GeochemicalJournalVol. 17,pp. 247to 255,1983

D istrib u tio n a n d c o rrelati o n o f to tal o r g a n ic c ar b o n a n d m erc ur y in A nt ar ctic dr y v alley soils, s e dim e nts a n d o r g a nis m s

G ENKI M ATSUM OTol, K AZUO CHIKAZAW AI, H ARUTA M URAYAM A2 TETSUYA ToRI13 HIROSHI FUKUsn IMA4 and TAKAHISA H ANYA1 DepartmentofChemistry,Faculty ofScience,Toky o Metropolitan University,Setagaya-ku ,Tokyo 1581, Facu]ty ofEducation,Yokoham a NationaiUniversity,Toki wadai,Hodogaya-ku ,Y okoham a 2402, ChibaInstituteofTechno]ogy,Narashino-shi,Chiba 2753,and Tokyo W om en'sCo]lege of Physical Education,Aoyagi,Kunitachi-shi,Tokyo 1864,Japan

(R eceived January 24,1983:Accepted M ay 12,1983)

M ercury contents of 19 soi]s,13Iake and pond sedim ents,8 epibenthicalgae (m ost]y blue-green algae) and 3 m osses(m ost]y Sarconeu ru m glaciale)from the dry va]1eys of Victoria Land and RossIslan din the Antarctic ranged from 3.0 to 54 krg kgﾖ1 with an average of14:i:5.1 at90% confidencelim its,from 2.4to

71 with an average of 17:!: 10, from 12 to 710 with an average of190:!:160 and from 99to 290 with an average of 170 :!: 180 ,rg kgﾖ1 dry base,respective]y. It wasindicated that epibenthic aigae and m osses accum ulatem ercury. Thecorrelation coefficient betw eentota]organiccarbon and m ercury contentsfora]] the sam plesstudied wasfound to be +0.69,indicatingthat total organic carboncontentsare anim portan t factor controllingthe distribution ofm ercury in soils,sedirn ents and organismsintheA ntarctic dry valley areas.

INTRODUCTION the soilsand sedim ents are considerably low, but

M ercury , the m ost volatile heavy m etal organism s concentrate m ercury . It has also been elem ent, occursin the naturalstate only in sm all show n that soil/air ratios of A ntarctic m ercury am ounts. It is estim ated to be 50 to 80 pg kgﾖl are low, resulting from the low m ercury con- of the earth, w hich is used widely in oursociety centrations on the ground and not from its (V OSTAL, 1972). It has been studied by m any atm ospheric value. W e report here the distri- scientists in the m id and low er latitudes princi- bution and correlation of total organic carbon pally in relation to environrn ental pollution, (TO C) and m ercury in soils, sedim ents, algae since m ercury and its com pounds are toxic and and m osses from the dry valley areas ofV ictoria cause seri ous environm ental problem s such as L and in the A ntarctic. M inam ata Disease. H ow ever, Iittle is know n on the distribution of m ercury in A ntarctica. EXPERIM ENTAL K OGA (1977) has reported the concentrations of m ercury in soils and D V D P (Dry V alley Drilling D uring austral sum m ers 1976- 77, 1980- 81 Project) sedim ent cores from the dry valley and 1981- 82, soil, Iake and pond sedim ents, areas and Syow a O asis and discussed them in epibenthic algae (m ostly blue-green algae) and connection with geotherm al sources. M ercury m oss (m ostly glaciale) sam ples contents of air, soil, evaporite, sedim ent and w ere obtained from Balham , W right, Taylor, certain biological sam ples from the dry valley Pearse and M iers V alleys and O lym pus R ange of areas and R ossIsland have also been investigated Victoria Land and R oss Island in the A ntarctic (M CM URTRY et al., 1980; SIEGEL et al., 1980). (Table 1-3). T he general characteristics of the They have revealed that the levels of m ercury in dry valley areas and R oss Island have been

241

242 G.M ATSUM OTO etal.

Table1. Total organic carbon (TOC) and m ercury concentration in soilsfrom the dry valley areas of Victoria Land in theA ntarctic

TOC Hg Locality (gkg~1)* (p;gkg~1)* Remarks

Balham Valley(77"25'S,161'O1'E) WestsideofBalham Lake 0.17 3,0 Coarsesand OlympusRange(77'29'S,161'30'E) Mt.Jason 0,037 4.2 Fine sand WrightValley(77'31'S,161'50'E) Labyrinth-1 0.15 5.5 Coarseandfinesand Southfork-2 0.15 3.2 Finesand Southfork-3 0.080 54 Coarseandfinesand Southfork-4 0.27 18 Finesand Southfork-5 0.74 9.4 Coarseandfinesand,andsilt Southfork*8 0.24 6.9 Coarse an dfinesand Southfork-9 0.81 23 Silt Southfork-10 O.18 5.0 Finesand SouthsideofLakeVanda 0.066 19 Coarseandfinesand NorthsideofLakeVanda 0,063 3.3 Coarseandfinesand TaylorValley(77'37'S,163"OO'E) Westside ofLakeBonney-1 ** 18 Carbonates W estsideofLakeBonney-2 2.3 16 Finesandandsilt SouthsideofLakeBonney-1 o.95 27 Coarseandfinesand andsilt SouthsideofLakeBonney-2 0.46 28 Coarseandfinesand,andsilt EastsideofLakeBonney 0.58 18 Finesandandsilt MiersValley(78'06'S,164'OO'E) WestsideofLakeMiers 3.2 4.8 Finesand SouthsideofLakeMiers 1.1 3.6 Finesandandsilt Averagei 90% confidencelimits 0.64 i0.35 14 ~5.1

*. Drybase. **. Mostofthesamplewasdissolvedwhenhydrochloricacidwasadded,

reported by m any scientists (e.g., T ORII and until analys is. Y AMAGATA, 1981). A Iarge variety of rocks are T O C w as determ ined using a C H N analyzer distributed com m only on the surface of these (Y A N A K O M T 2 C H N CO R DE R) after treat- cold deserts. V ascular are absentin the m ent of the sam ples with 6 M hydrochloric acid areas studied, although rare isolated lichens to rem ove inorganic carbon. T he concentrations and m osses are distributed. The lakes and ponds of m ercury of the w et sam ples (10-100 m g) studied are all saline. L akeshore and ponds are w ere directly analyzed w ithought any treatm ent usually covered with epibenthic algae com prised using m ercury analyzer (RIG A K U M E R C U R Y m ostly of blue-green algae. Soil, epibenthic SP), w hich has a 900'C furn ace for m ercury algae, m oss and pond sedim ent sam ples w ere analysis and no digestion procedures are re- collected with a sm all stainless steel scoop. quired. Spiked experirn ents show ed that the Lake sedim ents w ere taken using a Kitahara- recovery of m ercury for soil, sedim ent, algae type w ater sam pler or by a diver directly. T hese and m oss sam ples w ere 88.5 (standard deviation, sam ples w ere w rapped each with a tefl on sheet, S.D., 2.6), 101 (S.D., 5.1), 100 (S.D., 1.1) and transferred into a polyethylene bag or glass 104% (S.D., 10% ), respectively. bottle with a glass cap and kept at - 20'C

Totalorganiccarbon and m ercury 243

Table2. TO Cand mercury concentrationinlakeand pondsedim entsfrom the dry valley areas

TOC Hg Locality (gkg~i)* (,rg kg~1)* Remarks

Victori aValey B-1 Pond* * 5.7 12 Coarseandfine sand,andsilt Wright Valley DonQuix otePond-1 Coarseandfinesand,andsalts 0.69 5.3 DonQuixotePond-2 0.36 2.6 Coarseandfinesand,and salts Coarseandfinesand,andsalts D onJuanPon d-1 O.18 4,2 D onJuanPon d-2 0.40 7.8 Coarsean dfinesand,andsalts L- 9Pond ** 1.7 6.8 Coarseandfinesand L-8Pond** Coarseandfinesand 2.3 6.6 L-4Pond** 0.94 2.4 Coarseandfinesand Coarseandfinesand LakeVa nda 1.9 12 TaylorValley

W es tlobeo fLa keBonne y 2.3 50 Silt LakeFryxell-1 17 18 Finesand

LakeFryxel- 2 20 25 Finesand Pearse Valley (77'43'S,161'32' E) Coarseandfinesand Lak eJoyce 3.6 71 Average~:90% confidencelimits 4.4 i3.2 17 ｱ10

*. Drybase. **. Unnamedponds.

RESULTS AND DISCUSSION sam ples. The T O C contents of the algae and T O C values in the soil sam ples from the dry m oss sam ples were considerably low as pure valley areas ranged from 0.037 to 3.2 g kgrl dry organism s, because they contain sandy m aterials base with an average of 0.64 ~ 0.35 g kgﾖ1 at as im purities, but m uch higher than those ofthe

90% confidence lim its (Table I ), w hich are soiland sedim ent sam ples (Table 3). com parable with those of the previous studies T he concentrations of m ercury in the soil (M ATSUM OTO et al., 1979), but m uch lowerthan sam ples ranged from 3.0 to 54 ,!g kgﾖ1 dry base those of soil typical of vegetated areas (B R OWN with an average of 14 d: 5.1 ktg kgﾖ1 (T able l), et al., 1972; M A TSUM OTO and H ANYA, 1980). w hich are com parable w ith the values (1.1- The T O C contents of the lake and pond sedi- 169 pg kgﾖ1) of K OGA (1977). T hey are also m ents ranged from 0.18 to 20 g kg~1 with an sim ilar to those of soils around a large coal- fired pow er , w hich did not differ sta- average of 4.4 i 3.2 g kg~1 (T able 2), w hich are also sim ilar to those ofthe results ofM ATUM OTO tistically from unpolluted background level et al., (1979), although they are appreciably (6-45 pg kg~1 with an average of 16 pg kg~l low er than C ROCKETT and KlNNISON, 1979). The levels of those of contem porary tem per ate lake and river sedim ents (W AKEHAM and m ercury in the sedim ent sam ples ranged from

CARPENTER, 1976; ISHIWATARI et al., 1980; 2.4 to 71 pg kgﾖ1 with an average of 17 i lO

1983). Extrem ely low TO C ,Ag kgﾖ1 (Table 2), are sim ilar to those of our M ATSUM OTO, foun d in the sed im ents from D on soil sam ples, but m uch higher than the results values w ere Juan Pond, w hile the highest T O C content was (2.0 :!: 0.8 pg kgﾖ1) of M CM URTRY et al., (1980). detected in the sedim en ts from Lake Fry xell. T hey are, how ever, m uch low er than those

In general TO C contents of the sedim ent sam - of unpolluted and polluted lake and river ples are fairly higher than those of the soil sedim ents (< 0.01-1 m g kgﾖ1 dry base, COPELAND,

244 G.M ATSUM OTO etal.

Table3. TOC and m ercury concentration in algaeand m ossesfrom the dry valley areasandR ossIsland

TOC Hg Locality (gkgHl)* (,lgkg~1)* Majorspecieswith decreasingabundances Algae WrightValley L-A Pond** 40 160 Synechococcussp.#,Phormidium sp.# L-12Pond** 23 39 Phormidium sp.# L-9Pond** 48 320 Synechococcussp.#,Phormidium sp.#, Oscillatoriasp.# TaylorValey EastlobeofLakeBonney 5.7 170 Phormidium spp.#,Hantzschiaamphioxys## MiersVa ley AdamsGlacier 78 41 Nostocsp.#,Chroococcusspp.# Miers-1 90 30 Nostocsp.#,Phrmidium sp.#,Naviculamuticopsis## M iers -2 95 710 Nostocsp.#,Naviculam uticopsis## Mi ers-3 26 12 Phormidium sp.#,Naviculamuticopsis## Average~9 0% confide ncelimi ts 51= 22 190 =160

Taylo rVa l ey Fryxelhut 110 99 Sarconeurum glaciale

Northsi deofLa keFryx el 21 110 Sarconeurum glaciale RossIsland(77'30'S,168'OO'E)

CraterHil 110 290 Sarconeurum glaciale Average~90 % confidencelimits 80i87 170 ｱ180 Drybase. *~ Unnamedponds. # Blue-greenalgae. ## Diatom.

1972; K ONRAD, 1972) and estuarine and bay 2). H ere w e first report the accum ulation of sedim ents (0.05 m g kgrl dry base-2,010 m g kgrl m ercury in A ntarctic m osses (Sarconeurm w et base, T AKEUCHI, 1972; LlNDBERG and glaciale). H ARRISS, 1974; E GANHOUSE et al., 1978). The Bio-concentration of m ercury suggested the low m ercury contents of our sam ples could be positive correlation of T O C and m ercury con- attributed to th e sa ndy struct ure of the sedi- t ents, because organic m atter is derived ori ginal- m ent sam ples and to the low TO C contents. ly from living organism sin naturalenvironm ent. SIEGEL et al. (1980) have also suggested that The TO C and m ercury contents of the soils, it is attributed to the low degree of bio-con- sedim ents, algae and m osses are plotted in Fig. 1 centration of m ercury. N am ely the concen- on the log scale. T he correlation coefficient for trations of m ercury in algal m ats from D on Juan all the sam ples studied w as estim ated to be Pond and Lake H oare in the dry valley areas are +0.69. T hese results indicate that T O C and 10.4 and 19.4 ,/g kg~:. In our case, how ever, m ercury contents of soils, sedim ents and living m ercury contents of algae and m osses are con- organism s are correlated and TO C content is siderably high, ranging from 12 to 710 ptg kgﾖl an im portant factor controlling the behavior w ith an average of 190 :!: 160 pg kgrl and from of m ercury in the A ntarctic dry valley areas. 99 to 290 ~g kg~1 with an average of 170 :!: 180 T he sim ilar cor elations of the m ercury and ktg kg~1, respectively (Table 3). They are gener- organic m atter contents have also been found ally one order of m agnitude greater than those in soils from Sw eden and Africa (A NDERSSON, of the soil and sedim ent sam ples (Tables I and 1967) and sedim ents from Florida Everglades

Totalorganiccarbon an d mercury 245

Fig. 1. Cor relation of TOC and m ercury in soils,sedi- R EFERENCES m ents and organism sfrom the dry valley areasand Ross Island in theA ntarctic. ANDERS SON, A.(1967) Mercuryinthesoil.G ru n4for- 3 battring 20,95-105. o:Soil JL e:Sediment BROWN, F. S., BAEDECKER, M. J., N rssENBAUM, A. JL:AlgQe and K APLAN, I. R.(1972) Early diagenesis in a C>:Noss L ｢ reducing fJord, Saanich Inlet, British Colum bia-III A l Changes in organ ic constituents of sedim ent. Ge(~ 2 (> <~ chim. Cosm ochim.Acta 36,1185- 1203. , COPELAND, R.A.(1972) Mercury inthe Lake Michigan ia, o , x A A environm ent. in Environm ental m ercury contami- aCD a, OOo , A nation (Eds. R. HARTUNG and B. D. DlNM AN), I O O O o e Ann ArborSci.Pu b., Michigan,71-76. a, , e 1 o CROCKETT, A. B. and KINNlSON, R. R.(1979) Mer- o' e. oo e o cury residues in soil around a large coal-fired power o e plant.Environ. Sci. Technol. 13,712- 715. o (b o ' e EGANHOUSE R. P., Y OUNG, D. R. and JOHNSON,J. N. (1978) Geochemistry ofm ercuryin Palos Verdes o sedim ents.Environ.Sci. Technol. 12,1151-1157. logToc(mgkg~1) FANG, S. C. (1978) Sorption an d transform ation of The regression of log Hg on log TOC is represented by m ercury vapor by dry soil.Environ. Sci. Technol. 12, log Hg = 0.42 Iog TO C - 0.12 with the correlation 285-288. coefficientof O.69. ISHIW ATARI, R., OGURA, K. and H ORIE, S. (1980) Organic geochemistry of alacustrine sedim ent (La ke Haruna,Japan).Chem. Geol. 29,261-280. and M obile Bay estuary (LlNDBERG and H ARRISS, KoGA, A.(1977) Preliminary geochemical prospecting 1974). T he poor correlation am ong the soil of therm al sources around Lake V anda, dry valley, sam ples, how ever, m ay be attributable to the .A ntarct.R ec. 58,138-144 (in Japanese). extrem ely low TO C concentration and the KONRAD,J. G. (1972) Mercury contents of bottom effect of the adsorption of m ercury by clay sedim ents from Wisconsin rivers and lakes. in Envi- minerals m ay play an im portant role on the ronm entalm ercw y contamination (Eds.R.HARTUNG and B. D. DlNM AN), Ann Arbor Sci. Pub.,Michigan. m ercury distribution (K OGA, 1977; FANG, 52-58. l978). In addition fragm ents of w idely dis- LINDBERG S.E.and H ARRISS,R.C.(1974) M ercury- tri buted dolerite (facetted pebble) and granite, organic m atter associations in estuarine sedirnents w hich are reported to contain large am ounts and interstitial w ater. Environ. Sci Technol. 8, of m ercury, 730 and 180 pg kg~L, respectively 459~ L62. (K OGA , 1977), are also possible sources of M ATSUM OTO, G. (1983) Com parative study on organic constituents in polluted and unpolluted m ercury in the dry valley soils. inland aquatic environm ents-V. Organic carbons and hydrocarbonsin sedim ents. WaterR es.In press. Ackn owledgements-We are greatly indebted to the M ATSUMOTO, G. and HANYA, T.(1980) Organiccon- Antarctic Division, DSIR, New Zealand, U S N SF, US stituents in atm ospheric fallout in the Tokyo area. Navy , Japan Polar Research Association and Polar Atm os. Environ. 14,1409-1419. Research Institute of Japan for th eir logistic supports. M ATSUMOTO, G., TORn, T. and HANYA, T. (1979) We th ank Drs.Y. YUSA,S.N AKAYA,E.W ADA,T.CHO Distribution of organic constituents in lake w aters and G. M. SIMMONS, JR. and M essrs. R. MILLlNGTON and sedim ents of th e McM urdo Sound regionin the and Y. TANAKA for their ki nd assistance in collecting Antarctic.in Proc. Seminar111onD ry Valley Drilling sam ples, and Dr. H. K ANDA for the identification of Project, 1978. M em. Natl. Inst. Polar R es. Spec. m osses. Th anks are also due to Dr. M. TERAIfor his Issu e 13 (Ed. T. N AGATA), National Institute of useful suggestion and Mr. M. SHIOYA forhis assistance Polar Research,Toky o,103-120. in calculating correlation coefficient. M CM URTRY, G., BRILL, R., SIGEL, B. Z. and SIGEL, S. M. (1980) Antarctic m ercury distribution in com parison with Hawaiiandlceland.A ntarct.J. U S. 14, 206-209.

246 G.M ATSUM OTO etal.

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