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

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

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Fig.1. Sam pling places of the principal 166 rivers and 3 Iakes in Japan

206 H. T ERA OK A and J. K OBA YASHI

Table 1. Places of sam pling and analyticalresults ofsuspended solids (S.S.) collected from theprincipal166 rivers and 3 Ia ke sin J ap an,fort h ree yearsfro m Octob er1972 th rou gh Septem be r19 75.Con ce ntr at io ns of S.S .,

I.L.and 21 m etalsare theaverage of12 dlfferentsam plescollected oncea month,12tim esayears.

No. Name ofriver Place of sa m pling S.S. I.L. Si (ppm) (%)

1 Teshio Hokkai-d~ N ayoro-shiNayor0-~ hashi 36 25 25 2 Ishik ari Hokkai-d~ Kaw ak ami-gun Aibetsu-cho Nakaaibetsu 104 17 26 3 Ishikari Hokkai-do Fukagawa-shiMidori-m achi 41 27 26 4 Sorachi Hokkai-do A kabira-shi 101 25 29 5 Ishikari Hokkai-do -shiUpstream theChitose R.joins 81 21 28

6 Chitose Hokkai*do Ebetsu-chiHashiof Nationalroad 12 110 16 29 Toyohira HokkaiHdo -shiToyohira-ku 81 27 26 Tokachi Hokkai-d~ Kasai-gun Mem uro-ch~ 61 37 26 9 Tokachi Hokkai-d5 Nakagawa-gun Toyokoro-ch~ M oiwa-ohashi 58 35 28 10 Tokoro Hokkai~lo Tokoro~un Tanno-cho 2-ku 79 29 26

11 lwaki Aom ori-ken Nakatsugar u-gunlw aki-m achiN yoraise 22 22 25 12 Hira Aom ori-ken Minamitsu gar u-gun Owani-cho Shukugawara 25 31 25 13 Ara Aom ori-shiTakada 52 37 28 14 Oirase Aomori-ken Towada-shiOsak a 11 35 29 15 M abuchi Aom ori-ken Hachinohe-shiK ushibik iKushibiki-hashi 23 31 26

16 Kuji lw ate-ken Kuji-shi Okawam e-ch~:M itsuka-m achi 3.2 41 25

17 Heii lw ate-ken Shim oheli-gun Niisato-m ura M oichi 4.1 31 26 18 Kitakam i lw ate-ken M orioka-shiTatem ukai-cho 17 52 19 19 lw ate-ken M orioka-shiOta 14 30 26

20 Sarugaishi lwate-ken W aga~un T~wa-ch~ 5.4 42 25

21 Kitakam i lw ate-ken Kitakam i-shiTachibana 16 33 26 22 Isawa lw ate-ken Isawa-gun Isawa-ch~ 9.6 21 25 23 Kitakam i Miyagi-ken Tom e-gun Nakada-ch~ 21 31 27 24 Hazama Miyagi-ken Kurihara-gun W akayanagi-ch~ Kawam inami 18 23 28 25 Eai(Arao) Miyagi-ken Tarn azukuri-gunlwadeyam a-m achi 9.1 30 28

26 Abukuma -ken K~riyam a-shiYasuhara-ch~ 20 40 26 27 Abukuma Miyagi-ken lgu-gun M arum ori-ch5 M arum ori-~ohashi 21 27 28 28 Shiraishi Miyagi-ken Shibata-gunO gawara-ch~ Oya 26 33 27 29 Yoneshiro Akita-ken Kaz uno-shiTowadanishikigi 14 35 27 30 Yoneshiro Akita-ken Kitaakita~un Takanosu-m achi 9.5 31 26

31 O mono Akita*ken Yuzawa-shiYuzaw a 34 28 26 32 Lake-Tazawa Akita-ken Senboku-gun Tazaw ako-m achi Obonai 9.7 47 30 33 Om ono Akita-ken Senboku-gun Nishisenboku-m achiK ariw ano 28 23 26 34 Koyoshi Akita-ken Yuri-gun Y uri-m achi 33 27 27 35 Haguro Yam agata-ken Yonezawa-shiHanazawa 34 22 28

36 Mogami Yam agata-ken M urayam a-shiNishig~ 30 40 27 37 Mogami Yam ag ata-ken Akumi-gun M atsuyam a-m achi Yamadera 74 26 26 38 Aka Y am agata-ken -shiDaihoji-m achi 12 30 26 39 Kuji lbaragi-ken Naka-gun Om iya-machiTomioka-hashi 11 20 26 40 Naka lbaragi-ken Higashiibaragi-gun Katsura-m ura Akasawa 15 24 27

Concentrations of 21 m etals in the suspended solids 207

Al Fe Ca Mg Na Ti M n Ba Zn Sr Zr V Cr Cu Ni Co Pb Sn Ag Be (% in ash) (ppm in ash)

9.0 4.3 0.67 0.73 0.64 0.36 0.22 600 360 88 130 88 100 240 360 63 34 (16 <1.3 1.6 9.O 3.9 0.93 0.80 0.87 0.35 0.14 620 110 110 150 1OO 52 160 160 38 28 (16 <1.3 1.4 11 4.9 1.3 0.92 0.77 0.27 0.34 560 340 120 100 130 85 290 410 65 81 26 2.3 1.6 9.5 3.9 0.68 1.2 O.68 0.37 0.10 550 100 150 230 100 120 100 290 44 16 (16 (1.3 1.5 10 4.5 0.70 0.90 0.72 0.37 0.15 640 180 110 180 120 74 110 210 39 19 (16 (1.3 1.8

9.5 4.3 0.66 1.0 0.88 0.34 0.11 540 340 100 190 100 110 71 190 36 17 (16 K1.3 1.8 9.O 3.9 0.60 0.77 0.68 0.30 0.18 580 170 110 160 83 100 110 310 38 19 <16 <1.3 1.5 9.O 3.4 1.0 0.68 0.98 0.37 0.15 640 100 110 120 75 57 150 230 38 30 (16 7.6 1.6 10 3.9 1.3 0.96 1.3 0.45 0.17 540 200 140 210 120 71 200 260 43 53 19 (1.3 1.5 9.5 4.5 1.2 0.66 0.79 0.26 0.20 580 160 120 190 110 34 150 220 37 30 <16 3.2 1.8

8.5 3.2 0.60 1.1 0.51 0.29 0.44 510 900 64 130 74 44 300 1,200 51 84 18 (1.3 1.1 8.5 3.6 0.86 0.88 0.66 0.32 0.34 65O 560 100 190 75 66 350 590 49 100 53 (1.3 1.2 6.9 3.8 0.53 0.44 0.43 0.14 0.04 300 (80 49 33 120 44 100 180 27 36 <16 (1.3 O.7 9.5 2.8 1.3 0.72 1.0 0.31 0.12 590 560 130 270 55 84 450 570 41 140 26 (1.3 1.2 8.o 4.5 1.6 0.71 0.64 0.32 0.22 390 220 110 1OO 110 60 270 440 47 67 26 6.7 1.2

6.9 2.9 1.7 1.O O.45 0.35 0.15 480 450 130 140 74 100 840 710 26 170 45 <1.3 1.3

8.o 3.5 1.1 1.1 0.60 0.33 0.15 420 260 68 440 75 130 670 770 46 39 42 <1.3 1.7 2.9 15 0.95 0.20 0.13 0.09 0.32 310 530 59 30 40 58 410 460 230 76 22 <1.3 <0.4 9.o 4.5 1.3 1.0 0.72 0.25 0.26 460 450 92 250 120 84 460 560 55 130 25 <1.3 1.5 9.5 4.8 2.4 1.5 0.55 0 .30 0.48 480 420 200 160 130 160 1,300 1,500 74 170 40 (1.3 1.6

7.4 6.9 0.72 0.67 0.27 0.20 0.39 300 260 70 46 84 54 450 370 160 100 17 2.0 1.l

8.O 2.6 0.62 0.53 0.39 0.19 0.16 370 370 61 88 48 33 280 260 24 54 (16 <1.3 0.8 10 6.o 1.2 0.84 0.76 0.35 0.48 520 280 120 180 120 140 490 500 120 81 35 <1.3 1.2 9.0 5.4 0.90 0.49 0.78 0.25 0.53 580 1,300 81 880 73 55 260 25o 52 96 22 <1.3 1.5 11 5.3 1.4 1.1 1.2 0.25 0.64 600 450 120 130 79 110 700 850 60 80 46 <1.3 1.3

8.5 5.o 0.83 0.39 0.39 0.25 0.48 440 530 70 71 61 72 220 170 45 53 66 7.6 0.9 12 5.3 1.4 0.71 O.73 0.33 0.48 550 880 120 440 120 90 25O 360 52 81 34 3.3 1.3 13 7.o 1.5 1.I 0.75 0.40 0.51 540 350 140 160 80 36 280 180 61 110 24 <1.3 1.5 10 4.3 1.5 0.92 0.68 O.30 0.74 560 1,500 86 160 94 96 1,300 670 48 130 29 1.4 1.3 9.0 4.9 1.8 1.I 0.64 0.28 0.50 680 1,200 95 120 91 44 1,100 510 57 200 32 1. 4 1.3

9.O 3.6 1.1 0.56 0.65 0.25 0.23 610 300 99 78 62 44 330 25O 28 120 18 (1.3 1.4 6.4 1.O 0.17 0.15 0.17 0.07 0.02 200 <80 32 47 22 55 230 390 36 66 <16 <1,3 O.5 8.O 3.9 0.68 0.70 0.57 0.28 0.31 500 220 69 130 70 49 150 180 39 68 <16 <1.3 0.8 7.4 3.2 0.73 0.61 0.41 0.29 O.16 5OO llO 92 130 67 72 210 370 38 53 <16 <1.3 1.1 11 7.8 1.2 0.99 0.86 0.33 0.24 520 450 110 120 76 93 200 270 45 87 <16 <1.3 1.4

9.0 4.1 0.75 0.78 0.75 0.26 0.45 520 260 77 130 58 59 90 150 39 51 <16 <1.3 1.0 9.O 3.2 0.81 0.82 0.62 0.23 0.24 500 290 72 110 50 34 260 230 70 66 20 (1.3 0.9 10 4.6 1.O 1.1 0.72 0.36 0.30 540 390 140 140 97 66 590 460 97 170 35 (1.3 1.1 9.O 3.7 0.78 0.84 0.39 0.34 0.15 590 110 86 120 82 77 44 36 29 30 (16 (1.3 1.4 3.5 0.80 0.74 0.44 0.31 0.09 450 80 70 130 53 120 43 33 25 25 (16 (1.3 0.9 9.5

208 H. T ERAO K A and J. K OBA Y ASHI

Table 1. Continued.

S.S. I.L. Si No. Nam eofriver Place of sa m pling (ppm) (%)

41 Tone 4.5 34 26 Gunma-ken Ton e~un Showa-m ura Dow nstream Kat ashina R.joins 42 Yu Gunma-ken Agatsum a~un Kusatsu-machiBefore neutralized b ylim e 170 29 35

43 Agatsum a Gunma-ken Agatsum a-gun -m achiN aganohara 59 34 27

44 Agatsum a Gunm a-ken Shibukaw a-shi Nanm oku 34 33 27

45 Tone Gunma-ken M aebashi-shiIshik ura-m achiGunma-ohashi 24 28 27

46 Karasu Gunm a-ken Tano-gun Shin-m achiKawagishi-m achilwakura-hashi 16 29 26 47 Tone Gunm a-ken Ora-gun Chiyoda-m ura Kaminakam ori 19 24 26 48 W atarase Tochigi-ken Ashik aga-shiTori2-chom e 15 25 27 49 Tone (Edo) Saitam a-ken Kitakatsushika-gun Satsute-m achiNishisekiyado 33 24 27 50 Daiya Tochigi-ken N ik ko-shiShim okawahar a 2.5 42 30

51 Kin u Tochigi-ken Shioyaigun Takanezaw a-m achiH oshakuji 8.2 33 27 52 Tone Chiba-ken Saw ara-shiSaw ara 23 21 30 53 Ara Saitam a-ken Osatolgun Yorii-m achiY orli 9.1 14 22 54 Tam a 36 12 27 Tokyo-to Nis hitama-gun Ham ura-machiHam ura 55 Sagam i Kanagaw a-ken Sagam ihara-shiIsobe 23 14 26

56 Sak~ Kanagawa-ken Ashigarakami-gun Kaisei-m achiY oshidazim a 54 14 28

57 Lake-Inaw ashiro Fukushim a-ken Yam a-gun Inawashiro-m achiJoko 8.3 37 31

58 O Fukushim a-ken Kawanuma-gun Aizubange-m achi Miyako-hashi 14 40 27 59 Tadami Fukushim a-ken Onuma~ un Mishima-m achi Miyashita 7.3 26 26 60 Agano Niigata-ken Niitsu-shiNanoka-m achi 14 25 28

61 Chikum a Nagano-ken Minamisaku-gun Usuda-m achiUsuda-hashi 28 20 29 62 Chikum a Nagano-ken Koshoku-shiChik um a-hashi 23 26 26 63 Azusa Nagano-ken M atsum oto-shiShim auchi 6.2 40 26 64 Takase Nagano-ken Om achi-shiTaira Upstream Kashim a R.joins 18 13 28 64' Tak ase Nagano-ken O machi-shiTaira M ix ed with waterfrom Lake Aoki 12 35 28

65 Sai Nagano-ken Kamim inochiigun Shinshushin-m achi 42 16 28 66 Chikum a Nagano-kenliyam a-shi 37 20 30 67 Uono Nilgata-ken Kitauonum a-gun Horinouchi-m achi 31 27 27 68 Shinano Nligata-ken Ojiya-shiOjiya 20 32 28 69 Shinano Nligata-ken N akakanbara-gun K osudo-machiSuita 37 24 28

70 Kurobe Toyama-ken Shim oniikawa~un Unazuki-m achiAim oto 1OO 7 28 71 Joganji Toyam a-ken Nakannk awa-gun Tateyama-machiYokoe 91 18 27 72 Jin zil Toyam a-ken Kaminiikawargun O sa wano-m achiSasazu 6.0 22 28 73 Sh~ Toyam a-ken Higashitonami-gun Sh~gawa-m achiKanaya 6.0 20 27 74 Sai Kanazaw a-shiKata-m achi 33 19 29

75 Tedori Ishik awa-kenIshikawa~un Tsurugi-machi 31 17 29 76 Kuzuryii Fukui-ken Yoshidalgun Eih eiji-cho Higashifuruichi 26 13 28 77 Asuwa Fukui-shiAsuwa 14 17 26 78 Kano Shizuoka-ken Tagataigun Nirayam a-ch~ N anj~ 6.0 26 27 79 Kam an ashi Yam an ashi-ken Nakakom aigun Ry~:~:-ch~ Shingen-hashi 23 19 27

Concentrations of 21 m etals in the suspended solids 209

Al Fe Ca Mg Na Ti M n Ba Zn Sr Zr V Cr Cu Ni Co Pb Sn Ag Be (% in ash) (ppm in ash)

8.5 3.7 0.98 0.88 0.65 0.25 0.33 500 320 91 1OO 50 190 88 230 47 38 <16 <1.3 1.2 2.0 0.2 0.05 0.02 <0.1 0.02 0.003 130 <80 <32 <16 <16 61 8 18 (16 <10 (16 (1.3 (0.4 5.3 11 0.34 0.15 0.25 0.09 0.02 140 <80 74 20 100 110 36 21 (16 18 (16 <1.3 <0.4 11 6.3 0.98 0.42 0.42 0.13 0.07 400 140 90 50 100 71 91 64 52 17 (16 (1.3 1 . 1 8.O 4.2 0.96 0.42 0.42 0.11 0.08 320 <80 84 40 80 120 85 80 78 (10 <16 (1.3 0 . 9

39 21 (16 6.4 0.8 7.4 3.4 2.4 0.66 0.42 0.2/ 0.58 640 390 140 1OO 68 180 100 370 8.5 3.8 1.2 0.64 0.48 0.26 0.35 470 230 82 80 63 140 94 240 54 16 <16 1.5 0.9 11 4.o 1.1 0.78 0.70 0.34 0.22 800 800 130 200 79 750 310 190 55 41 40 3.2 1.5 9.5 4.2 1.3 0.86 0.52 0.31 0.17 500 160 140 100 70 150 96 170 42 85 <16 (1.3 1.1 9.5 3.8 3.7 1.1 1.0 n.34 0.12 580 390 170 90 81 460 430 200 24 58 <16 29 1.4

8.O 2.8 1.5 0.76 0.58 O.13 0.08 480 110 70 44 48 250 160 160 20 29 <16 1.8 1.1 11 7.O I.3 1.2 0.80 0.19 0.26 520 85 80 65 80 290 74 140 36 26 (16 1.7 1.4 6.9 3.1 11 1.2 0.44 0.18 0.16 510 120 180 73 88 310 70 72 34 45 (16 2.9 1.3 10 3.2 5.2 1.3 0.70 0.19 0.08 480 (80 140 80 90 140 51 75 23 34 <16 <1.3 1.7

10 4.8 1.7 1.4 0.39 0.23 0.13 560 140 58 75 110 260 65 280 37 28 (16 5.O 1.3

12 8.4 2.7 4.0 0.75 0.36 0.14 210 120 150 38 200 100 120 82 48 30 (16 <1.3 1.O

4.7 1.9 0.32 0.17 0.13 0.07 0.076 220 100 32 22 19 35 230 330 23 61 29 (1.3 0.6

6.9 2.5 1.6 0.75 1.O 0.20 0.30 530 220 100 110 42 54 300 550 47 70 34 (1.3 1.1 9.O 0.72 0.94 0.68 0.19 0.48 1,000 490 100 130 ' 53 96 620 700 55 130 28 (1.3 1.6 3.6 11 4.9 0.85 1.2 1.2 0.32 0.42 700 610 120 140 87 43 310 320 61 75 23 (1.3 2.9

14 5.7 2.5 0.79 0.71 0.48 0.18 630 150 140 120 140 57 270 280 56 64 19 <1.3 1.2 12 2.5 2.4 0.72 0.81 0.42 0.17 640 240 240 260 140 140 240 750 58 58 42 25 1.3 8.5 3.1 1.2 0.64 0.88 0.25 0.26 940 410 140 130 59 96 730 810 51 110 52 (1.3 2.2 11 2.7 1.5 0.51 1.3 0.20 0.28 640 470 100 110 29 72 300 290 23 140 30 <1.3 3.0 9.5 2.8 1.1 0.46 1.8 0.35 0.15 620 250 96 120 32 42 80 150 16 46 <16 (1.3 3.1

9.5 3.o 0.78 0.68 0.92 0.35 0.14 520 120 130 160 72 60 120 200 48 39 (16 (1.3 2.0 9.O 3.2 0.82 0.57 1.0 0.29 0.17 600 160 130 110 66 52 120 240 30 37 (16 2.6 1.6 10 4.4 1.8 1.3 1.1 0.43 0.20 600 290 160 390 110 160 210 280 54 80 (16 (1.3 1.3 10 6,o 1.4 1.0 1.1 0.34 0.27 800 340 160 160 lOO 130 300 680 68 120 38 24 1.2 10 5.6 1.3 0.94 0.94 0.36 0.26 520 250 140 140 110 110 230 190 52 61 26 (1 .3 1.2

9.O 2.o 1.2 1.1 1.5 0.23 0.076 540 (80 180 76 37 60 60 130 21 17 <16 (1.3 1.4 9.5 2.8 1.7 0.55 1.1 0.33 0.061 540 100 230 200 62 12 92 54 27 25 <16 <1.3 1.4 12 7.o 2.5 1.4 1.1 0.46 0.38 1,100 620 200 180 100 120 870 580 52 24 63 3.1 2.7 8.5 2.8 1.1 0.72 0.89 0.24 0.30 510 250 120 82 58 55 310 330 34 100 30 (1.3 1.9 11 4.5 0.87 1.2 0.80 0.38 0.092 550 200 160 170 74 78 37 82 32 27 (16 <1.3 2.3

12 4.1 0.82 0.88 0.92 0.35 0.10 760 300 150 180 78 84 44 77 22 34 (16 (1.3 3.0 11 4.9 1.O 1.O 0.86 0.41 0.17 600 290 200 180 110 44 54 88 42 34 (16 (1.3 2.5 11 4.6 0.78 1.O 0.65 0.40 0.10 520 150 150 150 110 140 37 110 47 21 (16 <1.3 2.2 O.82 0.37 0.23 0.17 310 180 60 40 120 44 88 92 27 23 (16 4.2 0.8 7.4 4.5 0.62 8.5 3.8 1.1 1.4 0.84 0.26 0.10 480 120 88 54 72 110 60 120 33 21 <16 1.9 1.3

210 H. TERA OK A and J. K O BAY ASHI

Table1. Continued.

No. Nam eofriver Place ofsam pling S.S. I.L. Si (ppm) (%) 80 Fuefuki Yam anashi-ken Higashiyatsushiro-gunIsawa-cho Kubonakashim a 25 31 26 81 Fuji Shiz uoka-ken lhar a-gun Kanbara-cho 66 10 29 82 Abe Shiz uoka-shiKadoya 32 4 27 83 Oi Shiz uoka-ken Shim ada-shiOka 49 3 27 84 Tenryu (Lake Suw a) Nagano-ken Okaya-shiAyusawa A yusaw a-hashi 14 34 27

85 Tenry u Nagano-ken Shim oin a-gun Takam ori-m achiShim oichida 25 14 27 86 Tenryu Shiz uoka-ken lw ata-gun Tatsuyam a-m ura 33 10 27 87 Yahagi Aichi-ken Toyota-shiSuigen-cho M eiji-yosui 46 12 25 88 Kiso Nagano-ken Kiso-gun Kisofukushim a-m achi 16 21 29 89 Kiso Gifu-ken Ena-shiOi-cho 18 24 29

90 Hida Gifu-ken K am o~un Shirakawa-cho Sakanohigashi 3.5 27 27 91 Kiso Aichi-kenInuyam a-shi 11 20 28 92 Nagara Gifu-ken Mino-shiHokiw ak i 4.9 29 28 93 lbi Gifu-kenlbilgunlbigawa-cho Kitagata 21 15 27 94 Kushida Mie-ken M atsuzaka-shiToyohara-cho K u.shida-hashi 13 15 27

95 Miya Mie-kenIse-shiKawasaki 7.1 16 26

96 Shingu W ak ayam a-ken Shingu-shi Minam ih izue 13 18 29

97 Hidaka W akayam a-ken Hidak a-gun Kawabe-cho W akano 3.5 16 29 98 Arita W akayam a-ken Arita-gun Kibi-cho 25 16 29 99 Kino W akayam a-ken Nagaigun lwade-cho Upstream Kishi R.joins 17 11 29

101 Yamato Osaka-fu Kashihara-shiKamiichiD ow nstream IshiR.joins 46 20 27 102 Echi Shiga-ken Y~kaichi-shi 16 15 27 103 Yasu Shiga-ken K5gaigunIshibe-ch~ 33 7 28 105 Seta(Lake Biw a) Shiga-ken Otsu-shi 5.8 16 28

106 Uji -fu Uji-shiByodoin Uji~)hashi 9.1 17 22 107 Kizu Ky~to-fu S~raku-gun Kizu-ch~ Izumi-ohashi 19 12 22 108 Yodo(Left bank) Osaka-fu Hirakata-shiDeguchi 110 9 27 109 Yodo (Right bank) O saka-fu Takatsuki-shiKarasakiDownstream Akuta R.joins 42 15 26 110 Muko H yogo-ken Takarazuka-shiH ~:rai-hashiU pstream Sakase R.joins 35 12 26

111 Kak o H yogo-ken Kat~-gun Yashiro-ch~ Daim on ll 17 28 112 Ichi Hyogo-ken Kanzaki~ un Fukuzaki-ch~ Minamitaw ara 7.2 12 26 113 lbo H yogo-ken Tatsuno-shiTatsuno-ch5 Higai 4.6 24 27 114 Yura Kyoto-fu A yabe-shiN anmatsu-cho 8.0 16 27 115 Maruyama Hyogo-ken Kinosaki-gun Hidak a-ch~ Doi 8.2 18 25

116 Sendai -ken Yazu-gun Kawahar a-ch~:Sanuki 9.5 33 27 117 Tenjin Tottori-ken K urayoshi-shiO har a 8.3 42 28 118 Ogamo Tottori-ken K urayoshi-shiK aw ara-m achi 7.1 40 28 119 Hino Tottori-ken Y onago-shiYahata 7.7 32 28 120 Hli Shim an e-ken lzumo-shiOtsu-cho 27 29 28

Concentrations of 21 m etals in the suspended solids 211

A1 Fe Ca Mg Na Ti M n Ba Zn Sr Zr V Cr Cu Ni Co Pb Sn Ag Be (% in ash) (ppm in ash)

11 6.3 1.8 1.6 0.64 0.30 0.12 480 120 110 70 150 85 120 98 38 35 <16 2.0 1.3 10 5.3 1.3 2.2 1.0 0.28 0.12 620 120 120 140 130 89 130 160 31 24 (16 2.3 1.5 8.O 2.9 0.74 1.4 0.66 0.22 0.068 680 100 72 92 70 96 60 120 23 16 (16 <1.3 1.8 9.0 3.4 0.23 1.2 0.84 0.24 0.11 560 100 41 120 86 72 70 85 31 20 (16 (1.3 1.9

6.7 2.9 l.3 0.56 0.40 0.21 0.46 420 420 110 85 63 390 560 400 27 65 (16 15 1.O

9.5 3.2 1.7 2.0 0.68 0.40 0.16 520 110 100 160 100 260 42 220 40 26 (16 <1.3 2.3 8.5 3.1 0.68 1.2 0.58 0.28 0.14 420 <80 75 130 58 120 39 120 30 11 (16 (1.3 1.7 14 3.6 0.50 0.36 0.47 0.33 0.14 500 <80 63 76 42 28 28 15 22 17 (16 (1.3 2.5 10 4.2 0.83 0.86 0.80 0.45 0.096 800 100 130 200 96 71 41 120 38 21 (16 (1.3 2.4 11 3.9 0.90 0.54 1.1 0.32 0.15 640 150 130 150 58 65 50 69 27 29 <16 (1.3 3.7

12 3.6 1.O 0.45 O.83 0.22 0.19 760 400 120 140 50 140 570 170 32 60 (16 (1.3 3.3 11 4.2 0.82 0.46 0.92 0.31 0.18 720 500 120 140 68 150 77 140 47 49 26 (1.3 3.1 10 4.1 1.2 0.72 0.85 0.36 0.16 800 380 170 160 80 200 58 160 36 76 (16 (1.3 2.6

11 5.2 0.68 1.1 0.82 0.56 0.22 600 140 97 140 100 160 65 150 52 83 <16 (1.3 2.4 41 27 <16 (1.3 2.6 11 4.8 1.4 1.O 0.82 0.40 0.11 600 120 140 150 1OO 87 50 94

84 120 68 150 49 34 <16 (1.3 2.8 11 4.8 0.84 1.1 0.67 0.45 0.20 800 130 94 200 82 54 28 25 <16 10 3.3 0.42 0.76 0.81 0.28 0.096 520 140 86 140 80 120 (1.3 2.4 9.5 3.5 0.69 0.64 0.80 0.30 0.096 520 90 110 170 82 170 55 110 24 32 (16 <1.3 2.5 9.5 4.3 0.75 1.2 0.84 0.45 O.11 480 650 100 180 95 120 370 120 52 81 (16 <1.3 2.7 11 4.3 0.76 0.98 0.80 0.44 0.15 560 120 130 140 100 120 61 120 48 21 <16 (1.3 2.8

72 140 58 38 <16 6.4 2.6 13 5.9 1.9 0.70 0.56 0.46 0.50 920 300 220 100 81 1,5OO 10 4.9 0.82 1.1 0.64 0.42 0.11 560 200 71 140 120 120 82 100 43 44 <16 (1.3 2.5 11 4.4 0.46 0.66 0.52 0.32 0.10 640 100 68 150 76 32 110 160 29 22 (16 (1.3 3.3 10 4.2 0.76 0.64 0.48 0.34 0.12 540 340 74 130 74 61 81 72 42 52 (16 1.7 3.1

0.90 1.0 0.90 0.48 0.38 880 290 96 160 130 120 110 210 64 210 20 7.0 3.4 19 6.3 18 7.o 0.80 0.88 0.88 0.52 0.35 880 250 120 140 110 82 68 88 56 46 (16 {1.3 3.3 9.O 2.9 0.31 0.36 0.48 0.28 0.096 560 140 55 170 40 77 52 32 32 17 <16 (1.3 2.2 16 7.o 0.72 1.2 1.3 0.56 0.46 1,000 660 130 190 120 140 190 330 72 120 77 (1.3 3.1 13 3.8 0.64 0.36 0.81 0.23 0.20 680 250 98 160 43 47 54 81 27 58 16 (1.3 3.1

11 4.1 0.71 O.68 0.70 0.29 0.34 640 250 91 150 110 78 80 56 37 38 (16 1.5 2.5 12 3.2 0.75 0.66 0.59 0.23 0.20 560 800 75 110 45 44 150 68 32 70 17 2.7 2.5 12 4.3 0.98 0.96 0.67 0.33 0.18 480 200 120 160 64 110 110 84 44 48 <16 2.0 2.2 12 5.O 0.48 0.92 0.39 0.41 0.34 640 120 68 160 90 1OO 82 150 58 26 (16 (1.3 2.7 15 6.3 1.1 1.7 1.0 0.43 0.29 590 340 130 180 110 260 110 250 60 74 18 2.0 2.9

9.5 4.5 1.5 1.O 0.90 0.37 0.12 600 180 160 140 86 66 120 82 40 95 (16 (1.3 2.7 10 3.6 1.6 0.70 1.1 0.31 0.23 500 190 240 120 62 48 70 47 25 82 (16 (1.3 3.0 12 3.8 1.6 0.78 1.O 0.27 0.22 520 230 210 140 70 73 54 50 25 60 <16 2.8 2.2 9.0 3.7 1.6 0.92 1.2 0.32 0.12 480 160 200 150 82 190 46 86 32 46 (16 <1.3 2.1

11 6.4 1.2 0.94 0.44 0.43 540 90 130 130 86 53 39 20 37 26 (16 31 2.3 1.3

212 H. T ERA OK A and J. K OBA YASHI

Table1. Continued.

S.S. I.L. Si No. Nam e ofriver Place of sa m pling (ppm ) (%)

121 Lake Shinji Shim an e-ken -shi 14 60 19 122 Eno Hiroshim a-ken TakataTgun Y oshida-ch~:Shim oirie 8.4 28 27 123 Saijo Hiroshim a-ken Miyoshi-shiMiyoshi-m achi 49 18 28 124 Basen Hiroshim a-ken Miyoshi-shiMinam ih atajiki-machi 28 17 27 125 G~ Shim ane-ken O chiigun Kawam oto-m achi Kawam ot0-~hashi 14 22 27

126 Takatsu Shim an e-ken Masuda-shiKanda Kanda-hashi 9.8 27 27 127 Saba Yam aguchi-ken H ofu-shiShinbashi-cho Shinbashi 6.6 36 28 130 Ashida H iroshim a-ken Fuchu-shiFuch~-ch~ 15 27 27 131 Takahashi Okayam a-ken Tsukubo-gun Kiyone-m ura 11 28 27

132 Asa hi Okayam a-shiTam agashi 12 28 27 133 Yoshii Okayam a-ken Akaiw a-gun K um ayama-cho Downstream Kong~ R.joins 24 24 27 134 Doki Kagawa"ken Nakatado-gun M anno-ch~ Sumishonishi 6.2 25 28

136 Shigenobu Ehim~~ken Onsen-gun K awauchi-ch5 M inamigata 14 31 28

137 Ishide Ehim e-ken M atsuyam a-shiShukuno-m achi 11 12 25 138 Hiji Ehim e-ken Ozu-shiY unoki 8.4 35 27 139 Shim anto Kochi-ken Nakam ura-shiD om ekiNakam ura-~ohashi 12 26 28 140 Niyodo Kochi-ken Agaw a~ unIno-ch~ K~tani 9.2 26 27 141 M onobe Kochi-ken Kami-gun Tosayam ada-cho lgenoki 7.3 28 27

142 Naka Tokushima-ken Anan-shiKamio no-ch~ 5.2 24 27 143 Yoshino Tokushima-ken Oelgun Yam ak awa-ch~ 6.5 30 27 144 Bansho Oita-ken Saik i-shiKamioka 4.8 48 28 145 Ono Oita-ken Oita-shiShiratakiShirataki-hashi 12 30 27 146 Oita Oita-ken Oita-shi Enokum a Akegawara-hashi 12 37 27

147 Yam ak uni Oita-ken Nakatsu-shiShim omiyanaga 7.5 36 27 148 Onga Fukuoka-ken N~gata-shi Kanroku-hashiU pstream H ik osan R.joins 26 27 23 149 Hik osan Fukuoka-ken N~gata-shiShim ozakai 60 18 22 150 Matsuura Saga-ken Higashim at suura-gun Ochi-ch~ M utabe 16 31 28 151 Honmyo Nagasaki-kenIsahaya-shiHonm y~-m achiTetsud~-hashi 13 34 28

152 Kase Saga-ken Saga-shiKanjin-hashi 12 31 26 153 Kusu Oita-ken Hita-gun A m agase-m achi 26 34 28 154 Oyama Oita-ken Hita-gun O yam a-m achi 12 33 28 155 Chikugo Fukuoka-ken M li-gun Tachiarai-machi 19 30 28 156 Yabe Fukuoka-ken Chikugo-shiOshim a 16 28 28

157 Kik uchi Kum am oto-ken K ik uchi-shiHirose 23 23 26 158 Kik uchi Kum am oto-ken Tamana-shiTakase 26 21 26 159 Shira Kum am oto-shi Oe-machiToroku 42 25 28 160 Midori Kum am oto-ken Shim om ashiki-gunJ~nan-m achi 25 20 26 161 Kuma Kum am oto-ken K um a-gun Taragi-m achiTaragi 24 18 28

Concentrations of 21 m etaisin the suspended solids 213

Al Fe Ca Mg Na Ti M n Ba Zn Sr Zr V Cr Cu Ni Co Pb Sn Ag Be (% in ash) (ppm in ash)

8.5 3.3 1.5 8.O 15 0.15 1.8 460 200 250 60 67 270 150 88 35 53 26 32 1.2 13 4.1 1.2 0.45 0.80 0.23 0.33 560 130 130 100 54 220 47 160 30 30 <16 (1.3 3.4 13 4.3 1.O O.68 O.90 0.34 0.096 520 100 150 150 82 63 38 59 30 41 (16 (1.3 3.0 0.28 0.084 440 80 100 140 65 98 36 56 33 21 (16 <1.3 3.6 14 4.4 0.72 0.62 0.54 13 4.8 1.4 0.76 1.1 0.30 0.10 560 230 190 160 78 180 72 69 38 48 (16 (1.3 3.5

1.9 4.7 14 4.9 1.7 1.O I.7 0.34 0.12 760 230 260 160 96 380 99 210 45 60 18 9.0 4.2 1.6 0.72 0.90 0.28 0.088 440 190 140 110 74 300 140 230 33 60 19 2.0 3.2 13 4.8 1.4 0.68 0.96 0.34 0.12 560 250 130 160 74 90 71 210 36 43 16 <1.3 3.8 13 5.2 2.0 0.82 0.74 0.34 0.27 520 180 180 150 82 120 120 150 45 92 <16 1.4 2.9

14 5.7 1.8 1.1 1.O 0.36 0.31 640 190 170 140 100 92 120 99 43 110 19 2.1 3.0

14 5.3 1.1 0.86 0.80 0.35 0.096 520 230 120 170 100 240 290 190 58 42 (16 (1.3 2.7 9.5 4.7 2.6 0.50 1.1 0.31 0.10 540 190 240 140 52 360 1OO 180 46 62 16 <1.3 2.7 4.8 4.8 O.84 1.O 0.33 0.38 760 250 290 120 62 240 1OO 110 46 50 18 9.2 2.6 9.0

14 6.3 2.4 0.96 1.7 0.55 0.10 540 280 160 70 90 97 45 75 48 30 <16 <1.3 3.6

9.5 6.4 2.5 1.8 1.O 0.60 0.11 480 600 140 180 150 210 260 300 72 57 21 l.5 1.9 9.5 4,o 1.4 0.82 0.95 0.31 0.090 520 120 170 140 82 140 80 110 43 57 <16 (1.3 2.5

9.O 5.3 1.7 1.6 0.85 0.56 0.20 520 140 130 160 110 230 98 180 66 38 16 (1.3 2.5 9.0 4.2 4.6 1.2 0.68 0.36 0.084 560 90 240 140 100 210 87 150 54 52 <16 <1.3 2.4

9.5 5.7 2.7 1.4 0.90 0.40 0.36 6oo 110 220 180 110 300 100 220 80 54 (16 <1.3 2.6 210 170 2.4 9.0 4.6 2.1 1.7 0.85 0.40 0.092 520 180 160 150 96 190 66 60 (16 1.5 10 4.8 5.1 1.3 1.5 0.40 0.23 680 340 280 230 100 420 210 430 64 170 34 16 2.7 11 5.9 1.9 0.88 0.97 0.40 0.10 640 410 210 220 120 180 110 160 56 100 23 2.2 2.9 11 4.6 3.5 0.98 1.4 0.32 0.12 800 250 280 140 110 64 80 78 48 48 (16 2.3 2.4

11 4.3 2.1 0.86 1.1 0.29 0.32 480 1,600 220 140 82 140 5,500 220 68 190 40 10 2.5 9.O 5.7 8.8 0.76 0.61 0.34 1.8 720 270 720 130 100 50 50 150 110 28 16 1.6 2.4

9.O 2.4 10 0.54 0.43 0.31 0.27 560 120 550 160 66 230 100 73 34 20 (16 1.5 3.1 10 6.7 1.6 1.1 1.O 0.39 0.47 540 200 220 170 110 180 65 210 86 31 <16 <1.3 3.1 10 6.O I.6 0.80 O.74 0.44 0.36 520 300 160 240 110 250 78 140 55 44 18 30 2.5

480 150 240 110 74 190 150 130 42 50 (16 <1.3 2.8 13 4.3 1.6 0.76 0.98 0.36 0.11 9.O 4.9 1.2 0.45 O.58 0.30 0.090 480 140 180 150 98 54 55 81 42 40 <16 1.9 2.5 9.5 4.8 1.4 0.54 0.60 0.32 0.40 760 250 200 180 92 180 84 220 50 74 17 2.8 2.3 10 4.5 1.3 0.50 0.62 0.31 0.12 680 170 190 160 82 120 70 140 42 40 <16 2.6 2.3

12 5.7 1.6 1.3 0.74 0.38 O.11 640 140 180 200 110 240 80 160 58 33 16 (1.3 2.6

(1.3 2.8 14 6.6 l.5 0.96 0.67 0.60 0.12 720 110 200 260 140 43 93 100 58 24 <16 14 6.4 1.7 i.1 0.96 0.43 0.11 640 100 200 200 120 130 60 100 50 26 (16 (1.3 2.8 10 8.4 3.O 1.2 1.1 0.41 0.16 5oo 330 300 170 200 110 180 130 72 58 30 (1.3 3.1 14 5.6 l.3 1.2 0.74 O.58 0.29 540 190 160 190 120 150 93 240 54 100 <16 <1.3 2.8 10 4.2 0.87 0. 66 0.94 0.37 0.10 600 200 130 220 84 130 55 lOO 42 40 (16 <1.3 2.8

214 H. T ER AO KA and J. K OBA YASHI

Table1. Continued.

No. Nam e ofriver S.S. I.L. Si Placeofsam pling (ppm ) (%)

162 Kum a Kum am oto-ken Hitoyoshi-shiKamisatsum aze-m achiNishize-hashi 26 24 27 163 Kum a Kum am oto-ken Yatsushiro-gun Sakam oto-m ura Yokoishi 13 36 28 164 Sendai Miyazaki-ken Ebino-shiK y~-m achi 9.4 21 27 165 Sendai Kagoshima-ken Satsuma-gun Tsuruda-ch~ K~shi-hashi 11 22 27

166 Sendai Kagoshim a-ken Sendai-shiCh~~g~-ch~ 18 29 27

167 K im otsuki Kagosh im a-ken K anoya-shiK awanishiTaisho-hashi 79 30 28 168 Kushira Kagoshim a-ken Kim otsuki-gun K ushira-ch~ Katada-hashi 20 31 28

169 Oyodo Miyazaki-ken Miyak onoj~:-shiNishi-machiTakeshita-hashi 22 22 28

170 Oyodo Miyazaki-ken Kitam orokata-gun Takaj~-ch~ Hiw atashi-hashi 21 22 28

171 Honjo (Ayaminami) Miyazaki-ken Higashim orokata-gun Aya-cho A yaminamigawa-hashi 6.2 37 28

172 Komaru Miyazaki-ken Koyu-gun Kij~-ch~ Tak aj~-hashi 6.2 32 28 173 Gokase Miyazak i-ken Nobeoka-shiOse-hashi 7.6 35 27

Table2. Correlation coefficients (r) am ong the am ount of suspended solids, theirignitio n lo ss es , and 19 ele m e nts i n t he ir a sh in w aters a m ples colle cted fr o m th e pri nci pa l166 r ivers an d 3Ia kesin Japan

ss. I.L. Si Al Fe Ca M Na Ti M n Ba Zn Sr Zr V Cr Cu Ni Co Pb Be

S.S. l.OO I.L. 0.33 1.OO Si 0.07 - O.04 1.OO Al - O,04 --0.23 --O 14 I.OO Fe - O.14 O.12 --O.25 0.26 I.OO Ca - 0.32 0.29 --0.29 0.03 0.3I l.OO M g --0.20 - O 17 - 0.30 O lO O 43 0.45 l.OO Na O.17 --O,03 - O.30 O.06 0.28 O.40 0.52 1.OO Ti --O,14 0.07 - 0.04 0.73 0.28 0.07 O.15---0.02 1.OO

M n --O 23 O.18 - O 45 O OO 0.37 O.30 0.33 O.18 --O.03 l.OO Ba --0.21 --O,14 O.Il O 51 0.19 0.27 O 3g 0.58 O 47 0.44 lOO Zn O 34 O 34 - 0 lO 0.04 0.23 O 15 O,~2 0.20 O 02 O 55 O 32 l.OO Sr - 0.20 0.25- -O.19 O.17 0.29 O 77 0.33 0.56 O.28 0.20 O.40 O li l.OO Zr 0.09 0.06 O 07 0.22 0.04 --0.02 - o.04 --0.02 O 36 O 04 0.27 O.35 O,II I.OO V --0.05 0.03- O 06 0.37 0.68 O.38 O,63 0.33 O.54 0.18 O 20 O 08 O,38 O.21 l.OO Cr -~0.34 O.13- O 02 O.12 O 13 0.36 0.26 O.10 O.!5 0.03 0.15 O.07 0.30 - O 02 O.17 l.OO Cu -0.27 0.37 --O.07 --0.04 O.15 O 23 0.20 O II --O 07 O 45 0.13 O.67 O 04 0.03 O ll O.02 1 OO Ni -0.22 0.32---{).17 --O.17 O.lO 0.19 0.30 O.12 - O.06 0.52 O 26 0.55 O 03 O 13 O.16 O.14 0.74 1.OO Co - O.18 O 26 -0.38 ----0.02 0.57 O.32 0.37 0,12 O 14 0.55 O 27 0.40 O 29 O06 0.47 O.15 O 42 O 49 lOO --0.44 Pb 0.40- O.18 0.09 0.23 0.29 0.23 0.29 O 06 0.49 O 28 O 69 O 22 O.]5 O.15 0.06 O.65 0.56 O 40 oo Be --0.28 --0.25 0.05 0.72 O.i8 O 27 0.32 O.65 O.49 O.12 O 61 O IO 0.5l 0.12 O 18 O.18- -O 13 --O.14 0.09 O 13 l.OO

*N um berslargerthan :t0.29indicatesignificantpositiveornegativecorrelation(p = O.1%,n = 169).

Concentrations of 21 metals in the suspended solids 215

A1 Fe Ca Mg Na Ti M n Ba Zn Sr Zr V Cr Cu Ni Co Pb Sn Ag Be (% in ash) (ppm in ash)

13 4.8 0.94 O.70 0.82 0.36 0.088 600 430 120 270 94 170 180 180 48 66 18 (1.3 2.7 11 4.9 1.4 1.2 0.84 0.40 0.12 600 520 140 160 96 140 86 160 46 48 (16 (1.3 2.6 11 6.3 1.4 0.57 0.92 O.33 0.14 580 170 150 180 140 40 70 110 54 34 19 2.0 3.1 12 5.6 1.4 0.70 1.0 0.33 0.13 560 130 150 200 120 40 65 100 47 36 18 (1.3 3.1 12 5.2 1.3 0.57 0.79 0.35 0.10 560 130 150 180 110 83 35 52 45 54 (16 (1.3 2.6

11 4.8 1.6 0.60 1.1 0.33 O.11 500 280 140 180 8S 66 100 60 37 37 <16 2.5 2.8 9.5 5.7 1.4 0.44 1.O 0.28 O.11 5oo 250 150 170 82 110 82 120 40 32 <16 (1.3 2.6 9.O 4.9 1.3 0.44 0.88 0.30 0.11 540 270 140 160 80 44 180 53 35 40 56 <1.3 2.4 10 4.9 1.5 0.54 1.O 0.32 0.11 6oo 220 140 170 92 95 200 130 42 42 140 (1.3 2.5 10 4.4 2.0 1.O 0.98 0.36 0.13 580 300 210 160 94 160 90 160 54 96 32 (1.3 2.8

10 5.0 1.4 0.94 0.96 0.34 0.11 720 240 170 170 110 110 80 120 60 80 24 (1.3 3.2 11 5.3 2.0 0.92 0.98 0.40 0.11 560 400 210 190 110 200 200 160 64 100 30 2.2 2.8

for each elem ent were draw n by m ean s of the Suspended solids and ignition losses The

Tw o Step M ethod (C HURCHILL, 1944; A STM , average concentrations of the suspended solids

1957). The m ean val ue of duplicate an alyses from the 12 different sam ples collected during w as ad opted. O ther details oft his m ethod such a year from each site are show n in Table I. as the appar atus, the full an alytical conditions The highest S.S. value w as 170ppm in the Y u and the accuracy are given by the other reports River (N o. 42) w hich was the m ost acid (pH of the authors (TERAOKA an d K OBAYASHI, 1977; 2.0) ofall the rivers and lakesinvestigated owing

T ERAOKA et al., 1978). to the influence of the K usatsu sulfuric ho t

spri ngs. This w as follow ed by 110ppm in the

C hito se River (N o. 6) and I04ppm in the A NALY TIC AL R ESULTS Ishi kari Riv er (N o. 2) in H okka id~, w hile

T he sam pling places, the am ounts of sus- the low est values were 2.5ppm for the D aiya pended solids, their ignition losses, and the Riv er (N o. 50 ) w hich pr oceeds from Lak e a nalytical results for 21 kin ds of m etal in the Ch u zenji in N ik k~ and 3.2ppm for the K uji ash are show n in Fig. I and T able I. C orrela- River (N o. 39). T he concentrat ion ofsuspended tion coef ficie nts am ong these m etals obtained sol ids in riv er w ater is greatly influenced by the from the an alytical results, relation betw een the am ount of river w ater, but these values seem to num be r of rivers an d concentrations of 19 sh ow th at th e w ater of Japanese rivers is m etal s, and distribution m aps of Cu, Ni, Be and generally clear owing to the he avy rai nfall, and

Sr are show n in Table 2, Figs. 2 and 3, an d Figs. rocky and steep topography of th e land.

T he general average of ignition losses due 4, 5, 6 and 7, respectively.

216 H. T ERA OK A an d J. K OB AY ASHI

60 ~ 2 40 zn cu N~ ~ :Otherdistrlets Top :Otberdistrtts '~: 30 Top :Otherdistricts TO~D Botam:NQrtheastem Botto'n:Nortt,eastem Bottom:NQrtheastem : 20 dbtrlets districts distrlets ~ I E 10 111 ~ Jl~' 1111 L I U Ld O Fe~*~ ~ " rH~-'=~ ,-~= ~~"- Q1or - 1 r III- - -t~ir - l l'~' r ~ r th r ~ 1 T rlll l r - ~h~~~+~

50 2 4Q Pb Mn Co ': 30 TQP :Otherdistrk:ts Top :Otberdistricts ToP :Otherdistrtts BQtQm:NQrtt,eastem Bottom:Northeastem BQtto,1F':N,xtbeastem ~ 20 distriGts disiricts disfrlets ~ ~ 10 ~

O ~- ,-- ~ ~ g g ~ ~ ~ . - - _ g ' ~ ~ I~ ~ 11111l r ~ ~ 11 I n ll - H ~~ l llll- ~ H ~ ~'- s

o Be 2 ~ ' 50 l EastJ~r] '" ~ 40 c* s' c' ~ 3 0 J l _ s ' ~ gg *' * ~ ~20l o ~ III lr ~

II ,~_ _ o _ p * _1' t iF'-'r~-f'Jh_ _ ~* "f~~- ~ ~~ gg ~ g~ ~ - ~~~ ~ v~t Jlym

Fig. 2. The rela tion betw een the concentration of lO m etals (Z n, Cu, Ni, Pb, M n, Co, Ca, Sr, Be, Cr) in ash sam ples of su spended solid and the firequency of their appearance.

70 60

.9)_' 50 Si AI Fe Mg vo 40 ~ 30 E ~ 20

10

f~l- " 'e " I~ I~ e' e'~~ e te ~ o e' e- ~ -~ - o- o -o~~ e " ~ ") - e- ~ ~S; .e .e e " r' kt~ :_: e b' ~ 1" o e 'r - - ~ ~, '~ ~ a i:' ~5 70

20 60

". 50 Na Ti Ba zr v ~o 40 i 3 0 E ~ 20

10

O e .e .e .- ' It_:_ e e e e e e e- -1'~ :_ ~ o b" " e'~5 - iQ ~ ~ ~~ a,~e e ~ ~ ~ ~ ~ ~ e e~ ee r-" "- ~ ~ e e

Fig. 3. The relation betw een the concentrations of 9 m etals (Si, A l, Fe, M g, N a, Ti, B a, Zr, V) in ash

sam ples of suspended solids and the frequency of their appearance.

Concentrations of 21 m etalsin th e suspended solids 217 to organic m atter in the suspended solids in lithosphere, the hydrosphere (Tu REKIAN et al., rivers and lakes was about 25% , w hich is m uch 1967; To RE KIAN, 19 69), theatm osphere(ZOLLER higher than those for rocks and soils. The et al., 1974;IA NTZY et al. 1979), and in the bio- hi ghe st val ue was 6 0% in the bra ckish L ak e s phere (TlpTON et al., 1963; TlpTON et al.,

Shinji (N o.121) which contains a lar ge am ount 1965, B owEN, 1966), because m ost of them of plankton. This w as follow ed by 4 8% in the are essential f or life (SCHROEDER et al., 1971;

Ban sh~ River (N o. 144) and 47 % in Lake V ALKOVIC, 1978).

Tazaw a (N o. 32), w hile, the lowes t w ere 3% It w as found, in this study, that these in the Oi River ( N o. 83 ) and 4% in the A be elem ents are widely distributed in suspended

River (N o . 82). solids (T able I and Fig. 2) and that the con-

A s stated later, significant negative and centrations of 6 of these m etals but Cr and A g positive cor elations w ere noticed (at p = 0.1% ) are m ar kedly high in the N ortheastern provinces between the am ount of S.S. and ignition losses of Japan (Figs. 2, 4 and 5).

(organic m atter) and betw een I.L . and m etals (1) Zn conten t in the ra nge of 80 - 350ppm such as Pb, Z n, Cu, Ni an d Ca. w as found in 68% of the total num ber ofriv ers

and lakes investigated. The highest values w ere

1,600ppm in the Y am akuni River (N o. 147), Trace elements Zn, Cr, Cu,Ni, Co, Pb, Sn and 1,500 ppm in the Y oneshiro R iver (N o. 23) an d Ag These elem ents,classified assiderophile 1,300ppm in the Hazam a River (N o. 24). The an d chalcophile elem ents, are distributed in the

P )~ ~ r' C) -~ Cu ~pm in ash) O･･････- 400 - It300 C *･--･ 20Q - 3eo ~~ ~ e-･-*･- Ioo - Ico ~ l:¥l ~L~j¥-:~'!~ :~ l~ O-･-･-- 75 - ,, :~;"'¥j¥.~_~;'~:A' ~ .4}// O･-･-- so - 74 T il ~'-~~4 IP'~~~'~' ~f O-･-･･- 8- 4, t;~~¥j~'-=~{~.l.~ ~~¥' " '( ' { o ';'1/~Y~:~'fl~~_'~l /Y¥'~'f ;¥C~;~:!"~~L:~ ~~:~iT~~it~;?~)" ~'''' ~ ~ / cr ' /' --~_!f"~t _ f~ i_;~~'~~J '1 ~:~'' ~Ir'~~t'"' ~Or ~ ~, ~'if::' ~' L'~ r7f~ ' L ' 'f> f~r '~r~~_~:Tl)~'~i' ~li~r;711i'~{･ ,:~i{/;:~ :;}~~

lfi"~~~~ / '- ' - ': ' I ="-~1' T ~'~~ ';- ~:' ~~ ~i~~J - - ' ~ " 'r~ h. [" ~ '_'~( I) ~' ~"_- y)~~ ~ ~l¥L '¥~ t~I ~~r~~;~ f( ~-'J ~'~r-:' ~~?~r_"~' ~~: Yt ¥;~;'~1)' r'~~l (' )~_i ~~ ~ IL~ ~;~r"/'; ?~ ;'~;?:~;~ ~ ~ . 4) .~7';~ *!O~~'_'"~: ;'{i~",f_~{(d"~i~:j} rL~':'.;~'t'*':~I~' ~I "~=';'~ ~i~;*'~"}+ '~1 =~~(~sils(;:'~T~~xJ~""~~r"l~';i;^'.~'"~'+I~:~~ I; 'L~'a~ I{/(1~ )b'~:)'f 'C~'!~'~'tL:¥~"t~' i~ ~r~ ' 'h ･ ~, ~ l.<-: ; i { " k/+ .'~ ok l " '_ :, ~. *:' i' ~ ~) ' ~_ _. -' ";{'ii 5~;~~~ ~) vtl:~ )~_;L~J( ;'-¥~. I t{' ~ '~_'~.lJ j" :t~,~~ '(,:~}l" ~;/'()~r';!L)~(,~ ''~'~ ~"'il~ ~r ' : ) (s~-'_~"ri~ '~ '~ ~ _ ~i jt~ *~ ~ -?; ':;L):~+1'~-;f (~j ~ :*7 w ef~ "~~ f ~ ~ ~7'~i{'~- 9?(Jk~ r : ~T:';~~:~(~:fj'~-;'~l:i";~' ;a:(~'.~ (~1~ {~"~~)r ~ ' ;~~/~ ~L !~~;~)1:i~lt~ i7 ~f?~) ~- ~ ~(J1 P ~~ ' ~ ~~~:{~ ~¥~r~~~ ~~ r f ~' ~_?_ ~ * ~Y'~"~)~"~+ ~; " '_ ~~^ -('"~' l_~ f~ 'ss '1_r' { 'L ~ '-~ ; ~~_= ~~' ~~ '* q¥r L)'- ~ ｲ;r' f(~ r- ;'1<. " " r ' / 'f~:~.~ ' . '~'~'~~l:{~h~~b( ;i ') ~e( ¥t/~~* ﾖ~ . o ~ ~!) o <'/~') 'i~F ~' is;~ ''

~1L~' /

Fig. 4. Distribution map of the concentration of Cu in ashes of su spend ed solids of 166 rivers and 3 Iakes in Japan.

218 H. T ER AO KA and J. K OBAY ASHI latter tw o rivers have Cu and Zn m in es along Sarugaishi River (N o. 20) an d the Y oneshir o their upper stream s. On the other hand, Zn River (N o. 23, 24). The lowest were 8ppm in could no t be determ in ed (detection lim it 80 the acid Y u River, 28ppm in the Y ahagi River ppm ) in such inorganic acid w aters as the Y u (N o. 87) and 35ppm i n the (N o.

( N o. 42, pH 2.0),the A ra (N o. 13,pH 3.6), and 166). the A gatsum a (N o. 43, pH 4.3) Rivers an d Lake (4) Ni content in the range of 30 - 300ppm

Tazaw a (N o. 32, pH 4. 4). w as observ ed in 78% of the rivers and lakes.

(2) Cr conte nt in the ran ge of IO - 200ppm The highest w ere I,500ppm in the Sarugaishi w as found in 84 % of the total rivers and lak es. River (N o. 20), 850p pm in the Arao River (N o.

The highest values w ere 1,500ppm in the Y am a- 25) an d 810ppm in the A zusa River (N o. 63). to River (N o. 101) an d 750ppm in the W atarase The low est w ere 15ppm for the Y ah

River (N o. 48). T he lowest w ere 12 ppm in the (N o. 87), 1 8ppm for t he Y u River and 20ppm

J~ganji River (N o. 71) and 28ppm in the Y a- for the (N o. 120). hagi River (N o. 87), w hich fl ows through a (5) C o content in the r ange of 20 - 70ppm granite stre am . w as found in 91% of the w aters. The highest

(3) Cu content in the range of 70 - 250ppm w ere 230, 160 and 120 ppm in the Kita kam i w as fo und in 76 % of the total rivers and lakes. River (N os. 18, 21 and 37). T his riverhas been

The highest were 5,500ppm in the Y am akuni polluted by aci d w aste w ater from the M atsuo

River (N o. 147) an d 1,200 - 1,300 ppm in the sulfur m in e, even though the m in in g operations

/( ~ r P ' ~ ¥' o ) ¥ Ni p in 8sh C l +J)

e-･-･- 33,- 1,,oo ~lIt~ Lf ~ e･･-･･･-230- 320 ' ~}) O-･･--･180- 22e fLVl ! . ~~:-'~/ r O･･･--･13e- ITo (~~ 'r,i+~"if~_*'j*i*;~_.~;"~+~( O･･････ 80- 12e .:-''-~ (-':~ c7 y :(!~,~~{'~~~~:~~~(f~'~'l/ O ..... 1,- 7, _ ;'e ~. 4 ' 1~l i~ ~ ~ ~ ~ "/~l ~;~ 'r-'¥d) ~ ;=~!_*~'~ <'r~_~"T~T~7

'~~~ {~*'lj~"f'(1;~~:O : __ ,~ _ . J~:j /{p ; ' ~ ~ '^ ? ~"o I~ 1!,r ~ _~J)"<~~i;"*'~1;~ ~l~ ~_; ~ r~ _ ~~-~'L-"'_'~h'~~ ~ ,"-'.^= ~ ; ~' r " :_' f'~~'+~' '*'*i~ = * ~!2¥~i~?~ o '.'~~ } P

' 'O /

Fig.5. Distribution m ap of the concentration ofNiin ashes ofsuspended solid sof166 riversand 3IakesinJapan.

Concentrations of 21 m etals in the suspended solids 219

have now been stopped owing to the overp roduc- 31 in the N ortheastern provinces showed an tion of S from the oil refinin g industry . The average value of 32 ppm an d a range of Sn con- low est values w ere less than 16ppm (detection tents from 18 to 66ppm . lim it) in the acid rivers Y u and Agatsum a (N o. (8) A g content w as not detectable in m ost

43). rivers (1es s than I.3 ppm ). H ow ever, rivers with

(6) Pb content in the range of IO - 90ppm noticeable A g content w ere found here and w as found in 84%. The hig hest values w ere there, such as 30 -32 ppm in the Bansh~ River

210ppm in the Uji River (N o. 106) w hich takes (N o. 144 ), Lak e Shin ji (N o. 121), t he H ii Riv er its rise in Lake Biwa, 2 00ppm in the Y on eshir o (N o. 120) and the H onm y~ River(N o. 151). (N o. 24) an d 190pp m in the Y am ak uni R iver s.

The low est w ere less than 10ppm (detection M ajor elem ents Ca, M g and N a, and trace ele- lim it) in the acid Y u River (N o. 42) and the m ent Sr These elem ents ar e easily soluble

Tone River (N o. 45). in w ater during the process of w eatherin g;there-

(7) Sn content w as not detectable (1essthan fore they are w idely distributed in the hydro-

16ppm ) in m ost rivers except in the N orth- sphere and biospher e at high levels. eastern provinces. The highest values w ere (1) Ca content in the range of 0.2 - 2.0%

140ppm in the O (N o. 170), 66 ppm was found in 80% of the total rivers and lakes. in the A bukum a River (N o. 26) and 63 ppm in T he highest w as II % in the Ara River (N o. 53) the Jin z~: River (N o. 72). T w enty rivers out of which fl ow s through a lim estone area. T his w as

¥J ･ C¥¥ l ~ ( O sr ppalW'Idl) d ; ~¥~)

11~-'--~f'e- 72e e -----Ise --'I" iL~~i)~~¥_if ~~ :'1¥ ';1 l~*~ O-- - 1-1 3e = 1 " r '';~~~i'-*~+ /+ O-----tl e'= "I2 0 .~' , _.~lf[ )L.,*'''-~l',^ IP f O-' - -'- 8 ' 0 - 1e o :'i'/r~~;'j,~e' O-'--'- 82 - 7' ~ 1' ~jt~'~ i ) J~~~'(r - :~~/LJ: ) l~ ¥-" . ' J ~L' ~ jL,1 l~l ~~ ; ,:/( r/ ~J~ : ~rh'~ ~ ~ ~~ " '~ ~ ~.;'. v~~/~'/';-;1 , ./_) ~ ~ i-"'- L ~" =- f I )O' .,, ~* ~'L:I)LJ~ ' ~>' O I .t'~;~i :i~~-. ~ : L/ '~ l~~"'__ L'~ /r _'1~{' ::¥~:.~fj~:if~::ﾖj~l~:'

'/ ' / / ¥ , r,~!~i~'~ /~~': ' ( ~ )~ ~~ ~~'~r~r'_ ){ -" '1,~ - ti ' / t :-~ . //h~ ~. , ;~. :¥!:j ¥¥~"~ sl ~I~ '~ ~ _ ~ AhL~ L"x/~TI~r~1~:~~~ ';:y;{~~':i;~J ~~'(/i)~}[~Y~~':~~r~~]~;~'~~~ r~ ~~ ' t - ' ;~:~("" "~ ~ I'~r'" ~(e~~I t ~ ._ ~~~! 4~ ~" j~ ~r f~~;' (!:l~' ;,; !;i:'(; ;- . ~' ~ ~ ~l ry~ t ''1:1~~ ~i~ 1:( ~~'~ ~'s / ~;~f': ~ ~ ~.:P ;'~ J' '- "I' ~ /1 :'t ~l~:~~'~: ~~ 'f_l ~ t f*O ¥ * ~:~-- (~tt"ri9'~~1: ~ _)~,~':!}~~{l!~ i"~~.~ '~i;~'~ ;f :~(_'1~~~.f.~'~'_!~ (f~I~l~t__ｭ '~:;'_~"I' f~" 'I _i_/ /' I " " *'I~~~;~'~ ~ ' 7; ~ ~ "] ~ i ~ ~ '_ ' ~~~;:r ~~ ~_"~:! ~ 11 "~'~:~:~f¥"(F~~l~"~!fl~:~#~~~~ ~ ':~~:~;/ l' 4F't~ e " Y'~~~i 'aV ~O l

Fig.6. Distribution map of the concentration of Sr in ashes of suspended solidsof 166riversand 3IakesinJapan.

220 H. T ERA OK A and J. K OBA YASHI

follow ed by 1.0% in the Hikosan (N o. 149) tions in the suspended solids and those dis- and 0.88% in the O nga (N o. 148) Riv ers, both solved in w ater sam ples w as observ ed.

of w hich ru n through the C hikuh~: coal fields. (3) Na content in the ran ge of 0.4 - 1.1 %

T h e lowest w ere 530 pp m for the acid Y u River w as fo und in 87%. T he highest w ere 15% in

(p H 2. 0) a nd 1 ,700ppm for Lake Tazaw a (N o. the brackish Lake Shinji (N o. 121) and 1.8%

3 2, pH 4.4). in the (N o. 64 '). T he low est w ere

Thus , C a concentration in suspended solids l ess than 0. 1% (detec ti on lim it) in the ac id Y u vary grea tly. It is natural that a significant River and 0.13 % in Lake Inaw ashiro (N o. 57) po sitive cor relation (n = 169, r = 0.70, p = 0.1% ) an d the Kitakam i River (N o. 18). A sig nificant w as o bserv ed b etw e en the Ca concentratio ns pos itive correlation ( n = 169 ,r = 0.72, p = 0.1%) i n suspended solid s a nd those dissolved in the betw e en N a concentration dissolved in w ater w ater sam ples. and that in suspended solids w as noticed as in

(2) M g content in the ran ge of 0.5- 1.0% the case of Ca an d M g. w as found in 72 %. The highest were 8.0% in (4) Sr content in the range of 50 - 250ppm

th e brackish L ake Shinji an d 4.0 % in the Sak~ w as fo und in 92%. A s show n in the distribu-

River . Th e low est,Iike those for Ca, w ere 200 tion m ap Fig. 6, there w ere higher Sr contents

pp m in the Y u River an d I,500pp m in the Lake of river w aters in the w estern half of Japan,

T azaw a. A significan t positive correlation (n = in cluding 720ppm in the O nga (N o. 148) and

169, r = 0.80, p = 0.1% ) betw een M g concentra- 550ppm in the Hikosan (N o. 149) Rivers. T he

~1 C. ~¥V l r- ¥ P O // /' Be ppm in ash) l'/~J e*-･-･-3,0- 4,7 e･----･2･6 - 2･e /i'~-/ ~',*~} O--･-･･2･c- 2･5 rJ; '//~~]~~*/ O--･---{･5 - 1.9 +~( : /~~ O----- t2- 1･4 ' '''/~ L/;'_)f~( /' O --･･･ e - 1･1 t -*',f,~- ) -'_~ .;'i~'.~ lil,~ ~1 (: ~ ,~~] 6';',~ ;'> ~~"L_~_ _ _ i>? -~ . ~; ~ -~~ Lt~ ~l! - 7/ ;/ / - ~l~~*'~ :~' ~r:'i~*f'J ~~ｪS +r) ~~~ :ef;{~/i- 1" ~tl ~ *'* l~ 7~~? /~ ~'L~'{~ /"~~ 'r"ii~ ･/~ r(~( ~~/~ I t ~): () ¥~~ / - ~lr / ~ ,i.'~j.~"~{~rii:_ i'' _ "'''~_T ?~~J{/~("rt/e'~)r~~~!i_~'~~if!+- (~ l'i~~<~~~j{ ~ l_ b.¥ir~**,:/~:;{:.;{*~i~'.. r- ~*¥"*~r ~'V ~ -1~~'~?i~~~~ ~~'~:~!./'_~}i{f~'iJ; ,.~ C~' ~: ~" rj/(~(.fd i~~~ ~ 4) ~!~l~;~i { ' __'_/ ~(;~":~r~i~f' ii~~*~! ~'~:~4 ~:_~6~{(!'':~~ :~:r~ L"~ k'~ l;~~,1j~:y f~~i: {/~U ~/)~f ) ~ ~~~~f $~"~'L~~ ;L~L~)':~ ~ i~?~{j~{~~'{r~:~ " ']'~-i ~ ~~ :- ~ ~ ._~i~;J._:~;~:' ~ ~'~~ .~ ::L~'.:~ a~_~;~;1;r_'::j~_:; 7 " a' '; ';^";'~~t'"~ ;'~'~~'/l;";'~ " 'qf*:~',-' ({p ~ nL~ ~.~/~';'fh ~PJ¥1)~1/ 1~" (~(?=:'~ ~ ~'~ 'i ~ j?~~~ t_ '~ '~{~ ~~:~ ~ -:~:r~T'~(/ ¥~ '~~eT~l J ~' ' ^' ' ~'~l"';'j')Y~ ~i~';~<'~"i'* :'~--7* ' ^ '~ ~. ~:;

~O l

Fig. 7. D istribution m ap of the concentration ofBe in ashes ofsuspended solidsof 166 riversand 3IakesinJapan.

Concentrations of 21 m etals in the suspended solids 221

Table 3. The average concentrations of 19 elements in ash of suspended solids com pared with those in the continental cru st proposed by TA YLOR (1964)

Elem ent (A) Suspended solids (B) Continental (A)/(B) (m ean :~S.D.) crust (ppm in ash) (ppm ) Pb 57 i 38 12.5 4.6 Zn 270 ~ 220 70 3.9 Cu 190 ~ 220 55 3.5 Ni 230 i 210 75 3.1

M n 2,100 ~ 1,400 970 2.2 Co 47 ~ 23 25 1.9 Ba 570 ~ 150 425 1.3 Cr 120 ~ 97 100 1.2

Al 100,000 ~ 23,000 82,300 1.2 Si 270,000 i 18,000 281,500 0.96 Zr 150 i 83 165 0.91 Fe 46,000 ｱ 16,000 56,300 0.82

Be 2.1:!: 0.83 2.8 0.75 V 88 i 29 135 0.65 Ti 3,200:i: 1,000 5,700 0.56 Mg 9,300 i 6,700 23,300 0.40

Sr 140 i 78 375 0.37 Ca 14,000 ~ 10,000 41,5OO o.34 Na 8,000 ｱ 2,800 23,600 0.34

10w est w ere less than 32ppm (detection lim it) and it w as follow ed by 18% in the Kizu (N o.

in the Y u River and Lake Inaw ashiro (N o. 57). l07) and 16 % in the Y odo (N o. 109) Rivers.

These 3 rivers belong to the sam e river system . As Sr is a soluble elem ent,a positive correlation The low e st v alues w ere 2.0% for the ac id Y u (n = 169, r = 0.66, p = 0.1% ) betw een the Sr Ri ver and 2.9% f orthe Kitakam i River(N o. 1 8). concentration in water an d in suspended solids (3) Fe content in the ran ge of 2. 0 - 7.0 % w as noticed. w as fo und i n 96 % . The highest w as 15% in the

M ajor elem ents Si, Al, Fe, Ti and M n, and trace Kitakam i River (N o. 18), and it w as follow ed elem ents Ba, Zr, V and B e These elem ents by 11 % in the A gatsum a River (N o. 43). T he

ar e classified geochem ically in alithophile group. form er has been affected by the w aste w ater

(1) Si content in the range of 25 - 29 % wa s from a pyritiferous m ine and the latter by hot

found in 92% of the total num ber of the rivers springs in volcanic areas. T he low est values w ere

a nd lakes. T he highest w as 35% in the Y u O .21 % for the acid Y u River (N o. 42, pH 2.0)

River, followed by 31 % for Lak e Tazaw a an d and 0.91 % for Lake T azaw a.

Lak e Inaw ashiro (N o. 57). A l of these are acid (4) Ti content in the range of 0.25 - 0.45 %

w aters influenced by hot sulfuric spri ngs. T he w as found in 60%. The highest were 0.60%

1 0 west val ues w ere 19 % in t he Kit akam i River in the Hiji River (N o. 138) an d the K ik uchi

( N o. 18) in w hich a m ar kedly high Fe content River (N o. 157). T he low est were 200ppm in

w as o bserv ed, 19 % in Lake Shinji, 22 % in the the Y u River and 660pp m in Lake Tazaw a,

Ara River (N o. 53)in w hich Cais abundant,and both are influenced by sulfuric acid hotsprings.

22% in the Hi ko san Riv er (N o. 149). (5) M n contents in the range of 500 - 2,500

(2) A1 content in the ran ge of 8 - 14% was ppm w as found in 67 %. T he highest w ere 1.8%

found in 90 %. Th e highest was 19 % in the Uji in the O nga River (N o. 148) in fluenced by coal-

Riv er (N o. 106 ) w hich ar is es from Lake Biw a, fields, and in brackish Lake Shin ji (N o. 121).

222 H. T ERA OK A and J. K O BAY ASHI

These were follow ed,in order, by the Y oneshiro appearance, Si in the range of 25 - 29% , A 1 8-

River (N o. 29, 0.74% ), the A r ao River (N o. 25, 14%, Fe 2 - 7%, Ca 0.2 - 2.0%, N a 0.4 - 1.1%,

0.64% ) and the K arasu R iver (N o. 46, 0.58% ). M g 0.5 - 1.0%, Ti 0.25 - 0.45 %, M n 0.05 -

The lo w est values were foun d in solids sus- 0.25% , B a 400 - 900ppm , Zn 80- 350ppm, Ni pended in acid w ater; 28ppm in the Y u, 170 30 -300ppm , Sr and Zr 50- 250ppm , Cu 30 - ppm in the Agatsu m a (pH 4.3) and 390ppm 350ppm , Cr 10- 200ppm , V 40- 140ppm, Pb in the Ara (N o. 13, pH 3 .6) Riv ers. H ow e ver, 10 -90ppm , C o 20 - 70ppm and Sn 20 - 50ppm in general, high er M n contents were observ ed w ere the m ost num erous of all the sam ples, in t he N ort heastern provinces asshow n in Fig. 2. except for Sn w hich w as detected only in the

(6) Ba content in the ran ge of 400 -900ppm N ortheastern provin ces (Figs. 2 and 3). w as fo und in 91% of the total num ber ofrivers As can be seen in Table 3 w hich shows the and lakes. The highest w ere I,100ppm in the average values of elem ents contained in sus-

Jin z~: River (N o. 72), and 1,000pp m in the pended solids com pared with those in the con-

Tadam i River (N o. 59) and the Y odo River(N o. tinental cru st proposed by T AYLOR (1964),the

109). T he low est were 130ppm in the Y u River concentrations of m inor elem ents su,ch as Pb, an d 140ppm in the Agatsum a River. Zn, Cu, Ni and M n are found to be m arkedly

(7) Z r content in the range of 50 - 250ppm high, w hile N a, Ca, Sr and M g arelow. w as found in 89% of the to tal num ber. The It w as found that (1) a positive correlation highest were 880ppm in the H az am a River(N o. exists betw een the am ount of suspended solids

24), along the upper stream of w hich a zinc (S.S.) in river w ater and the size of par ticles m in e is lo cated, an d 440ppm in the Heii River tested by scannin g electron m icroscopic m ethod,

(N o. 17) and the A bukum a River(N o. 27). The and (2) that a positive correlation exists at p = l ow est w ere less than 16 ppm (de tection lim it) O.I% betw een I.L. an d the concentrations of in the Y u River and 22ppm in Lake Inaw ashiro. Pb, Zn, Cu and N i w hich are abundant in sus-

(8) V content in the range of 40 - 140ppm pended solids as stated above (see T able 2). w as found in 92%. The highest were 200pp m It is interesting that, in com par ing the con- in the Sak~ (N o. 56) and Shira (N o. 159) Riv ers centrations of 21 elem entsin fractions of var ious w hich are influenced by volcano es. The lowest size from sedim ents collected at 6 points frorn were less than 16ppm (detection lim it) in the the estuary of the Takah ashi River (N o. 131 in

Y u River and 19ppm in Lake Inaw ashiro. T able I), the ignition loss and m in or elem ents

(9) The distrib ution of Be concentration, as such as Pb, Zn, Cu, Ni and M n w ere found to be show n in Fig. 7, happened to divide Japan in to m arkedly enriched in finer particles (12- 0.4 tw o halves roughly bo unded by the Tenry ~:(N o. pm ). T herefore, it can be understood that the

85) and the Sai (N o. 65) Rivers. B e co ntent in finer the particles of suspended solids, the the w estern half w as found to be about tw o greater the quantity of organic m atter and Pb, tim es as great as that in the eastern half. The Zn, Cu, Ni and M n that they contain. O n the highest va lues w ere 4.7ppm in the other hand, the concentrations of soluble ele-

(N o. 126), 3.8ppm in t he (N o. m ents such as C a, N a, Sr and M g were found to

130) and 3.7 ppm in the K iso River (N o. 89). be m arkedly low er in suspended soli.'ds and

The lowest were less than O.4 ppm in the inor- estuary sedim ents than in the continental crust. gan ic acid rivers and lakes w hich are distributed This m ust be due to the results of w eathering in the eastern parts of Ja pan. an d solution.

F in ally, the concentrations of Si, A1, Fe, Ti and Zr, w hich are classified in alithophile group, DISCUSSION A ND C O NCLUSION w ere not correlated w ith I.L. or particle size 1. A s to the relation betw een the con- and agreed approxim ately with the average centrations of m etals and the frequency oftheir values of the continental cru st (see T able 3) as

Concentrations of 21 metalsin the suspended solids 223

Table 4. Com parison of concentrations of 21 elements in fractions of various size fr om estu a,y sedim ents and suspended solids in the (N o.131 in Table 1)

Suspended Sedim ents,se parated by sieving solids Diam eter of >15Opm 150- 74~m 74- 37pm 37 -12ptm 12 -0.4,lm <74ktm sediments Distribution 64% 21% 7.7% 6.0% O.85% lgnition 6.9% 8.6% 10.0% 11.4% 27.7% loss 1.0% Si 330,000 290,000 290,000 280,000 270,000 270,000 A1 82,000 120,000 130,000 140,000 140,000 130,000 Fe 24,000 48,000 50,000 58,OOO 58,000 52,000 Ca 7,800 11,OOO 10,000 6,800 5,000 20,000

Mg 4,400 11,OOO 12,OOO 14,000 13,OOO 8,200 Na 13,000 9,800 9,100 8,600 7,000 7,400 Ti 1,700 4,100 4,100 4,200 3,400 3,400 Mn 510 980 990 970 1,000 2,700

Ba 610 500 510 540 480 520 Zn 35 120 130 160 170 180 Sr 140 130 140 120 110 180 Zr 89 160 140 110 77 150 V 48 100 110 100 110 82 Cr 45 79 100 120 110 120 Cu 8 45 46 62 72 120 Ni 28 55 59 78 89 150

Co 21 33 35 38 38 45 Pb <10 25 30 31 33 92 Sn <16 <16 <16 <16 <16 <16 Ag <1.3 <1.3 <1.3 <1.3 <1.3 1.4 2.2 2.5 2.7 2.7 2.9 Be 1.5 did those in the sedim ents in the estuary ofthe Al and Ti also showed a tendency to be

Tak ah ashi River. abundant in the w estern part of Japan, an d, as

2. T he concentrations of M n, Zn, Cu, Ni, show n in T able 2 and Fig. 8,positive correlations

Co, P b and Sn ar e m ar kedly high in the N orth- at p = 0.1% (n = 169) betw e en Be an d Al (r = eastern provinces (see T able I and Figs. 2, 4 and 0.72), Al and Ti (r = 0.73), and Be and Ti (r =

5). T his m ust be due to the higher con cent ra- 0.49) w ere found. ti ons of these m etals distributed in geologic N a, B a and Sr (Fig. 6) also show a tendency form ations in this section of Japan as w ell as to to be abundantin the w estern provinces. the influence of m an y copper an d other m ines. 4. In the Y u River (N o. 42, pH 2.0) af-

In addition, as show n in T able 2, positive cor- fected by K usatsu sulfuric hot sprin gs, w hich r elation s at p = 0.1 % (n = 169) ar e observ ed was the m os t aci d of all the rivers an d lakes am on g 6 of the above elem ents but Sn. in vestigated , concentrations of all m ajor ele-

3 . A s show n in Fig s. 2 and 7, the di stribu- m ent s, such as A l, F e, Ca and M g, except Si tion of Be happened to divide Jap an into tw o and m in or elem ents such as Pb, Z n and C u halves roughly bounded by the Tenry ~~ River show ed the low est values, w hile this river had

(N o. 85) an d the (N o. 65)in the center the highest value for Si. O ther in organic acid of Japa n. A nd the histogram of Be in each w aters,i.e.the A gatsum a R iver(N o.43, pH 4.3), half show ed a pattern ofalm ost norm al distribu- the A ra River (N o. 13, pH 3.6), an d Lake Taza- tion in the range of I.O - I.5ppm in the eastern w a (N o. 32, pH 4.4) and Lake Inaw ashiro (N o. half and 2.5 - 3.0ppm in the w estern half. 57, pH 4.5) also show ed about the sam e tend-

224 H. T ERA OK A and J. K O BAY ASHI

ency. This phenom enon m ust be due to the K OBA YASHI, J. (1971) M izu no kenko shindan (A health exam ination of w ater) (in Japanese). 44- 59. acid soluble nature of m ost m etals except Si, w hich rem ains relatively concentrated in the lw anam i, T okyo. K OBAY ASHI, J. (1971) R elation betw een the "itai- suspended solids. itai" disease and th e pollution of river w ater by cadm ium from a m ine. A dvances in water pollution research (ed. S. H. JENKlNS). I- 25, 1- 7. ~'?: ~ / _ K OBA YASHI,J., M O RII, F.,M U RAM OTO,S., N A K ASHIM A, ~4 g 08 S., U RAK AMI, Y., NISHIZAKI, H., TER AO K A, H.,and ~3 ~.!0,6 'i 's'*: '/ N A G AO, N .(1976) Chem ical investigation on the ~~~'~~: /'' h e.4 :;iie't_f ~ ,:~i;~"' 2 quality and characteristics of river w aters in th e 0,2t Tohoku district. N ogaku K enl~ru 55, 103 -144. 15 ' Y'F,r-* K OBA YASHI,J., M OR H,F., M U R AM OTO,S.,N AK ASHIM A, ol0l8 / 1 oloe S., U RA KA MI, Y., N ISHIZA KI, H., T ERA OK A, H.and o,8 a" ol04o N A G AO,N .(1978) Chem ical investigations on the lo98e=~1'2+15109AI l IogTi=-17*1.2~gAl n=166'rsso72 n=~6g r=0.73 quality and characteristics of river w ater in the 002 H okkaido district. N ogaku K enky u 57, 17- 54. Ll'~t-11'-IT~ ~~i~l L4 6 a Is 15 20 2 a G 8IQ t5 :o K OB AY ASHI, J. (1979) Pollution by cadm ium and the AI('1L, AIt,Ge itai-itai disease in Japan. Toxicity of H eavy M etals in the E nvironm ent (ed. F. W . O EH M E).Part I.199-- Fl~. 8. Correlation between Be and A l, and Ti and Al 260.M arcel Dekker,Inc., N ew Y ork and Basel. M ASIRONl, R., PISA, Z. and C LA YTO N D. (1979) in ashes of suspended solidsin watersamplescollected from 166 rivers and 3 Iakes in Japan. M yocardial infarction and w ater hardnessin the W H O m yocardial infarction registry netw ork. B ull. Wld. H lth. Org. 57, 291- 299.

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Concentrations of 21 m etals in the suspended solids 225

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