Geochemical Journal, Vol. 14, pp. 203 to 226, 1980 203

Concentrations of 21 metals in the suspended solids collected from the principal 166 rivers and 3 lakes in

HISAYUKI TERAOKA and JUN KOBAYASHI

Institute for Agricultural and Biological Sciences, University, 710, Japan

(Received July 21, 1980; Accepted October 20, 1980)

In the analysis of natural water, it would be interesting to determine small but significant quantities of trace metals which are concentrated in suspended solids, since some of these metals, derived from geologic formations, mines and industries not only influence the environment for men and animals, but will also help us in tracing metallic resources. Taking advantage of the nation-wide chemical investigations conducted by JUN KOBAYASHI,FUJI MORII and coworkers on various constituents dissolved in the principal Japanese rivers and lakes, the present authors could analyze major and minor metallic elements in the suspended solids by the emission spectrographic method. The following are the results obtained: (1) Markedly higher concentrations of minor elements such as Pb, Zn, Cu, Ni, Mn and Co were found in the suspended solids than in unpolluted soils or in the continental crust reported by TAYLOR (1964). (2) The concentrationsof Mn,Cu, Ni, Pb and Sri were found to be markedlyhigh in the Northeastern provinces. This must be due to the higher concentrationsof these metals distributedin geologicformations in this section as well as to the influence of many copper and other mines. (3) The distribution of Be happened to divide Japan into two halves. It is markedly lower in the eastern half. Positive correlations were also observed between the concentrations of Be and those of Al and Ti. (4) Owingto the extremely acid nature (pH 2.0) of the Yu River(No. 42) in the system, caused by the Kusatsu hot sulfuric springs,the concentrationsof all metals except Si showed the lowest values,while Si had the highest value. Other inorganic acid rivers which are distributed mostly in the Northeastern provinces, i.e. the (No. 43, pH 4.3) of the same system and the Ara River (No. 13, pH 3.6), and acid lakes, i.e. (No. 32, pH 4.4) and (No. 57, pH 4.5) showed about the same tendency.

INTRODUCTION water samples collected once a month, 12 times a year, from more than 500 selected sites along Information on the amount of chemical con the principal rivers and lakes throughout the stituents dissolved in river water is important whole territory of Japan (KOBAYASHI,1951; not only for studying the process of weathering KOBAYASHI,1960), and moreover from other and erosion of the surface of the earth, but also Asian countries (KOBAYASHI,1959). for a wide range of human activities including In this study covering various geological agriculture, industry, fishery and hygiene. As features, KOBAYASHInoticed striking correlations early as 1941 when the water had as yet hardly between (1) the distribution of Si02 content been polluted, KOBAYASHI,one of the authors, dissolved in river or irrigation water and the SiO, started a nation-wide chemical investigation, content in rice straw by districts on the one hand continuing for several decades, on the dissolved (KOBAYASHI,1967; KOBAYASHI,1971), and (2) constituents, such as Ca, Mg, Na, K, HCO3, the chemical composition of river water and SO,, Cl, SiO2, PO,, NO,, NHL and COD in the death-rate from apoplexy (stroke) which has 204 H. TERAOKAand J. KOBAYASHI

been the leading cause of death in Japan, on river water for such purposes as irrigation of rice the other (KOBAYASHI,1957). After this second fields, industry and tap water, but also for finding, many articles have been published show avoiding man-made pollution caused by waste ing an inverse relationship between the hardness water from industries and cities downstream. of local water supplies and mortality rates from In the actual sampling at the selected places, cardiovascular diseases in various countries care was taken to collect the water from the (SCHROEDER,1960; MASHIRONIet al., 1979). midstream of the river, where the water moves Further, by means of emission spectro deeply and rapidly. As a rule, the water samples graphic analysis, KOBAYASHIfound in 1960 the were simultaneously collected once a month, first clue to the cause of the "Itai-Itai" disease 12 times a year, from the selected 169 sites a very strange and miserable osseous disease along the principal rivers and lakes. The sampl inducted by chronic poisoning with cadimium ing period continued for three years from which was released into a river from the biggest October 1972 through September 1975, as zinc mine of Japan around the time of the Japan was divided into three parts for analytical Second World War (KOBAYASHI,1971; KoBA purposes. YASHI, 1979). After this finding the present It was fortunate that, in selecting the places authors made further applications of this method and collecting the samples, special cooperation which permits simultaneous determination of could be obtained from 36 prefectural govern many kinds of metal even with a very small ments in response to KOBAYASHI'srequest to quantity of sample ash (TERAOKAand KOBAYA support this nation-wide investigations of waters. SHI, 1977; TERAOKAet al., 1978). From October 1972 to September 1975, Analytical procedure The suspended solids when a second series of nation-wide chemical were filtered out with a small piece (3.6cm investigations of river and lake waters was diameter) of Toyo filter paper No. 6 fixed in a carried out by JUN KOBAYASHI,Fuji MoRHand filtering funnel, dried in a drying oven at 105°C, coworkers to make clear the chemical influences and measured for the dry weight of the solids. due to the marked pollution in the 1970's The 12 solids obtained from each site during a (KOBAYASHIet al., 1976; KOBAYASHIet al., 1978), year together with the filter paper were mixed the authors took advantage of this survey to and ashed at 450°C. After measuring the determine the concentrations of 21 metals (Si, weight, the ash was analyzed by emission spec Al, Fe, Ca, Mg, Na, Ti, Mn, Ba, Zn, Sr, Zr, trographic method. This analytical method is V, Cr, Cu, Ni, Co, Pb, Sn, Ag and Be) in ashes of one of the most appropriate methods for analyz suspended solids obtained from water samples, ing various metals in suspended solids, because it which were collected from 169 sites along the makes possible the simultaneous determination principal rivers and lakes of Japan. The results of more than 20 elements with only a small thus obtained are reported in this paper. quantity of sample ash. Sample ash mixed with carbon powder con taining the internal standards (Pd and Gel was EXPERIMENTAL burnt until the mixture volatized in a do-arc Collection of samples The sampling places generated in an argon-oxygen atmosphere which shown in Fig. 1 and Table 1 were selected with is effective in eliminating the CN-bands and preference for those parts of the rivers where decreasing the background. The gap between they are about to enter the downstream plains the electrodes was kept at 4mm during the after running through the mountainous upper burning time, and only the middle part (1 mm) and middle stream areas. In Japan, where the of the arc was passed through on the spectro topography is steep and rivers run swiftly, these graph slit by midway focusing method. A 7 places are important not only in utilizing the step rotating sector was used. Working curves Concentrations of 21 metals in the suspended solids 205

X "a9 rCA~r '_

P, lY -\

n

C\

FId

r J J i

1 0

~,r a.

:-,~ O n

Fig. 1. Sampling places of the principal 166 rivers and 3 lakes in Japan 206 H. TERAOKA and J. KOBAYASHI

Table 1. Places of sampling and analytical results of suspended solids (S. S.) collected from the principal 166 rivers and 3 lakes in Japan, for three years from October 1972 through September 1975. Concentrations of S. S., I. L. and 21 metals are the average of 12 different samples collected once a month, 12 times a years.

I.L. Si No. Name of river Place of sampling S.S. (Ppm) (%)

1 Teshio Nayoro-shi Nayoro-o hashi 36 25 25 2 Ishikari Hokkaido Kawakami-gun Aibetsu-cho Nakaaibetsu 104 17 26 3 Ishikari Hokkaido Fukagawa-shi Midori-machi 41 27 26 4 Sorachi Hokkaido Akabira-shi 101 25 29 5 Ishikari Hokkaido -shi Upstream the Chitose R. joins 81 21 28

6 Chitose Hokkaido Ebetsuchi Hashi of National road 12 110 16 29 7 Toyohira Hokkaido -shi Toyohira-ku 81 27 26 8 Tokachi Hokkaido Kasai-gun Memurocho 61 37 26 9 Tokachi Hokkaido Nakagawa-gun Toyokoro-cho Moiwaohaslu 58 35 28 10 Tokoro Hokkaido Tokoro-gun Tanno-cho 2-ku 79 29 26

11 Iwaki Aomori-ken Nakatsugaru-gun Iwaki-machi Nyoraise 22 22 25 12 Hira Aomori-ken Minamitsugaru-gun Owani-cho Shukugawara 25 31 25 13 Are Aomori-shi Takada 52 37 28 14 Oirase Aomori-ken Towada-shi 11 35 29 15 Mabuchi Aomori-ken Hachinohe-shi Kushibiki Kushibiki-hashi 23 31 26

16 Kuji Iwate-ken Kuji-shi Okawamecho Mitsuka-machi 3.2 41 25 17 Heii Iwate-ken Shimoheu-gun Niisato-mura Moichi 4.1 31 26 18 Kitakami Iwate-ken -shi Tatemukaicho 17 52 19 19 Iwate-ken Morioka-shi Ota 14 30 26 20 Sarugaishi Iwate-ken Waga-gun Towa-cho 5.4 42 25

21 Kitakami Iwate-ken Kitakami-shi Tachibana 16 33 26 22 Isawa Iwate-ken Isawa-gun Isawa-cho 9.6 21 25 23 Kitakami Miyagi-ken Tome-gun Nakadacho 21 31 27 24 Hazama Miyagi-ken Kuriharagun Wakayanagicho Kawaminami 18 23 28 25 Eai (Arao) Miyagi-ken Tamazukuri-gun Iwadeyama-machi 9.1 30 28

26 Abukuma -ken Koriyama-shi Yasuhara-cho 20 40 26 27 Abukuma Miyagi-ken Igugun Marumori-cho Marumori-ohashi 21 27 28 28 Shiraishi Miyagi-ken Shibata-gun Ogawaracho Oya 26 33 27 29 Yoneshiro -ken Kazuno-shi Towadanishikigi 14 35 27 30 Yoneshiro Akita-ken Kitaakita-gun Takanosu-machi 9.5 31 26

31 Omono Akita-ken Yuzawa-shi Yuzawa 34 28 26 32 Lake-Tazawa Akita-ken Senboku-gun Tazawako-machi Obonai 9.7 47 30 33 Omono Akita-ken Senboku-gun Nishisenboku-machi Kariwano 28 23 26 34 Koyoshi Akita-ken Yuri-gun Yuri-machi 33 27 27 35 Haguro Yamagata-ken Yonezawa-shi Hanazawa 34 22 28

36 Mogami Yamagata-ken Murayama-shi Nishgo 30 40 27 37 Mogami Yamagata-ken Akumigun Matsuyama-machi Yamadera 74 26 26 38 Aka Yamagata-ken Tsuruoka-shi Daihoji-machi 12 30 26 39 Kuji Ibaragi-ken Naka-gun Omiya-machi Tomioka-hashi 11 20 26 40 Naka Ibaragi-ken Hgashiibamgigun Katsura-mum Akasawa 15 24 27 Concentrations of 21 metals in the suspended solids 207

At Fe Ca Mg Na Ti Mn Ba Zn Sr Zr V Cr Cu Ni Co P6 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 9.0 3.9 0.93 0.80 0.87 0.35 0.14 620 110 110 150 100 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 0.68 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 (1.3 1.8 9.0 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 9.0 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 0.34 650 560 100 190 75 66 350 590 49 100 53 (1.3 1.2 6.9 3.8 OS3 0.44 0.43 0.14 0.04 300 (80 49 33 120 44 100 180 27 36 (16 (1.3 0.7 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 8.0 4.5 1.6 0.71 0.64 0.32 0.22 390 220 110 100 110 60 270 440 47 67 26 6.7 1.2

6.9 2.9 1.7 1.0 0.45 0.35 0.15 480 450 130 140 74 100 840 710 26 170 45 (1.3 1.3 8.0 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 9.0 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 1.1 8.0 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 6.0 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 55 260 250 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 5.0 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 0.73 0.33 0.48 550 880 120 440 120 90 250 360 52 81 34 3.3 1.3 13 7.0 1.5 1.1 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 0.30 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 1.1 0.64 0.28 0.50 680 1,200 95 120 91 44 1,100 510 57 200 32 1.4 1.3

9.0 3.6 1.1 0.56 0.65 0.25 0.23 610 300 99 78 62 44 330 250 28 120 18 <1.3 1.4 6.4 1.0 0.17 0.15 0.17 0.07 0.02 200 (80 32 47 22 55 230 390 36 66 (16 (1.3 0.5 8.0 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 0.16 500 110 92 130 67 72 210 370 38 53 (16 (1.3 1.1 11 78 12 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 9.0 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 1.0 1.1 0.72 0.36 0.30 540 390 140 140 97 66 590 460 97 170 35 (1.3 1.1 9.0 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 9.5 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 0.9 208 H. TERAOKA and J. KOBAYASHI

Table 1. Continued.

I.L. Si No. Name of river Place of sampling S.S. (PPm) (%)

41 Tone Gunma-ken Tone-gun Showa-mura Downstream Katashina R. joins 4.5 34 26 42 Yu Gunma-ken Agatsuma-gunKusatsu-machi Before neutralized by lime 170 29 35 43 Agatsuma Gunma-ken Agatsuma-gunNaganohara-machi 59 34 27 44 Agatsuma Gunma-ken Shibukawa-shi Nanmoku 34 33 27 45 Tone Gunma-ken Maebashi-shiIshikura-machi Gunma-ohashi 24 2R 27

46 Karasu Gunma-ken Tano-gun Shin-machi Kawagishi-machiIwakura-hashi 16 29 26 47 Tone Gunma-ken Ora-gun Chiyodamum Kaminakamori 19 24 26 48 Watarase Tochigi-ken Ashlkaga-shiTori 2adrome 15 25 27 49 Tone (Edo) Saitama-ken Kitakatsushikagun Satsute-machi Nishisekiyado 33 24 27 50 Daiya Tochigi-ken Nikko-shi Shimokawahara 2-5 42 30

51 Kinu Tochigi-ken Shioya-gun Takanezawa-machi H shakuji 8.2 33 27 52 Tone Chiba-ken Sawara-shi Sawara 23 21 30 53 Ara Saitama-ken Osatogun Yoril-machi Yorii 9.1 14 22 54 Tama Tokyo-to Nishitama-gun Hamura-machi Hamura 36 12 27 55 Sagami Kanagawa-ken Sagamihara-shi Isobe 23 14 26

56 Sako Kanagawa-ken Ashigarakami-gun Kaisei-machi Yoshidazima 54 14 28 57 Lake-Inawashiro Fukushima-ken Yamagun Inawashiro-machi Joko 8.3 37 31 58 O Fukushima-ken Kawanuma-gun Aizubange-machi Miyako-hashi 14 40 27 59 Tadami Fukushima-ken Onumagun Mishimamachi Miyashita 7.3 26 26 60 Agano Ntigata-ken NBtsu-shi Nanoka-machi 14 25 28

61 Chikuma Nagano-ken Minamisaku-gun Usudamacbi Usuda-hashi 28 20 29 62 Chikuma Nagano-ken Koshoku-shi Chikuma-hashi 23 26 26 63 Azusa Nagano-ken Matsumoto-shi Shimauchi 6.2 40 26 64 Takase Nagano-ken Omachi-shi Taira Upstream Kashima R. joins 18 13 28 64' Takase Nagano-ken Omachi-shi Taira Mixed with water from Lake Aoki 12 35 28

65 Sal Nagano-ken Kamiminochigun Shinshushin-machi 42 16 28 66 Chikuma Nagano-ken Iiyama-shi 37 20 30 67 Uono Niigata-ken Kitauonumagun Horinouchi-machi 31 27 27 68 Shinano Niigata-ken Ojiya-shi Ojiya 20 32 28 69 Shinano Niigata-ken Nakakanbara-gun Kosudo-machi Suits 37 24 28

70 Kurobe Toyama-ken Shimoniikawagun Unazuki-machi Aimoto 100 7 28 71 Joganji Toyama-ken Nakaniikawa-gun Tateyama-machi Yokoe 91 18 27 72 Jtnzu Toyama-ken Kaminukawagun Osawano-machi Sasazu 6.0 22 28 73 Sho Toyama-ken Higashitonami-gun Shogawa-machi Kanaya 60 20 27 74 sat Kanazawa-shi Kata-machi 33 19 29

75 Tedori Ishlkawa-ken Ishikawagun Tsurugi-machi 31 17 29 76 Kuzuryu Fukui-ken Yoshidagun Etheiji-cho Higashifuruichi 26 13 28 77 Asuwa Fukui-shi Asuwa 14 17 26 78 Kano Shizuoka-ken Tagata-gun Nirayama-cho Nanjo 6.0 26 27 79 Kamanashi Yamanashi-ken Nakakoma-gun Ryu o-cho Shingen-hashi 23 19 27 Concentrations of 21 metals in the suspended solids 209

Al Fe Ca Mg Na Ti Mn Ra 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 91 100 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 8.0 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

7.4 3.4 2.4 0.66 0.42 0.21 0.58 640 390 140 100 68 180 100 370 39 21 (16 6.4 0.8 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 4.0 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 0.34 0.12 580 390 170 90 81 460 430 200 24 58 (16 29 1.4

8.0 2.8 1.5 0.76 0.58 0.13 0.08 480 110 70 44 48 250 160 160 20 29 (16 1.8 1.1 11 7.0 1.3 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 5R 75 110 260 65 280 37 28 (16 5.0 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 1.0 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 1.0 0.20 0.30 530 220 100 110 42 54 300 550 47 70 34 (1.3 1.1 9.0 3.6 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 11 4.9 0.85 1.2 1.2 0.32 0.42 700 610 120 140 97 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 28 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 3.0 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 9.0 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 6.0 1.4 1.0 1.1 0.34 0.27 800 340 160 160 100 130 300 680 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

9.0 2.0 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 7.0 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 2.3 11 45 0.87 1.2 0.80 0.38 0.092 550 200 160 170 74 79 37 82 32 27 (16 (1.3

3.0 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 11 4.9 1.0 1.0 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 1.0 0.65 0.40 0.10 520 150 150 150 110 140 37 110 47 21 (16 (1.3 2.2 4.2 7.4 4.5 0.82 0.62 0.37 0.23 0.17 310 180 60 40 120 44 88 92 27 23 (16 0.8 1.3 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 1.9 210 H. TERAOKA and 7. KOBAYASHI

Table 1. Continued.

S.S. I.L. Si No. Name of river Place of sampling (ppm) (%)

80 Fuefuki Yamanashi-ken Higashiyatsushiro-gun Isawa-cho Kubonakashima 25 31 26 81 Fuji Shizuoka-ken Ihara-gun Kanbaracho 66 10 29 82 Abe Shizuoka-shi Kadoya 32 4 27 83 of Shizuoka-ken Shimada-shi Oka 49 3 27 84 Tenryu (Lake Suwa) Nagano-ken Okaya-shi Ayusawa Ayusawa-hashi 14 34 27

85 Tenryu Nagano-ken Shimoina-gun Takamori-machi Shimoichida 25 14 27 86 Tenryu Shizuoka-ken Iwata-gun Tatsuyama-mura 33 10 27 87 Yahagi Aichi-ken Toyota-shi Suigen-cho -yo sui 46 12 25 88 Kist, Nagano-ken Kiso-gun Kisofukushima-machi 16 21 29 89 Kiso Gifu-ken Ena-shi Oicho 18 24 29

90 Bids, Gifu-ken Kamo-gun Sh rakawa-cho Sakanohigashi 3.5 27 27 91 Kiso Aichi-ken Inuyama-shi 11 20 28 92 Nagara Gifu-ken Mino-shi Hokiwaki _ 4.9 29 28 93 Ibi Gifu-ken Ibi-gun lbigawacho Kitagata 21 15 27 94 Kushida Mie-ken Matsuzaka-shi Toyoharacho Kushida-hashi 13 15 27

95 Miya Mie-ken Ise-shi Kawasaki 7.1 16 26 96 Shingu Wakayama-ken Shingu-shi Minamihizue 13 18 29 97 Hidaka Wakayama-ken Hidaka-gun Kawabe-cho Wakano 3.5 16 29 98 Arita Wakayama-ken Arita-gun Kibi-cho 25 16 29 99 Kino Wakayama-ken Naga-gun (wade-cho Upstream Kishi R. joins 17 11 29

101 Yamato Osaka-fu Kashihara-shi Kamiichi Downstream Ishi R. joins 46 20 27 102 Echi Shiga-ken Yokaichi-shi 16 15 27 103 Yasu Shiga-ken Koga-gun Ishibe-cho 33 7 28 105 Seta () Shiga-ken Otsu-shi 5.8 16 28

106 -fu Uji-shi Byodoin Ujiohashi 9.1 17 22 107 Kizu Kyoto-fu Soraku-gun Kizu-cho Izumi-ohashi 19 12 22 108 Yodo (Left bank) Osaka-fu Hirakata-shi Deguchi 110 9 27 109 Yodo (Right bank) Osaka-fu Takatsuki-shi Karasaki Downstream Akuta R. joins 42 15 26 110 Muko Hyogo-ken Takarazuka-shi IHrai-hashi Upstream Sakase R. joins 35 12 26

111 Kako Hyogo-ken Kato-gun Yashirocho Daimon 11 17 28 112 Ichi Hyogo-ken Kanzakigun Fukuzakicho Minamitawara 7.2 12 26 113 Ibo Hyogo-ken Tatsuno-shi Tatsunocho Higai 4.6 24 27 114 Yma Kyoto-fu Ayabeshi Nanmatsu-cho 8.0 16 27 115 Maruyama Hyogo-ken Kinosaki-gun Hidakacho Doi 8.2 18 25

116 Sendai -ken Yazugun Kawaharacho Sanuki 9.5 33 27 117 Tenjin Tottori-ken Kurayoshi-shi Ohara 8.3 42 28 118 Ogamo Tottori-ken Kurayoshi-shi Kawam-machi 7.1 40 28 119 Hino Tottori-ken Yonago-shi Yahata 7.7 32 28 120 flu Shimane-ken Izumo-shi Otsuch i 27 29 28 Concentrations of 21 metals in the suspended solids 211

Al Fe Ca Mg Na Ti Mn Ba Zn ST Zr V Cr Cu Ni Co P6 Sn As 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 8.0 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 1.3 0.56 0.40 0.21 0.46 420 420 110 85 63 390 560 400 27 65 (16 15 1.0

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 1.0 0.45 0.83 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 11 4.8 1.4 1.0 0.82 0.40 0.11 600 120 140 150 100 87 50 94 41 27 (16 (1.3 2.6

11 4.8 0.84 1.1 0.67 0.45 0.20 800 130 94 200 84 120 68 150 49 34 (16 (1.3 2.8 10 3.3 0.42 0.76 0.81 0.28 0.096 520 140 86 140 80 120 82 54 28 25 (16 (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 0.11 480 650 100 180 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

13 5.9 1.9 0.70 0.56 0.46 0.50 920 300 220 100 81 1,500 72 140 58 38 (16 6.4 2.6 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 1n 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

19 6.3 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 18 7.0 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 9.0 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 7.0 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 S8 16 (1.3 3.1

11 4.1 0.71 0.68 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 2.7 12 5.0 0.48 0.92 0.39 0.41 0.34 640 120 68 160 90 100 82 150 58 26 (16 (1.3 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 1S 1.0 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 2.2 12 3.8 1.6 0.78 1.0 0.27 0.22 520 230 210 140 70 73 54 50 25 60 (16 2.8 2.1 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 Q.3 11 6.4 1.2 1.3 0.94 0.44 0.43 540 90 130 130 86 53 39 20 37 26 (16 31 2.3 212 H. TERAOKA and J. KOBAYASHI

Table 1. Continued.

No. Name of river Place of sampling S.S. LL. Si (ppm) (`k)

121 Shimane-ken -shi 14 60 19 122 Eno Hiroshima-ken Takata-gun Yoshidacho Shimoirie 8.4 28 27 123 Sago Hiroshima-ken Miyoshi-shi Miyoshi-machi 49 18 28 124 Basen Hiroshima-ken Miyoshi-shi Minamihatajiki-machi 28 17 27 125 Go Shimane-ken Ochi-gun Kawamoto-machi Kawamoto-ohashi 14 22 27

126 Takatsu Shimane-ken Masuda-shi Kanda Kanda-hashi 9.8 27 27 127 Saba Yamaguchi-ken Hofu-shi Shinbashi-cho Shinbashi 6.6 36 28 130 Ashida Hiroshima-ken Fuchu-shi Fuchu-cho 15 27 27 131 Takahashi Okayama-ken Tsukubo-gun Kiyone-mura 11 28 27

132 Asahi Okayama-shi Tamagashi 12 28 27 133 Yoshu Okayama-ken Akaiwa-gun Kumayama-cho Downstream Kongo R. joins 24 24 27 134 Doki Kagawa-ken Nakatado-gun Manno-chi Sumishonishi 6.2 25 28 136 Shigenobu Eh me-ken Onsen-gun Kawauchi-cho Minamigata 14 31 28

137 Ishide Ehime-ken Matsuyama-shi Shukuno-machi 11 12 25 138 Hgi Ehime-ken Ozu-shi Yunoki 8.4 35 27 139 Shimanto Ko chi-ken Nakamura-shi Domeki Nakamura-ahashi 12 26 28 140 Niyodo Kochi-ken Agawa-gun Ino-cho Kotani 9.2 26 27 141 Monobe Kochi-ken Kami-gun Tosayamada-cho Igenoki 7.3 2R 27

142 Naka Tokushima-ken Anan-shi Kamtono-cho 5.2 24 27 143 Yoshino Tokushima-ken Oe-gun Yamakawa-cho 6.5 30 27 144 Bansho Oita-ken Saiki-shi Kamioka 4.8 48 28 145 Ono Oita-ken Oita-shi Shirataki Shirataki-hashi 12 30 27 146 Oita Oita-ken Oita-shi Enokuma Akegawara-hashi 12 37 27

147 Yamakuni Oita-ken Nakatsu-shi Shimomiyanaga 7.5 36 27 148 Onga Fukuoka-ken Nogata-shi Kanroku-hashi Upstream Hikosan R. joins 26 27 23 149 Htkosan Fukuoka-ken Nigata-shi Shimozakai 60 18 22 150 Matsuura Saga-ken Higashimatsuura-gun Ochi-cho Mutabe 16 31 28 151 Honmyo Nagasaki-ken Isahaya-shi Honmyo-machi Tetsudo-hashi 13 34 28

152 Kase Saga-ken Saga-shi Kanjin-hashi 12 31 26 153 Kusu Oita-ken Hita-gun Amagase-machi 26 34 28 154 Oyama Oita-ken Hita-gun oyama-machi 12 33 28 155 Chikugo Fukuoka-ken Miigun Tachiarai-machi 19 30 28 156 Yabe Fukuoka-ken Chikugo-shi Oshima 16 28 28

157 Kikuchi Kumamoto-ken Kikuchi-shi Hirose 23 23 26 158 Kikuchi Kumamoto-ken Tamana-shi Takase 26 21 26 159 Shire Kumamoto-shi Oe-machi Toroku 42 25 28 160 Midori Kumamoto-ken Shimomashiki-gun .)onan-machi 25 20 26 161 Kuma Kumamoto-ken Kuma-gun Taragi-machi Taragi 24 1R 28 Concentrations of 21 metals in the suspended solids 213

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

8.5 3.3 1.5 8.0 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 22n 47 160 30 30 (16 (1.3 3.4 13 4.3 1.0 0.68 0.90 0.34 0.096 520 100 150 150 82 63 38 59 30 41 (16 (1.3 3.0 14 4.4 0.72 0.62 0.54 0.28 0.084 440 80 100 140 65 98 36 56 33 21 (16 (1.3 3.6 13 4.R 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

14 4.9 1.7 1.0 1.7 0.34 0.12 760 230 260 160 96 380 99 210 45 60 18 1.9 4.7 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 R2 120 120 150 45 92 (16 1.4 2.9

14 5.7 1.8 1.1 1.0 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 52 360 100 180 46 62 16 (1.3 2.7 9.0 4.8 4.8 0.84 1.0 0.33 0.38 760 250 290 120 62 240 100 110 46 50 18 9.2 2.6

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 1.0 0.60 0.11 480 600 140 180 150 210 260 300 72 57 21 1.5 1.9 9.5 4.0 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 9.0 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 R7 150 54 52 (16 (1.3 2.4

9.5 5.7 2.7 1.4 0.90 0.40 0.36 600 110 220 180 110 300 100 220 80 54 (16 (1.3 2.6 9.0 4.6 2.1 1.7 0.85 0.40 0.092 520 180 160 150 96 210 170 190 66 60 (16 1.5 2.4 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 R00 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 9.0 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 9.0 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 1.0 0.39 0.47 540 200 220 170 110 180 65 210 86 31 (16 (1.3 3.1 10 6.0 1.6 0.80 0.74 0.44 0.36 520 300 160 240 110 250 78 140 55 44 18 30 2.5

13 4.3 1.6 0.76 0.98 0.36 0.11 480 150 240 110 74 190 150 130 42 50 (16 (1.3 2.8 9.0 4.9 1.2 0.45 0.58 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 0.11 640 140 180 200 110 240 80 160 58 33 16 (1.3 2.6

14 6.6 1.5 0.96 0.67 0.60 0.12 720 110 200 260 140 43 93 100 56 24 (16 (1.3 2.8 14 6.4 1.7 1.1 0.96 0.43 0.11 640 100 200 200 120 130 60 100 50 26 (16 (1.3 2.8 10 8.4 3.0 1.2 1.1 0.41 0.16 500 330 300 170 200 110 180 130 72 58 30 (1.3 3.1 14 5.6 1.3 1.2 0.74 0.58 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 0.10 600 200 130 220 130 55 100 42 40 (16 (1.3 2.8 214 H. TERAOKA and J. KOBAYASHI

Table 1. Continued.

LL. Si No. Name of river Place of sampling S.S. (PPm) (%)

162 Kuma Kumamoto-ken Hitoyoshi-shi Kamisatsumaze-machi Nishize-hashi 26 24 27 163 Kuma Kumamoto-ken Yatsushvogun Sakamoto-mura Yokoishi 13 36 28 164 Sendai Miyazaki-ken Ebino-shi Kyo-machi 9.4 21 27 165 Sendai Kagoshima-ken Satsuma-gun Tsurudacho Koshi-hashi 11 22 27 166 Sendai Kagoshima-ken Sendai-shi Chugo-cho 18 29 27

167 Kimotsuki Kagoshima-ken Kanoya-shi Kawanishi Taisho-hashi 79 30 28 168 Kushsra Kagoshima-ken Kimotsuki-gun Kushiracho Katada-hashi 20 31 28 169 Gyodo Miyazaki-ken Miyakonojo-shi Nishi-machi Takeshita-hashi 22 22 28 170 Gyodo Miyazaki-ken Kitamorokata-gun Takajo-cho Hiwatashi-hashi 21 22 28 171 Honjo (Ayaminami) Miyazaki-ken Higashimorokata-gun Ayacho Ayaminamigawa-hashi 6.2 37 28

172 Komaru Miyazaki-ken Koyu-gun Ktjo-cho Takajo-hashi 6.2 32 28 173 Gokase Miyazaki-ken Nobeoka-shi Ose-hashi 7.6 35 27

Table 2. Correlation coefficients (r) among the amount of suspended solids, their ignition losses, and 19 elements in their ash in water samples collected from the principal 166 rivers and 3 lakes in Japan

SS. I.L. Si AI Fe Ca M Na Ti Mn Ba Zn Sr Zr V Cr Cu Ni Co Pb Be S.S. 1.00 I... -0 .33 1.00 Si 0.07-0.04 1.00 AI -0.04 -0.23 --0.14 1.00 Fe -0.14 0.12 -0.25 0.26 1.00 Ca -0.32 0.29 -0.29 -0.03 0.31 1.00 Mg -0.20-0.17-0.30 0.10 0.43 0.45 1.00 Na -0.17 -0.03 --0.30 0.06 0.28 0.40 0.52 1.00 Ti -0.14-0.07-0.04 0.73 0.28 0.07 0.15-0.02 1.00 Mn -0 .23 0.18-0.45 0.00 0.37 0.30 0.33 0.18-003 1.00 Ba -0 .21 -0.14 --0.11 0.51 0.19 0.27 0.38 0.58 0.47 0.44 I.00 Zn -0 .34 0.34-0.10 004 0.23 0.15 0.12 0.20 0,02 0.55 0.32 1.00 Sr -0.20 0.25-0.19 0.17 0.29 0.77 0.33 0.56 0.28 0.20 0.40 0.11 1.00 Zr -0.09-0 .06 0.07 0.22 0.04 -0.02 0.04-002 0.36 0.04 0.27 0.35 0.11 1.00 V ---0.05 0 .03--0.06 0.37 0.68 0.38 0.63 0.33 0.54 0.18 0.20 0.08 0.38 0.21 1.00 Cr -0.34 0.13-0.02 0.12 0.13 0.36 0.26 0.10 0.15 0.03 0.15 0.07 0.30 0.02 O.17 1.00 -0.27 0.37--0.07--0.04 Cu 0.15 0.23 0.20 0.11-0.07 0.45 0.13 0.67 0.04 0.03 0.11 0.02 1,00 -0.22 0.32-0.17-0.17 Ni 0.10 0.19 0.30 0.12-0.06 0.52 0.26 0.55 0.03 0.13 0.16 0.14 074 1.00 Co -0.18 0.26 -0 .38 --0.02 0.57 0.32 0.37 0.12 0.14 0.55 0.27 0.40 0.29 0,06 0.47 0.15 0.42 0.49 1.00 Pb -0 .44 0.40-0.18 0.09 0.23 0.29 0.23 0.29 0.06 0.49 0.28 0.69 0.22 0.15 0.15 0.06 0.65 0.56 0.40 1.00 Be. -b28-0 .25 005 072 0.18 027 0.32 0.65 0 49 0.12 0.61 010 051 0.12 0.18 0.18 -0.13 0.14 nlw 0.13 1 00

* Numbers larger than ± 0.29 indicate significant positive or negative correlation (p = 0.1%. n= 169). Concentrations of 21 metals in the suspended solids 215

Al Fe Ca Mg Na Ti Mn Ba Zn St Zr V Cr Cu Ni Co pb Sn Ag Be (% in ash) (ppm in ash)

13 4.8 0.94 0.70 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 0.33 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 0.11 500 280 140 180 85 66 100 60 37 37 (16 2.5 2.8 9.5 5.7 1.4 0.44 1.0 0.28 0.11 500 250 150 170 82 110 82 120 40 32 (16 (1.3 2.6 9.0 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 1.0 0.32 0.11 600 220 140 170 92 95 200 130 42 42140 (1.3 2.5 10 4.4 2.0 1.0 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 element were drawn by means of the Suspended solids and ignition losses The Two Step Method (CHURCHILL,1944; ASTM, average concentrations of the suspended solids 1957). The mean value of duplicate analyses from the 12 different samples collected during was adopted. Other details of this method such a year from each site are shown in Table 1. as the apparatus, the full analytical conditions The highest S.S. value was 170ppm in the Yu and the accuracy are given by the other reports River (No. 42) which was the most acid (pH of the authors (TERAOKAand KOBAYASHI,1977; 2.0) of all the rivers and lakes investigated owing TERAOKAet al., 1978). to the influence of the Kusatsu sulfuric hot springs. This was followed by I IOppm in the

ANALYTICAL RESULTS (No. 6) and 104ppm in the (No. 2) in Hokkaida, while The sampling places, the amounts of sus the lowest values were 2.5ppm for the Daiya pended solids, their ignition losses, and the River (No. 50) which proceeds from Lake analytical results for 21 kinds of metal in the Chuzenji in Nikko and 3.2ppm for the Kuji ash are shown in Fig. 1 and Table 1. Correla River (No. 39). The concentration of suspended tion coefficients among these metals obtained solids in river water is greatly influenced by the from the analytical results, relation between the amount of river water, but these values seem to number of rivers and concentrations of 19 show that the water of Japanese rivers is metals, and distribution maps of Cu, Ni, Be and generally clear owing to the heavy rainfall, and Sr are shown in Table 2, Figs. 2 and 3, and Figs. rocky and steep topography of the land. 4, 5, 6 and 7, respectively. The general average of ignition losses due 216 H. TERAOKA and J. KOBAYASHI

0

e u m Cs Ni f se q :o fit. :oosr w * np :on,.Ases. era.: Naa.ao erW :Lm

to

soBola

E 440 Po 0n co up :(/llsSsake xp :aem0.ew:o Top :oe,md.aw so erao: ara:,:eMao.am era,,: x .amrmo x0 dSb u m Marm e•u F t0

S88tyE 5883 tee C 00 4 g to a. gym e e0 u 1 xo kk kY~ x0

10

0 • e c:kkk`e 0 a 00 i aw+ym lilts-if

Fig. 2. The relation between the concentration of 10 metals (Zn, Cu, Ni, Pit, Mn, Co, Ca, Sr. Be, Cr) in ash samples of suspended solid and the frequency of their appearance.

70

00 E Y 50 Si Al T M0 a 40 30 E z' 20

IQ

w,.~xsx fl - a m O N~ w a M e m a m m m

70

so

50 Na TI Ba Zr a 40 V E 30 e t 20

70 0 eee : ~CrYEEM

Fig. 3. The relation between the concentrations of 9 metals (Si, Al, Fe, Mg, Na, Ti, Ba, Zr, Y) in ash samples of suspended solids and the frequency of their appearance. Concentrations of 21 metals in the suspended solids 217

to organic matter in the suspended solids in lithosphere, the hydrosphere (TUREKIANet al., rivers and lakes was about 25%, which is much 1967; TbREKIAN,1969), the atmosphere (ZOLLER higher than those for rocks and soils. The et al., 1974; LANIZYet al. 1979), and in the bio highest value was 60% in the brackish Lake sphere (TirroN et al., 1963; TlrroN et al., Shinji (No. 121) which contains a large amount 1965, BowEN, 1966), because most of them of plankton. This was followed by 48% in the are essential for life (SCHROEDERet al., 1971; Bansho River (No. 144) and 47% in Lake VALKOVIC,1978). Tazawa (No. 32), while, the lowest were 3% It was found, in this study, that these in the Oi River (No. 83) and 4% in the Abe elements are widely distributed in suspended River (No. 82). solids (Table 1 and Fig. 2) and that the con As stated later, significant negative and centrations of 6 of these metals but Cr and Ag positive correlations were noticed (at p = 0.1 %) are markedly high in the Northeastern provinces between the amount of S.S. and ignition losses of Japan (Figs. 2, 4 and 5). (organic matter) and between I.L. and metals (1) Zn content in the range of 80-350ppm such as Pb, Zn, Cu, Ni and Ca. was found in 68% of the total number of rivers and lakes investigated. The highest values were Trace elements Zn, Cr, Cu, Ni, Co, Pb, Sn and 1,600ppm in the Yamakuni River (No. 147), Ag These elements, classified as siderophile 1,500ppm in the (No. 23) and and chalcophile elements, are distributed in the 1,300ppm in the Hazama River (No. 24). The

I 0 Cu (VPm h, .6h)

~...._. 111-1.114 T S..- l/1 iM 5..- 111 111 p...._ 11 x I 0..... M 74 p..... I 42 r 11 Xtrk

!P Y rt

J e\, L fin' I r

l 1 ?t 1 a_ lV~

. o„

Fig. 4. Distribution map of the concentration of Cu in ashes of suspended solids of 166 rivers and 3 lakes in Japan. p 218 H. TERAOKA and J. KOBAYASHI latter two rivers have Cu and Zn mines along Sarugaishi River (No. 20) and the Yoneshiro their upper streams. On the other hand, Zn River (No. 23, 24). The lowest were 8ppm in could not be determined (detection limit 80 the acid Yu River, 28ppm in the ppm) in such inorganic acid waters as the Yu (No. 87) and 35ppm in the (No. (No. 42, pH 2.0), the Ara (No. 13, pH 3.6), and 166). the Agatsuma (No. 43, pH 4.3) Rivers and Lake (4) Ni content in the range of 30 300ppm Tazawa (No. 32, pH 4.4). was observed in 78% of the rivers and lakes. (2) Cr content in the range of 10 200ppm The highest were 1,500ppm in the Sarugaishi was found in 84% of the total rivers and lakes. River (No. 20), 850ppm in the Arao River (No. The highest values were 1,500ppm in the Yama 25) and 810ppm in the Azusa River (No. 63). to River (No. 101) and 750ppm in the Watarase The lowest were 15ppm for the Yahagi River River (No. 48). The lowest were l2ppm in the (No. 87), 18ppm for the Yu River and 20ppm Joganji River (No. 71) and 28ppm in the Ya for the (No. 120). hagi Rivet (No. 87), which flows through a (5) Co content in the range of 20 70ppm granite stream. was found in 91% of the waters. The highest (3) Cu content in the range of 70-250ppm were 230, 160 and 120ppm in the Kitakami was found in 76% of the total rivers and lakes. River (Nos. 18, 21 and 37). This river has been The highest were 5,500ppm in the Yamakuni polluted by acid waste water from the Matsuo River (No. 147) and 1,200 1,300ppm in the sulfur mine, even though the mining operations

( ~~' J -.J

/`..~ l ~. x!i ,~ ~~ 5"'o r .~, GL~ .'~, ~_ ~ v

<>

r i. wf i.

I

' o y

Fik. 5. Distribution map of the concentration of Ni in ashes of suspended solids of 166 rivers and 3 lakes in Japan . Concentrations of 21 metals in the suspended solids 219

have now been stopped owing to the overproduc 31 in the Northeastern provinces showed an tion of S from the oil refining industry. The average value of 32ppm and a range of Sn con lowest values were less than l6ppm (detection tents from 18 to 66ppm. limit) in the acid rivers Yu and Agatsuma (No. (8) Ag content was not detectable in most 43). rivers (less than 1.3ppm). However, rivers with (6) Pb content in the range of 10 90ppm noticeable Ag content were found here and was found in 84%. The highest values were there, such as 30-32ppm in the Bansho River 210ppm in the Uji River (No. 106) which takes (No. 144), Lake Shinji (No. 121), the Hii River its rise in Lake Biwa, 200ppm in the Yoneshiro (No. 120) and the Honmyo River (No. 151). (No. 24) and 190ppm in the Yamakuni Rivers. The lowest were less than l0ppm (detection Major elements Ca, Mg and Na, and trace ele limit) in the acid Yu River (No. 42) and the ment Sr These elements are easily soluble Tone River (No. 45). in water during the process of weathering; there (7) Sn content was not detectable (less than fore they are widely distributed in the hydro l6ppm) in most rivers except in the North sphere and biosphere at high levels. eastern provinces. The highest values were (1) Ca content in the range of 0.2 2.0% 140ppm in the Oyodo River (No. 170), 66ppm was found in 80% of the total rivers and lakes. in the (No. 26) and 63ppm in The highest was 11% in the Ara River (No. 53) the Jinzu River (No. 72). Twenty rivers out of which flows through a limestone area. This was

i C v 0

vy

L U It F a L (0 ~; 4x-1

(WQ I U... ~~4 11

0

I

Fig. 6. Distribution map of the concentration of Sr in ashes of suspended solids of 166 rivers and 3 lakes in Japan. 220 H. TERAOKA and J. KOBAYASHI

followed by 1.0% in the Hikosan (No. 149) tions in the suspended solids and those dis and 0.88% in the Onga (No. 148) Rivers, both solved in water samples was observed. of which run through the Chikuho coal fields. (3) Na content in the range of 0.4 1.1 % The lowest were 530ppm for the acid Yu River was found in 87%. The highest were 15% in (pH 2.0) and 1,700ppm for Lake Tazawa (No. the brackish Lake Shinji (No. 121) and 1.8% 32, pH 4.4). in the (No. 64'). The lowest were Thus, Ca concentration in suspended solids less than 0.1% (detection limit) in the acid Yu vary greatly. It is natural that a significant River and 0.13% in Lake Inawashiro (No. 57) positive correlation (n = 169, r = 0.70, p = 0.1 %) and the (No. 18). A significant was observed between the Ca concentrations positive correlation (n = 169, r= 0.72, p = 0.1%) in suspended solids and those dissolved in the between Na concentration dissolved in water water samples. and that in suspended solids was noticed as in (2) Mg content in the range of 0.5 1.0% the case of Ca and Mg. was found in 72%. The highest were 8.0% in (4) Sr content in the range of 50-250ppm the brackish Lake Shinji and 4.0% in the Sako was found in 92%. As shown in the distribu River. The lowest, like those for Ca, were 200 tion map Fig. 6, there were higher Sr contents ppm in the Yu River and 1,500ppm in the Lake of river waters in the western half of Japan, Tazawa. A significant positive correlation (n = including 720ppm in the Onga (No. 148) and 169, r = 0.80, p = 0.1 %) between Mg concentra 550ppm in the Hikosan (No. 149) Rivers. The

rte. 0

S. C.wn In.sh

--+ e-. i n S .-t b .-2 o o .--I f-I 0 .-1 4 P

CV f

t ac '" i JP Tu 1 n

J

k

1 0 y

Fig. 7. Distribution map of the concentration of Be in ashes of suspended solids of 166 rivers and 3 lakes in Japan

1 Concentrations of 21 metals in the suspended solids 221

Table 3. The average concentrations of 19 elements in ash of suspended solids compared with those in the continental crust proposed by TAYLOR (1964)

Element (A) Suspended solids (B) Continental (A)/(B) (mean 1 S.D.) crust (ppm in ash) (ppm) Pb 571 38 12.5 4.6 Zn 2701 220 70 3.9 Cu 190 ± 220 55 3.5 Ni 230 ± 210 75 3.1

Mn 2,100± 1,400 970 2.2 Co 471 23 25 1.9 Ba 570± 150 425 1.3 Cr 120± 97 100 1.2

At 100,000 82,300 1.2 Si 270,000 ± 18,000 281,500 0.96 Zr 150± 83 165 0.91 Fe 46,000 116,000 56,300 0.82

Be 2.11 0.83 2.8 0.75 V 881 29 135 0.65 Ti 3,200 ± 1,000 5,700 0.56 Mg 9,300 ± 6,700 23,300 0.40

Sr 140± 78 375 0.37 Ca 14,000 41,500 0.34 Na 8,000 ± 2,800 23,600 0.34

lowest were less than 32ppm (detection limit) and it was followed by 18% in the Kizu (No. in the Yu River and Lake Inawashiro (No. 57). 107) and 16% in the Yodo (No. 109) Rivers. As Sr is a soluble element, a positive correlation These 3 rivers belong to the same river system. (n = 169, r= 0.66, p = 0.1 %) between the Sr The lowest values were 2.0% for the acid Yu concentration in water and in suspended solids River and 2.9% for the Kitakami River (No. 18). was noticed. (3) Fe content in the range of 2.0 7.0% was found in 96%. The highest was 15% in the Major elements 5i, Al, Fe, Ti and Mn, and trace Kitakami River (No. 18), and it was followed elements Ba, Zr, V and Be These elements by 11% in the Agatsuma River (No. 43). The are classified geochemically in a lithophile group. former has been affected by the waste water (1) Si content in the range of 25 29% was from a pyritiferous mine and the latter by hot found in 92% of the total number of the rivers springs in volcanic areas. The lowest values were and lakes. The highest was 35% in the Yu 0.21% for the acid Yu River (No. 42, pH 2.0) River, followed by 31% for Lake Tazawa and and 0.91% for Lake Tazawa. Lake Inawashiro (No. 57). All of these are acid (4) Ti content in the range of 0.25 0.45% waters influenced by hot sulfuric springs. The was found in 60%. The highest were 0.60% lowest values were 19% in the Kitakami River in the Hiji River (No. 138) and the Kikuchi (No. 18) in which a markedly high Fe content River (No. 157). The lowest were 200ppm in was observed, 19% in Lake Shinji, 22% in the the Yu River and 660ppm in Lake Tazawa, Ara River (No. 53) in which Ca is abundant, and both are influenced by sulfuric acid hot springs. 22% in the Hikosan River (No. 149). (5) Mn contents in the range of 500 2,500 (2) Al content in the range of 8 14% was ppm was found in 67%. The highest were 1.8%n found in 90%. The highest was 19% in the Uji in the Onga River (No. 148) influenced by coal River (No. 106) which arises from Lake Biwa, fields, and in brackish Lake Shinji (No. 121). 222 H. TERAOKA and J. KOBAYASHI

These were followed, in order, by the Yoneshiro appearance, Si in the range of 25 29%, Al 8 River (No. 29, 0.74%), the Arao River (No. 25, 14%, Fe 2-7%, Ca 0.2 2.0%, Na 0.4-1.1%, 0.64%) and the (No. 46, 0.58%). Mg 0.5-1.0%, Ti 0.25-0.45%, Mn 0.05 The lowest values were found in solids sus 0.25%, Ba 400-900ppm, Zn 80-350ppm, Ni pended in acid water; 28ppm in the Yu, 170 30 300ppm, Sr and Zr 50 250ppm, Cu 30 ppm in the Agatsuma (pH 4.3) and 390ppm 350ppm, Cr 10-200ppm, V 40-140ppm, Pb in the Ara (No. 13, pH 3.6) Rivers. However, 10 90ppm, Co 20 70ppm and Sri 20 50ppm in general, higher Mn contents were observed were the most numerous of all the samples, in the Northeastern provinces as shown in Fig. 2. except for Sri which was detected only in the (6) Ba content in the range of 400 900ppm Northeastern provinces (Figs. 2 and 3). was found in 91% of the total number of rivers As can be seen in Table 3 which shows the and lakes. The highest were 1,100ppm in the average values of elements contained in sus Jinzu River (No. 72), and 1,000ppm in the pended solids compared with those in the con (No. 59) and the (No. tinental crust proposed by TAYLOR(1964), the 109). The lowest were 130ppm in the Yu River concentrations of minor elements such as Pb, and 140ppm in the Agatsuma River. Zn, Cu, Ni and Mn are found to be markedly (7) Zr content in the range of 50 25oppm high, while Na, Ca, Sr and Mg are low. was found in 89% of the total number. The It was found that (1) a positive correlation highest were 880ppm in the Hazama River (No. exists between the amount of suspended solids 24), along the upper stream of which a zinc (S.S.) in river water and the size of particles mine is located, and 440ppm in the Heii River tested by scanning electron microscopic method, (No. 17) and the Abukuma River (No. 27). The and (2) that a positive correlation exists at p = lowest were less than 16ppm (detection limit) 0.1% between I.L. and the concentrations of in the Yu River and 22ppm in Lake Inawashiro. Pb, Zn, Cu and Ni which are abundant in sus (8) V content in the range of 40 140ppm pended solids as stated above (see Table 2). was found in 92%. The highest were 200ppm It is interesting that, in comparing the con in the Sako (No. 56) and Shira (No. 159) Rivers centrations of 21 elements in fractions of various which are influenced by volcanoes. The lowest size from sediments collected at 6 points from were less than l6ppm (detection limit) in the the estuary of the (No. 131 in Yu River and l9ppm in Lake Inawashiro. Table 1), the ignition loss and minor elements (9) The distribution of Be concentration, as such as Pb, Zn, Cu, Ni and Mn were found to be shown in Fig. 7, happened to divide Japan into markedly enriched in finer particles (12 0.4 two halves roughly bounded by the Tenryu (No. pm). Therefore, it can be understood that the 85) and the Sai (No. 65) Rivers. Be content in finer the particles of suspended solids, the the western half was found to be about two greater the quantity of organic matter and Pb, times as great as that in the eastern half. The Zn, Cu, Ni and Mn that they contain. On the highest values were 4.7ppm in the other hand, the concentrations of soluble ele (No. 126), 3.8ppm in the (No. ments such as Ca, Na, Sr and Mg were found to 130) and 3.7ppm in the (No. 89). be markedly lower in suspended solids and The lowest were less than 0.4ppm in the inor estuary sediments than in the continental crust. ganic acid rivers and lakes which are distributed This must be due to the results of weathering in the eastern parts of Japan. and solution. Finally, the concentrations of Si, Al, Fe, Ti and Zr, which are classified in a lithophile group, DISCUSSION AND CONCLUSION were not correlated with I.L. or particle size 1. As to the relation between the con and agreed approximately with the average centrations of metals and the frequency of their values of the continental crust (see Table 3) as Concentrations of 21 metals in the suspended solids 223

Table 4. Comparison of concentrations of 21 elements in fractions of various size from estuary sediments and suspended solids in the Takahashi River (No. 131 in Table 1)

Sediments, separated by sieving Suspended solids

Diameter of )ISOgm 150 74pm 74 37µm sediments 37-12µm 12 0.4µm (74µm Distribution 64% 21% 7.7% 6.0% 0.85% Ignition loss 1.0% 6.9% 8.6% 10.0% 11.4% 27.7% Si 330,000 290,000 290,000 280,000 270,000 270,000 At 82,000 120,000 130.000 140,000 140,000 130,000 Fe 24,000 48,000 50,000 58,000 58,000 52,000 Ca 7,800 11,000 10,000 6,800 5,000 20,000

Mg 4,400 11,000 12,000 14,000 13,000 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 AS (1.3 (1.3 (1.3 (1.3 (1.3 1.4 Be 1.5 2.2 2.5 2.7 2.7 2.9

did those in the sediments in the estuary of the Al and Ti also showed a tendency to be Takahashi River. abundant in the western part of Japan, and, as 2. The concentrations of Mn, Zn, Cu, Ni, shown in Table 2 and Fig. 8, positive correlations Co, Pb and SO are markedly high in the North at p= 0.1% (n= 169) between Be and Al (r= eastern provinces (see Table 1 and Figs. 2, 4 and 0.72), Al and Ti (r= 0.73), and Be and Ti (r= 5). This must be due to the higher concentra 0.49) were found. tions of these metals distributed in geologic Na, Ba and Sr (Fig. 6) also show a tendency formations in this section of Japan as well as to to be abundant in the western provinces. the influence of many copper and other mines. 4. In the Yu River (No. 42, pH 2.0) af In addition, as shown in Table 2, positive cor fected by Kusatsu sulfuric hot springs, which relations at p = 0.1 % (n = 169) are observed was the most acid of all the rivers and lakes among 6 of the above elements but So. investigated, concentrations of all major ele 3. As shown in Figs. 2 and 7, the distribu ments, such as Al, Fe, Ca and Mg, except Si tion of Be happened to divide Japan into two and minor elements such as Pb, Zn and Cu halves roughly bounded by the Tenryu River showed the lowest values, while this river had (No. 85) and the (No. 65) in the center the highest value for Si. Other inorganic acid of Japan. And the histogram of Be in each waters, i.e. the Agatsuma River (No. 43, pH 4.3), half showed a pattern of almost normal distribu the Ara River (No. 13, pH 3.6), and Lake Taza tion in the range of 1.0 1.5ppm in the eastern wa (No. 32, pH 4.4) and Lake Inawashiro (No. half and 2.5 3.Oppm in the western half. 57, pH 4.5) also showed about the same tend 224 H. TERAOKA and J. KOBAYASHI

ency. This phenomenon must be due to the KOBAYASHI,J. (1971) Mizu no kenko shindan (A acid soluble nature of most metals except Si, health examination of water) (in Japanese). 44-59. which remains relatively concentrated in the Iwanami, Tokyo. KOBAYASHI,J. (1971) Relation between the "itai suspended solids. itai" disease and the pollution of river water by cadmium from a mine. Advances in water pollution research (ed. S. H. JENKINS). 1-25, 1-7. KOBAYASHI,J., MORII, F., MURAMOTO,S., NAKASHIMA, S., URAKAMI,Y., NISHIZAKI,H., TERAOKA,H., and NAGAO,N. (1976) Chemicalinvestigation on the quality and characteristics of river waters in the I Tohoku district. Nogaku Kenkyu 55, 103-144. KOBAYASHI,J., MORII,F., MURAMOTO,S.,NAKASHIMA, S., URAKAMI,Y., NISHIZAKI,H., TERAOKA,H. and NAGAO,N. (1978) Chemical investigations on the quality and characteristics of river water in the Hokkaido district. Nogaku Kenkyu 57, 17-54. KOBAYASHI,J. (1979) Pollution by cadmium and the AIM AIM itai-itai disease in Japan. Toxicity of Heavy Metals in the Environment (ed. F. W. OEHME).Part 1. 199 260. Marcel Dekker, Inc., New York and Basel. Fig. 8. Correlation between Be and Al, and Ti and Al in ashes of suspended solids in water samples collected MASIRONI, R., PISA, Z. and CLAYTON D. (1979) Myocardial infarction and water hardness in the WHO from 166 rivers and 3 lakes in Japan. myocardial infarction registry network. Bull. WId. Hith. Org. 57, 291-299. REFERENCES LANTZY,R. J. and MACKENZIE,F. T. (1979) Atmo spheric trace metals: Global cycles and assessment ASTM (1975) Methods for Emission Spectrochemical of man's impact. Geochim. Cosmochim.Acta 43, Analysis. pp. 20-23. Philadelphia, Pensylvania. 511-525. BOWEN,H. J. M. (1966) The elementary composi SCHROEDER,H. A. (1960) Relation between mor tion of living matter. Trace elements in biochemistry. tality from cardiovasculardisease and treated water 61-84. Academic Press, New York, N.Y. supplies. JAMA 172, 1902-1908. CHURCHILL,J. R. (1944) Techniques of quantitative SCHROEDER,H. A. and Nason, A. P. (1971) Trace spectrographic analysis. Ind Eng. Chem. 16, 653 element analysisin clinicalchemistry. Clin. Chem. 17, 670. 461-474. KOBAYASHI,J. (1951) Chemicalinvestigation on the TAYLOR,S. R. (1964) Abundance of chemical ele water of rivers in Japan 1. On the quality of water ments in the continental crust: A new table. Geo in . Ber. Ohara Inst. landw. Biol. chim. Cosmochim.Acta 28, 1273-1285. 9, 329-356. TERAOKA,H. and KOBAYASHI,J. (1977) Chemical KOBAYASHI,J. (1957) On geographicalrelationship investigationon mineralsin humanhair (1) Analytical between the chemicalnature of riverwater and death method and its findings on 25 elements in hair rate from apoplexy. Ber. Ohara Inst. landw. Biol. samples from various parts of Japan. Jap. J. Hyg. Okayama Univ. 11, 12-21. 32, 574-587. KOBAYASHI,J. (1959) Chemical investigation on river TERAOKA, H., KOBAYASHI, J. and SANG, T. (1978) waters of South-Eastern Asiatic countries (Report 1) Concentrations of 22 metals in the internal organs of chromium plating, chromate refining The quality of waters of Thailand. Ber. Ohara Inst . , aircraft landw. Biol. Okayama Univ. 11, 167-233. painting, and masonry workers. J Set Labour 54, KOBAYASHI,J. (1960) A chemical study of the 413-422. TIPTON,1. H. and COOK,M. J. (1963) Trace ele average quality and characteristics of river waters of ments in human tissue, Part II: Adult subjectsfrom Japan. Ber. Ohara Inst. landw. Biol. Okayama Univ. the United States. Health Phys. 9, 103-145 11, 313-356. . TIPTON, 1. H., SCHROEDER KOBAYASHI,J. (1967) Silica in fresh water and , H. A., PERRY, H. M. and COOK, M. J. (1965) Trace elements in human tis estuaries. Chemical environment in the aquatic sue, Part III: Subjects from Africa, the Near and Far habitat (ed. H. L. GOLTERMAN). 41-55. East and Europe. Health Phys. 11, 403-451. Concentrations of 21 metals in the suspended solids 225

TUREKIAN, K. K. and Scow, M. R. (1967) Con VALKOVIC,V. (1978) Elements essential for life. centrations of Cr, Ag, Mo, Ni, Co and Mn in sus Trace substance in environmental health-XII (ed. D. pended material in streams. Environ. Sci TechnoL 1, D. HEMPHILL). 75-88. 940-942. ZOLLER,W. H., GLANDNEY,E. S. and DUCE,R. A. TUREKIAN,K. K. (1969) Handbook of geochemistry (1974) Atmosphericconcentrations and sources of I (ed. K. H. WEDEPOLE).pp. 279-323. Springer trace metals at the South Pole. Science 183, 198 Verlag, Berlin, Heidelberg. 200.