasratreBion ot pakrsbn rturtu aJld mrShbonns 64'rl @unh.3 ar d.veloping @unEics and '$ r rha Rsion

lhe awams Eg&ding mdirc pollution ws initiard Ery tarc compdljve ro rhc

develop€d wo.ld. Fcw govemm.nral ad non-golcnmenht asenci€s are doins aood

pnjecls n thn r€sard, bu prop.! or conrinuo$ Hg monirorins prctocol is nor ycr

phcticed, Palistari eFdch€B e moniloring H8, sihe n€ety t98o's. Neurotosy patienr in KaFchi ciry de haling THg contcnt in rh.ir blood ed the pot3bte water is idenlifisd 6 $uce ofmehl pollurion (t?l),

DiiTerenl orgs of fish mpl.s froh $c K@hi c@ ofAfrbjd S€a @re ahaly&d !o di$over the &cumulation ofEg i! {ishes ad found rhlt kidncy !@wulats higl6r rh.n liler ad very low in Eucrq of fish (t 74). Thc avcEge Tss conr€ offish dsue inrhe

Fgion of Ambi& Sa foud l.2oAelg wt M (t 75). Jalel, Jafia ad M()aza in l99t (176) moiilored pveat tHvy hcr,ls ii rBh fbn Anbis Sa Kehi c@r ard '@ jn_ rcponed 0.00j-0.631r9/a eEl He ia firh larr on O.t2-4,tD8/g THs is reponed in edio€nrs of f@shwtcr swrd inrdfac. in rtrc p.tisuni cgjon of Arabje S€ (177).

TIE rsnbling Bulls e atso cvid.ic.d i. study.nq a yer (l?8). .taleel, Ashraf ed Jafid ih jn 1994 { 179) eponed lowr THg conrdt seawacl ed hishr TH8 i. sedihflt of Kaachi Hebor in compdison with olh.r t!ac. mclal, tn dothd study $e ene nalu,e orehpl6 wee analrzed and reponed 0.012-0.?4fusl8 wer wl. Hg in fish (l8o). rn $e smr rhe THg reForled red i. other fish sp.cies is in range of 0. 10-0.94 pgls wet {1.

(l8l). derailed A study ot heavy nehl nonitorinS reponed rhe Hg conrnt in fish, sedinent fEshwaler palbr&. ad ofdiffcei!.ivds h It rcponed THg cont nt O.O?,

2.E4ls w€t M. in ditr ie sFci6 of fi sl!; O. IG5.?l|rg/g wr 91. in *dinenl &d o.OI 7_

2.35 I msn in war€r (182). Anorho study by Jsl4t, Ashdr, d .1. in l99E ( r 8j) DonnoEd

4l THg nngiig 0,02?-0,468rg/e wt *1, io dillicnr llsh species caughl ircm lhc Pakisld resion ofAiabian sca. Fahwter dd ir fish sadples ofdifieEnr riverofPakisran werc dalyzcd and folnd elelacd THs (0.91 l-2.301 Fg/8 wct *1.) dd other merals in the fith soplcs of rwo rivds, indus&ial @te wa id.n{fi.d 6 . sowe oI ponudo. (lE4)

Comprrien of the dala of y.d 2000 wirh thc dai! in 198? rno*€d incFm€nl in lhe THB l.vcl ed fa orhq u&e melrls in fish melc on cdible b6is (185). tuorho sludy cov.ring th. Pcriod of 199-2000 for monilorin8 *v.rd lre melals in w.tldds of

Pakistan including Kuchi Eabor. THg cponcd in thb sludy is quire alming in th. snsc $al in iish, tbc TH8 lcvcl h v.ry ncar lo the guideli.e value lor huNan consuhplioh oaHg. Seawaler sples of Kalachi cost weE oalyzed by Naqli, er al. in

2002 (186), higirst llis rerc rcport d 0.110 ed 0,l93pg/1. M€rcury in i!. $afood availablc in Kdcni lcal ffitelr 9@ siudi.d ed Eponcd 0-0204.t l5rg/g ( I 87).

Aftd Tahd Spirit oil spill in luly 2003, Es.mh.r honitorcd rhe cfi*rs of cddc oil disFed iI a hlge @astal bcll of Kdcni, I w .ls rcponed de.ldacd THg in scdim.nt ofthe lcation tnai is a snoe (Clifton) l.w kiloieles away ftom rh. ple. of

In nciShboring country the TH8 conl4t in fish is rcponed in hisher amounls like 2066-

2l46nglg in Munbai,Indh (168). Anorhcr $udy rcpon d THs in rese of5.22 ro 0.64

r |rg. g in sdimdls and O.l7 ro 4.62 !g, 9r in n&inc org6is6 sl th. sm. l@iion

( 189). In Bahnj. n 6 cpo cd 0.0E4 .!d 0.042!g/s wer vl- THs in lish dd sh.llfish

(190). l. Doha, Qaw a m€rcury sp€iatio. M dorc &d fourd 3.5ry, disslvcd THg in sawal.r.nd 0.6ngl OH8 (191). In the coasbl Egion of Bmglad.rh the THg conknl ol fish h repon€d lo be io safe limns(192). lnstead of oonibrir8 ol Hg ih ndine or fi.shMre^, patisrani r€*dher nonirorcd

othq obFcts dd sourccs for Hg pollulion, W.lsi @des fom rh. oil fietds were

moniroEd md EDofled hider m€tal @nr.ni inctudins H8 (l9j). Etehent inctudins H8

in coal used d tucl in Fowq @doE B d.t mincd &d found .t.vacd n@l @mqr

(includine Hg) in co.l rcddld (r94). C@b, v.8.labter, re4 cigenc bbacco, ed ban

foh hmes ve invesrisacd ed Elacd fo! s.v€61 melars includins Hs (195).

|s(hcrs of lahoN (irom dilTer€nL @ in patistd) wrc cxmincd for ra@ ncl'l

nrcluding Hs od noried rcladon of m€'al conrcnr with ase oi bird (196). Tt{E in t@l

h.6al nedici& nh.ty Salljif is ir6dga&d for r&e met2l md lo4,92ppm Hs is

Uprake HB of by f@d h a major rcuG tor Hg poisonins 6 happ.ned in Minmara Japan,

*wol edible obj.ct w.rc invesiigaled for Hg conr.nl. Like eae m.tals *cF detemin€d ,n veos v.ecrable ad 2.590!c/g, dry vt THg is cvido4d I ddimun levet in

comhon ves.rablcs (198)i (19). r,t€at is th. l.r8d food compon nr of parislani popllation. the uacs hcrah (including Hg) wcrc dctchined md esrabtishcd latucs for

darly intalc of eah ncr2t. T1lcs valucs aE cohparcd wilh vatue suSecatcd by world

Hqlt Orgeiaion for wkly roletua l.vct and no si8nifi6r difcrcncc is rcFncd (200). Studi6 hlvc b.an don in ordd lo insrigarc diabry inktc of rracc neral

esp.ciauy Hs in diftcEnr es of pa&isle (201), (202), (203) jn lD huesubjecbTIlg hair is d indiabr for Hg poiening o. exposurc Conpanson

ror Ihe haii sples liom p6ple of ruEl atd ubm 'fu slablish* O.| urbtu lif€ is hoE qd dpoed lo H8 (204) at$ hair ealrsis of indsEial s*cr compaEd wirn who lhos. e nor .xposed ro industrial cnviroM.nl has ben csne

Aned, .l al. 2007 ii {206) inwsrisd.d dErcury ir stp h.ir orciriaG or L.hor cny in Prtis|!., This srudy cFncd 0.3e,60ppn THg in htjr lanple &d did ml ,how

coRl.tion wnn tuh oiswplion, ag. ad tdjliry_ Tltc THg itr fchst. is hi8[d thu pcnirc dd.. A @fthion *t5 cs!.btbhcd baEn THg i, $.tp hrj6 ud fish corsuhption i! hltu ebjal' Btood u.lyrt of n.uotogiet padcnb in patdian de indiel6 th. pt $ncc of fu(t?3).

1.19 Scope of thi. study Thi5 study @Es lh. monirori.g of Hg in ruiF 6viro,u6r for ca|.blishjnS rhc pouudon mdie sr.rE of K@hi cost l ,@. Th. sudy hs b.d feu$d b idcn$fy

$. $uB ofpolurio4.nd p{ran oflDltw,r( @rcnt in diff@r *r'so.s &d h yc6 and als (r .si$tish I rid lhc sulnuldio. outc in tuiE or8rnis. Ti. study .le l@b inlo in4niglrjon for upcrt. of Hg h food-Eb, lo hw& @nmlniry.

46 2 Experimental 2.1 Satety: Mercury dd its compouds dc roxh s dhc$s.d dlier thal a number of dis6te6

rcgdding Hg exposure have already b..n ftpon.d rh@udout lhc Wond. Safety is tbe

naue! of higbest priorily ii dy chcnical Mltsh, Uthosl cde in rhk Egard us

und.naken ahile pusuing the cu.ni study. As

The following s€ps hav. b.en &ssurcd whit€ p.rforhirS analys.s:

In $e whole study n ws dcd lo cnsw cLp (Cood Labo,arory pradic$).

MSDS (Malerial safely d.1a sher) of all @e.nrs nsl b. nldi.d pior lo uc n.

Ahhoush tnc extqt of mcrcury ir vcry low dd ac@rdin8 b USEPA in One

daup procrd (20?), &d n q bc ef. io dtain n in Erq bu th€ rclubtu

w dtpGed ir s Fol @nt iaing 5% KM.O. $lulior in ord.r to oxidiz dy

cldeorrl mercury in enc. Tlc soluion in rhG poot ir lhq disposcd codjng

A propd ventilalion syslen ws coonisiord vcry n€d to ourter of M@ury

Hydride Syskn {M HS), Uris eun.d sfery wjthin th. mlysis ea.

AU appmrc vcE disinfdt d frod h.r.ury Bidlals !sjn8 erons olidizing

Duin8 smplin8 ald prior ro ihc d.v.lopn nl of th. smplins pld, safery

policies rerc taken iiio ecohr. Prcpetion, colt.ction dd eairsis of lhe

sdples de uied accodingly ro rhc saf.ry poticies (Appendi, B). Special

atlention should be givon !o phylicat degeB 6uch a slip, Lip and faU burds when wo*jng aloud wter. In sen.Bl, it is @nn6d.d rial rh€ tuple cotlero{t avoid stin contacr wnh arl mplc ItF dd inhalation ot odor % avoid.d. Sp@ial prcquion rt srps wE adopcd while wrkj.g witn qont ninated smpl.s of semler and *dihe.ts espeiallt n€r porcnrial or knoM conrdmi.mr so@6, lardflb oi h@dous w8G aires.

2.2 Samplingardstorage: It is & inporia tasl Egdding qlnomatal monilorin& sple ncr be rcprcsonrarive offie populdion. Diffftnt mcrnods weG u*d for each sarplc rype that is briefly disc6*d in lhissection

2,2.1 S.nplitrg of seawatcr: Monly *awler spl* we oll@Ld ftom surfe .t rh. rhoEs- Smpl€s wee collccrcd in PTFE Tenon sdmpleG of 1,5 liter c.paciiy. Tbese samplers aE soaled olenighr in dilured (-4. I N) nific acid (208), and tha! wlshed with DD warcr

'ft* @plss (Botd6) kE n.ed tdoughly .t l4r rhrie wirh rhc swald ar

3dpling sne &d th€n fiU.d lnd filltarion thrclgh ordimry cmic 6hcr wiin ldeer poosjly. About first 200hL of filtmle is discard.d and rcmaining were collected in $e plstic bonl.s. Ir is $en acidili.d (6nL cor@nr'.i.d niric acid per hd).

Thc* didified mpl€s \,w tFn @ied to lab.Flory dd in 0E s. d.y wnee $ey ffi.g.in filt Ed Bing 0,45tm toe size @llulor. filter papd in ordcr ro spaBt€ ey ub-dissolved impurily e.l trmlf.rEd 1o borosiliet glas bonlq fo. storaSe. As il w6 rponcd good stabihy of swler sdplB in ds @nrain r for stor!8. (209), (210), (2ll).

In soh. expdimenls the Brq fon difeEdi dcpth! e collccted using Nntin smpleu.

4E pH, Thc TDS, Disolrcd oxtgcn vft m6!r.d 6ins porrabte n 16 l1 th€ dmc of splins ed for this puQos *ples ac co|.cl.d in a pldlic bealq Gtrcadr wshed ard nn$d). Th6e enples aF nor rcrained for srong..

2,2,2 Sampliraorserlincnt: Scdimcnts 6on lne shor. or @6ts e cou.dd by shov.l ichriqu. !o etsb smptes.

Tcnon shovcls weE employ.d for this purtosc; mpl.s sre @ll.clcd in I n: ofsl€cted d.r, with deplh of 4cm while coUeciing sudacc sedineft, The samples kre honoS.nized ad thed srotcd in a pl&stic 0blrtnyl.@ bags). On $c spot d@ouDinado! ol sedim.or smptjng cquirndr a i a$ciacd ulmils

M conducred at r}e mpling slaliotu. ti odd ro enov€ excess smple nardial, scrubbing wnb a brush and wahins wirh phosphabrie deterge solutio. M p@dced. AU equipm€n ws rhco r\orcuehly ris.d wi$ cla mr.

2.2.3 SadplinC of firhes: Fo! outinc Mlysis 6sh Erc @llded by qrch o$@ise thce \^@ ohaircd fmm dF qays local nalkeIs. Eithe! of stchins, i.e. uing nel o! hook w6 employed. pior to digcaiion sdples wre inrn diaiety plead in plasric bsss dd then in hc-box dd tituly srorcd in l'e@r ar renpcdra bctow 4oC.

2,2,4 Samplingofseaw.cds: Sewccds welc not colle!.d by plucking, Ttcse wE cou€cled wh€n s4w.cds itself lpploochs to shorc wifi lidcs. S@weds wplcs weE thcn plcd jn plasuc bass md rhcn in icc-box ad nnally s|orcd in rear ar rclDFnlure b€low -4t tor fudlrcr 2.2.5 Slmpli.sotnlterfied.B: Th. Oy$ers, Bamd6 &d Mleb vw coucdcil from the @k5 { r6hoE uuaily durins low tidc. Diles hllFd in mplins ai snd (like Maots)i . eainlc$ srel

$npp3 is usd !o djsplace the oyster ed bdnmles, vhile nueh src collected by sinplc pluctins or pulling $cm by hands.

Thc mpl€ rc.e slbc.qudtly placcd itr pllsli. b.gs whlcn wrc @ .jn.d in ie-box.

Frnally the) wer€ nored fc.hr d hpebtuE belo* -4!C 'n

All Eag.nts of nieh puity gEde w@ us.d hlviDg Hs cont nl rcponed in rhet

@nifiarcs of ealrsis. Dcionizlddistillcd w.cl {DD mrer) w u*d rhouBhour thr

2,3.1 0.01% Dithiozonc.roluenere6r.nt In a 200nL s€panlory fuMcl disohed 0.01 lg ol dipn€nyhhicab€ene (CAst60- 10{)

6 dislv.d in l00ml ot loleoe. 50mL of -0. lN Naol'l @ added ud bd.fly sh,l@n to extact Dirhiodne into thc .queous phe Oonom phac). An.r sclding it vas tdsfcded ro a glss cont inar litt d wnn a glss stopp.r. lN HCI wa drop wise addsd lo m.tc th. solution ilighrly eidic (blekish-grn dy$als e pEcipibrcd). l00DL of

!olM. m .ls add.d dd lh6 it *6 sh.td to obrain pui6.d 0.01% Dithioane-

Afier enling ol phdes, botloh phe wd discad.d by ddwing olt of s.paBlory funhel

dd t. olhcr ph$ ws stond in a @l d4t pl@. F.sh @gen w pEpdd for.&h

50 2,3,2 sto.kHgsolution: Conmercially availabl.6iock solution of looorsppm Hg us obrrjncd aron Fisher

Sci.ntiflc (Code: ,804708; 8a!ch: 0416?23). Th. cdtificate or@tris for such slanddd

H8 srGk sp4ificd thc csulrs 6 999 ! 5pph Hs(fl).

2.3,3 Crlih.ationsolntion Srock solution wa diluicd ro obtain lng Hg/L in L5% ttNor, sratilizcd by rhe addnion of lew drops of 5% KMnO. solution.

2,3,4 Diluentsolutl.n: L5% (v/v) $lution of niuic &id (CAS t 7697-17-2).

2,3,5 Aeductrntsolnti.n: 3 0g of(l!aBHr) sodiuh borohydide (CAs t:16940-66-2) in t%NaOH.

2.3,6 Anlifoami@aeent: Sili@ie adfomiis asar (BDID is u*d 6 &dfodins as6t in tbh md nttc. feds

2.3,7 Nirrouen '.s: A urlrogen sas cylibder llll.d qith N, s6 ofpudry (4N) w6 provid.d by BOC, Palisran

Lrd. The puiry of rhc* nlling sr&ds bdwi (99.995 ro 99.999%) &codins to

4nilic.rc ofanalysir povidcd by BOC, Pari$lr

2.4 Airpa12tus: Thisanalysis is penains to uhra r@ level ofhcrclry .nd irr€quis€xtra ordinaly cdc.

All lhc appdatus re wdhcd wnh d.tergds sd rtEn $atcd ovmighr in 0.lM HNO].

'no n 6 aeajn Bh.d &d rin$d Mlh DD srd. .A. All gl6sw u*d aor qldtilltiv. aial'sis ir $b srudy h6 ben ofct6 of pyal

Engled, Pipenes de also of'A clN ftoh Dunn Schoro cemdy. Tbrc€ micropipeues

5l covering tuge of 50tL to IOoOFL fom S@Exo, Swilzerland h!!. been used

2.5 lnstrumenrs: . Atonac ab6orprion sp.cnohela, P.rkin Eln6n AAnalys ?00 .quippcd *ilh

MHS-15 analyzr Bscdbly ad also sohcnmes Pdkin lllftqrN AA3jO0

equipped wilb MllS-10 analyrerasembly is uscd in $is srudy.

. A vollamelric workst tion MelrchfM VA Trac. analy&r 746VA is usd toi

dodic sfippinS volr.nnEtry thrr is @lplcd wirh 74ryA sr.rd_ A pH nelr, M.t{.. Tol.dofl (D6krop) &d Htuatx

pwnv/Tenpchiure deler Model HI E3 l4l .

TDS/ Conductivily m.te! JoEyn Mod.l 470,

2.6 Digestionof samples

2.6.1 Dir€.tinn or r.aMt.r sqples: As ihc @nqtnlbn of tocl d.rcury @nr GHg) in Fawt r is @nsid.6bty lovct ihd lbe dd4tion linii of CVAA, the sa*aler !ffiplcs were uully pre-conccntrated

Th.E de sevelal wys ro pEroncarrale I (212). rn cumr srudy a slvdr cxrrdrion method is enploycd (2 l3),

A 250nL of &idifi.d 56srcr smpE n tr..sf.Fd ro a *Fdtorr tunn.l. 2.rol of

-20N H:soa is a.lded ald nixed. IlEn l.25nL ofo.5% KMnoa is addcd widl senrte nixins, allo{in8 rhc solurion ro se(tc for 5 minurss. Thcn 5nL of-loN NaOIIh added to neutralr€ riB acid. l.25ml ol l0% NHOH.HCI solurion is dcn a.ldrd ed hixed.

Ans d elaps ot20 mi.ur.r 1.25n[ of loq. EDTA elulion 6 addcd fouowd by

70nL ofpuilie

52 Aqu€ou phs. w6 dk6d€d lnd o.gdic phe q6 @llected in a.orifuge ubc, dEn

0.1259 or NarSOr w6 introdlced dns enllsion fomiion. Thc cont€nrs wcE rhc. sbake. fouowed by certiitugalion at 1500 for 2lo 3 minutes, '!m Ou oa lool orSeic phde, cx&tly ?mL G F.nsLred !o splc dig.srion fl6k and rhc conlcnl is evapoFild to dryness at low lenFrar@s over a hotpht., -lnL DD qatd is added fouowed by 2nL of (lrl) nixt@ of HNOr:HClOa od 5nl of HrSOa. Th€ nixuE is tlEn hatcd aI200-230"C for 30 hiiuas. Aftd @lin8 lhc whotc coilcnl is rdsfeded qudtiratilely lo 25nL rolum.tic fl6k and 6n lly th. volume is mdc up.

Tns @ ohain digested supl., 5mL of dts dig.srcd sple ws ruh ar CVAAS lo.

[&lor for Pr-concentrarion of Sqwatd smple ws de€min€d a follows: pzrtwpd,ontdld to, y3*."= ?H3^-,-,;,;.;

2,6.2 Dieertion.f .edimentsamples: Tmfered 0.5-0.759 of wt scdincnB to digcsdon ndt followcd by lhe addirion of lml DD watci,2mL of(l:l) mixtlE of HNOIHCIO. md 5nL ofHrSO.. H.akd ar

200-210'C for 30 minues using hoQl{e. Aner c@ling fiheEd thc whole contcnt (usins

Whathm 540) lo 50nL voludetiic fl6k &d lin.lly fiU€d with DD water. 5nL ofil is

Pt..orc^nc.lo tu.o. for edha.nt e4'Lt =

rHr{--d r:: \- := t0 r':;'.44u4

2,6.9 Digestion orCshsm.le.: Foan fisb supl.s wft thasld ed then llnall, th! lissua aG cu uing cldcd and dcconhinated s6lFl. The* wer. l!.n ginded wirhin a nond phtoq minun Loe

tl of such gindcd past. b rdsleEd to a l00ml bq|

fimUy mrd€ up to lhe voluh.. 5nL of such digesred samplc ws run at CVAAS.

p 4. on..aioto F oa of I o, ! i:.h,,,,.-.,,, +. *:,. =, .,+#

2,6.10 Di!..rion filbr feed€r: ^f Frcan nher aedfi spl.s we rbavcd a

Mdihm ol 1.08 of such ginded pdre is iresf.dcd lo a l00ml beak€r. 2 OmL of de'onized wat.r, 4mL of (l: l) mix of HNOTHCIOT is added, follow€d by.ddition of lonl- ofHrSO..Il w6 auosld lo s,and oycniShr IEn ln. @ enls w€r€ neacd al2OO,

230oC on horplrt lor lboul lO ninut6, @l.d &d rBnsf€Ecd lo 2jol volmctrjc fldk.

Finallylhc volnmc w.s madc up.5nLofthGdigcslcd samptc \m tu al CVA S. p,^on'tu F q@ dio tu Fuq r eed$ - t H s x,; x N,,,,-d w#; = ", ry#

2.6.11 nigesti.n orse.we.d: Aboul 508 of wholc Fawed % grinded in r nona ptron; mdimm LOg of srch

is ro a srinded ,@sG lr&f.r.d loolnl b€kd, 2,OnL of dcioniad @tc,, 4mL of ( I : I ) hix ofHNOrHClO. is added, followed by additior of I ODL of H2SO.. It \6 altowcd to stand ovmigni Tncn heared al 200.230.C o. horplar. for.boul30 minules. Cooled a.d lrMsfened ro 25mL votud.rlic fl6k. Fitully rhe volM. is made up lo mdk. 5nL offii dlg.sed smple was M ar CVA,AS. tue@vq'a'ionF*b,ttsaw",='","-_*,?,".*a=,"ry#

54 The elysh is cdicd out at lwo aroni€ absolion sp{trcphotooeleB, pc,kin Elner rM

AAll00 ad AAnalysl 700. Borh arc equipFd wnh mcEuy dalyzcB MHS-IO ad

ror sbbility, Hollow Ca|hodc kmp (HCL) orElccrrcdc lss Djschdsc kmp(!Dr_)16

dd the inslrunc is poseied on for aboll 15 minures prior ro running 'nslalled rhen rcquifd condirioN e adjustcd @orniody Gabl. 2- l)_

Holdd for Qu'nz ccu aFnbly (QTA) is @misioocd ar thc bM., had of AAs dd 'Ilis QTA is plac€d in ir QTA is alisn€d according ro th€ |mul of the irorrumen sjrhin rbe parh of el.ctrohagn€tic hdiation &om (HCL)r'(EDL).

QTA C dtached lo eithq MHS.I0 or MHS-15 sysr.h ed maio purge 8s Tygon tube is pled in betren QTA &d N? gs cylind.r. A pEsE in tug€ of 2.5 ro t.5bd is nainhin€d with rtE hclp of 8s agulator, .omi$io0cd at s6 cytindr.

Somc es is allo*d to prine $e sysi€m. Pe-ct.!n.d leducbnr bonlc is til.d wnb rcduclet solution aR€r prc{insing it wirh sde sotution. The resr sotution is then cohmissioned at MHS syst.n. Flow of reduchl is checked with CARE! {sodiuh bobhy&ide G rcrclive ed codosive Mg.n0.

A bldk is tu by lrefeEing l0nl diluerl soluion &d rwo rtrops of j% KMnO lo lhe pG-cleded reaclion lessel.

A corsponding rolume of standar(ysmptc having panicutd @ounr (ng) ot l.tg h trdsfen€d (sing ftictupiFti.) lo Ection vc$cl of MHS stst€n follow.d by addilioh of lonl- dilEnts eid ed rwo dops of 5% KM!Oi solution. Tt , vc*t is ihcn connissioncd ar rhe MHS syst€m ed rh.n plung4 h p6ed. Simulraneouty

55 istwsl Rcad butlon i5 pB$4 Thc pluge ir Ftar.d ar rhc diepp.@ce of lne

AAS w6 alrcady adjustcd to notice pqk ea wilh in 20 s@nds rih. int dal. Anr

.onplefion of lm d. v@l b Bhed wilh DD wld @ll€ctine r]l v.rhin$ i. a b6sin

T.bk 2r: lhrrunmtl .otrdxlorr Ior Cv^As

2.5.1.5hd

tinp muulacrw' (HCL)

Ldp mmufactM (EDL)

AuroD.ticrlly adju$.d by AAn lyst 700

S|n heiahl 2.7.2 An.di.sti.tinp voltanmehi.ana vsis: In dodic slripping vohme6ic (ASV) aalysb M.rlobnw 74ryA trace mlyz.! wnh

747vA i$d is us.d [email protected] lo lhe following i6lMcnid @ndirions.

Gold RolarinS disl micro-el.c'rcde

l.ooMKCl

l00s

Ca$odic d.posnion poh'ial

The voltamcrtic @ll is @hcd with DD Mr6.nd dn*d wirh $pponing .lccoolrle.

400!L of 0.1M Na,EDTA, l.onl of o.lM NaCl dd t00FL HCIO. ir rddcd, The .Slart, requiEd volme of smple or slsddd is resfcftd |o ihe se cell. bu(on is pres*d on thc keypad ll automatielly perloms d.rcminarion.

51 Quality Assurance Measurements

Quality !sum@ nqsurcs * the sreps tale. during e elysis lo cnsue that tie

ealysis is dependable and eproducibte. An an.lysis havins covemge ofa good quahy

6suac. sysrd is morc infomativ., fr of mi$haFn, tuE erc. tl is c6| ercdivc.

Tl. t.minolosy al vlklatiok i,s .oncn d wirh euacy, pr.cbion, seledivny,

sensilivity elc. A iew of validarion pdlmeters d. .xdined fo( dy stldy b provide a

3.1 TnrouSI quality conbol $cFs n is .o$ed $at d Dalrsis is being cMi.d out unda

coftecr stltislical rcsin€. Sohc salierl featurcs for .sudne eC in ey .nalysis aE

3.1,1 SvstematicErroB: Abscn@ of syskmlic mors cslabbnes Muacy of! dat! Th. 6e of corljfi.d Eternc. mak.iak ctu eerlain the accuracy, Duing ceenr study sihur@

CRM (cenifi.d Ef€rcne Mtcnat) of sdim.nl SRM 1645 harc bc.! cod.d ro d..roiD aelmy- Tabtc 3-l d.picrs a eood agllo@t b€$sn th. m*ucno$ on cenifi.d mtcrials md th. sMplc Esults.

Idcltifidlio! of CRM (Ds/Kd (os(d

Sediment sRM 1645 Ll + 0.50 1.09 4 0.35

58 For olhn suplc ItFs dE w CRM in TH8 &.lysis by CVAAS is w.lt rcpolrcd

(214), 047) , (21 t ed bbnaled

Trbk l-?: A$sinrcv^^s i

CRM

Seawatet NIST SRM 16416

cRit 5?9

cRM 461

DORM 2t Fish

DORM2I

TIE abov. catificd valEs (in Tabte j,l) e @mF&d Bing sienifiae Gsr (Srd.nt,s

, re$) al 95% @n[d.n@ tcvcl 6Miry nult hyFrrlsbl / _ r l= O j *hft,l, is diti.d v.le and r k obFFld wtE. Th. lull hypo66i! i! FraiGd for CRM} !d 'fttiqrc, thd d@ is no siSnificdl diff@ce bct,en enifi.d ed obsfled valua sr 95%

59 3,1,2 RandomFrr..s: Mioind rddon dors @espold 10 pruirion of s.dt5b. For €stiDating uncclrrinty

valrc, qch splc (yp. E m for r t4r in l0 cplidree ircluding $.i( csperirc

digeslion. Relativ. slddard ddiatioro for @spooding sel of wplc lype arc

Rclativ. Standard Dryiation

0.05 0.07 0.l5

0.10 0.r8

:r.1.3 Eeteatnlllitg !l conhls witlin-M pGisio4 Table 3-t lte d@ou0d6 g@d rcpeaiabjtny.

3.1,4 nebrodn.ibilite: It is a factor $ai dctcminB lh. vdiaionr in baw.-m prsision sd in ord.r to eval@F the degre. of Fploducibiiity; aliquois of slord wpl.s ot each ryp. werc digBted and analyad in dir.rcnt days (wirh diff.Encc in tedpeErurc in .nbicir condiao.s). A, A ed C @ ditfcEnr dayr.

Dry B Day C

96.5 93.6 98.6 2.51

.250.1 248.J 233.t 216.4 2J1.4

19.2 40.2 42_1

254.4 256.4 260.1 r.95

60 In Table 1.4 values fo! cach salysis of corapondtug suple typc is close as $eir respslivc standad deviadon values a!. quirc low It demoNuat$ rhat hcrhod has a good reprcducibility aor all samplc typs.

Reploducibiliry pdanerer ha .ho b€.n cxamincd for two diffe€nt available mcrculy analyrcB (MHS-10 &d MHSn5).

Rcl.tiv. Slard.rd Ddillion

,Mlls-10 MUSn5 0.053 0.05t 0,156 0.t50 ln Table 3,5, RsD for MHS-10 t quitc nidi n @y b. duc lo old.r.quipnenr |ha'

MHS- 15. But it is also nill 3nowing bdrd Eprcducibility! od onc @ fcly e borh of rn rtu6 lor in a sinSle trudy. RSD for fish higho du. ro fomation of moE fom 's duing oalysis. Us of Si edfominS a8.nr is 6s1..

3.1.5 I inearEnle: At rhe qlibElion by na ir !.€d rh&udou rhc cmnr $!dy, diff@d volm6 in inMiDs ordtr we tun fiom long Hg(ll) lo l000ig Hs(ll) with in En.nt of 5oos

(Fi8w 3-l). h odcr b d*ide lin@ re8c for tn da1a in x-y @rdiBrq lhe ordercd dara ir r'imed (216). Fi61ly all thc .Lu et is mScd in incrc.d.8 ordd (Table ].6)

@d $en the lin6 rcer$sion valuc is calculard. Ir is found io ba 0.97?6 for rhe dala Frs of l0 b 1000is of H8 {ll). Tl.n onc dala st fom hiehq .xilcme (1000, t9?4t is ercluded ad the @delation coemcienr h reqatcular.d. Ir is stitl lowd the rarScr 0.9998.

In nexr itcmrion data ser rron lowr cxlcD. (10, 856) h excluded abd rhcn alain $e corelado. coefilcienr is sill nuch lowci rhd tdsct. This wa dode conrinuously until

6l the corelrrion @.fficienr be@mes 0.998. Ans all |hc rang* for the r4ofrponc ordcr.d pair comes oul to be betven I00 ro 600n8t this is the lincar range d.t.ftu.tion. Nonlinea €UlB also G ona u$d in .ronic sFcrro$opy (2 I ?). Irbh16. Dru r.r CrtibErD! ,r.r,

(rlc)

16392

FtuE !t: crlrbrijor .uft. ror rxs ro.ty,i,.

62 J,1,6 S€nritivitv: h is th. ratio oa rhc q@tiraiv. ourpul md $. iiplq for . giv.n qudnadv. rsgc (2 l8).

-dt

wh.c .9 is s.sitivity of @ltsis. Wirhin rlE lincd 68. of th. sbovc cw. (Figure

l-l) for TXg d.l.miErion rhc $tunivny of 25og k 6rimrd,

3,1,7 l,inttordct.iion: h givcs lne ninimum conc.ntrdio! of a conlDn.nt rhar.s bG d.r.ded. In til€Erurc

(21E), (21 9) n is sum of thq md of bl.nt damiMtion dd rhric of nandjd d.vi.rion

X =r,+3o"

\vhcrc X is th. limit of dd6rion, &' k h6 of bhrr! EptiqrB dd .r. is sr.nd.rd ,ra. &viarion of c!€rad bla* d.l.DiDtion. Th. !t@s. of U. blad. ehrion fo. dc

aboE calibtslion plor is .bour 25ns eih rtald{d d.virrion (r.) of 5Ig. ir csrabtilB

40rU a th. limit of dcrcclio(rr. tr h@r in B..rio. vlgl of MHSI5, 0!c coropondins arnount o. rcllnr. of ter $nplc mu$ bc addcd rhar k having THg lor

love tlEn 40ng to notie at ch..gc.

'nE findilgr ot ssnivny, Umii of d.kction &d lit@ tus. is v.lid for gcncEl nqd.rd slutioa of TH8. l. ihc followin& (r.bL 3-7) e .niD.r. of fic vrlu6 oa rhe pddctcG dc lislcd for .ll spL lypes by cdcrl.tion sjng lh. pc-@nce ition or dilurion faclo. ca Sccrion 2.6). Trbk .r?: Firimrr.d vrl!6 0r dir.ni. u.ldlol

Suple Type

t00 100.600 25 28.51 2E0-l?00 700 Il50

2.00 200-1200 50 80

5.00 500J000 15 200

5.00 500J000 75 200

5,00 500.3000 75 200

3.1.8 lnterleren.e: Thcre is alMys chdce of interf.€nc. in th. qwtilative dalysisi it 6 be of eve6l ryp€s (209). Usully envnomental enplcs hsv. nadx aft cl, i.ldferins efl4ts @ be

Doliccd by l1ming s?iked spls (21 7), ln ordd ro do r,h|t & @oDt of THg is added lo aralt4d sple lo tom spike.

TIlaftr THe addd (%) 50 209.5 1998 95.t7 .:00 I150

t02

200 450 37.60

Such oalysis of slil€d @ples (Table 3-8).stablishes thal lhe recoveries for sssarer, sedinent ad swecd de ecording !o eip.crdion, Such sdples ce be analrzd by l]tring extemal sledads. Vhil. for fish &d liltq fed€rs 6uhs m ld aon

64 cxFcratioN. Th.s sple d. h.ving hiSher marix ctrstl\ e such ttge of enplcs e analyzed 6ine slanddd addilion mcood in fttthci srudy.

3.2 I nves iioadnq Chemical lnre.fer€n.e' odn to discovft chmiolly inrcddng agotl, ene €r'oN md anons *cR cxdin€d for any possible i crLr.ne io drn study.

Caions rike K', Na', Fe', zn", cl', co,', Ni,', cu,' v€E exmin€d. Diffcrenr

@nccntdio$ of sid ionic $lulioB E€ add.d to rhc THC eturion in such a wly tlEt

lh. ultinat djlution ftat6 il loppb THg. R*overics we c.lculated wnh r.sp.cr !o

loppb THg, tos like K', Na', Fe", Zn':' e havirA almon 100% r@€r, of Ttl& for ercn & addition ofsuch ion up b lOOoppD. Cl', Co:', Nii' ed Cu" d. .xnibiins diflcrcnl

.xlebrs of intfifercn€s as shoM in Table 3-9:

119

55 30 3&

600

In pesdce of morc thm loppn ofNi(lt) ad doc lhe 1000 ppD ofco(I) ions, $e nercury sistul is conplelely losr (Iisre 3-2). while in ce of Cu(lr) dd C'(rrr) d.@de in signal ir aidered with in@ing @n@nrzrion of inr..fc.ing .€pnts (Figur€

3-3).

6t rlrry. !.1 qtr9.i 09 r.o!..y r !0ppb rH3 by c(ll) rid c(lll)

120 ! 3 c(fl)

0 2W 400 600 1000 conccnitrllon or mot l lon.

F'tuE !5: tnd or mrt or loppb TBa by Ni(Il) .rd Co(lI)

E i.ct on Bcov€ry ol loppb Ttlg by Ni(ll)and Co(ll)

A tosiblc EGon fo! euch behavior is th.t Ddury foms mslglns wnh sev€r.l nnals And fomrlion of rcr.l iDlibiB r.dwti@ of |Er.try Girg CVAAS, s &ndgd is dener dd gels senlcil in the bonoh of egent flark, 11 dod not sllow mlSrmatcd Hg to reel wilh NaBH. or other EdkinS aSdts in th. rcacton vwl.

66 Anionr vw d$ dmin d for thcir pGsiblc incr|lEn@s in sinile fahion- By addin8 dif.dt dodls ofrulD.ct d eio! slurion ro loppb TH8 $lurioB. Previdcd d!l! is

% R@v6y of | 0!rb fi3 cl' 101,0 Bi 93.5

95.2 t00.8 Cor' t09.9 cto.' 96.8 tF{cN)61* t02.4 94.0 0.0

A! 6 b. s.!n in T.blc 3-10, thcE is no EMtlbb intdf.rcn€ duc ro &ioN. only I- in pl!s.@ of MnO. i5 showinS mri@bl. iDFct (Figun34). ln this nudy KMIO. is outimly !d&! to dE E!.liotr v@l ro iilibn rdudion of nduly prior ro M on

67 rtuE!4: % Rry.ryotloDpb Ht(lI)aildonri d r.i. .ofurikr o'orlodtd.ro.ri,€ricc ofp.mfl|irrroi.

'tzo

100 a 8o 60 40 20 0 -20 0 50 100 150 conc. lodid. (ppn) wlilc ddinirg I ion, no sislrl i! ob{lircd in Fe!4c of MnO. (Fi8w34} h na, b. de !o oxidnrion ofl by MnO. ed *icn BtL is.rtd.d it 8.rs conruoad in rcdocing of rhar oxidizrd ptodet in'llad of EdEin8 iodc rcEu.y.

Th@foE, d!. die.stcd mpL s qBribtiv.ty ch.ct d for lE pr.scc of iodid. ar nl,m l.vcb prior ro tu or CVAAS.

To ...uc tu qu.lity of ddrn3 .dplq uF .r.lyz.d b, erhd ir&t n&nr ndho

68 AliquoE oflh. .re di8.sr.d spl4 rft tu $rcugh both (cvAAS 6d ASv) Eins

sr.rddd.ddirioi h.rhod (dd.ik of Asv is in chlpLr.l !d*don'). TIE 6ula

Pod@ Pond dd|! dva h T.blc l.l l:

TEt V.l!s cvtts tsv 96.5 95.2

250.3 265.1

Ftuh (ng/g) 2lE.l 230.9

Saelc! (trs/s) 19.2 40.5

25E.4 263.2

On rhc lpplication of p.iEd 'r' |!st rt (P = 0.05) for d.r. n Trblc 3-llsing MS.Er.cl,

dEF i5 no siSnitiot dilfclqr didgl.cil h rh. d.lr ThccfoE, boih mdho& (rh!r e

iDd.pddcnD @ slDwins @mp.nu. Bull'

3.4 oldissi Outlting 6ulc e r.r.ly qFcr.dr n dk6 rhc *holc &r. nnp.t!i$ lad lG.6 i6

cr.dibihy. A Diioi\ Q csl ii G.d fo. si.8l. oudying strc (2 t6). qlw- ^ lsutp..r N.Mt wtt l - Ranz.

In 6. ot nolt t6 tm oudyitrg d.ri poinB; ori6 iarinic.t rr.luncfis lit .r/di [email protected]@s ad wcai|. ptue.tw wcucn(221)-

3.5 Oual itv Control in S.hplinS

Th. {alyictl Esdt is ncw bdcr lhd rhc @dc it is b.*d or! n].s orc cd ey

splinS b thc b..ir of a$l$ir. A qultiry s.mptinS i5 tl. similsiry b.1vg wl.d dd

69 estinaled pmp€ni€s. A plihary enplc qualitt par.m.te! is repr€sntativenc$. md secondey ptrmercis de size, slabililt and cosr. The most inpona euices oi sadple deterioration tre iEppopriatc smpling $heds (smpling flcquency, incr€memsi4, or

3.5.1 dlrEbglafucdi!3leri Tnis is impo.'sl to krow leasl nunbn of eplical* (pdor to do chcmical aholysis) lhal e sufficienl. In ordd to do il e .belulc etur A dd rcliability interyal L e elculat€d

ror incEdinB nwbcr of dereminario.s (216). wh.rci

L= t 00a

where, r' is $an

50ng/1, wherc n' is nuber of !.pliei6 dd z' is apFoxim.k Frcenrage l.vel, $al n about 200nsl b.ase of th. srar|{d hplc of seh @ncdtraion is used. Such evalurios de bbulated in Tablc 3,l2: rrbr.!rr; f,rrurrioi oIlar rlrb.rolForktr . tooa

2 12.706 r 50 x 0.71= 451,1 225.55

l 4.101x 50x 0 58- 124.79 62.40

].182x50x050-?9.55 39.11 2263 5 2.776 x 50 \ 0.45- 62.46 Jt.21

?571x50x0.41=52.71 26.J5

2.447 i 50 x 0,38 = 46.45 23.23 312

Table l.l2 show $a1 thc dificence b.com6 roo low for I or 4

doing Malysis in rdplicate

70 3,5.2 Pamm.t.r rdr ..nh.l $lection: Idedtilying c ooDpuison of wholc atudy wirh rhe conrol lt.lion o. sanple is inpon2ni h dales $e va.i$.. in ealtical loolnole pfonindt. In sllrisrics ! way of idcndrying siSniliql difcrcne in data q b. c8iq{t o!1 by ANOVA. lt w6 dieitally calcllakd uinS a slalirliel soft\N@ nm.ly Minir.bo.

FiBrly orc way ANOVA i3 lpplied fo! dl th. sl|tioF {d it is in thc folloqing ourpur

(Fig@ 3.5: ODc-way AMlysis of v{iea for rll {!iiom.) of rlid loffq@ 0E1 dl pr of trara G sisnifidrly difi4nt wirh @h othq .t (P-0.05), s fd>f'.o

frlur. !5. olFi.r AurrrL of v.rnrc ,or.[ ri.iod

Thcn th€ s. Onc-way ANOVA is rpplicd for rhc thrc. sir.s thar d showinS lo{.r co dr i. Clt (confddcc intco.l) fisw. nrc ourput is dv6 bclow (Fi8uE 3-6):

7l ri ANOVA for rhu r.t.cr.d ,ilo One-Way AnalFts of Vari.nce

170,33 t5 219. O0 Indlvidual 95t cI6 For rleaD B.!.d on Poor.d srD.v 1-----1----) 49.333 (,- --. __ _ l

In thc above lql (Fi8uc 3{) ar6 is 3.6E fiar t sucl rhla f.d |har is 26.s. Acain dd md values for rhe sr6rioos N sigaifica.tty dif.ql n!. abov. Iis@ of cl! js d@BEalirg rhar lhc rrc sl.rioB Kltipj. &d S.rdspn qun kDblc Ega

II@. so, on epptyinS rhc sft 1.$r, rh. foltowing But (Fisw l-t) is obLin d;

ror ,ok pir ! s'.d.pir. 'tall!::r*+* " ".l.i(

&3.d or Pool6d stD.v

72 In lh. abov. r$r !.d(4,,mcss 4.67< 4,94 ih6foE th. ncd for K.l.pir dd

sedspn dc h.vins no signifi@r difid.nc. (P=0.05). H6c. H.wkbay is sisiificetly

low.r in THg conlent th.r ell oih6 ed fiit ii is cosida.d ro b. a coorol 3lation,

1.5.3 Sbbility.fqmpla.: Slorcd @pl* havc plnicula lihit of dAys lor slob8. lik. i1 is Gpon d b sbr.

$d'm.nt 5opl6 in dfriScr.r. for 28 d.y! (22a). ArDdd inporrart thinS is ro tjow

how long d. digcaEd s@pls 6 b. ioEd prior ro &slt!is. Tnis ws .xmincd

a@dins ro GlDned $udy (209), by rstirs it (in i.iptioc). Th. .riq@r of @c

digded empl. wc rcsrod in dir.E daya MowhiL mpl.s serc slorld in d&l

dd in dbidll @Ddiliotu. TclDF6turc va.icd iom 25 ro 3dC. Th. asullr d rlbulacd

in lne following T.blc 3- | l:

T.bl.3-13: St bilitvotl.bor hbontory r.DDl.|. 'l'ry

Day I D.y 4 Day 7 D.y 14 D.r l0 t02.0 99.0 9E.2 9E.4 91.7 452.0 4t0.0 454.5 455.5 450.0

65.5 65_2 65.5 64.9 64.7

155.0 t48_5 I45..1 101.2 45.2 295.0 230.0 150.1 BDL BDL . BDL (B.ro* D.@ion Linir),

No decli.c i5.vidd for spt.r of ewr.r, $di6qnl, &d sosed d{. (Tabl€ l-ll). As on essiog i1 uin8 stud.nfs r cn .|(P=0,05) th.re is no significal diil€Encc in thc dat! poirc for sdo.l days of rh. sid dEc spl. ryp6, rbw.vcr, iDt bility is .vidcned in diSsrcd 5drl6 of frhca &d filter f.erhs, p.rhaDs such insr.biliry is de !o hiSh oa&i. mfix tn.| b having pl.nty of proreins. Thes

7J pmlciB u. uist bl. if FB6r eilb nlny H8 conpou.k tr mly b. pEcipihcd rnd

$nLd in lh. spl. robrion 0l.r hrlca it ulvjbbt. io dilpc@ ro racdm \cascl of nErcury.n.lye.. Fish spl6 !$r! rt|. do|t rdrzcd *irlin ! wct and fitr.. f.cd.r spl.s e!t! .D.lyrcd within rlG dtys filn Oc rim ofdi8.sion.

Ihb inlalilitr is . siou! ttd of cm6n wlB .rutysi5 i5 6i.

74 4 Outcomeofstudy In lnis sclion anattlical sllls h.ve b@ rabut{.d. Ale fi8ws and chds e psenred For makins r.able sinpte, sd ,norc undcurddablc, Bulrs or tout ncrcury con€nt (THe) is sumaried in th. fomar of (M€m + Stadard deviaion) instead of shown8 €ach ftplicale value.

4,1 Resultsof seawareranatyses:

THr tno/D

50.5.1.4 52.7r0.9 51.6$.8 49.6rr.6 €.8+1.I 95.411.6 102.511-7 125.311.6 112 6*1 4 85.8r1.3 85.011 9 90.311.2 85.1rO5 80.3r0.7 92.o}2.5 42.7111 95.610.9 100.112.1 115.9r2.3 102.4^o.7 89.0r1.7 79.011.2 35,711.3 75.511.1 70 1r1.1

ttic {norl)

45.3112 50.311.3 53't11.3 512r!.9 52.5+16 51311,5 53,611.6 51.2t0.6

105.511.0 120 5*O.E 116.8i1.9 88.211 1 82.tr 0 a 87.8rr.0 926t1.7 95.8*1.3 48.M.1 810r1.5 375r1.3 92.3!1.4 95 3ir.5 103.0r1,8 105,3118 65.2i1.4 80.0'2.0 723\1.2

15 rHl (ndr)

51.2115 52.5 .S 56.311 3 52.2!1.1 5s.0r0.9 56.311.6 516i1.6 135 311.6 100.311.6 93.311.4 8.2a1,2 6t.ot1 7 125.3dr 9 92.0r2.0

T.bk a{: % trc@ or s4*.kr TIi r. }or 2txy, rDt yar 2)l}6

0 053 3 045 3.001 3.025 4.762 3 024 3.156 3,020 6107 3.523 5.691 3.354 3102 3.067 3.,450 3.500 4211 3 256 3.050 3.571 3110 5.124 2.353 3. r3,l 5.556 3 048 3.121 3.32r 3000 3.002 3.016 3087 3.145 4.211 3.050 3.123 3.075 5618 3.180 I 563 3.M2 4.f6 3.112 3.240 3.045 {.349 1. t79 1.445 2.727 2.619 0.760

2.124 2.426 0.959 3 650 1.990 2 812 3 367 20,1.1 3318 3.039 r.969 0.917 7,497 7 333 9.388 L loT 6.8r8

6.130 8.639 6.424 5.701 5.656 6.130 6.411 6.224 5.656 4.780

6.947 8.000 9.130 7 333 8.576 5 734 2.$A 3.571 5.424 1779 4.216 1.46

Trhk i-a: c.Drrrirn orTH

10211O.5 60111.5 40.98 4500

9.52 426

'%rc rpdd Inddutrt contri!,non) Trbk +7: Prefl. of THr to. dftm. d4 Hieh

47,8!0,5 117 48.O1{.5 a€.Er0,4 102

1.13

57.&O,e 55.0i0.4 4.80

0.60

57.8i0.0 48,610.6 9.17

58.2d.4 46.310.6 9.15

47.214,3 rltl.7*0.6 4.36

18 Trbh a-t: Tfi! orenE ro. dtr

s0.3r0.6 2

3 49.810.3

2 62.8r0.3 3 62.3c0.6

2 53.,rr0.2 3

2 57.0r0.3 48.210.4 3 576i0.5 I 58 3r0 0 2 56.5!0.3 3 58G03

50 310.6 2 51.3r0.2

19 Trbh +t: TH! of.ahr.r i. sotkr colL.rqr thn lD..ifid dnbnc. D o!.p $r. Phiti-

4.05305 '0.9312

15.5 '2.52

80 4.2 Resul ts of sedtm€nts ana tys€s

hbh+t0 conpr,noi dfTHr h d

214 2tt.5 215.311.6 220.2r1.3 259.310.9 251.6d1.3

540 3+2.1

303 6ir.2 335.5i1 3

415.3!0.9

247.8ri 3 248.011,f 246.611 7

fis {nc/s)

214.2r1.5 216 011.6 205611.6 198-010.9 215.2t2.1 215.1it 6

258 3*0.9 2512l1.6 23r 2!1_A 243.5t2.3 249 412.3 2Y.3!2.3 245.3!,6 253.411 7 247 6!1.3 5486t3.1 472.2t2.A 509 9r14

404 511.3 408511.5 373 6113 374.611.5 397.611.1

361 3r1.6 ,r13.3i1.6 4109r10

247.8r1 3 247.412.1 213.711.6 219.2!2.1 236,311.7 2454i1.9

8I I!!!4rr, rH8 h r.drb6' rmor. ork |.d ror y TBg lns/g)

215.3!12 207.3r1.2 218.3a12 2516113

250 9r1 2

554.611 2

369.ar1 1

363.3!1.3 422 6!t.7

215 2!1 I 239.3r1.4 309.5i1 1

THO (ng/g)

220 2r1.3 210.2t1.4 210,311.6 204.3!t 2

252 7116 243.511.9 238611.5 254.311 5

252.2tt.4 253.(}11.7 249.9r1.2 245.311.9

476.3i1 2 552 9i1 9

385.511 3 368.6*1.7

413 0r1.8 375.0i1,2 370.5i1.9 423 312.0

4131120 410.0r2.0 367.8!17 365.6114 406.012.0 4151!17 U6.6r1.7 216.9t1.5 216 2r1.2 248.611 5 4.3 Results of fish anatyses

Trbh 4-ta: THr ln mu*tcorfirhq.ot JHs(ns/s)

1,€.6*1.3 157.211.9 155.9*1.5 156.711l sNcl

252.9r1.1 234.311.9 sNc 227 4r1.9

s45.6r1.5 336.7t.0 U2.9!1.7 365.8rr 6

T.pk415, TH! h rBh'6Dhordtt Tflg 1.9/9) in tishes ot ditf6r. sizos

r60611.9 185912.0 r80.711.3 sNc

aDft iat 2*1.6

ADL 150.9i1.6 221.7x1.1 280.64.1

322.611.5 527 4t2.1 sNc

I!!!+16: cod[rnor ofrt I!9l!e/e)

GE€nbad( !44ds I mu|l.l lMushka 223611.2

sNc 215 7i1.5

252.3119 2301t12 222.4t1.9

I sNc. samptG e xd co[.q.d

83 T'bk 1-rr: cdnpr.nor orTHliodrra

THg {ng/gj Organs 'n

152.3i1.1

123.6i1.6 432.611.6 351.9r1.7 823.5r1.4

rrbh4rS: T8i D n6dBot Sc.food |pcc's Snago ehatu 129.52j0,93 hz flbv;id! PMWB Etafrcw tcrub) /tri6 dattni.ti Pohrdarys *eaten akpa n lohopkru Pohp6 otg.n!4 119.25+0.95 ch,e,nt6 ai.b

prc.tltth tadpl4 N.D. Dn.A fuh tudpl. 3 N.D. 4.4 Results of seaweed aralys€s

32.1rn.1 32.8i0.6 sNc sNc

49.28 31.925 45.3 32.2 32.6 397 2,1.3 371 241

Trbh 420: TH8 [lu. orra'edt .on(ed ii Flb4rr.

34 510.5 . sNc 55.310 7 41310.2 58.2t0,8 39.2r0.6 sNc 34.710 5 37.5r0.6 395+0.6

54.9 40,75 44.65 .r0.56 60.4 5a.6 58.2 52.6 59.6 46.5 y.7 37.1 306

' 1.s3 av.rabiri9 ot sd@d in Gid .r€.k .nd phi$ @k

85 45 Results offrlrer feeders analyses Trbh!,|:TH![finFfd'o|ld.d|E[M THE (ng/g)

324.512.5 542.212.3

264-1!31 458.613.6

2,r5 313.6 sNc 210.6*2.9

r.bhj2?ll!l.frc.kd!E!!4de ph s "K.k THg (ng/g)

252.6t2.1 sNc 364.5i29 397.a*3 2 sNc 557.2.3.5 sNc

THs (ng/Ol in Filer feedeE St€

245.6!2.6 542,212.1 356 2r3 6

258.413 1 4546!2.4 348 6i3.1 276 3!3.2 sNc

86 r'bb .14: c.hp.rlol o| % ol TH %ol TH g 6l.valed !i r,t Hawksbay (conlrot 3ii€ )

100 lo0 100 1t)0 100 100 109 75a1 106.8860 113.6364 t17 361 120 115.6202 115 r15.90S1 116.9841 120 231.1073 231.20e3 277.n74 2U 5445 202.*1 195 207.3171 206.0767 200 193.1018 1330952 192.5 2U.87A 206 9767 2t1t.545€ 200 205 231.TOfa 232.55a1 255.55€6 231.8162 211.00a3 197.5 156.0976 162.7907 188.8889 1?04545 r66 66€7 160

E7 4,6 lles!lti ofPhysicochemi@l paramcrcrs on analyses

Physicoch.mical Fmcl6 @ wfirl t@l toi ssing $e chdiql lado6 inihc.cing enwonnenral prcblens. Ther.aore, ar rh€ lim. ofsnpling at riplicsr. stddons olsi|€s

Salinily, pH dd Tenp€larurc fte r&orded od rcporred in rhis ecion.

4,6,1 Out.oF.of physicochenical pa6mcters for2OO6

247!0.9 25 9r0 4 35.6+1 4 25.611.2 37.6rr.6

28.610.1

69910.9 38,4r26 28.1i0.5 6.99i09 38,8i3.0 28 7iO 6 30.r12.8 28.9!1.1 34.412 7 281r!.6 35.1!1.4

88 E!la4,r: Piy,i.(h.ni$)

32.sin 2 35,1r0.6 32.9r0.3 7 81r0.2 32.4!A.1

8112.7 32 5r1.2 32.7r0.5

35.7n.O 32 611 0

3s 2!4.3 30.9101 31 1rt'.2 35.1r0 7 31.3r0.1 3r 4rO9 38.112.1 7 2ri0.5

89 35 1r0 7 29 9r! 2 35 510.4

30.6!0 5 38.4t2 A 29.9r07

36.2*20 30 7r1 1

T,br. +.]o, Phyti.chmioj DdEd.u ror D4

35 2i0 5 25.9r0.1 1.421f2 35.410 6 25 9r.1 25.8r0.5 25.4106 35.112.9 25.711 0 7.15r0 9 36.9124 26110.9 2a ir1.1 4,62 Oul(omcufpIysi(oclemi(rlprrunrrtlrstorZ00T

Trbr. 4J | | piEr4b.nist prdn{6 ror F.b

35.31r.4

25h42

25.7r0.9 7.2810.5 35.6113

34,2r0.7 28.8104 712lrJ.3

17.4t2.a

39.1r17 7.6110.2 28.1ir.0

9l I4bl! 4 ll: : Phyricmb.niBr Drrndq! ror J!r. 200

7 9910.3

79402 351i0.3 32.6*0 3

38.912.9 7.0210.6 38.4t6 331!!.9 7.25x0.4 35.4i3.4 32 6i1 3 39,212.9 32.9j0.6 7.2a.O.2 35.5rr 5

Trbk 4J1: PiriiMb.nsr drtr.r.ij I

7.89r!.3 35.7r!.7 31.3i01

39.7r2.S 30.610.8

38,612.7 31 5*0.4

30.5r0.6

92 Trbk 4r5: Phs'ldhoftj [dr.kB ror Od

35.910.6 30.2r0.3

35.1i05 30 210.2

30.610.0

7.25r0.8 37.912S 30 611.1

3a.oj2-1 30.ar0.6

35.911.7 29_711.2

T,bk 4-16: Ptryrt(o(h.nj..l

7.t9$.5

25 9i0 2

7 82!O 2 35.7r0.2 26.1i0 3 30.4!3.4 26.4r0.9 37.9!3.1 25.9$.8 35,112.1 25.1rr.0 37 6d2 5 26.5i0,6 257r12

9l 4,6,3 Out on€ orphysico.hemical par/m.te6 fo.2008,

r.d ror F.bmry 1003

351r0.5

26.511.2 36,9'27

35.&2.0 25.5r0.9

36.9!2.2 25.t!4 ?

!r!h .n: Pry'i*hlDrol

35.7r0.3 29.5r0.3

3a.9r0 3 29.1r0.1 29{r!.9

39,4r2.9 29.610.9

7.34r!.5 36.712.6 289r10

39.412 5 24.7i0.7

7_75142 35.912.0 28 610.9

94 Trhr. +J9: ftbElrh.bt.rt ,.nD*d for JuR 20{6

35.9104 32.9r0.1 3 0610.2 35.7i06 30.7r0.3 32.5r4.2 40 913.1 36.913.0 32.910.8 7.0610.9 6.412.4 32.1r1.2

37.812.9 33 610.7 35.e11.7 32.6tr I

I4!.-40, Pbyich.niqr mnrd.B I

7 3510.1 321!O 2 6..*0.2

40912,8

38.4121

36.8r3.0

31.5+08

95 Trbh 4-11: Pi"(o(t.nhrr E.n.rcE ror odobs 2OO3

36.910.3 31 1rO.2

7.9210 5 36 5i0.5 30.6i0.3 7 t2r09 30.1r1.0

36.0i3.2 30.511.0

39.5!2 7 30.611.0

34.7*2.1

29.410.9

rrblc.-,r1: ?h$iuh.mkrr Drnn{.trInn{.tr r0rD(enber2003a

25.9*0.3

35.610,5 25.4r0.3

8.02io 2 35.710.1 25 9t0.2

38.$2.9 26.1r0.7

25.9r0.6

37.212.1 359t1.3

96 4.7 Figures

ln (hb scrion chans and ngures a€ rcpresenring lhe ourcomes of rhe sludy.

4.7.1 Charts regardhg scdwater analyscs,

4t: cdhprrtoi bdrc! ne or nrd.

-?h

Sit t

FigtrP +2: Comp.ri$n beeeen TH q. rqr?qq,

9l F4uru{-l conp Kn bdf,*nlHgof &.ri.r jd,n r.nr,k,for}.rr2003,

-=L. _ -:1--_

98 Ftu* 4.s-Moirh-w|n prcut. orrfi Lorred.rror y.tr 200?.

t" -.. \:

99 6

t00 ( ri8!r ..0: drprrlor nd6.r'-rrkr I,ig d{nbdjoi drd ot Mrion tid orhcr $r. r($

't------.! =

qdldofdi'o|rgr.h'TH Y!!e,

r0l !

v.lu{ olr.di!.rr 4 5'...r for Ht?rrb|v:

i I

102 Dsrncewi! lrofit. ror rrrr.. *1G.

d5ba 116 !.ir.E

6 to 3rm Dkr|le|bi'..fio4

l0l FtguR1.l3: D6rocri* profih 0t {rrr.. wd{ THt for sr. fe

k orkd.d ftJ rilE.ry.

5?s

104 ._: --.

.u!o,ffrE!4,ry 4 rgra

t05 I

tiarn+!0:srdrorTgsbanrdhrn r[!J.s *rdh.ftmotrortu,Ury

I06 ; I 16.00

H:rby r.r.d s..d${r Mimr ctutd.* xs.rrl

rE +tt: Ptd ofdtfi.r-a oftH

Hdtq|*'tl|dd

lo 4.?.2 Charu regarding sediment analyses. Fl.oft Gl3: slb ri,! rFfd. ror THr olr.dh6e o ..r.d ror sr 200d

Mano.. 6izi .rcdorangr c?arrui cdRon Odh

rlAE.rl' sib-!!9tr.j!_&!]!t4!slD4qs!q1{&L9rl!!?.

H*r$ay r.krer gnd.eit M.noo 6Ld .Elor.iei crdi.ni cErod arsifr

108 .. . Fisuru .-15. Sr. t ik rrofih tor THr or !.d,tr.r& oti*'.d ror Fr!!!q

e6E ciri a.&d'ci cdrtu (Jcron o&m

. Fsln r-16: Mold 'r* oofik ror rflq orsrhsa orkr.d ror q_r r_!!!

109 fXlE 4?lil!!!!Irl E 99!!e!!!

u!!!!!l*is4._!d!r-el!{!'!!qe!lJ!!d,!err!|! z!9q

ll0 fiI!!!a4tTHc!!s&!t44qr!_rd HDkrDr' !.din.Ds rr dr!!i ,u,,

!F Yar o!dri'o! ofTH 'LXl '&

l 4.1.1 Charts regarding Rsh analyses, E'rsr!!:!!: Co!!!4!!!-!Mci!' qEsg'!! s!z!19!gl!!

FnuB+11: conDrdor ofTHs itrdrtftdr oE.d orfth

E 500 E 400

200

|2, 4,7,4 Ch.rts regardinSseaweedranatyscs I{ull,!!li9qp{!egl-I4tldrqsq!4.rr!.!r!.r.4!.

{ i

lll 4.7,5 charts.€8a.dhg Alter feederanatyses. rise 41!.IEc4@c]FJ4fssq4!-

I I

.t f'rE ftql6 d{ciql fm. drftEr dr&

l14 ir!rd!!i!e!s!!!!19!!t!rE!!!iTEs-&d!l.i-@Ja.,,

,,/",ii,,.

ll5 4.7,6 Charts regarding tempe.ature srudy, Fhu!. .l-3?: ConprilDi oI t.Dpdtrrc Nhb TH! yrrud or sflkr shpis ouer.d tor F.bn.ry2006

','-"\------.--\ g a30 g Ia! t

FislE +J& coitrrts or boldrbE rlr! Trlg nlB otenct lopkJ.olrd.d r0r Jun.

\ v \ /,' ! 3,.4',, F

s.npll.8slta

r'goR .$ Cotrr.rlro! or r.np.n pl. s,td.d r.r O.bb.r

l16 Fr3ur. ir-.ro: conpr'lotr ol rnp.n npls o[d.d for r._lury ?.0o1

./"- ,6} // n ,. I

Fisur4-at: co'p.rtdol|.bD.n.drr.rTssv.b.orsnr.r.DDt .orr...dtor Juc

,,:\ /' ,,.! tr..a :60 \l ],':i nE

sr.drplt M.iorr Grrr.Rk KoEml !.rrt4dt. cd*

\7 F{.lE a-ar: Co!!.rl'o! or &lpcrtrF il|r THt v.t!6 ors'.&r srpr6 o[..r.d ror o.r 200?

s60 I t* !

rawrrbrY rakr9r tandi9Lr ManoE Gh.i|.8.3|Ph|it|P.ft

Figln +43: coDrrrtor or eoFn.rE *1.! TIll nba.rr-ei.r rnpkl colkd.d lor r.bnrry tiff

\\-.\ r I

i.'rsb.Ybk|ptf

rEm +..1: conprlrd or bDr.n .?hr .orhsd r.r

+m \ 4\ .E& Y.' E50 t

saersb.y Krk prr sand$Ll ManoE s.irell{!16 crd( /,_cr..l( ctek - ardm

llE Fltun 4-45: Corprrrt . ol cbp.Er!* Dt nh. ot hrbr rDpkr .orr6rd r.r O.6b.r 'itn 200, clhPrisn .i hedruE wlth rt

l.- s5l FE ,,'5 F

Hawrrbry brr9L bn'r4f

4.7.7 Charts lor pH study tl Y.hB olsnhr tu ftd 'hok

I r8*

pH n.g. of @rm.r *fl.r.R

9 F{!Eq7: E|lx!4d9! rHs nh. or c]nf !ppt6.q!44 ror fJbn:., rood

,,\Y| - -r-\---.i\ i \,/ \ i i

*n .rf "d "c

Fisrj:..,|3: effd orpH or rHr rlu.oij.rwlarppl6oll6'd rorrum 2006.

..t' ,f *d ""0 "."..Ja."

120 F sl4 a9: Er..fgl&4!!s y!!!.ir nlrkrlgl|g.orr..rd r.r o.rob.r :006,

T EI

;',l.J"""s"C

'\. ,/ \=---" \ I ;

J "..-"d"/J-.-

l2l !lN.jr1!_!: q!!€l !II!_o! !!L!r!!il!9!r'.r{!!Ii!€ olt!.!!d ror r!.. 100,,

o"o J -"o "to

f!rr!l!:iq{r4!!lp!-qnllrr!!9!9!e!!!!!r-!l!! o 9-'!9.!i?!02,

../ J'u C -".dlisa-"/' "'" ".9 -J "d

t22 Figuft 4:!j llr.d o-r p!! o! rllsrtiq. or l.!ut.r srdpl!3 lolhcr.d &r r.b'urry 2003, i

"-'**'lo.d..d6d

-d r."".rCsd"d

l2l f"--'-l-\ ! )(

d/ d /i /o"rl".ot.n/ r4ltt -

tu 4.7-8 Chd(s fo.Srtiniry study lcgs +!i-cr9.4E!!ol!!l!!4!!lt!i!!TH! orer.cllEptg-9.rkr.d lot F.b!u.!, !l)l)6 -+\--

;-\i- .A -c 60

,.'', J

R30 ; -64

-J 64qctb:n!l

t25 Ftsq" t!! asr!!s!9!!!!1!&t!!!!I!!!t oudrd f.r (r.bb.' 2fi)d

il .--\v -4::./

9rd4@|,u

nic'tr MDel

126 Inr. 4!qt '-c!!r!4r9!!!!4!!gJ!!!!!Srts,rd rppr6 .orkc..d f!. rui. 1o,x

/\--l.--\ I \J 35 I rs -r- 't

G[rida.k xoa^3i

Pi$nrEl: Co.otu.orsuri ri.l Tfir ol srG r!D!r6 old.d ror Onoh.r 1OO?,

t I I

t21 Inr or-'!rr+r rlElrlr srrdr.d ror r.brusy :0o3.

..\

! \ --"--;'-".

si.drpn M.non Grr.td*l xoroi3t phLl!

...-!!!!!!rrT6i!!q _ -

128 I

_aa -___t thtrr/(prrt N.*r!..Y br.r& crdcr rq.id

l; a !l! Ia lo M.1.06od45^'.o?

t29 4.4 A MultiEriate techniqu€ fo. Prlnclpal Compooenr Analysis:

Pri.cipal omponenl @lysis (PCA) ir on fom of nul vdiar€ dara qatulion. Ii is t wy of idendrying pau€m il dara, &d .xpr$iog th. dara in ruch a wy d lo highliehr lben sinildiri€s md diffemccs. Sin@ parl.ms in dar. c& b. hard lo find in dala ofbiSh dineNioh, wh@ the luuy of gFphic.l rpEenration is not available, PCA is a powsful tool for &alyzing data. TlE oth$ m.in advmragc ofPCA is rhsr once you have tbund lhee pauems i. lhe dala you cdn omprcss rh. daia, i.c. by educing $e nunb€r of dinensiohs, wnhoul nuch loss of infomafion. Thrcugh lhis study, lhe principal compon€.ts (PC l -PC3) were dnlct d Fnainins to .v.ry ycd and 4ch sire. da.1 Principal ComponentAnalysis of SeawaterTll!. PCI for $e 2006 sawarer dara (Tabl.443) Eqb trt ir b primdjly inlluemed by dr.

TH8 in Fcbruary, Apil ed Aueu$, PC2 is toad.d bt J@, AugEl ad D.{4hq_ pcl t Foindns out tovardi F.btuar, Jee &d Odob.r.

E|rtiotrMftlrlo'Il*rtrTHgror406'

130 The PCA odin.t.r d. pEsntcd in Figw 4.66 3 s soE plot ofPcl sd PC2 lt shos wll-hdked *paBriotr ofvdio$ mPling 3iEa lt show th. gmuping ofempling sii6 e@rdinB o pollnion st.ts. ThrouSlt thi! 4dy3k th. d!i. could b. glolFd inro ihE dkrinqr s.gncnu. Or. pqt itu 1o H.eLb.y, Sddtpil .nd Kr*tPir b.lon8 b I sp@lc

to sroup lhar b h.viry f.M load! of Dollu!.nt3. Ko..n8i C@k !d Cidi .Ect b.lor8

@thd srup, d*!. @ adj@t 3itd (?.51 of Appadl\ E).nd mthrcpos.nic activhica

Frtln ,r.66: s.G ploi ol t lDc h. €rk ltla ro:2lto6.

9 Hfl*lrEl E ."'M' s.,*iit -.'' a . i---r,7adt d I j .c$i|'-t .., K.dtr ,c_'ti

Fitlt ComPomnt

lli PC I for lhc 200t *awarq d.1a (Iabt. /r-44) ev.lti.tbat it is pdMily [email protected] by rh.

THs in Fcbruary, pC2 Aplil, Augusr md oc!ob.r. is lolded by ,un , Alglsr and

Dechb€r. PC3 is poinlin8 out loBards Februrry, .lunc hd Odob{.

rrbl. .{.: Elur.rr}rit of.r. cor..j'ito! M.rrtr ror sn., Txr fc 200?.

Colpdo. I : Erg.nv.rn. 5. r6?t o 09tt

Tr. PCA ordilrc .F drid n. FisuF 4-5? $ ! @r plot or pC I &d pC2. ! ts good ag@hsr wih lhc pCA ealysi, of 2006 seaw|tq dala It d$ h5 w.lLMtcd $pmtion of veious sdplinS sircs a6ording |o pollulion stans,

tJ2 FIgurc +67, S$a Dtot ao. F.!-D( *.w.l.r THr ro, ,007,

o.'rii. l*nq:

E \! ?-'ltdptuk Pon Q€dh y*;i S..d.pir 0.0J. .i, ,,,/ _l iI:F'' 6 rcrri 9-!

Fil3t Component

PC I fm dlc 200E 185) s*rr dit (r.bh BaL dEl it i3 Fituity in0ufud by |hc I1Ig in F.bnury, pC2 AFil rnd rw, k to.d.d by,tw, Augur $d Dlembd. pct is

Fblng out rorarll F.bru.ry, Ju. &d octoba.

Trbr. a-!5: Etadrrtrrt oro.CorFt o! Mrt.t to.

Dl Th. PCA odhd.! e pE€6bd in Fi$r. +5t !r rrc.t! dor oflcl .nd Pc2. Ir k dro

$otrirS sdl-rdd .c!.dion of Eio$ rEDlira di4.

t- a'a& so.r Da. dt !D. fi. t-* t||a ]rE 1[.

tv 4,8.2 PrirciD.l Compo!.rtAn.ly.l. of S.dinentTHt: PC I for U. 2006 s.dim.nt d.ta (Lblc 446) Evals rh.t it b mt Fiosly in0wnc.d by dyof thc llls qlB. PC2 is Doildns our F.U!ny, Apdl dd Juc. PC3 ir Finrins oul

|o*!ds Aug!5r &d octob6. TrtL a-a6: rlltautrh olrl. corELlor M..rrr lor t dhor THa aor 200t

Th. PCA odild4t e p@nrld i. Fisu 469 r. . lcoE ptor of PC I {d PC2 e rclt- rulcd $paFlion of sdiry iiGs iD two grolpr Slch Souping of !.hplin8 rit6 i!

!o pollurion 3rnB, Haq!!b.y ud Krbpi! b.loug !o . s.p.rdc goup lhd h.v€ '@din8 fer lo.d of Flluta s. Unlik s.3*|Gl PCA, Srndlpit do6 not pbnircnrly b.lons ro lhis sreup. I t|).s S&.htit hls diIIcMt &gr. of .c.unuhrion of H8 h $diNnr ths

KoE Si Oer, Oizi cGk lld Phird C!r.l b.tory ro m0E s. Eoup, rh.s..tt .!!

CEt @ (s.r tmp in stion 7.5.2 otAppcndix E) ed ir i! hay b. dw ro sanc d.sEc r8l p.tr.n of polllr. @uuhion in s.diMt,

Mdo6 is dilI.Gnt in thi5 eE plor FigE 4-59: S@F plor of F.l-De fo! 3.ditMi

THg for 2006. is scrdcd lDd ir hls high lotdin8 ofTH& n tu ns rl|c a.cMut.t d Hg

lt5 h hieh in such sdin nls. Thcrc i5 a 8blpiDg ofcEt .njs in lia@ 4{9, rhis gtuupinS

subnartiales lhar s€dimrs ir thc @k .q h.tng low gddicnc, eunulal.s for norc

pdiod dd ba@ chlGs of neral &chul.rion in@s*_ Figur r-69. scon ptor or F.EDR ro*dtE..rT$t ror t000.

K..'rdF4:e.?t 8 ,i!,'Ci" i'.GEic@k s.ndlDd ,@^0' oadl j

FilEt Cornpon€nt

PCI for th. 2007 s.dim€ d.ra Oablc 44?) ,.v!.ts rhal n b piituity infiu.nced by

FebMry and April THg pC2 vdu4, is pointing out ,tunc, Ausut ed Decefth.r. pcl is po,nxng out lowddr F€bruary, Junc dd Octob.r, rrbh ril E4.mortyrr orrh. cor

D6 The PCA oldinaks e prcenled ia ri8urc 4-?0. A $ore plor ofPCl ard PC2 is again a sepaolion of wpling sites in 1lo erolps quitc di$imila! lo the sore plol for year 2006

(Fi8urc 4-69). Tlis yee (2007) S&&!it joins thc g$up unlike prcvious yee. Thcr.forc

Hrwtsbay, K.kapi dd S&d5pir bclonS 1o a lcpdc grcup th.r t having fe@ loads of

A$in KoMgi CFek, Gizi @k ud Phini Cr.k bclonS lo su. goup bnl rhe loading of TH8 is hidd $d in 2006.

ManoB in rhis scoe plot Fisw 4,70 h s.pd.r.d ed it hd hid losdins of TH8, ir hds ihe 3ccwulared Hs emis hign in such s.dimenrs.

Figurcr-70: S.o!. plo. or F.b-Dc. edln.or THg ti yor2007.

,q ', g

PC I fo r rhc 2008 s.dimenr

137 T rbh 4-43: Eigdrorryrhotrh. cor

Th. PCA odimr.s e pEdted in liiurc 4-7 t .! ! rcoE plor of pcl ed pC2 i3 ag.in a prcftin.ni *pm$on of mplilg 5ft9 in twD groups dil|Mrty with tt€ sE ptot of pEviou two ys (Fige 4?0, Fi8!E +69).Ihi! y€, (2008) poir e6siE jois ir.

8r@P of @diig sir. of efc .n! ft ndr rh|l 16 t@ @und i! pon '..@ut

A8.in Korusi CFI cizi d.d(.!d Phini Cr!.t brloog to su. gDup bur &.lolding of IH8 ir difcsn liom pFviou yd dlrt

l3E rtstE +7r: soE ltor ir' r.LDc r.d|!o. tga br y-r 2lrn

E " ogs'm K.k$h .. . , k,w|3b.v 8 jru_a_r s.ldlrd K.E^O' CE.ti .. ..2 -! Pla CE\

FiBt Component

PrinciFl coupomr o.ltsis of !.diMl THg h lhF yan.tisibind.s sfe .m hr1 it ds i&l'id6 Pott @rin $dj'ncd. TH8 to.d in Phiai.Et and Kodd CEk belong ro se aoup (ra!b 4r, Fige rt-72).

Trbh a-,tt: EisNirtyd. oa ri. CorFr. o! Mr.nr tor r.diD.r!

l19 frr!fta72: sconn.olrcocto(a.vrEa.r.rli.o.Ta&

E E d 3 1'l

4.8,3 Primip.l Componert Amlysis of salinlty datu: Piirciprl @mporcnl drlrsir ofsduity (ht b the 16 suppons the oorcdcs ofTHg dat of ssi.r rnd $dindG Glblc +50). TrbL a-10: EigDult|| or.!. CofrlrtLr rrr.rh lor,lilny drE

t ,

t40 Sc@ y'ot of ftr tro cooqoo Gig's +7!) frr. Snra d!& sr nd pdr a.riD r.trdi!8 rliriry Fdle A .b rD.:lr fr bSh Tl|g crcdlr i! r,i.s| |h cnrblidB ih. bigb polluioo sar of6ir dla

i|tln +7} se,t ..rr.t4a.o*aa lrdt.r.d i------

lal 4.4,4 P.incip.l Compomlt Aetysis ot o'| d.ta: PCA lor rh. pH dlt| of rh. whole $idy . .ililhB Elllion wirh TH8 noriced in 3rudy (Iabl.4-sl).

r.bh aSr: Ft<-..rrn oru. conbd.. Mr.rtr ror Ds d.d

sc@ plor of &3t $o coDpo@ts (Figu. GZ4) d|ow . gtoup ofsfc .d polbrcd 'M @ n8!di!g pH ,I}n drlr is d di&irc! ofovq.I poltuio! in Fltur€d Bgion.

t42 Figui. ,r-74: Scorc Pt0r ot Fqt06.Ds-03 ,H drk,

z ' :*o* r .ty!ff'' 6,:g:!y_t-''

E 8

FilBl Component

l4.l 5 lscu n d.ia h* b@ rabulard 6 csuhs of bblc &d figue in the pEviou seclion, ps.mr outcome or rhre y@ spdin8 lhc p.riod (2006.2008). tr Fnains lo st$ies

rchred ro inv€sliSarioo of n rcury rcl.rcd pouulion in Kehi's csrrt b€lt. Tne study ptovidssabdelimpofileforn rcory ba$dpollutionof Kdchi\mdincdviome . Tte djscusion thal follows debate $e Eudny.rd ruthoricily of the* re$hs on one

hed ed ako o atehpt ho be. m.d. lo indprel these ,€sulb in le@ of

enviromental veiabld lite *liniry, pH, dc. Ti. esults nave al$ been foud justifrcation ih cotopdison wilh simil& studi.s caried our ar othe, esrablhhcd resesrch porld ccntcB or fte dd have been publishcd al rcgdd inrcflals.

Tokl hcrcury onrrdr (rlts) of .nviromcnBl mplc ,s cho*n 6 r@t ,o ndr@xon ot ovcrdll rolluion. Allhoud, noniroriis ofdjrcrcnr foms ofn.rcury (havi.g do moE loxrci9 @ be @riroEd like se$ylmocury crc, bul ir rDk6 6e srudy qune l6ghy dd redious. Ale lhe basis of robl ll@lry b hor. $sirive s n ,s noe abuddt oralt forms oi nercurr (225). In compdison wirh orhcr lacc mehls hcrcury bG qujre low natursl abunddce. Also iLs usagc is timii.d in indusrli.l ed dom€sric acrivilics,

Thercfo!€ it5 honnorins @ sensitively ses th€ pollulion st tus.

5.2 Choosingstationsr Sawala is th€ in ldg6r volue dd abund&e, rh4forc ir is focued pfttihjndy. A1 pElininary slage @ples sw @uered fiom thc dGore ofal tasl t5 Kh ofcosLl b.h on dc b6is of dififtre in simudilg a.d &[viiie. Innialy 6fta. dife€nr lootioB kE spLd. Oul of $e, 5*n s|lios q@ ctr()s on lhe b6sis of dqu,Ehenll for srarisricjl rdrn€nl ANOVA (Fige 3_5 lo 3_6) ofsaMrer dara for H8 conk and exposure level. Each ofs*en siaiions h bavinS rhee

lo made sdpling repEsenrarive of$e wbol. e4 Scdim4| and

also @ll.cled frch aU $ae slado6.

5.2.1 Brietdescflptionofemptinasttes Hrwkbay. Krlapir ad Sddspr 116 hive v.ry tintc hum& driviljcs dd preFnc. of &y industid unn is @r didoced. Oaly a nuclcd ct.cdc powr gdeFdon pl.nl is s'tu.led n.d Hawhbay, Soru mtt boat Dating dd Epaidng eivitiA de ooried in

Kakapir and Sedspil. Th@ e one or iwo ln{c villag€s situa&d netr each ot rhes.

st tions otbei the Hawksbay, Kakapn &d Se&pir e siluted at the coalat dea of nai cnr. Th6e nve staiioE (MdoF, Ciai scck, Ko@gi ceelq phini cr€ek ed pon

Q4im) @ id€nrifi€d in rhe vicinity of civil popul.tion. Thci. doncstic nd i.dusrial qrc is exposd lo rtE dvioMal. Emu.ds .rd tun6 fiom indGEi6 e @i.d ro s tln difccnr industial uirs t@t d at dift Hr al*, Th. tm major palbs of cmumb 10 co6r.l hrqs 'ndusrrid e Ly&i &d Maln Rivs. tn a&ition ro th6c sidr palhs ol.nidcing poltudon theE &. nulnqous olho charneh ofE.iery of sies.

5.2,2 Classifying rhe srarion Thc cur.fl sludy cove6 the ye4 of monnorine co4iat sirs of Kmchi city, Hawrsbay, Ka|apn dd S&dspit d. rhskabty tow in H8 coorent ot eauler (Fi8urc4-1, Fisue 4,2, Figurc 4-l)i (Ialrlc 4-1, T.btc 4.2, T.ble 4j), Fdimen (Fisu.

4-23.Fi8uc 4-24, Fig@ 42j; TabL 4.lO, T.bt. 4-l l. T!bt. +12, Table 4_ l3) dd lilrr fed.R. (Fism 4-15. Tabte Zr2t. Tabt. +22, T.bl. 4-21, Tabb a2a, Rc;Ls of $c stations high in deEuly 4 o cnr. Thc E$lrs from sd*"la spl4 or u4e sradoM e within the vatue which euidelioe is 50 n8/t for sswalq (226), ,nd accordins to rhe @bpciion of *awler Eponcd (227)- IHg 5rarG of swt€r in rhc sil6 liLe (MeoE

Giui creek, Kotugi cEk, Philli d.et and Pon Qsin) is aboul 2 lo 4 ins higllci.

Sbtisric.l noltivaiat ,nalFis PcA (s snon 4.8) .le h.b6 ro .lsit starioN. Pca oi THg dd physicochemical ptuet4 (Fgw 4?3.Fi8ur. 4-?4) suppons lhc cldsification of snes into tvo gtoups, one of then is Kal€pir, Sddspit, Hawksbay aG r.latively polhtio! fE ad orhc having highd polhdon load.

On the b$is of abov€ facls th. smpling sbtions cd be clGsifi.d into 1wo clsca,

HEwksbay, Kalapir dd Smdspil s r e.r.. dd st of the slations s pollut d rre.,

Amthd subclN ir thd of.r..t @ sd n is ale sub61aldacd rlrcu8n PCA &aly3b of

$dineifs THg (Fig@ 4-69, Fi!@ 470, Figw 4-71 , Fiele 4-72). ll suCeests rhat lhc sedineni profile of THg in cre.t alq eembl. .sch odr.r. lt .stablishes dal thc emdation ot THg in @k .B k diild tom othd tr?cs of sho6. Howvd, laMter md olhq oimal's TH8 load do not suppon sutsclassificalion of c@k arca.

Thh bebavior h6 to be ud€6!ood, cosidering th€ ilmovabilily of lhe scdin.nt

@mpooor of lh. l@d natrix.

Adons aU of the seplinc sialions, Mdola aid Phiti Creek arc identiiled as most toUul€d tr.4. Slatus of toial m.rcury @.tcnt in scawacr spl.s fbn Mdo6 &d

Phird c@t slllions e fairly hi8h- (Figw 4.2,4-1, Figw 4-3) in onpdi$n with ilos sil€s drat e .ven hishd the the suidclin. value of 50 ns/|. (226). PCA of s..wat€! ealysas in all y{s of study also Soup M@6 &d Phitd crc.k in me clas orhisb THs. (Fis@ 4-66,

t46 5.2.3 Choosim stati.n a. , .dnrml: On r\e sbdnical fta[ndr of data ir T.blc 4-1, T.blc 4-2. Trblc 4-3 dd Table 4l t.

Tlble 4-12, TabL 4-13 o&-wy ANOVA (Epon d in stion: 1.5.2, pagc: 7l); What il

8or esrablishe

Effil€bly low lalues in H8 @nrnt of F!w1.. (Fi8w 4-24-l,Fi8ur. 4-3), sediiqts

(Fig@ 4-23Fiew 424Figurc 4-25FiguE 4-26Fig!rc 4-27) ud Filld feeds er.

(FiguE 415). Elen the sedim.ht THg profilc for Hawksbay dns€s fiom 200-220 ng/s

(Table 4-ll), lorE rhe Kalapii (23?-258 ns/g) did Sddspir (244"2569 ns/d. This

rend conti.ucs ih even the result of n.xl y.ar (2007) s.diBat analysis (Table

4-r2,Tabre 4r3) for Havksbay <206'220 nttg), K6kapit <237-258 nc/s) dd sedspir

(244-256 ng/d. rlaslcbay is rhu again id.irifi.d .s a conrDl ea mons lhqc th@

lcs contahinaled srrtions. All of 1h.* 6ulL e tow rha Eponcd guid.lire valw of

o.l s ppn TEs (D.@ 150 trs/s) dry qr (228).

Low vdB oI IIls ia rbe filt r f.edcs for fu @nair have dso pDvcn thar I(lhpn or

ndby slatiom lit€ thwk$ay ald Sd&pit e noti@bly lgE o. vcry ls pollurcd

@6. Bdnmlc have THC in m8e of252J5Z lg/g, Oystd h6 THe in Boge of 245-

364n9/e md Mussls 27c245nglg dcphdinS upon |h.ir !8c ed size (Iigw 4-15. Tabte

4-2J).

l4l 5,3 Polhtion pidfil€ for nsh and seawa.ds: Unlikc *.ml4 &d scdimm! fish ad s*.d datysis d6 nor 6rabtish ! popcr

rclaliob of lolluiioo sla1s egdding mpliig sn . Fishes m deloqliz€d cqurcs dd

that ils exposurc lo pollutanls is hot sile or sourco spccilic.

Fish is quire lcas in th€ !€sion ortlawksbay dd Sddspit in comparkon lith K*apn.

Dne ro non availobility of fisb c*ching f&ilny sd tow abudde of 6sh .| shor6 of

Havt$ay &d Sddspi! fEh @pt6 v@ not cottatcd from Ihe trc sir6. HoEvcr,

ar Kakapir lh.G is a snall 6shma villagc ad hcncc $e facihy of hovinS thbugh

sau boat! is av.ilable. Fish smpla wc @llcclcd by carch vnh $e hetp of ncl

Tle thEe shtions (Hswksbay, Kalapn dd Sandspn) hrle horc abuddce ofsawccds.

THs in sawd does not eskblish ey pafiem of polurion due b its lower abitily of

nercury accunllaton (Table 419, T.ble 4-20), THe lcvet in swed is uneiDousty

hign in MdoE E8ion, Othd sradom havc no proFr Glarior *irh THg @Dt of

5.4 Details for individuat sites h ods ro obtain eliicicnr iisight inlo infolhation from dal4 firstly data of individual

smple starions arc di*ued ad tren lh.y d. conside!€d vis-a.vh sm. orhd

5,41 Detailcd prolileoaMaron: MeoE is silut d ncs the op.nins of tlE chdd of Lyli Ri€ D,iic[ i. rhoul O,75to j6 wide ar i.lerfa@ wilh em. This chmcl is u?d 6 a palhMy of lhe sepon, ,mcly

Kemdi which h s b$y seaport. It hs quirc hqvy fiafltc ofl&g€ ed Malt ca8o ships, oil lanlers, fishing t6rlcrs, vessels ed pt.nly of snalt fishing boats. Atong with rhes. activities lhere d. oil BcRois ddj.tri$ tunc$oniq day dtl nighr. Funllemo,.,lhcc

l4E de ships &d boats @ufac$lins ed repaiiing sir€s, shipydd. A huge Ushery is also

Lyari Riv.r is one of$c hain $!@ otduDping a large body of wstcwarer f,om

Karacbicny.Il l6vek abou 45 Kn $lough rhc cny and cari€s domcstic and indlstriet emuents 8o.!aled noo a vdi.ry of indurial dd .ton sric acliviri.s, Ftow ac of Lyari

PJvq ldies.d deFds opoi thc activirlB .nd usasc of wt.r. In thc sU@6 (May-

Jue) thc flov mr. is hish.

The cohtinuou dEdge of s.a noor in Meo,a chmet is eoli.r possibte f&ror for highd THg contdt of wrcr. Ir dhubs rhe nFhsis of @Muladon dd d$ chdges tn equilibdm of disfiburion ofwcrsedimenr phs6. (3?).

The seawau dala of Mdora sration hs quite wid. rege ?5-t35n8/t THg, sdimcnr eulll .&g* fton 46O.550n9/8, Hg co ent of Oyslcs is lhc high.st (2j0-j5ong/e) s

@mparcd lo bamls (250-a5ong/d &d elsls (210_3tO nels) ii rhis Ggion (T.btc

4-21) Tnc vrriarion in Eslh m.y bc aflributcd ro difcrcnce in aninrt size and se{son od thar s.dioe.t md fth sptca do not exbibil concwnce wirh polludon profile.

PCA for s.wald GiguE 4-66 to Fig@ 4{E), *dincnl (Fig@ 4-69 ro figtrc 4_?l) [email protected] ad pamc!:F .le restifis M&oE lo be al a hi8nc. bvct wie sratus

Ihis snc h alsopeculirdlc to& ilcjdem ofoilspill in July 2OO3 followins m incidenr of si*ins of d oil 1a*.. (M.ly Tasn& Spnn) fitkd wirh crudc oit dd rhis polludoo reveh 4e lft cly ro b€ elevdcd (188).

149 5,4.2 Prolileof Phitti creek: Pbitd cek sknds second in pollulion slorus as pe! data coll4€d durins tho curEnl study. (F,sur. 4-2.4- l,Fisw ,l-t) Th€ swr.r reulrr @ r&ge fen 78- l25nslt ( Tabl..D,dd loisedin nll?5-a|5 ng/gGablc4-lI). SanEds@leinrhisEsior

The appeardce of sawater in this @ is nostly tike ihat of sekSe water. l'e major soucs of su.h swas€ @ indsris (in Lddbi indlsrial ane $d Expon p'@esrins indutrial @nc) d

5,4.3 Ko'?ngi & cizri Creek resembl€l ANOVA, ar P=0.05 Gee secrion 1.5.2) applied ro THg lqels tor Kormei &d Gizd cEk5 dmoNtrars iosignillcdr dir.Mc6. On th. orha h&d pCA anatrsjs plac6 u* cEctl on tlre ffie pollurion sIaru fi8tfr 4-66, FiC@ 4.69). Maln River is exposed to sd ar cidi cEek aF cad6 efihenrs ftoh indurlis of Komgi indusrrial d€a, asliculruhl w6te ed rhc donsiic souMs. In Ko'mci Crcck sr2rion a snall fishing tDn. oil rfin ris ad a lhftal powr Scturdion pldr My be lhe po ulion

5.4.4 Profi le oaPo.t Qasim: Pon QGim ir @mplebly d indsuial anc. rt d$ hs a snDll spod, oit ien, bd

$emal powc gcneEion plst. Thc THg conlent for Fawtc' (65-l05ne/l) scnihcnt

(2l0Jl0 hg/d is lowesl of.ll statioro thd are clssified s pollur.d aMs (Tabte l"l)

PcA for diftcGnr oarriG (likc searer, s€dind( er.) also rtac.d rhis sn€ in ! sDdale deg@ of pollution )dd (Se setion 4.8). Lrw levcls of THs in lhis loqlny

150 m.y b. explai.ed in terms of il beine a neNly ddclop€d aEa s ns hislory of industial

dcrivily is not more ftan 20 rces old, wbeE6 arcas having bigi€r TIIg lelch have been

ilritrs itrdlsrJ'al od doncnk cxcerions fo, morc than 70 yea6.

5.5 Season wisc comoarison: Thc scenal veiadoN d wcll noti€€d in tE sludy. Il is cl6 from Figurc 4'1, Fisurc

4.2 and l:igae 4-l lhat ftere is similrily in palLn of curyes for €dwlter smples

oollNrcd ircN lollurcd sk(ioDs. lor rhe monLh olJuic dd Trls coilem k high al alnost

4ll orrhcs srarions. Unlilc sawarq patt€n, rhc scdinent THg is los in June. (f_ig!re

!L 4-26, Figurc 4-27, Figurc 4-28; Table l|.l I, Tablc 4- 12, Table I l)

Thc cnhanced lalues for sawald sples dd low aor sedim€nl in Junc arc pobably duc

lo ibllowin8 few reasons. Onc may be thar therc isnonsoon s@si in Junc,duiig which

idcs ac very fEqueirly chaigins; oth€$ie, hish dcse ofinpu$ froft urba. runofin

@NqEi@ of hishq @nsuhplion dujrg iunm... Such incm. is lowcr in swarer

rd higher for edin€nl in sialions iddtified s $.fc dcd 6 these loedons have no contributions f@n u$an runoff (Figure 4-11, Figurc 4-12) sbich arc conspicuousll

frbing in June in $is locs|ny.

Thc fador of ridal chanSc is 6mmon for all rhc l€6ed sbrions but lhc sludsc fom

human acivnies n nor a natlcr of concen at sfc sl1tions (llavksbay. Kakapi and

Sandspil). Tidal changc disiurbs de soluble and scdinent THe disrriburion (t9), (60)

Mercury load in !ate! will be morc whcR thc &cwul.lcd THg in edimcnl h high. In odcr to di*ovc. rhal vherhd id.l chag6 is th. only f&tc,r for such changc in summtr for all *rions or othcr f&!o6 dc also @nribufing rh. clcvation of T1I8 in sunme!, a panhclcr rhar cr synchenirc thc cinerion is nedcd The 6tio offic lltg latN ror

.ach srarlon wnh THg ofllawksbay 6 conrtolsn. for Uc sme donrh can nomaliu lnc l5l effed ofridal change. If the elevalion is only due to lidal cba.8e lhen this raio has to sl$w closc vnlucs throughoul ! Fisrc {-? is. plol olsuch parancter in srmrncf lor 'ear. rhis fteioo (in perce.tage). h is high in qe of Ma.oia Pbittr Cleek and Pon Qdim d conpd.d wi$ rhe oter 6on1tu of sme $ation3. ThGc slalions de looM lo haviig chs.l oFnrnss lhat d'sp6e s6L6 8.n@'.d followrns hmM diriries t. rism rr (Table 4-24) MdoE, Phtui Cck, Pon Qsim etc. haw noi nomalizcd by this taclor or patulerer. Il med the larg* volum. of wdrcwlcr is also 3 succ fot such incremcnis in sunmer 6 eil€ct of tidrl chdgc b hiddcn her€. Vhil€ in sfe areas

thc high values ol THB m striclly tidal chang. speci nc.

Anorh$ asscssFcnl of such identifisrion is nomalizing by the dislribulion atio 'D of

THs in sdinent 0d vater.

D -!!819.) I H8@)

THs(sd) is io6l m.rcury in *dindt dd THs(w) is rhc @ftspondins ulue lor

PloG ol disribudon dio D 6 funcrio. of honrhs (rA@ 4{risd. +, shov rhc

gradienr duing sunner in polluted dea b pronincnr *hile in saie deas rhe effecl $

Tns fr.qu.nt chanse in th€ tid.s is a f&tor for in EaF in rhe fig in suhoer Als silcs

wheE $. pollndon is alEady hiClr and lhey d hrvinS chmelizd %Ewarer inpur5

t@rd cnhdced THs ldels. Not only warq @nsunplion in smer is high pmducilg

highcr no! 6rc ol Lydi od Maln Rivc6, bur dc consuhprion of (fuels, el6tricny cr.)

is highcr during smmer. Reodkable chdgc in q6tc disposal load in said rilen dd

othc! wa$e*aler chmcls ullitralely qdics pollulanG lo sea Data lor Fiher feedeh

lt2 (Oysrcrs, Bd&les and Mus*ls) confrrms thc linding ol high valu$ oilHe in summc!

(Fi8ure4J5).

'ft. dala tor lisb malysis (Tablc 4-14) and lor $ascds (T.ble 4-20) have rc tadicular relation otic THg r6lne dr wtr. h h.y bc due lo lhtt nEhanism of ec@ula on ia risu6 rale lons expcuE period (tE). Al$ fish e moslly dclmliEd a dsnb€d dlicr dd @ nol rcpBolalivc ftr lhc TH8 vlluc fo. p.nicular ma and edon.

5.6 ysrl4is!-preElsfq!-lqsEurLoad. -fhh srudt covcu thrcc ycas lor lhc THg lhllysis ol *!w.tci.nd scdincDls.-fhc dlla for $h long p€riod is loding low..ds som. fdclg a.d llgurcs, thc sm€ patlem is noliced in th€ sedon prelile for 4h trd Gigurc {-4, Figur€ 4J. Fig@ 4-6). In lieur€ 4- 16 lhe -fHs ii sa@ter mpled in Feb and figurc r-r? for snple ofJw for all y6 b shoM. A slalislical inv6tiEatjon for lim&

@rclarion is shoM in Fieue +19. Inn.ld of lhstsboy all shtions ha @rclalio.

@llidor wry I@ ro 0.9999 ClabL 4-9). This is sother sood justifiqrion ror sletion ofdis stalion a @nlrol d&ughou fte sludy.

5.7 lrt!!!4!!&fut!Ie-I}ls-uollle.: How much ihe pollution load is enhan€in8 ca. be noticed by calcullli.g nle of THg incMe per yed. ln order lo do this, slope oflh€ valucs in Fi8ur€ 4- 16 md

Fi8uE,r-'7 e plotted in FislE 4'18. Thc de h fafly high in the polluted Rsion $d loa ii sfe egion. Again n is hieh6l in th. Mdo6 GSion aboul hoe |h& t.0 nEll Hg

Fr y.ar. HeE th. Ble ofincEm€nt is highd in monlh ofJu. comp@riw to FebMry.

OB cd predict ior MaoE sL1io, it sh 6tc is .vd nlintaire.l lhd ancr ren ,.6

T;e valu. vill b€ norc rhd 2oons4 (i.c. moE ths I o0% or rhc cm6r sratut.

r5l Yd *i$ omFisn for the sldircnr sple is dllblirhins no nori@abrc chdgc

du ns y@ (FieuE $@ 4-30), RcgrdinS $awald d.lysis, THE votuc for ,!.r 2OO7 is 5,5 b 1.5% hiSh* Crabh a-4) and aor ycd 2006 n is 9.0 |o 2.5% nigh.r ta rH8 i.

ycd 2006 (Tablc 4-5). Ir nar b. dN !o narud phcrcnctun or diftusion th.r w6hcs

.uy rhe aemllarcd THg in ordcr lo nainrain thc tcvct.

Tl. sple EE @llal.d in rcn.hol@; 5.en wirh Esp6( ro rid. h.i8ht.

by cl.$ifying $. spling in|o th@ mrlc ot dc Ljw, M.djuh &d High.

ii @r noe rhe 2,0i mlim is nol hoE rh& j.O &d hieh is nor noc lhs 4.0. Irt@ is noully io.fier ofdd$ but in Egion ofcizi CE.k |o phiui Crct, lhc THg of sw.rcr oll.crcd ar low d. ir high conpldirc |o nediuo and hish. (Fisuc4.2r) 'ftis irduc ro dilTcEr..s tt itr rhe n.rr of boch. Thi, ESion i, cEk G! &d in skh aB d.prh is ituEhg snd@[y. So,n.rih., duing low rid. of s.w.rcr is $d 'low lo b. rilcr litc toM.ds oFn $a {d conEBly in hish lid* ir h.pFtu b bc nowin! v.ry lar roMdr shoE fiom olq s. nc @6ral g.t hr6 @nrsmiMlcd thrcu8h *v.61 ,ow.s s ndtoldl €sli*. Wh.n lx.E low ir ddc, 0!c potlucd swlc. nos lowids op€n *a and uhih.rct, g.t, dilur.d. Thc low v.lB for THg in sw16 in hi8h &d ncl[n fide cvat $.t frcsh wt r infloB a@n op.. s h.lp lo d.clls po udon tdcl.. Thc eradual s@*rt in lold of Tg8, b.ins i.u.

t54 sFcific sd(on. For qmple rhis di{ferene is 9.l5ns/t ro. Phnd C@k (T.bb a I.

turuming tlEt loe likr swarcr is hv.lin8 dlring singtc tidal chdge n Lads lo suggsl

$ar 9.15 s ofTHg is inroduccd ro op.i *. in a s'ngtc ridal chdge tom a pbili creek.

Mercur! loss !o slorc saLe6 was rcponed 8.6 lo. yir in a simjlar suBey for Fntmd O).

5.9 Surface valer sdples wcrc collecred fiom rhc lhiiily of seashores spannins from

surfaces aboul r okn offsho'e wirh a dhlone inrcflal of .r 1e6t 2kh (Soc Appendix E).

Conpdison of rug dala of rhesc sMples dg0in sumorts rhe chsifierion ot sate ffd

pollued a.qs. As elide froo Figm 4,l3 thc ch&8e in THg in efe ared is tower rhan

tbr polluted ones. furlhcr to $ai lh. gradicnll in THg in suter and codelarion

coeltrcienls for THg dala of su.h ea hrv. no sralistisl Ftevdce {Table a 9}. No panm is evidcnced in di'lmce pofit. of saf. &6 tikc Hawksbay, Kakapi, and (Figurc Sed$it 4'lJ). Howver, MaeB h6 hi8h SEdiot in THB wilh esp€.r ro

disbe ad logeithmic @ftlalion abour 0.99999 @npaRrive lo olher pouutcd sn6.

Thc Ee of lhe a@ e @* a@ ud the d.pti of sawlr, incrc66 *jrh lesser stope

$an Mdo6 chanel. As no ced in th. b.h.!ior ot rides wlio (Fi8urc 4- r 4)

5 1 0 El!i!r4i!4-La

t55 *iddlced (Figw +20) for Mano6, Kor'n8i Cl€k Phn[ A pomindt dift lm. is 'nd input hE b'en Crcck sbtiont but lhis

a likeblc sourcc lo Thc difrcm@ in th. THg l.v.l for w*i!g tnd noi sllin8 davs '5 Ning lh' c$imr. thc F@nns. indusni.l @nribltion (% rC) in THs lt k c'l'ulst'd

w r xrcu =WE):f!EQIr/s(*)

wh@ THs(w) ir hNury.ont nt of swcr.r in s.hPld @llatcd is *orkitrs d'F ed

THg(O) ir hduty @irdt of swlt.r in sple coll*cd in oll-rclking &rs

ftc %lC it r.bllar.d (T!bl. 4-5) {d lhc hishcn v.lG of il is to' M@r. Th' avcd8c

indusuial @n|riblion 10 THg in coa$al wt{ fon Ktt&hi citv is.stinaGd lo b' 40%

ot rh. br.l THg (Tablc a{}

Ar pElihirEy t!t8., *v.dl fish sp@i6 rcrc .xdimd ror THs o.blc 4_17) Out or

$.* four sdc sclel.d for flith.r.tut)sis on lhc bsis oawtil.bililv sd thcn habit.r'

Fishcs dd e trs.boundary cstuEs (o.$ rhv.ling v.rv lons d5Lft*) wcc not

Ar ir ws di*usd dlia no FoniMt P.ucm of Tfl8 b cvidcne.l wirh BFcr to lbh

qah Fruinin8 ro diff.anl sals Cr.bL 4n4) od sutios (T!bl. 416). Ahhough, M

in@aing v.lE ofTHg is turic.d in fish.r of difcMl si6 or.96. It. cxlcfl ofTHg

lo.d is difrcFil for dillcFnt lpeie bul in.lnsr dl !pei6 thc TH8 valE 'mrces wirh sia or l6sr.\ (230). It is sss6tcd ro bc th. our.otu or long.r dp.suE for

156 a@wuladon in rh.ir body (Tablc 4-15), as prcposd by a iumb€r of sinitar srudies

OrgN like b6in, liver and nuscles of rhe ssmc fish wre aho lested for TLI8. T1le THg

aeunulat'on parchs in diffelent oBans havc aho bcsn rcponed canier (2ll). i.his

sludy al$ found liver ro be containing bjghesr buid.n ofTHg toad (t.abtc 4-t7) (t;isure 4-t2).

M.rcury h6 sreal altnity tor prctciis (86), (51). rt qdjty roms d.ivarives ofpror€ins Fomarion of rhes polcih nftury dciv.tilcs h onc of dc ou$ for toxic acrions of

5.11.1Co smpl6 of a wi.ty or fishe, co*--O p* *-Eii*u rom l@ar turdr &d rhe cdihle pan (eMlc) of n ws l.srcd for Tt& AU Erulr. @ eithin l5ons/g THs. only PsedNcioeM situ t6rP.s aboul 875.50n8/g Gabt. 4-18). Thc THs EIB de within eI€ or allos€d tibiG of I n8&g G9),

a wy or silg lish 4 seaf@d js p,io! dryjnS r,o cootdDg. TlE fish Foesing prior to mrk€xnB involves mdy sr.ps n@ty clc.6ing, sating, oonarns wiln spices and dryios in sulish. Tbcse dri.d fist!.s c& bc ,lorcd aor honr8. h is then f,ied o, c@tcd to @ Sucn dried sdples w.rc atso col.d.d trch !o.al ouftls &d r.sl.d. A of $e couected smples bave b.low dcterion l.v€ts ofTH8 Oabh 3-7, see sec on 1.1.7). Hg bang a volar it€ subsluce co utd 8cr et ininarcd d uri!8 rh.sc proc€srn8 sreps.

The safood avaitable &on Kardchi codr hs bec, found to be sfe regarding Hg exposlr€ in contrer lo host of rhe j incide of hcrcury expos@ reponed D rhe wortd where scafood was identified as lh. maio surce ofailnenr,

157 5.12Se.weeds: A gel vdiety ot sawced n lbuddr .t dosl of thc Kdehi @dlal al@ Howevq

creek areas lack in rhis comnodny.

in seawarer also apan fo@ Mdor4 thelc h no posirivc i.diarion for ary pollurion

parrern THg in b' other stations (Table 4_19, Tabh {.20).Il hay be due to re$ abitiry ror diilusion of THg in rissu.s ofscaweed froh war* ctc, White THg in seawftd coll{ted

nee MaoE is highq, po$ibte a physicalfacror is rhat high exposure ofTHC in MeoE

warer rbal 6 €xpecred to force the difiBion or ir&sponadon ot THg in seaweed,s bod, (231). AnodB impon2 @nrriburiiS faclor is dc deg@ ofTHg ih sdiDenrs foud netr lhe saweed. Accunutared ll@ury 6 b. ffied by rcots or olhcr s*ding po6 of sqwcd ro irr body (2t l).

Fou sp€cies EE chcm tor nfiher sody d€p.lditrg upon $ei, availabitiry drcughou. a In orda ro @mpe THg toad in di'IcE.l lyps ot *.recd or l4l singlc sp€.ie 'ear of r.d arg&, bbh sawed dd 8Ed s*ed E eldred.

Ge.enlly csul6 arc in $c anSc of 25-6onys THg fabl.4,2O) and ou dara ases wnh studics Eponed ftlicr (212).

UhaAtur, ha lhe bighesl THg dong all t.sr.d s..wc.ds, tt is.lso knou G Creen

leltuce, ed il is presm lite a bed lhc ii uodo wat r floor. rhis appearance can male n moft feaible ro accuoutarc THS fion suiioundine s€dimcnr. Orher seaweeds nosrty vacillare ude alel sd hale tihircd acce$ ro rhc $dimenr through few poles ro.U!q 14Jj4!!!(.231). s-r3 li!+r+:te!+alqedcljAtiq-indi.r,o.r: uyneE. Musiek ck.) @ sood bo{d,cdror pollurion. Unfonumrely, ther. is ho population ofsuch mdin. crcarws ar

t58 of Hawksb.y lrd Srrdspn. wlil. a pl€nry oa lh.* celuEs @ available a! tbc rocky co6t5 likc Kalapir dd te* otner d@, &d th. sdple, of B@lcs, Oy$* .nd Mus*ls w.e cxoined fro6 lhe s.ations tor THg load, B€inC locali&d crcauEs &ey

spend then wholc tife a in conin€d ptace sincc rtrci, hda srage ed rhus &. a por.nrial bio-accunulabr for herclry (2lt). Also rb. nechokm of t€ajjns in lhe* sp.cies is to filtr eawat.r dd cosm€ rcsidner. ThcEfoE $e filrr fede6 de Bood biorndic.rob

Tn THs l@ds highq G wid! as. or ii& G|bt. 4-22) owing ro lo.g cxposu,. or consunins larg.! ecoum of turradoh Gi

rug is highest in Meora (540450ng/e) ed bwn in KaxaF (2a0_2S0,g/C) smpt.s

(rabL 4-21). It ds r€*hbls thc swrer ed sedihcnt eal,s,s esardang po u on dana, No rclalio, is didened in @npei$n wirh THs in Bamcles, OrsErs and

5.14 PhysicocheDicat paramerers: rncsc paratodcrs nosrty slppon lbe inrcrprcradon of rhc o$er piincipal 4alysis. In $is stldy rmlEnrft, pH, @nducrivity m6u]q€nr dd non'bEd lo! alhsr all rh€ swarer @pl6 al rhc rin. of wplin&

No plopcr relado.ship is evid€nced for tb. eiT

In few smpl.s oudying values of ldpeste (in ihs oi 50-60'c) de noriccd 'angc nct rhe slldoi of Ko,.nsi €Eek &d pon e6ih. T.hpcErqe of sewarq at th.se shorcs

159 serc Dised for few hos. 'ntis happens qhcn emuens frch @olins s]stem of the

rl.ctic posi geoeraiog lldt get disposd, Hot wal.r llows our ofde eid po*ei pl&l

nce lhc shall fishing pon nm.ly tbElid Hydcri . Sidilely it $nerin6 h.pp.hs al

Pon Qain sitc *hcn hol cmumts fren big indGrrial ulil Pakisla St@l Mill elcvarc

th. t.mF6rre of csion for a timc being. Such ourlyinS valrcs of Empe6ru6 ad

omilt d fron the eported dala oflhb $udt in coN.qu.rc? of a stali$ical Diront Q l€st.

But fie stbddd deliarion or Ekdv€ nmdard dcliarions for such siles is quile bigh in

companson *nh otber snes Gable 4-25 ro Tablc 4.42)

S,l4.2pHl ln rhc rcgion of saae deaspHofseawatcrsanpt.s is qunc hisher,vhile in polturd rleas

thc valuc of pH is loq but no1 raBsily midh. Ii Mmora md Cizi cEek acas

$meines thc value ofpH is nwly ncuhl or linlc acidic &d monly not lilcly ro b. jn

th. pH .&sc of nodal swrq (Figw 4-46). a g@d asrcenat betwa rhe pH ad Tttg valq b ob*r.d jn sawb @pls (Fi8:

46-54). High THB values in th€ Egion of low pH des d ob*rved fld vice versa. Ir shows thar exisrences ofdillere.t chehhal foms of H8 @ srbnsty dependenr upon rtrc pH of sca*arer Low pH lalues @ noriced in no$ of rh€ polluled deas. Neullal or low pH favo6 tne production ofMeHsovd DMcHg (51). TherefoE d€F,egions e likety lo b. high.r in MeHg contdl.

DMcHB noq ino aunoslh@ s ifdjc pH h highq in pollurcd al6 ir influoc6 rbc dirtibulion ol Hs in alnGph.Fqr.r phas* (18), Tbjs may b€ a po$iblc panem for lhc Kotugi Creel dd Pon Qsin wh@ highs pH valu6 rc notied, @d nay bc dother case of low THg l€v.ls at pon easih,

160 Ar highcr pH valus lh€ sedim€nlalion ofhcrcury h also favonble in preFnce of sulfide in higher dbuns. pH At big! ed low eduction potential m€rcury is precipilarcd in

lom of ituoluble HsS jnhibirl dd ndhylalion (50) lo brins th€ dbient THs load doq. .5 $c ce of Pon 'n Qsin

5.l43Salinlty: Sdinny is qlculded by lt)e 6nd!€r.n@ ncsu,cn.nr, Th. .ondu€ivny of eawr( setl.s is due to disslred ioff. Sodiw dd chlorid. ft the eajor iotu thar de prcsc.r in *awaler dd th€y have get contribudon lo rh. conductivily value.

Ano$cr srcng relationship ofsaljnily and THg h6 bcen norrced (rrsuE 4-561o Figur.

4.64). Tlls Sers cnhdced in hish satinil, watcrs. This rctalionstrip ofsatinny mry bc duc lo lhc presence of orha ionjc aubsr&ccs hlh.r rhd incrcsed levet of THg. THC a.d slhn, gcr incrced wnh inclte io d.eG of pouuion Grgu€ 455).

h hid slinity, lhe nre of biorcrhylario, is toer s Epon.d by Blw & Beflha io I 980 (45). Aiom.thylariotr is atso afat by biqbon.G cont nr of swds (52), sllfde (49) dd chlodde conlenl (53). ?@mtage of McHg in TH8 ,s rower m satjne MeBi ir prclects llsh.s dd orher living bein8. ftom EoE loxic M€He qposw. Hence ue could und.Ntand high pouution lev€ls al Manoia phirii and cE.\ whee elinity lelcts are

l6l 6 Eibliography I M/th)tded a.zd ekaenot nr.u, cwtng u surte. o4d de?p oc.on \ ap6 ol pollulio., vatd, An {d Soil vot. 80, DD. 66t-67?. 2. Prc.a.tks: o! th. orcndasa Lk R.;;diatoa Con!.rene Srrorr, s. T. N.w Yollr: N* York sbk D.pafun nr oalawdd N.w yort Sbk Dep3nn? En Dmdr.t ol Cotr.fution, 1990. Onondaga rare Reftcdiadon C;nf@ce. . p. (^l^rk,R_B. 1. Muae pdtuhi,a Oxford .Ctdcndon pa, 4 5.::4at t9o2 e.oEruphrot ana rz.-indu..d \uiabihty u nea try cantent at ulht,t

1,4,e L!.a1,u.1OL|.of \ lar..a.. Cosr. D..rd Rond"_.J. c, o85, vd,ne B'oto8y. vol.38. po.414a. Dot 0 loo' BFool91o42 >.- M..'.1ry ,reci.ian \L-Ja.c t4 Fe$\aw tlrens in aa!{or4n a4d ott a\a: c'0.C, A.and Bnland. K, w.9. t990, in\ ibnmenkt Sc.ence dd rechnotog), vot 24, pp |]92-t400. 6. Mc'.Ltt palhvtts n the Carsoh nNerlahonbn Ratwil Srsten Ne'dda, U5,4. soDonBo. JJ.. I t. | d 5, 996. Enqron. foxhoi edChem,vol.15, pp 67?-

' I:!!::::'I:'*:':tb Mitabtc drtu,v r a snd, 6,a,r Luoma,s.N. t Mu. Sci., Vot. i,DD.641.652. !:.un.irdb:.or!p: ! b) pl""tud anl bnht. _,.ded ot {;x::!#,:t:;::::x.r Aqudrw:::L1ff::,:::'i:#:.;x:ffi sc hc.a vot.45. pp. I7,r{-t?57. ^ .,v;toM.dar - rye..B.ot to.tot! on ret.d. ol na.uD fton B.iri .rc.r (N., ",{i;i';i!ixu:;

, tu r4dit.,4s the bb@anobh+!,ffi,tr,rf,#;x':;ff::ff:1,yri,r;:r;i,,. ol ntdt! ^ ant n.tat,adpkxe. c,tot ;?. rcn ot &l v I $iu'j*; KJ 2oo' f n:: iT"i \'::,i'#b'' "nd ^^n ' i'l'i;(T:lflfi,',;,1'ii o' -'"' Hlrr B raai wde' tz haaoe?rea^E ;;;;;;' p.^r rea.hanorESa ntu H.AnO,( t]!l. atu (HrtS. ';:":i:,:'; f,"";;i"'"' rokor' J et aL rac8. Aho' Frv rcn. ll. Reaclians o.fg6aw """'aa nac,ryryrhatoaic ohd nolecu!fr hatogens: kinetij, p' adh Lqdiet ahd dhatphenc rdplrtaros p.A,, ueo,^.Auz., Anya. Kh.tiuor, A,nd j, rh)s rhcn,vol. t06,pp 7lt0_?r2O a urere rev at .ph^. '. th.-B reachoh bcNan h. hr&o9t tudrca! z?(,ry sodeer.J.'.rat.200r,Aunos. oad ahnrc ,. Enlhn, v;t j5,pp ]O4a lO\4. '' #:X::f.i::{;:;'l;{,!ti;1.*"nt' -"," nruorarr. rorz ar.o" "2t":'?".i1:.:#:"rf :|;rK:,i#:ffi '{##xfl;i.:x";;:.,

r62 t1. Intsconrytison stu.ty oJatn8phqk tutcnt kodek: t. Conpoiw olnoders eith shorr-retu neNurehents. Ry.b6h.pkot A., .r .t. 200?, Science of lh€ Tobl Envnomcn! Vol. l?6, pp, 22E-240. 18. M.cury .lcling in nrean E.osyst.kt. L Ttophic DtMjcs ahd Methtlnet.uty Bioaccunulation Cn rerjL.R,.r d.2009, Envioo, Sci. T€chnol., vol 41, pp. 27ll-,2'lo Dol 10.102r.cs8027567. 19. Resional pecipitatjon her.wy h.kds in the e61an t/SA, t99A-2A0j: Dectihes rn the Norheasl and Midwes ho tend in ttu Southeasl, Bttler. t.. et dr.ZOOa. Attoospheic E.viromcnli vol, 42, W. 1582-1592. DOI: 10.101 64,arft oseh!,2007. 10.084. 2a. A , a*p4 h, n,i,, E,krian no,.l.thns han!, -tk lt u dnrnLtcut\r.,i\ ii:#x:3;|;:"!,?{';tr;:b'?E"op' Pcrcr*n G'' qr' 2oor A'.o' 21. lna,phet,- n rcuy rimutanon ,rag th. CtL4O nodel.latn"tonan damphan a4aa4orynt oJ net depattia4 rctltr. Bu[ocb K,A, ud BRhDe, O.R.2002. AhosEhvno., vol.36, pp.2rl5 2146. D. Mod.ttinE aj hercwy in the /1rc1ic ||ith th. Dchish Ert.rion lleniqheric Modc! Chr i ds.n. J,H., .t .t. 2004. Aunos Ch.m phys. vol.4, pp 2251_2/t?. 2) Synkor, D, On r Pc-orienkd Eut.iM MUIF;\ctMod.t tor LonC.lem cdlcularoN of drc R.sonat Sulphu Dcpojrjon edi!o6. gyn^C lb@* auLh.l Schcmes | \ st. , n ponuion nod.rhnA and it! awticohon XL Nev y otl Prenm PG: t99t, vot.21, pD.64t_646. 24. Global cn.uloton ol [email protected] d(cuy a nod.ltirg rudy. Drrr@r, A.p. .!d L.rocqtrq Y.2004, Ahos Env'rcn .. vot. 38. bb la7;l 25. Fut'dnedal rcks ol btotogtal t*i,,s io niiu,y oc,u^ut"ton and hwte, n at oryanqh dsa c.tt and l1:!'::kt.4o:):k!'-(al!.t!$6ordd.r"..r.t. nok.'to, k,eis) l9{t,w.lq,An,ardSoitpo urion,vot.56.pp 807.s?2. 26. .tomanntahoa ot nacury i, a nuin. gazinSloodrhon otsal.pth .tr UrtitB .dul u ,nd lo!,n B ptdrhlhrs r:'tr:!^* tuthod ") l:y."1'.*l!t'.r.dktio4.cvaa Rjnsrn, i. u. ,nd hractr.. s. 19e0. Muinc Ecology pro8r.s Scn.s. vot.62. pp-2re-2?0 27. ryr& Schro.d.r, w, H.,nd Mu,the.J.,, ryy6. Ahos hnv@n, vol.32. oD.809-e22 Ch.ni.dt .rJns and .lepoti@n ilarnotptrnc ne,cu4, Otobat.onr,aina S.lin.N, E,.q rl,2007. J. ceophJs R*..\o..D2.p 2 DOr r0 1029/2006JD007450 29. F,a*o/::1: h tr.e ,!or pr,.,r/s p. 1i:1': etob:! M*on. R. rndsh€u. G. R... zuuz uroMr brogeoch.d cyct.s, Vot 16, p t09l t0. x.d.h\p E^eo-t necurt kthe mtuMe bouaddl lalu aadettkgaaJ tpchd. nbt-eqderce aI h ltdatiaa in the tardrctoneaa rye@a Hedercock, r. M.. {.1.200J. Ahos Envircn.,vot Mt.,'\.hedstt,a l7.DD.s4l-s49. rh. MBL M.d\enaaea;.ate ond jLdrc, Lrna t,h.. 4M.O.IS "h,h,tD /Atno-lphenc Mtcu| Ched\ry aw h. S.a, hoa.t Hrdzeco.l, r. M..€t rt. ro.2005. Ahos Envrrcn., vot.18, p!.,2t7.rlru.

t6l jutl, 12 Crrhoun.nd Pr6rbo.ltclE ot th. Fat phd? ox,.tanon oJ plcnd.l n?h Ltu br notp.uto .h|onft s€nte, $ A. : flonrG! ccosrenk) In!.. 2o0l asc ed by Bullek od Br.hDc,2002. 33 Modetke chluhdioa Ilon aqkos N4Cl pntict.r: .ridene oI inkrlaciat t:!.:DN itap! olca ::d lnge deconpbitior in atkatine sotution. Knippins,- E.M.ardltbdub, D. D18,2002, J. ccophys. Rcs., Vol. I O?, p. 4360. IiOIj 10.t02912001JD000367 1 yod. 4 LaB 4dogc n. h. ^6t' y,4 th. hxn boLtuJ,r! ta.ct - t ( lod!,,..U Bt von c-la:N. R.. er ar. Dt7,2002. J. ccopn)s. vot. lo7. p 414 | DOI t0 t02'r/200tJD000942 Js A nbama atuenatiohs of DMsa, DM\, ah.t oH at na re troprcar Now*,J.8., eiat.28.200 . Ceoph)s Res. Letr., \o.. , on 2201-220. 16. Lindqrij. O. and Rodhc, H. 1985, Tc us, ;; 116.r59. Ra oacn t )' ae hade t! aad \a,*.aut! ra a" tE; tu ad,, a atnovh. n, a. rcu, r,? Slrderhnd.f. .rpp,r M,,drl, 5t6.535,2008. Enqronm;nrat po ...o; vot t56. p. t56 DOt:t0l0t64.cnvDot.2oo8.ol 02t. 18 Munlha J,. xiro. ZF..nd Lindqvilt, O, r991, wakr. Atr, Soit po.,Jr, \ or 5b.

19. 6.'iddt0n ofetedentot netcrry by aqueos chlotire (rrocuocD. impri.atio8 to, hop^ph.,t qcreEr p€hkrotrer, chcn\try Lin, C. .nd S. D2 l, | 098, J. ueophys res., vot. r0l,pp 28093-28102. a0 R.dthon olthe oqueou n+tuE ioa b, jLgk Lv,tErruhalHgrOJandt: tatanokcuta, ndot Ra.non v.a Looq L., M.d.r,E. rtrd Sion,S.t.:Ooz, t Pbys. Chco , vol. A l04, Dp. t62l_t626. d *."::!: o.y ndhrtahu ol dncury h !h. aquoh. ^ .ntonn"nt.!:::y w.hr,J.8.16.1991,[!'-abnti. 0) ., ChcnosphcE, Vot |l,pp t06]-rO?7. aL u\ t: ot ch.nirut wt\6 btotoskat nahrbroa ot nacury n p.tih?ntt. Berb,n, M.,od A.nhr, & 1c86, But h ot En'vionhrnht conbminanon ed Toxicoloe/, Vol. 16, pp. 40l_404. ai. 9a.atul oa,:pd'al vuetion! D h.t.rt, ndhrlaho4 andd?neth)lohoi,n u8o'tophc a4 tau.Korrhrt,E..f.nd Winfr.y, M. R, Io8?. Appheo dnd rn!tromtu|at Mrcrcbiotogy, Vot. t3, pp 2197-2a04. v,_ ryarr 4!Lh4 ^,etbtn?.u.) t. th. wabqoa^EaE!,!h p,v.t.t are,rer cedian !_111-1: {.1: ll8.l rohdorf.snene, ed Aqua... rcrences, i"1,y".vor 46, pp 2t34.2202. a5 F-?c.ala,iait) or aat),t.toa a, ne\u4r Btum,J, M,,nd Brnha, R tq80, 6!ir 1d I N I obmbt .onumr 4hlL:::::::::|J7b'mdJrce'oDl.d'lbh1'ono/d.re, iariol and lo\icotog). vot 25.pp aO4J(]8 , B,H. rnd Coopcr. R.C, to70. warer R... Vo.

Ewtr oh derh,hLaa ^,,j::::, ::-!":* !:*r::a ^,lca otu paatioahs aJ ,"ft: ^ il^,i;i;i,li!W#;,:::",p:;::: #';;::;i:!.i;:i:{ f :l anvtonhental .h$ges .a6ed b, th. Chu/chill.Netsoa Riw div.rtion Ollwa I Govclmcnc of C&ad. and Mairoba., 1982. [email protected] Ae@mcnr on Study lnd Monironn8 ofMcrcury 'hc in hc Churchr Rivcr Divcr;n. sufak ninutahon ol mnaty nab tanoi n lt thrd.t *din nts citnow, C.C,,H.!ry, E,A,.trd Mllch.tl. R 26,1992, Envuon. Sci. Tahnot, Vot . w 228t-2281. 50. Reldiotuhip b.tuan Eg dahytdron a"d th. lutlu .r.L n .,,uarine scd,4td, Giloour,c.C,rndCrto&,D,c, 198?,EOS,vot.68.D. l7t8 51. B.ijd, K. .tr.l J.r!.|.v, A, Mdhyl{jon of m*uty iD riu.tic cnqoM.nE. lb@k auth.l J. O Nnagu. Ir. , iog.uh.nL rt of Mercwi t" th. Envnom.nt Nw Yort ElsdErNonh.Holt$d Biom.dical pe' : Et;vic,/Non r.Ho ed Siomcdiql Pca., l9?9, pp. 2Ol-210. 52. E[..8 ol t.a sdh o"io6 on th. l@@ion and sbbttiD of dethyln tc,ry. compqu, c. rnd B.rth.., R 198t, ultcrin ot Envirc;md ConhiMrcr qd Toxicology, vol. ll, pD. 486-491. 5i. The-rc|. oJsp.ciatid i, dq.Lrr tuthyldion h ptti@,ns ad @ter. Cnt'-pJ. &rl poUuior Morcron, P.A- t985, Etrvib6qiut S.d6 B, Vol. lO, pp_ r4_i

Ir. tuk oJ hwic tub'ta@s k the nobirizdid of a.rcuryttu vatash.ds. Mi.'l.t C. rEd hgnE, R r99t, w.iq, An, dd'Sojl poUirioi, vot.56. pp.

55. Btndkg ot nahtlmt.ury cod?aund, by hrdi. ad luteic @id, P|itr.tnr^n, H., W.lbourn,P. M..d EvruR D.1995, War;, Air. &d Soitponurion, vol.80,pp.l0ll.l0.t4 56. y.td?.!tthyta:@.4 srstry allut..t b, aed d.positio, citDour, c. !-f'!E polurioD, r,.rd ndr', ts. A. r99l. Envid'mnrrl vol 7t,pp. t] l- t69. 51. ne tugGn-'/abtg@n Riwr SN/kn L A,rnthsi, o/r.c. r.!.a..hwthatiew towa6 ht.uryturiotunm. Rudd, J. w, M,,.r.t. 1983, c.radiM Joumst of r EEn s tud Aqlll'c Sci.nce, Vot. 4n, w 2206-221j . 5E. good pt.aaot ol n.ttjt n*.rty co,a"tnon n aqrarc tysl@! K.ny,c,a.!.r.t. 1995, w.tcr, Air. &d soit polurion, vol.

59. * kt !tu,etiory atl.ctina [email protected],ry uvtD,ho"sI::1!:-t!:t h "j Lanp"1rr.".1-"j Fu ty^t R.s.Nn. CztiJtno. r.t. U.S. GEOLOCTCiL 5-URVEY, 200!. Walg-R.sws Inv.$igd,o;, R.pon O3_alaO;. nnp/,pu06.w.tcr.c3'eov/wi03_4 t40/ 60. Joh!, A"Colb{. .r rf. Dtrr,Du ioa ad fta&po,t oJ Totar Mac,ry and ll M*:,,r'c-tanitut.d s..ti*ds in x.'enov' tud vatand! oJ'::!v':':.*'v tE rMoury t(Mt, t:a!.c.tuat ru.sd.rBdr Ncw york : [email protected] sufrcy. 1999. pp. 994060, U.S.C@logicd Sw"y w ?FRc$|@s Dvcsngauons Rcpon. hft//ww.usgs.eovl up@e^ tun,iry and tmphn Da4l.t ol Mrcury in a .@stat tliatoh M.son, K.r., K.i .td.r,J.R.!d MoEt. F.M.M. |995. Envkon. Sci.T€chnor., vol. ru, DD rEl5.l845

r65 62. Mer.rry speciation anl biMccrnulat)on in lotic yinar! pto.Ircet$ anl p,ituu! .,,rrnoru Hill, w,R,, Stcwrrt, A,J. .nd Napolhano,G.E, 1996, Can J.lish. quaL. Sci , vol.51, !p.812-819. 6t. Mercury in the Svedish enrionne,t: Recent esut.h on cautes, cawequencd and coiactit nethods Lindq\i.l O. 55, Sp.cial Issuc., l99l , \valo. Air. and soil Pollurion, voh. (l'2). p.261. Windon, H.L,and K.ndall,D, R. Accutrulation ed biolansfomation ol mercury incodal a.d @in. bio$. lbook aurh.l J.o. Ndagu. rt [email protected] of Mercury in t e E vtr,,u.,r s l. : Elwiet^onh_Holland Biomcdical P€ss, l9?9, pp. 2?7-302 65. Tenpqatwe ellects oh codhiurn ahd nqcuty *inetict ih!rcshw.tu nattrscs ud* laborutory conditio8.T.ssier, L.,V.illancotrrl, G. rtd P.tdemik, L lso4. Arch Lrvmn Conwn. Toxicol. Vol.26, pp. 179.184 Recent inneoses in dtharph.ric daposiljoh af Dqcury to no h-cenial hscahsih lakes ihloredron vdime"t ahalls?s Rada, R. C" et st I 989, Arch. Envnon Contam. Toxicol., Vol. 18, pp. 175-181. Mt.ury in ctayl5h tpacies Lon thifleen Ontuio Lak t in retalioa to \eater chenistt, and sdalltuouth bdt (Mic.optetus dalanieti) n rcu! Al|,rd,ll and SIokes, P, 1989, Cdadid Jouml of Fisheies dd Aquric Scicncs, Vol.

68. sertut dfierenus ih d.cunulalion ofnqcfJ in fot species of.antrnchid lsres Nicolcno, LandHcndri.kr,A.l98?, Canadian Joumal ol Zoolog/, Vol

Hmkrbcq J., Et*ood,J. rnd Hildebrrd, S. Accmulotion ofnercu.t in fi€sh*alcr biota [b@k auth.] Nriagu. ,e ,i"g€o. henntry of M.tcwy in tha t v,ro,rer!. Nes York i Elsevicr^onh-Holland Bioncdical Prcss, l9?9. pp 2n-342 70. Envnonnedal lak ol wcw! dit.hataed ihb thc npPU vis.o,rh ,{i'dr R.dt, RG., Fi lcy,J.E...dwicn.r,J,C.1986,Wat t An Soil Pollur', Vol 29,Pp 51-16. 11. Factat ollcclins htctry accthulatioh inlsh in the rppat Mi.hisanPenihs!]a Creib, T.M., .r .1. 1990, Enliomental Toxicolosy a.d Cheoisq, Vol. 9, pP. 919,910. 12 Mercwr in toun tq (Ptatichthtt llet6 L ) fiom 6t"arie' and c@stat vat.6 ol the rcth-east lrithSaa Lcah. R,T.. S,J. Ev.ns. .nd M,S.Johnson l992, Dnvircnmenlal Pollution, Vol. ?5, pp.31?-122. 13. Longle t n efe.tt of ne t htln t.w ic chloride on three Seretot ions ol broo* hout Gabelinu lontinalit): Taticitt, accuhulatioh, .lktibution, and elikindti@. McKin. J,M., et l9?6. Joumal Fish€riss Resdch Board ot Canada, Vol. 3 ], pp 2726-27)9 "1. wicnc., J. G. ,nd SpD, D. J, I or'@losnl iigni fidce ol m€rcuq in fr6hwalc fish. [b@k au6.] W.N. Beycr, C.H. Hei.zmd A.w. Rednon- NoNood. Enwondehtot Caitaktnants in Wildlfe : Inkryreting nsue cohcehtrutio^. Florid^L.wisPublishe6 : Lcwis Publishcrs, 1996, p. 494. sp.cirl Publidion of 0E Socicry olEnvionl@br Toaiolosy ed Chcmisry. .

t66 15, Eislct,R- Ma.w, haw.h lol6h. vitullile, and inre ebrutes: a sybtic .eiee. W.thinglon, D.C. : U.S. Dcpanm. of d. lDLriof,. 1987. U.S. Fjsh sd Wildlife ScPicc Biolosy R.pon. 8t(1. l0). U.S E.eno.neddl Prot.cion AA.rct 4Atlatio6 and oiktia Iot w.urt in wte. SMn@r prc&itatiu to th..ootdiMtiu t.M. g.nt n,D.t. Atska I U,S. D.F. lnllior, Mircd M&!g.mmr S.die, Anciodgc,, 1989. M.rclry in rh. Msine Ervioh.nt. . ocs shdy MMs 89-0049.. ElIedt of heaey n.tatt @ d.dtopn ht oftk tdltilsh Ft"&nw h.Etocritu. w.ir, J. S. r.d w.it, P. l9?7..t. Fish. Biol., Vot. I l, nD. 49.54. 78. fh. .n d ofph.nytnq.uk e.tat. upon th. h.qQrcy of hot.hi.g in th. r.D.a/itt. Kihlroo, J. E . l llqtrh, L 1972, BuU. Envion. Conh. Toxi@I..

?9. Birg., W. J., .. d, Thc cffet' ofn.dury on Fproducrion of fish dd dphibiu. lbook .urh] J. O. Ndtas. TIE Biog@chnisry of Metq,t in he E vto,rfir Ncw York : Eh.vi.r^onn-Ho a Biom.diet prs.. t9?9, pp. 629-6t5, 40. Chrcn'c and bi@ccduldio" ol h.r.kic chlorid. i, th. nhnov 'ort.ity lath.atl !in.pt:d.t [email protected]@). sn B,ti, v. M..trd Otro'. c. F. 1982, ;qurc Toxicolosy, Vol.2, rp. I43-156. 8t. Ene.r o/ n tcutt on ttu prdobrnh no utc C4piduta Acd. lehat lq"icata. .fh.ia, tuicit a.d .n4$ o. grovlh ar.l r.p.odktiu of chronc .,p6ua. J. E. 1984. Md. Envir. R6., Vol. 12, pp.2E5J09, 82. ElI...t heavt pb, ol daats (za Hs. ca Cd. Ni) on h t.nsth stueth ol Mrtitu .d,/e SfroDgr.!, T. 1982. Ma. Biot., Vot.12, po. 69-72 81. Abtotic nerhrlation oJMcurt tn th. [email protected];ituM.nt. C.to,V.,L.r^, D_.vid.RS. rnd SB.!uh, L S@ri. 2005. Sci4. ofth. Tot l Envionnrnl pp 126-137. DOI:10.1016/j.*noa.v_2005.09.041. 84. R!.ent adv@cq k tox@bg ofmrc,ry vith enptwi, ot the alkrl nrcutiat! cl.rkon, T. w. l9?2,Crir. R.v. Toxicot.. DD.20j-234. 85. FlIc.E olfl.'hylnftuy oa h riw ptokin idhait n isot /.d.a.b.at Md .ncNutu-n uto8 SwcB. iT. l9??. Ncuop.Lhot. Appl. N.uobiot., Vol.3,

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l7l l1O. Qtuntit4liM of Lrebl Codeht in the Sila.Astist..l Grovth oJAold iiaturodt Chrisroph.r, J., Orcdorfi.od Crthcrir.,J Morphy. 2006. J. Phys Chen B vol. I r0, pp. 19G1994. DOI;10.r0211jp0570972 t7l. Pushih.the Linils ofMqcury S.BoB,xh Goltl Noroodt. M.trh*, R.r' Flor.n.io, E. H.rn.nd@ttrd CrDpiglir, Andres D.20M. Anal Chem., Vol 78. pp.44t-451. DOI: I0.l02l /e051166r. r72 H.ich.W. R,$d on w.L, 1968, A.al. ch.m., vol. 40. p. 2085. r13. Poldbk waE 6 a tource oJ heav hetah ia th. btood ofreto patieds of (drz.ir', Pa*,nu,. N.rgin Y, Sb.rif, M. .nd Abo.d, w. l, 200?, Jolful of thc Choical s@icty of Pfist4 vol. 29. pp E6_93 '174. S.l.ct.d tlac. netot corcenttuti$ in dif,rcnt iss'es oflish lron coonat wat.tt ol Pavsm Utobin s.a). l.fi.n M. .trd &lnf, M. 3, I988, ;lndid Jo6al of Mdic Scid€s, vol- 17,pp.231-214. t1t. "Truce tutal l.rets in s.tecte.l cre.k fth found atory the A.abian sea @tt o1 P4tjnan J.ft t M- Abnf, M. rod Mo.z4 M. 8, 1989, Peslicidet, vol. 23, pp.49-52. 176. Conce rutiob correlatiow berw.., majot catioks and heav metals inlshton the ArcbiM sea. J.|e.l'\ttiq' L lf.r' M. .nd Mo@m, M. I I , | 991 , Meinc PollulionBuui.ltrL vol. 22, pp. 562-565. r11 . Potluion assetsde"t th'o,sh nace netol akabtit oJ kdihehtt oJhv tib"lary tirtt olPakistandralnirAi o th. ,lrabih Sea. Athdt, M.,'f.riq, Jrlcl .nd J.fi.r, M. 4, 1992, lndiar Joumd of Mdn. Scicnc6, vol. 2l, pp. 292-295. 118. Heort netal corcennaio$ infsh, thridp, [email protected], sedim.ht, and ezt{ lion th. lrubiai s.d, Po*ist@ Itb.l, T.tiq, .r .1, I l, 1991, Maine Polludon Bullal.. Vol. 26, p!. 6.14317- 't19. A$8tn,nt oJpo iata of riwts J.hlun ond Sunej. Pal.ista, thturEh t/ac. h.tak inJish, vdine"[email protected]'tid J.lc[Trriqt Asbnf,M.. J.fi.r, M. ]4, 1994, [email protected] od Enyibm.nnl Chcmhry, Vol. 43, pp. 169- l ?4. lEA. /*4!nent olcwtunt t@e naal polluioA status ofthe soiteast Arubian ed .oott of Pakitton thrclghlish aetrir Jilf.r, M., khr.f, M, md J.lcl' Trriq.4, l995,[email protected]!l.,Vol, l?, r81 S.ltkd tra.e tuetdlahd noqo&iieit cohtents olsixJish species ton the lrabian Sea, Pakistan. ttlel,'f.rtq, Jrllr, M. rnd Arnnf, M. l -4, 1995, Toxiolosical dd EnvircM€ntal Chenhq, Vol, t0, pp.207-212. 1E2, Pollution !at6 ofthe L.l6 riwr, Pakistah, thtough h.av neral and tuctun ltie4t cotterk ofJisl\ t..line"t.nd \|ateL $le.l,'Itiq,et tl. 6, 19 . 'W.1. Rs., Vol. 30, pp. 133?13,14. lAJ. Szl.cted nace netal cmeit.ation i, t.wr tsh sp.cict lron th. Arubidh S.a, Pdt$ran J.lel T.nq, .. .1. 4, l9E, .,otr. Ch.h. Se. Pat., vol. 20, pp. 249- 2'. lE4. Ditnibution oftrce netak in vdin.at and *Nat.t fron the contirental sh.lf o/Pal'!,ar T..iq, JrLel d .l- 3, 1994, Indim Joubal ofMdiic Scicnc.s, vol. 23,pp,147-151. 185. Trac. netdl buil.l in th. nuire en,nonnent ofeuth w.st coast oJ Ptkittdi: "p .rid.mlion the edible lsh nele J tr., M.,.t d,l,2000, Pakhh Joumal of Scicninc 6d Indstria] Res*ch, Vol.43, pp. l3?-140.

113 186. Deteminalioh of Hs( ) as a palutont ih Koru.hiCoastal tutet b! cotdvop.l atotui. obsorption spectrascoP! N.qri, I.l .l .1. I , 2002. Jour' cben sG ' 181. lnaltsis of nercvt ih s.aJ@d by cold wPo. atohic absorptiot sPecbascapr' N.qvi, r.I., er .L 24. 2001, Pak.J. Biol, sci.,vol.6 Pp 20l0-2012 t88. 1s;srzent ol eit e4aks ofk, th. ditut.t ofTNhah sPi,it near the clilon 8.a.h f@achi, Pokistan.tbiid,T ir.!l Z.hd' Muhl.quc 6.2005 E EAFChe. Eletronic Jouhal of EnviDm.nlat, Agticulnml ed Fo.d ChcmisEy, vol. 4, pp. 109+l l0l. lE9. Mq.w! polhdion in th. $t@ire rcCion orcun.! Bonbat klad M.hrj.n' B. A, $d Sri v!s!, M. 4. 1988, EnvitoM.nt l TaluoloA/, vo! 9,Pp 33l_116 t9O. trce retab corcedrcdod il hdtin. orydhisnt lton the coatat tuos ol Batuoih, arubian OuV Mtd$r, Iln.il M" w.h.b' AbbN Ali A. !trd Al' Ahwi. Z 34. 1996. \vat*, Ait, ed Soil PoUuiion, Vol 9l, pp. 213_248 l9l . Mer.q polh ioh in Doha (9atd4 coaeal .hrttom,nt Al-M.df.' H.' D.hrb' O. Aboul.nd Holail. U. 5, 1994. EnvircM€ntrl Toxicoloev md Chemistrv. Vol. 13.tp.725-?35. )92. Dektuin nion of *vnic, .tuonirn, her.ury, s.l.nium ahd zirc in troPical hoih. jsh bt reutran octiwtion Sh.rif, A. K. M , .r al. 2, 1991, Jourul of Radioa!.lrlical ed Nucled Chemi3try, vol l?0, pp.299_30? 193. Vater pollutioa i" Pakhta, ,t/reldj Abb4 G. rnd Qumhi, R. A. l-4. 2001, Patnr.r .loumal of Sci6c., Vol. 51, pp. 91.t6 194. Utili2dion of a ]N pMer 4@tot to ibtrun ,tal neut.on acti'.dion atulysk of 40 .leh."ts in tuL Vltn d,S., .t .L 7, 2001, Rrdiochinie A€la, vol. 89, pp- 425431. 195. Neuttun @ti@ti@ anolttit of t,@. .l,n hts in bioloCical naleiols Qnrani" tqbrl E) .r .L I -2. 1984, NuclN, vol, 2l, pp. 15-22- 196. Heary netal dhd othet ,.si.tres in l.athe* oflaesor Jol.on Fdlco bionicr! jqEer lrod sL\ districts oJ Paht z,. M.vrlll, P, .4- 2, 2000, ENirodenlal Pollulio'! Vol. 109, pp. 267.2 75. 197. Diochenical and t.dce tuin{alatulytit ofsilajit sampbslron Pahstan. rnti^t St.fiq, M" Nren, Sred anb.d rld B.lool' N.y.b. l, 2006. Nuuiional Sci€nces, Vol- 9, pp. 190.194, 198. Selecte.t trace netal lerek in cannon wg.tablet gouk ih NtyFP, Pakhtan. Msd, Kndid r J.frr, M,3, 1998, Jomal ofrbc Chenical Sociery of Paid$an, Vol. 20, pp. 186-190, 199. &|e.bd nke'etat bvets in tocalwsaabht procuredfon Punjab Pakista, M$od, K!.lid rid J.lf.r, M. I, l997, rowl of lhe Cb@ical Seicty of Pakisla4 Vol. 19, pp.49-53. 20o- bdluation of ttee.lencds inrh.at andwh.at Wodtctt. Atrnr4 Snuj{r,.r rL l, |94, Joa)al ofAOAC I .fudoEl, Vol. 7t, pp. I l-l8. 201. Detmi"atio" ottw el.nentt in int.g.ate.l htu dtet t@ dktary 8sestudt QuBbi, L q., .r .1, 4, 190, Inr.mdo.d Joldl of Enwircm.r$l Ar2l,tial Chsistry, vol. 38, pp. 565-?7. 202. Dietaryevluotiok oltoxic el.n.nB throtgh integatad.lial M.nnan,A.,.l.l. l. 1992, Jounal of Radiodaltlical a.d Nuclcdr Chenhtry, Vol. I 62, pp I I l _ 123. 2O1.Tru.eelenentilta*eahddietarystotutofhrts.onlunedirPakistai:ludyusing / 14,.{ wrh..d, S., Siddiq!€, N, and R.hn.n, A. 4, 2007, Radiochinica Ada, Vol. 95. pp. 219-244. 204. Ldek ol ehchd noc. metdb i3 hoir ofuban dd rwol adult tule poPtlation ol Pat6l44 Arhnf, w., J.ft r, M. rnd Moh.mncdt D.2, 1995, Bull€tin of Ehviome.t l Contahimlion and Toxicology, vol. 54, pp. 207-21 l. 20s. Levels ofkkct.dtrc.. n.tak in the scalp holt ol M industiall, etpavd poptl4tiak Mgthent of Pakistan A!br.f, W. 8d J.ilrr, M. l -4, I 996, Toxicologiol ed EnvnoM.nt l Ch.misq,vol,56, pp.75-83 206. S.alp hait Nrcutt concentrctio,s in Pakinm AN.r' M.'.r.1.4.2001, EnvircMenul Sci.nc6 (Tokyo, ,apdn), Vol. 14, pp. I67- l 75. 207. EPA, Us. one cl.mup Pogtd . loilift] 2008. lciicd: lu. 10, 2009.1 hnpr/w..ps.8ov/os*.r/onelc&uppio8nr/ind.x.hltn. 208. USEPA. Reconnended eti Llin t lot tanpling n4rine tedin.,n, rater colunn, and tiss"e ir Prget Snu[d. s.l. : Us-Envtom.nlal Polfttion Agency, I9?. SmplinS guiddinB. hap/wrspachiv.s.coh/public.lionJou_sru$i.n€e/probels_guidelin€J

709. StabiliD of M{.ary in *tuat.r &rpl.r G.rd!.r, M. .!d Go!n, A. 199?. Aialtdc,l@'mbiedoi!Vol.34,pp.245-246. 210. M.tdry Codanination of&a Woter Sanpl.s got.d in. B6rhn r,Mint l n. .!d Rob..ton, D, B l. l9?5. Ardytical Chmislty, vol.47, pp. 59-595. 2l | . Conp.otr. T.R ,{,atr6 ,/&dd!i s.l. : Springs pub., 2006. DOr: r 0. r 007/t95901. ISBN: 978-3-540-26162-t . 212. Owni.\' of,lmltlical Methodologi.t lor S.a wotet AMI)lis: Pad l-Metols Rro, T.Pj M.dld., P. rod Mrry GLdit, J. 2005, C.idcal Rcvids in Anal)ical ChmilEy, vol. 15, pp. 247-288, DOI: 10.1080/10408340500431272. 213. Smki, Tsuguyorhi ,rt .dry )lzltlis MMl. s.l. : Mini{tt ot $. Eolilom.ot, l.pe, 2004. An lnicrl mcilod.. 214. P.S. Anaryic.l Appricarion NoL 008. todin l2009. tcir.d:May lt,2009.1 hnp/w,[email protected]/, 215. Bor€., Andrs Drvftl. Sp€chot@praia tug,ine. 2009.\ol. 5,2. 216. Meldhm, J., .r tr- /oarl't T.ttboot olQuantitati* ch.n Lal aetrit N.w Yoik : tuntia Hall Publicadon, 2000. pp. I 12-131. ISBN 0-582.22628-7. 211 . Atde!,DNid. Modem Analt ical Chenittrt. Bosron . Mccnw Hill Pub, 2000. ISBN 0.0?-23754?-7. 218. Milfen J.C. .d Mi[.r, J.N, Stahtlct Jor onaltri.al chen srry. 3. Ncw York : Ellis HoNood PTR Prnlicc Hall, 1991. pp. l2E-130,ISBN 0.ll-030990.7. 219. Coop.r,D.nrL Sanples md r,arddrdr, [.d.] Nomn B. Chapmm. New York : Johr Wilq & Sou. 1999. 220. Krien.4 G. rlrf Euydent,L QlaUt, cohnol iiAnalrtical Chehtny. s.l.: John Wil.y & Sons, 1993, pp. 8l -84. ISBN 0471.55?77,3.

175 221. P.sol, S.l.! r.d Contt tr! M. C. vtr d.n B.r& 2006, Atul,Ilical Chemislo ' vol ?8,pp.5052.t060. 222. Elec!rcch.nkal d.tqniMnon ol utt.o lot l.*h ol He bv lsv utine a chemicattr nodir.d .thnode. T Dry& I. lnd M.dler' D 1994 El4todalysis, vol. 6, PP 833 841 223. B.rn.rt, V. c'rd Kcwi!, T. Otiliet in Slatistlcol Data 2 Neq York : Wiler. 1984. 224. Mile., J, N. .bd Miff.., J. C. Stdittics aid Ch.nonetrics lor.lmltrical Cr.'6,ry. 4rb Edhion. New Yort : P.!@n Pnitie Hall. 2000. 22t. Ail.b, i- s.b*indr, .. .1. 2008, Envitun Sci Tdbrol, vol 42,pP 1165 1370 DOI: l0.l02l/.s?023ltb 226. Rifcy, J.P. md Ch6r.r, R- lntodrction Io M4tire Ch.nnry Londo : a€adfricPrc3s. 1971. 227. Trr.kiD, Krrl K. Ocez6. New York ; Pr.ntice_Hall, 1968 228. Pre.lictinA rh. tdicitr of sedin [email protected] hace netals eith sinultaneoalt dtaded na@ n !al: @id-toldil. tdJiae [email protected] ann dry weiEht norulizd cotue ratiN: A dti.dl @ruP.riton L4' E.R, .l .1. 5, 1998 ENillmoLl Tori@logy md ChmisEy, Vol lT 229. Aa 6s6swt't olth. nasnitu h oJ.Mtal poll,nion in Paust4n tttuush a tne, of its nuitu JaMo andfgheriet AtD.d, M. l9??, J Thalssia Jugoslrvica. vol ll,pp.395-412, 2Jo. Relatiokthip betve.i hea'y netat cont.rt an4 bod, veisht offth lroh the KelanA 6tur!, Malalsia. ntbilio!, E.I. 2, 1991, Md. Pollut Bull , Vol. 22. pP 86-89. zJl. Belvt,.t rl" Cod.miu,ls in Aqtuti. Hobitats dt H@ordo6 Wate Sites: n&..r/ Haz,tdos Maldrls R.spoM ald Aw€nt Division. Narional Oc@ic 6d AnnosDbdic Adbinislddon. &!nle : Nadond Occoic ed Ahosph.ic AdrnidbFarioq 1996. P. 74, NOAA T.chnical Mchordd@ NOS oRcA 100, 232. N,nidoMl tulw of eNud Bunin, hr.icir. 4, 2001, Eleciro! J Envion. Agljc- Fmd Ch.n,. Vol. 2, pp. 498-503. ISSN: l5?943?7 233. Sdastsw *N..d 6 bi6o.be"Uo kav netats. D'rii I. A., vol6ky, B. rod vidin, R H. S. F. 17, 2000, \v!t. R.t., Vol. 34, pP. 42?0-4278. 234, Met.uo distibulon in tA. vdet colum oJthe sndfi.d Kt*2 Riw .stua4 (Ct@tia): tnw an e of tutuat osanic tun.t ohd otstrcncvid& trttk^' aliBki, d i. 7, 2000. wai. Rcs,, vol. 34, pp, 2001.2010, 235. Nutritional tuIue of ENud Ptrrici., Bunir 4. 2001. Eleciton J Envnon. Agrjc. F@d Ch.n.. Vol, 2, pp. 498{03. ISSN r l5794377.

t16 7 Appendices

7.1 Introduction of Mercury DESIGNATIONS

CAS No.: 7419-91.6

Chenical @: M.Mry Stnon ns, Trade nan$: Qric}liltq C h. k i c at n am e (G e r n a,) : Qo.crtitbel Chenical raue (Ftench) : Micw. ,{ppdrd@r silvery white, shiny clal, liquid ai rcon tedpdturc

BASIC CHEMICAI- AND PTTYSICAL DATA

n rair 60 rrl 1 20'c, 2$ !M d Joec

BASIC DATA OF SELECTED COMPOUNDS

t11 ORIGINANDUSE

Md.uy is ed s ! olhorh in {E €larrely3is of.lloii-ndal chldid.s, in th. prcdEti@ ofbsrdi.s .nd p6licid6, ir thc nEdictl s.cror (dulsrns .nd ditinfd.nt!), in 0E clc.fic.l irdurly (brdt6 .rd 6npoM|!) a Ell a i! prse sDsE3 ud ralFrtr tt]affit Fdroxicologic.l E-o ilt [$ h oirtnctns ad di.ilfalrlts i! m ldes sldrd pr-tic..

Thc Ear$'s dfi cont ins e !rcrag. ofapprexin.tlly 0,02 ppm of lhb cl€m. on lvmeg Cimbd (HsS) k tb. n@t wi&spud m.rcury nineal.

l?8 7.2

"Nonh c.rclin.D€pr h€nl of Envionm€ni.l .nd N.tnnl Retourc€r" NCDENR Srf€ty Rl!l, M.nrg.n.ot bnp://9/sT.er.st t .Dc.uds5f€ly/

SAFE OPERA'IING PRACTICES Marine Life Research aDd Serfood House Sampling

Hrard Rcvicv

Poieno6 PldttAnimls

l. Fdilidi& yours.lf{ith and folow ef. bo.ibg op@t oN. 2. B. awd. of*ct n@rs, linca ed neis o.botrd the ves*l ed ily clcd of $em. 3. (now tbe Ec. dd b. caulious of wh.rc you e workiry. 4. Poperly lift h.avy cquipm.ni. Get h.lp ed ue nechdical d.vies *h.n nem is

5. w@ clortil8 not lB@nbh lo being elght i. @plilg sa- 6.

8c fmilid *ith nrfi.h ad sh.llfLh $.1 mry yield polenlial h.a& Gdnes, bnes, puclutct. Use apprcpiiarc PPE or oih.r dcvices to avoid direct cont cr

8, U* €lrion wh@ hodliDg dsrg@E tuirc spei6 lite 3haiq srinlraF, j.Iyfah Portusu@ l'llrf-*&, .rc. U* prcted@ gloB 6d clothing. 9. KnN fic &y-rGd.y oFtato6 of sdf@d hous ro avoid itrju'y. 10. Norit suFNisor or dy 3qio6 injui6. ll. Revid tht SOP at lc6t muUy,

Sounc: h, t : //w e N s to t . rt. us/Sa{.NMSl'vA 0 2 00 vC l@I.,nh2 0 2 6NMd i h.% 2 0 Litey"2 0 R e * a rc h%2 0a rd/6 2 0 & d{oodi2 0 Ho e%2 0 ol i k ht n t 'atu

119 7.3 Appendix C

Habitat of Fish sampled.

Dorab wolf-hening Adibopkrlgii Clueifom.s CluNa dotub. Chift.enlns hdelonM. gllp@-4ttltL - !!t9I9

100.0 cn SL aDlc/lNxldi 36.6 cm SL (fema].) Ref-Mialcd; dphidrcnoB; bE *ish; bditui d.plh tdg.

120 m Tropral, lt'lJ. 20'S, 40'E - 156'E lndo-Peific: prebably trougholrr the lffier co6ul s.tcrs,

fron 6. Rcd Sa md E st Africa lo th€ Solonoo hlmds, noflh to $uthen J!pm, $!th io nonl.m Auslralia. Reccody

180 lndian ilisha

Actinoptdyeii lelud&@$ | bigiles$iCee Clupa m.lastom CluE indicu. Pcllona b6hv$ma Alose indicMe. Sddircra Indica c$Muda l7.0cn SL nal./bsd.d Pelagic-ncriric; hphidrchou; brsckisni @inq deril rdge 0 - 50m

Topical: 29oll - E S, ?2'E - 124'E

Indo-P&ifiq Indis O..e (Malabd oan to calcutta), .,ava So (ofi Jav.), Ariin S.., Sotth ChiM Sa (Singaporc, cull oflr'.iled), Ean ChiF So (mnl b Taiw lsldd).

l8l Actircptcrygii P.rifom.s I Suonarc'dr. St'onards da. .B Srroror.oidca dc.nt€B- Shp.rioid.s @?!!4! Ailmn &e.n*. Palooct6n !l!rd, Vhitc @nfEl

Bo'hqrrtr, ..!.IeIe1 lum. d.rd q. J. rid;

r. M'rb6Mdqls E\fud

lE.2 Liza subviridis NA" Greenback mullet

Ms8ijid|c (M!ll.t!)i Mrdlf!@s (Mull.ts)r adircpcryg'r

40.0 qn SL (nd../wx.d: NA NA tldcPFif.: Rld Sc. ro S.nor. mrt|t ro ,!o. Collcrcd ar

l8l endix

Profile ofthe seaweed examined in this stud

Ulva fasida, lle knou as lD u palahalaha dn lea k uce, is d .affian gEen al8a thar is nsed for @rouplion in iany p.n! of th. world. High nlrien|s dd frshmld de ono indicaied by iis prc*n@. h h shed-like, consisring of widc blad6, l0-!5cm widc al b6e,opering upMd lo les lhai 2.5cn qide at tip. Up ro I D.tcr long bsdly bro.dcncd, bur upp.r ponion is divided deply inlo My ribbons likc scgn otsr mdSins shoorh, otun odulare. Holdf4r is small wiihout ddk ftiaids. Ils @lor is bnghl SB grccn b det ereen. gold at n rgi6

UIva fasciab is disribltcd worldwid., ud @mmorly fourd in u6 *tEE nuric s e js hieb *ave forc6 m low and hdbisc r.duc.d. Ir rot@r of srBtut coflrilio$_ rrs p'l34e ono indi@rcs frcshMle. inpur or pollulion.

E@logically succe$^ll gr€en alga lil. 4 /as.,a?a is poicnrialy invsiv€. CoaGl wa|e6 n d habo6, indsEial compl.x.s &d tcsid.fijll d6 wirh nulri€ft nch d&or fresh wlei irpul oft.D have bleru ot afta s!@ic! thll corr ship!' hulh, covq pilings dd sho&]ins. ed resrdct ourflow pip6. u /a.ia,a is clsin.d s s naine fouli,s orgdism, ald studi€s ir @nrol dd.ndhado. sc pFscilly ude'wy. .

184 7.4.2 Hypnea muscitormis

Htpn o d^.t/o.nL $ , tuetny opFnusric Elr knom for ill ldg€ ooating 'n\.d.r bl@m in @airl b.lr 'Itis alra is.dily idorili.d by lh. fl.tt n.d. brcad h@k at th€

Clmps or 6ses of l6kly inrnwir.d, cyliidical bdchci lO - 20 cn rall,0.5 - l.O cm diM.rd rhar b6on6 progEssiv.ly hoc aldd* rowd. dps. Fim, cditaginour hjghly bmchcd. Brdchin8 is vdi.blc s.t i@gut*, oncn &nddflike od M$ed eurd d6 ofoths alg&. Th. c8b ofnsy d* ed bmche d flanencd *ilh bbad h@ks Hofdfa$ e srll, in@ns!ic@s, or lackinS. rtpr., rwilomis cN 6itl disrinsuish n o olhd nativ. FB,Ed spp_ by lh. pEscc of tt.ncEd, btu.d hok at lhe tips of lhe b@ch6 (c lmw or lbovc fige), OfrGn found s d €piphrt on ef atg& s\$ a Sa€dtun echin$@pun SoSattM Nbplr,llw, 8n A@rhoph@ 9,.ir.d. Usu.xy rcd, bu 6 be ycuoish btou in hi8h liShr ovioh.nl. or nulnor Dor

7.4.3 Sargassuh muticum 5,196r!r z!ri.!z Gowr or h'd sub6rata i, sh.Iov war,s md d also lolmr inons, .$Eire o i1cs oukomp.r t@sl sp*ics b.calc ir is fs1 srcwing, @ rcprcd@ wilhin the frsr yes of lifc dd ce f.nilia i$.lt

A ldg€ bFM *awed (wirh a frud ond o!.r ln lons), rh€ siem hs ,€sutdty alrcmdne btuches wih naneed oval bt.d4 sd sphaicd gs bladd6. tr is highly .lislitrdive ,t!d olive-b@M in @lor, Wi|4.d is d inlsiv. sp.cics non Ue pacific ihal app@ed o. thc Isle of Widi in l9?3. h.ving sprcad ro Brillin fon Ftuce. h

185 comF6 wnh Ddvc sFei.s *h - s Ct.gs ed is co$i&Ed . luise in habou. bah.s dd d!.llow w.r6.

&r8dJ!r rd&r frdds @ on i noE Ou I n iD lcDslh rnd oliv+brcM in color- R.gU&datuftg h.lahcs !!! prlsat donS nd. Fl.tt n.d o!.1 bhd* dd sphcdcal ga bltddd @ dona b|eh6.

7.4.4 PalnrarL palmata

Prltui^ Pattua de c.ll.d d!L, d0urlt, dihk or .Erh!.ch, k . Ed .tgr rRD.

Pat@ia Nlkata i. to b. t@d greving iw nid{idc of Oc intdlid.l zonc (thc G bd@n th. high dd. ed low d&) to d.D$s of 20 n or hoE itr bolh 3tEtlarn .d

,EA&B FIori.hoolvc* Pdruid.s P.ltui&* aslulis

Irlhui! Parmr, aDs .n .hcrl b, iB disid holdftn lo ta Dct!. Th. iods e @i.U. ad v.'y in @lor tlD deFros. ro Fddbh-Duplc 5nd e .dicl tanhcry ii tcxnlt. Thc fl.r folios. bl.dc gr.dull, Gxp$& rd dilide' inro brold s8h6!, nnsina in rie ro 50c[r loos.nd 3O-Em h widh $iic! o ha. fl.t s€dgdhrDcd DrelifdioB im lhc cdg.,

tE6 G.odrphicd loclrion hapg

7.s.1 Co.st l belt of lor.chl clty,

tE7 7.5.2 Lo.ation mao for s.npling ritcs

24.8586750098943Et 6864724t59240n

24.E422E15506245t6 66.E9?,168566E9451

24.834959E0782473 66.9tE41r25488281

24.79tt I E902945E6 66.9E372E4oEE I147

24.?8003294009055 67.05076217651367

24.?91{0986t8!95 67.146?)0EE623047

24.749t419tt61575 61 .t45344696O41e2

24,813848955588067 61_2214011\339844

24.1E7357y2l4t6n8 6?.33I4514160t56

t88