Concentrations of 21 Collected from and 3 M Etalsin
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Geochem icalJournal,Vol.14,pp.203to 226,1980 203 C oncentrations of 21 m etals in the suspended solids collected from the principal 166 rivers and 3 lakes in Japan HISAYU KI T E RA OK A an d JUN K OBAYASHI Institute for A gricultural and Biological Sciences, O kayam a U niversity, K urashiki 710, Japan (R eceived July 21, 1980, A ccepted October 20, 1980) In the analysis ofnatural water,it w ould beinteresting to determine sm allbut significant quantities of trace m etals which are concentrated in suspended solids, since som e of these m etals, derived from geologic formations, mines and industries not only influence the environment for men and anim als,but will also help us in tracing m etallic resources. Taking advantage of the nation-wide chemicalinvestigations conducted by JUN K OBAYASHI, FUJI M ORII and cow orkers on various constituents dissolved in the principal Japanese rivers and lak es, the present authorscould analyze major an d minor metallic elementsin the suspended solids by theemission spectrographic m ethod. The following are the results obtained: (1) M arkedly high er concentrations of minor elements such as Pb, Zn, Cu, Ni, M n and Co were found in the suspended solids th an in unpoluted soils or in the continentalcrustreported by TAYLOR (1964). (2) TheconcentrationsofM n,Cu,Ni,Pb and Sn were foundto bem arkedly highinthe North eastern provinces. Thism ustbedueto the higherconcentrationsofthesem etalsdistributedin geologicform ations in this section as well as to the influence of m any copper and other mines. (3) The distribution of Be happened to divide Japan into tw o halves. Itism arkedly lowerin the eastern half. Positive correlations were also observed betw een the concentrations of Be and those of A1 and Ti. (4) O wing to the extremely acid nature (pH 2.0) ofthe Y u River(No.42)inthe Tone riversystem, caused by the Kusatsu hotsulfuric springs,the concentrations ofallm etalsexcept Si sh owed the lowest values, while Si had the high est value. Otherinorganic acid rivers which are distributed m ostly in the N ortheastern provinces,i.e. the Agatsum a River (N o.43,pH 4.3) ofthe sam e system and the Ara River (N o.13, pH 3.6),and acidlakes,i.e. Lake Tazawa (No.32,pH 4.4)and LakeInawash iro(N o.57,pH 4.5) showed about the sam e tendency. water sam ples collected once a m onth, 12 tim es INT RO DU CTIO N a year, from m ore than 500 selected sites along Inform ation on the am ount ofchem icalcon- th e prin cip ai rivers an d lakes throughout the stituents dissolved in river w ater is im portant w hole territory of Japan (K OBAYASHI, 1951; not only for studyin g the process of w eathering K OBAYASHI, 1960), and m or eover from other and erosion of the surface of the earth,but also A sian countries (K OBAYASHI, 1959). for a wide ran ge of hum an activities including In this study covering various geological features, K OBAYAS HI noticed strikin g correlations agriculture, industry , fishery and hygiene. A s betw een (I) the distribution of SiO . content early as 1941 w hen the w ater had as yet har dly dissolved in river orir ri gation w ater and the SiO . been polluted, K OBAYASHI, one of the authors, started a nation-w ide chem ical investigation, contentin rice straw by districts on the one hand continuin g for several decades, on t・he dissolved (K OBAYASnl, 1967; K OBAYASHI, 1971), and (2) constituents, such as Ca, M g, N a, K, H C 03, t he chem ical com position of river w ater and S04, C1, Si02, P 04, N 03, N H4 and C O D in the death-rate from apoplexy (stroke) w hich has 2 04 H. T ERA OK A and J. K OB AY ASHI been the leading cause of death in Japan, on river w ater forsuch purposes asirrigation ofrice the other (K OBAYASHI, 1957). A fterthis second fields, in dustry and tap water, but also for fin ding, m an y articles have been published show- av oi ding m an-m ade pollution caused by w aste i ng an in verse relationship betw een the hardness w ater from in dustries and cities dow nstream . of local water supplies an d m ortality rates from In the actual sam pling atthe selected places, cardiovascular d iseases in var ious coun tries care w as taken to collect the w ater from the (SCHROEDER, 1960;M ASHIRONI et al., 1979). m idstream of the river, w here the w ater m oves F urther, by m eans of em ission sp ectro- deeply and rapidly. A s a rule,the w atersam ples graphic an alysis , K OBAYASHI found in 1960 the were sim ultaneously collected once a m onth, f irst clue to the cause of the "Itai-Itai" disease- 12 tim es a year, from the selected 169 sites a very strange an d miserable osseous disease al ong the principal rivers and lakes. The sam pl- induc ted by chronic poisoning with cadim ium ing period contin ued for three years from w hich w as r eleased int o a river from the biggest O ctober 1972 through Septem ber 1975, as zinc m ine of Japan around the tim e of the Japan w as divided into three parts for analytical Second W orld W ar (K OBAYASHI, 1971; K oBA- p urposes. YA SHI, 1979). A fter this finding the present It w as fortunate that, in selecting the places auth ors m a de further applications ofthis m ethod an d collecting the sam ples, special cooperation which perm its sim ulta n eous determ ination of could be obtained from 36 prefectural govern- m any kinds of m etal even with a very sm all m ents in response to K OBAYASHI'S request to quantity of sam ple ash (T ERAOKA and K OBAYA- supportthis nation-wideinvestigations of w aters. Sm , 1977; T ERAOKA et al., 1978). From O ctober 1972 t o Septem ber 1975, A naly tical procedure The suspended solids w hen a seco nd series of nation- wide chem ical w ere filtered out with a sm all piece (3.6cm investigations of river and lake w aters w as diam eter) of T ~yo filter paper N o. 6 fix ed in a carried out by JUN K OBAYASHI, F UJI M oRn and filtering f unnel, d ried in a dry ing oven at 105' C, co w orke rs to m ake clear the che m icalinfluences and m e asured for the dry weig ht of the solids. due to the m ark ed pollution in the 1970's The 12 solids obtained from each site during a (K.OBAYASHIet al., 1976; K oBAYASHlet al., 1978), year together w ith the filter paper w ere m ixed t h e authors took advantage of this surv ey to and ashed at 450'C. A fte r m easuring the determ ine the concentrations of 21 m etals (Si, weight, the ash w as an alyzed by em ission spec- Al, Fe, Ca, M g, N a, Ti, M n, B a, Z n, Sr, Zr, trographic m ethod. Thi s analytical m ethod is V, Cr, Cu,N i, Co,Pb, Sn, A g and B e)in ashes of o ne of the m ost appropriate m ethods for analyz- suspended solids obtai ne d from water sam ples, ing various m etalsi n suspended solids,because it w hich w ere collected from 169 sites along the m akes possible the sim ultaneous dete rm ination principal rivers and lakes of Japan. T he results of m ore than 20 elem ents with only a sm all t hus o btained ar e reported in this paper. quan tity of sarnple ash. Sam ple ash m ixed with carbon pow der con- tainin g the intern al stan dards (Pd and Ge) was E XPERIM EN TAL burn t until the m ixture volatized in a dc-arc Collection of sam ples T he sam pling places generated in an argon-oxygen atm osphere w hich show n in Fig. I an d Table I were selected with is effective in elim inating the CN-bands and preference f or those parts of the rivers w here decreasing the background. The gap between they are about to enter the dow nstream plains the electrodes w as kept at 4m m during the after running through the m ountainous upper burning tim e, and only the m iddle part (Im m ) an d m id dle stream areas. In Japan, w here the of the arc w as passed through on the spectro- topography is steep and rivers run swiftly,these graph slit by m idw ay focusing m ethod. A 7 places are im portant not only in utilizi ng the s tep rotating sector w as used. W orking curv es Concentrations of 21 m etals in the suspended solids 205 / ' i_/-- L l+¥_~~'/~ JI~'~H8-fj fl_¥? 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