The occurrence and distribution of tin with particular reference to marine environments

Geochimlca et Ccemochlmlca Acta.1972,Vol. 36,pp.621to 629.Pergamon Preea.PrintedIn Northern Ireland

NOTE

The occurrence and distribution of tin with particular reference to marine environments J. D. SMITH and J. D. BURTON Department of Oceanography, University of Southampton, England. (Received 27 July 1971; accepted in retied form 6 January 1972) Ab&&-Concentrations of tin in sea water decreased from estuarine and ehelf (0.02-0.04 pg/kg) to surface Atlantic waters (0.009 pg/kg). Mean contents (ppm) in other materials included: ultramaflc rocks, 0.8; basalts, 1.7; silicic rocks, 2.5; red clays, 3.4; amphibolites, 1.2. Oceanic ferromanganese deposits contained from 0.2 to 5.8 ppm; tin and cobalt contents were correlated. INTRODUCTION

THE RECENT review by HAMAUUCHI and KURODA (1969) of the geochemistry of tin showed that for many materials there are few accurate abundance data. Further information is particularly needed on metamorphic and some sedimentary rock types, the hydrosphere and marine sediments. This work is concerned mainly with the marine distribution of tin but results for some continental rocks are included. METHODS Tin was determined by a precise spectrophotometric method using phenylfluorone (Sxrrn, 197Ob) which, in conjunction with purification by solvent extraction of stannic iodide from sulphuric acid, was essentially specific (SMITH, 1971). h4irninax-y treatments are outlined below. The procedures were designed to minimise contamination and avoid the loss of volatile tin compounds. Purification of reagents was often necessary. The limit of detection was generally about 0.1 c(g of tin. Sea water Samples of from 10 to 60 kg were collected and stored in plastic apparatus. Immediately after collection llYin wss added in sufficient hydrochloric acid to bring the pH to 1. Subsequently, carbon dioxide was removed by passing nitrogen, the pH adjusted to 96 & 0.1 with dilute ammonia solution and the solution pumped, with exclusion of carbon dioxide, at 500 ml/hr through a 25 cm x 05 cma bed of acid-washed “Spectrosil” quartz wool in a plastic column. The container and column were washed with 100 ml of deionised water and then with 60 ml of QN sulphuric acid which eluted tin. Blanks were run on sea water stripped of tin by coprecipitation on hydrous manganese dioxide. Determinations were corrected on the basis of measurements of the recovery (67-82 per cent) of the llemtin tracer; it was established that identical recoveries were obtained from spikes of radioactive and stable tin. Measurements were in duplicate and the reproducibility is shown for the individual results. Experiments to establish optimum conditions for uptake suggested that the adsorption mechanism probably depends upon reaching a state of incipient precipitation of magnesium hydroxide. Other 7nateriale Up to 1 g of dried ground material was used. Silicates were digested at 100% in vented polypropylene bottles, with a 4 + 1 mixture of concentrated hydrochloric and hydrofluoric 621

J. D. SXITFEand J. D.

622

BURTON

acids; hydrogen peroxide was added to samples containing appreciable organic matter. The solution, diluted to 6N in hydrochloric acid, was passed through an anion exchanger (Amber&e IR 400) in a. plastic column. After washing with 6N hydrochloric acid, 1N citric acid and water, tin W&S eluted in 2N sulphuric acid. Carbonates, phosphorites and ferro-manganese materials were digested at room temperature with 6N hydrochloric acid and the solution treated similarly; residues were usually retained for separate analysis as silicates. These procedures are described more fully by &KITE (1971). Tissues were digested, under reflux in a silica flask, in concentrated sulphuric acid with addition of 50 % hydrogen peroxide; the excess peroxide was removed by boiling. amounts of stable tin were complete Recoveries of spikes of radioactive llWin and various for these materials. Replicate determinations on the U.S. Geologica Survey reference basalt @CR - 1) gave a mean tin content of 1.81 ppm with a coefficient of variation of 1.8 %. Results for tin in the current series of U.S. Geological Survey reference rocks are mostly too disparate to provide a basis for assessing the accuracy of new data; the present values are generally consistent with the neutron activation values of DAS et al. (1970). A coefficient of variation of 3.3 % was found for replicate determinations on a ferromanganese concretion with an average acid-soluble tin content of 2.7 ppm. For a tissue containing 0.23 ppm the corresponding value was 14%. Manganese, iron, calcium, cobalt, nickel and copper were determined by atomic absorption spectrophotometry on the solutions of ferromanganese materials. Coefficients of variation were between 1.3 and 1.7 % except for cobalt (2.7 %).

RESULTS AND DISCUSSION Igneous rocks and residual products of weathering.

Results for igneous rocks are given in Table 1. The mean value for three ultramafic rocks (0.8 ppm) is somewhat higher than the weighted mean (0.6ppm) of the results of ONISHI and SANDELL (1957) and HAMACWCEXIet al. (1964). BROOKS et al. (1960) reported O-3 to 1.3 ppm for three such rooks. The average of the thirteen basalts of differing occurrence was 1.7 ppm. Three sea-floor basalts showed a similar range and mean to the remainder. Previous extensive analyses of basaltic rocks are those of ONISHI and SANDELL (1957) for six composites (mean l-4 ppm) and DURASOVA (1967) who found an average of 1.5 ppm for 25 samples. The dispersion of tin in such rocks appears greater than was hitherto apparent. The average content of the silicic rocks (2.5 ppm) is significantly lower than the general average for such rocks which appears well established as about 3.5 ppm (HAMAGUCHI and KURODA, 1969). This probably reflects the small number of granites examined here as well as their origin, Four brown earths and a gley soil from Great Britain had tin contents varying from 0.3 to 2.8 ppm (mean 1.4 ppm) the highest value being for the gley soil which overlaid

shale strata.

Clay from the Dalradian

Bed, Co. Donegal,

contained

1.4 ppm. Sea water and marine organisms.

The concentrations of tin in sea water (Table 2) decreased from estuarine and near shore to oceanic environments. Samples from Southampton Water were filtered through acid-washed 0.5 ,u glass fibre filters. Experiments with the particulate material indicated that for the other samples, which were not filtered, the contributions to the measured values from leaching of suspended matter did not exceed about lo-15 per cent. The average concentration found

The occurrenceand distribution of tin with particular referenceto marine environments 623 Table 1. Tin in igneous rocks Tin Type and origin

Ref. no.

(PPm)

Ultramafia rocks Dunite, Washington* DTS-1 Peridotite, California* PCC-1 Mylonitized peridotite, St. Prtul’s Rocks P5(5) Basaltic and intermediate rocks Basalt. Mid-Atlantic ridge. 29’04’N 45’Ol’W (22OOm.) 1963.896 Basalt; Mid-Indian Ocean ridge, 24’04’s 70’12’E (3692 m.) 1964.740(7) Basalt, South-eastern Pacific YOS’S 107’3O’W (2857 m.) 1969.0.23 Olivine basalt, Eniwetok Atoll (bore sample at 1284 m.) 1964.128 Olivine trachybasalt, Mt. Gower Lord Howe Island 1966.P6.2 Olivine basalt, Mt. Gower, Lord Howe Island 1966.P6.8 Olivine basalt, Mt. Gower, Lord Howe Island 1966.P5.16 Olivine trachybaselt, Mt. Lidgbird, Lord Howe Island 1966.P6.26 Basalt, Mt. Lidgbird, Lord Howe Island 1966.P5.40 Tholeiitic basalt, Hawaiian Islands c9 Ankaramite, Hawaiian Islands C67 BR Basalt, Francet Basalt, Columbia River Group* BCR-1 AGV-1 Andesite, Oregon’ Silicic rocks Granodiorite, Colorado* GSP-1 Adamellite, Co. Galway$ CWC 132 Granite, Co Galwey %‘A 60/l(2) Granite, Co. Galway 1 BL 2762 Granite, Co. Galway Westerly granite, Rhode Island* G-2

-

0.74 0.88 0.80 0.70 1.1 2.7 0.92 1.8 1.0 1.8 1.3 2.1 3.5 l-8 2*1(O) 1.8(l) 3.0(3) 4.3(5) l-6 2.5 1.0 2.8 1.3(2)

* U.S. Geological Survey reference swnples (FLANAGAN, 1967). t Reference semple from Centre de Recherche PCtrogrephique et GBochimique de Nancy (ROUBAULTet aE., 1966) $ Results for 38 elements given by LEAKE et al. (1969)

Table 2. Tin in sea water

Origin Southampton Water English Channel 49’28’N 4’4O’W* Gulf of Naples N. E. Atlantic 33’35’N 13’39’W 22O38’N 2O’Ol’W

Month of collection 1969

Salinity

Tin

(%o)

@g/kg)

Oct.

34-l

o-040 f 0.007

Nov.

35.6 37.3

0.033 f o-001 0.022 f 0.002

36.8 36-S

O*OlOf 0.003 o*oos f o-003

May Dec.

* International Hydrographical Station E2. for surface

N.E. Atlantic water (0.009 -& 0.003 pug/kg) was about two orders of magnitude lower than that (0.8 pug/l.) reported by HAMAGUCHI et al. (1964) for waters at 500 m in the North-western Pacific. The values found in coastal water are similarly lower than that (1.8 pug/l.) given by SHIMIZU and OGATA (1963) for Japanese inshore water. Data are given in Table 3 for tin in some fixed algae and the soft parts of some common molluscs from coastal waters in southern England. Concentration factors were of the order of magnitude of 104, expressed on a tissue dry weight

J. D. SMFXH and J. D. BURTON

624

Table 3. Tin in algae and mollusca from coastal waters of southern England Tin (ppm dry weight) Algae Pheeophycoee Deamareatia aculeata Larnkarkz sacharina Larnimwia digitata

Dictyota dichotorna

O-65 o-29 o-13 o-10

Mollusce

Gastropoda Cre@dula f ornicata Buccinum undaturn Lamellibranchia Card&n edule Mercenaria memenaria

0.71

0.33 0.67 0.23

basis. Phytoplankton collected in Southampton Water showed a higher content of tin of 3.5 ppm dry weight. ikfarine sediments The results for tin in marine sediments are given in Tables 4 and 5. Concentrations in red clay ranged from l-8 to 83 ppm (mean 3.4 ppm) and in calcareous oozes’from O-27 to 4.6 ppm (mean 1.9 ppm). These are considerably lower than the results reported by EL WAKEEL and RILEY (196lb) but agree satisfactorily with those given by HAMAGTJCHI et al. (1964). SMITH (1970a) showed that calcareous skeletal material in molluscs and echinoderms is low in tin (
The occurrence and distribution of tin with particular referenoe to marine environments

Table 4.

Tin in marine

sediments,

other

than

ferromaaganese concretions W&Z depth

Ref. no.

Argillaceous

625

Type and origin

Tin

Position

(m)

35’41’N 167’42.E -4’lQ’N 130’15’E 14’44’N 142O13’E 2O*OO’N 80*02’W 21”4O’N 80°00’W IQ”53’S 9Q063’E

4200 4860 4200 6070 5930 8110

2.4 2.4 8.8 2.1 3.0 1.8

S’OO’N 121’42’E 36039’S 50947’W 1’45’5 41°33’E 40’80’N 12’11’E

4060 3470 219 3809

40*2@‘N

1023

(PP4

sediments

M.306 M.273 M.290 D.23.22 D.23.21 1964.743 M.270 M.395 1964.526 TS 13

TS 21

1955.71(31) 1955.71(35)

Red clay, Paci50, Challenger Station 241 Red clay, Paoiflo, Challenger Station 216 Red clay, Pwitia. Challenger Station 226 Red c&y, Atlantio Red cl&y, Atlantic Red clay (with rcadiokis), Indian Ocean, Argo Station DOD0.66.B Blue mud, Paciflo, Challenger Station 211 Blue mud, Atlantic, Challenger Station 323 Blue mud, Indian Ocean, Owen Station 38 Silty clay, Tyrrhenian Sea. 20 am. depth Silty eley, Tyrrhenian Sea. 70 cm. depth Silty clay. Tyrrehuisn Sea, 160 cm. depth Silty clay. Tyrrhenian Sea, 13 cm. depth Silty cley, Tyrrhenian Sea, 40 cm. depth Silty clay, Tyrrhenian See, 60 urn. depth Grey-green mud, Mslaye, Dampier Station 31 Green-brown mud, Malaya, Dampier Station 36

5O30’N 100°OO’E 5O14’N 100°lO’E

15.5 14.5

4.1 1.8 0.11 3.2 2s 4-o 4.3 4.4 4.4 2.0 3.1

Globigerius ooze, Peoific, Challenger Stcation 224 Globigeriua ooze, Atlantio Globigeriua ooze, Atlantic, Buccaneer Station 409 Glob&ins ooze, Atlantis, Mutine Station 13 Pteropod ooze. Atlantic, Silvertown Station 12 Globigeriua ooze, Indian Ocean, Egeria Station 15 Globigeriua ooze, Red Sea, Calcareoun ooze, Red Sea Caloareous mud, Darvel Bay, Borneo, Dampier Station 47 Cslcsreous mud, D&we1 Bay, Borneo, Dampier Station 48

7*45’N 144”20% Q065N 63%9’W OO”O1’S lV’38’W 24’22’N 18%‘W 27’54’N 14’42’W 20’00’8 87”33’E 17’35’N 40’2l’E 21’20’N 39’00’E 4O48’N 118O21’E 4’42’N 118’22’E

3380 1790 3370 1680 840 2940 1050 900 68 42

4-2 4.8 1-2 0.27 0.68 I.3 1.4 1.5 (0.06
Diatom ooze, Southern Ooean, Challenger Station 157 Send, Cardigan Bay, Antar Station 230 Phosphor&*, Atlantic, John Murray Station 148 Phosphorite*, Off Cape of Good Hope

63’55’5 52’40’N 31’17’N 34’43%

14’08’E

Carbonate sediments M.288 D.23.34 M.3434 M.5170 M.7876 M.3786 D.23.36 D.24.7 1981.269(47) 1981.289 (48) Other sediment41 M.191 1984.277 1988.0.429 l?Q/PT-4 l

103’35’E 3660 4’17’W 18 10’24’W 260 18’12’E 367-615

IS 0.68 0.25 0.11

Acid soluble material

only for the Missouri fossil nodule (see Table 6) and the Blake Plateau nodules (64 and 61% &CO,). For the others the correction was less than 7% and usually below 2 %. The acid insoluble residues, mainly clay minersAs, feldspars and quartz, ranged from less thrtn 4 to 39% of the total nodule weight. Six residues were found to contain up to 2.9 ppm of tin, with a mean of O-7 ppm. Three concretions from off the California coast showed significantly lower concentrations of tin (0.2-1.6 ppm, mean O-9 ppm) than the nine from other oceanic environments (24-S-S ppm, mean 4.2 ppm). This difference is more distinctive than are the differences for other elements, although cobalt also shows a clear trend towards low values in the marginal samples. These marginal noduIes do not appear to belong to the distinctive group (MERO’S “B” regions) charrtcterised by particularly high ratios of manganese to iron and generally low trace element contents, occurring in parts of the East Pacific continental marginal region (MERO, 1966; TOOMS et al., 1969; PRICE and CALVERT, 1970).

J. D. SMITH and J. D. BURTON

626

Table 5. Tin in ferromanganeseconcretions (acid-solublefractions) Concentrations in dry, oarbonate-free material

Ref. no.

Origin

Water depth (m)

Position

Mn

Fe

Co

Ni

Cu

Sn

(%)

(%)

(%)

(%)

(%)

(PPm)

30.6 25.8 28.6 28.7 26.1

18.5 22.4 13.3 11.0 18.4

0.17 0.39 0.28 0.11 0.18

1.29 0.90 1.59 1.69 0.45

0.74 0.56 0.80 0.33 0.04

4.1 3.6 6.8 0.21 1.6

39.6

28.1

0.02

0.29

0.19

0.91

20.4 17.3 24.6

0.41 0.43 0.63

0.72 0.91 0.33

0.02 0.12 0.11

6.0 4.3 4.3

Oceanic M.313 M.316 M.35’7 1963.910 1963.913

Pacific, Challenger Station 248 Pacific, Chellenger Station 252 Pacific, Challenger Station 285 Pacific, off California Pacific, off California, Argo Station BAC-56 1965.0.243 Pacific. off California, Horizon Station 65.1.38 M.3028 Blake Pleteau, Blake Station 317 Ag Cl1 Blake Plateau 1969.0.5 San Pablo Seamount (%TOmanganese pavement) Hudson Stn.54 1969.0.5 As above, different sample Atlantic, Discovery St&ion 4799 96626 F(40)C Atlantic, Mobahiss Station 166(40) Outer layer of nodule Inner layer of nodule 96626 F(40)D As above Core of nodule 96626 F(40)F As above

37O41’N 37’=52’N 32’36’N 22’00’N 22’50’N

177’04’W 160°17’W 137’43’W 114’06’W 109’33’W

24’24’N

113’16’W

6800 6480 4760 4000 1700

78’19’W

640

39”OO’N 60”67’W

2000

16.0 27.5 20.8

26,=04/N 6’55’N

2300 4790

18.4 18.1 26.9

28.6 25.7 20.7

0.47 0.60 0.16

0.31 0.31 1.06

0.09 0.09 0.31

4.0 6.6 2.1

24.2 18.1

20.2 25.7

0.19 0.25

0.88 0.33

0.32 0.19

2.8 4.1

47.0 41.3

2.2 4.1

0.03 0.03

0.03 0.07

0.005 0.01

0.20 0.20

31’67’N

-

22’22’W 67’11’E

Epicontinentel M.9155B 1969.0.1

Loch Fyne, Scotland Jervis Inlet, Cenrtde

56’60’N 60’06’N

5’2O’W 123’47’W

210 370

Fresh W&x -

Lake Lilla UllevifjBden, Sweden

about 10

24.3 24.3 0.04 0.06 0.007 0.136

Fossil 1938.1316 1961.70

Noil Tobe, Midden Timor, Java Missouri, U.S.A. *

8”OO’S 125”OO’E 39’16’N 93'16'W

* As disousaed in the text, this concretion contained 86 % C&O, occurred.

33.3 13.7

26.4 1.8

0.57 2.88

0.82 0.14

0.60 0.04

1.3 7.7

and considerable post-depositional alteration had probably

The values are consistent with the results of AHRENS et al. (1967) who found from cl.5 to 6.2 ppm in whole nodule material. For the oceanic nodules, including those from off the Californian coast, there were significant correlations in concentrations, positively for tin with cobalt and nickel with copper (both, P < 0.01) and negatively for tin with manganese (P < O-05), cobalt with manganese, and nickel with iron (both, P < O-001). No other statistically significant correlations were found. Isomorphous replacement of cobalt (III) for iron in goethite was demonstrated by BURNS and FUERSTENAU (1966). The correlation between tin and cobalt might imply that tin is also primarily associated with iron phases. The ionic radii of tin (IV) (0.71-0.74 A) (H EYDEMANN, and iron (III) (O-678) 1969) are sufficiently similar to permit ready substitution. However, in the present series the concentrations of cobalt and tin were not significantly correlated with that of iron, perhaps because of variable degrees of association of iron with the manganese phases. The two concretions from different epicontinental environments each had concentrations of manganese greater than 40 per cent, weight ratios of iron to manganese less than O-1 and concentrations of tin, cobalt, nickel and copper all distinctly lower than the average for oceanic nodules. The Swedish freshwater

The occurrenceand distribution of tin with particular referenceto marine environments 627

lake concretion, with a much higher ratio (1.0) of iron to manganese, was likewise low in trace metals. The Timor fossil nodule had a composition which was consistent with an oceanic origin, in accordance with previous findings (EL WAKEEL and RILEY, 1961a). Sedimentary

and metamorphic

rocks.

Concentrations of tin in carbonate rocks (Table 6) ranged from 0.23 to 1.7 ppm. The fractions of tin dissolved by hydrochloric acid were very variable (6-48 per cent); they overestimate the true fraction in carbonate material since some tin would be leached from other minerals. The low total contents presumably reflect relatively low amounts of non-carbonate impurities. Extensive spectrographic analyses (WEDEPOHL,1955; RUNNELSand SCHLEICHER, 1956; DEBRABANT,1970) suggest a mean tin content of 4 ppm for carbonate rocks; they include some high values which may reflect metamorphic segregation. Values for some metamorphic rocks are given in Table 7. The pelites and Table 6. Tin in carbonate rocks Tin Ref. no. GFS GFS GFS PK BL

400 401 402 180 762

Type and origin Dolomite, Woodville, Ohio Limestone, Marble Cliff, Ohio Limestone, Spore, O&o Marble, Perthshire* Calcite marble, Connemara, Co. Galway*

(ppm) Total Acid-soluble 0.08 0.60 0.03 0.24 0.44

0.23 1.25 0.47 0.81 1.66

* Results for major elements are given by LEAEE et al. (1969) for PK 180 and by LEAKE (1970) for BL 762. Table 7. Tin in metamorphic rocks* Tin Ref. No. PK 170 BL 1103 BL 360 BL 1714 BL 245 BL 3570 BL 3571 BL 3615 BL 3617 BL 3633 BL 3634 1968.P.21

Type and origin Muscovite-rich phyllite, Devon? Semi-pelitet Schist Biotite-sericite-quartz-sillimaniteschist Siliceous granulite Amphibolitet Amphibolitet Amphibolite Amphibolite Amphibolite Amphibolite Brown hornblendemylonite, St. Paul’s Rocks

(ppm) 3.0 5.8 2.1 4.3 2.5 0.37 0.63 1.4 1.5 2.4 0.92 1.0

* All rocks are from Connemara, Co. Galway, except where otherwise indicated 7 Results for major elements are given by LEAIXEet aZ. (1969) for PK 170 and by LEUE (1970) for BL 1103. $ Results for 38 elements are given by LE~LKE et ~2. (1969).

628

J. D. Srma~~and J. D. BURTON

schists generally contained somewhat enhanced contents of tin, consistently with the known enrichment in shales (HAMAGTJOHI and KURODA, 1969). The average content of l-2 ppm for six amphibolites is similar to that in basalts. Most amphibolites are derived from metamorphosed basalts or dolerites and evidently there is little change in tin content with metamorphism. Achmozuledgemem%-The authors thank Dr. 5. Ii. H. WISEand the Trustees of the British Museum, Dr. B. E. LEAKE, Dr. B. W. A-Y, Dr. G. T. BOIIZCH,Mr. D. L. CR.AIYI, Dr. P. S. LISS, Dr. A. I?. EA.LOCKWOOD,Mr. R. J. MORRISand Dr. A. I. REES for their help in supplying samples. They are also grateful to Dr. Lr~m and Dr. WISE= for helpful discussions and comments on the manuscript. One of us (J. D. S.) thanks the Natural Environment Research Council for the award of a research studentship.

Arrn~~s L. H., WILLIS J. P. and Oos~rm~z~~ C. 0. (1967) Further observations on the composition of msnganese nodules, with partioular reference to some of the rarer elements. Geochim. Cosmochim. Acta 31, 2169-2180. BROOKSR. R., AERENSL. H. and TAYLORS. R, (1960) The determination of trace elements in silicate rocks by a combined spectrochemical-anionexchangetechnique. Cfeochim. Cosmochim. Acta 18, 162-175. BURNS R. G. and F~ERSTENAUD. W. (1966) Electron-probe deter~ation of inter-element relationshipsin manganese nodules. Amsr. Mineral. 51, 895-902. DAS H. A., VAN RAAPEORST J. G. and URNS H. J. L. M. (1970) Routine determinations of Al, K, Cr and Sn in geochemistry by neutron activation analysis. J. Radioanal. Chem. 4, 21-33. DEBR~BANTP. (1970) Typologie geochimique des calcaires. Application B. l’etude de l’origine des calcaires m&amorphiques des Massifs hercyniens frangais. D.Sc. Thesis, University of Lille. D~ASOVA N. A. (1967) Some problems of the geochemistry of tin. #eochem. I&. 4, 671-681. EL WAEEELS. K. and RILEY J. P. (1962a) Chemicaland mineralogicalstudies of fossil red clays from Timor. Ckochim. Oo8mochim. Acta 24, 260-265. EL WAKEEL 5. K. and Rmsu J. P. (1961b) Chemical and mineralogical studies of deep-sea sediments. Geochim. Cosmoohim. Acta 25, 110-146. P~LANA~AN F. J. (1967) U.S. Geological Snrvey silioate rock standards. @eo&m. Coals Acta 31, 289-308. tieucm H. and KURODAR. (1969) Tin. In Handbookof Ueochernietq(editor K. H. Wedepohl), Vol. II. Springer-Verlag. HAMA~UCHIII., K~RODA R., O~oad~ N., KAWABUCRIK., MITSU~AYASHI T. and HOSOHARA K. (1964) The geochemistry of tin. Geochim. Cosmochim. Acta 28, 1039-1053. HEYDE~YLANN A. (1969) Tables. In Handbookof @eochemi&y (editor K. H. Wedepohl), Vol. I, 376-412. Springer-Verlag. HORN M. K. and An-s J. A. S. (1966) Computer-derived geoohemical balances and element abundances. Ueochim. Cosmochim.Acta 30, 279-297. LEAKEB. E. (1970) The origin of the Connemaramigmatites of the Cashel district, Connemara, Ireland. Quart. J. cfeol. Sot. Lord 125, 219-276. LEAKEB. E., HENDRYG. L., KEMPA., PLANTA. G., HARVEYP. K., WILSONJ. R., COATSJ. S., AUCOTTJ. W., L@NELT. and HOWARTER. 5. (1969) The chemicalanalysis of rock powdersby automatic X-ray fluoresoenee. C&em. @sol. 5, 7-86. MERO J. L. (1965) The i%fimeraE Rssarces of the Sea. Elsevier. ONISRI H. and SANDELLE. B. (1957) Meteoritic and terrestrial abundance of tin. cfeochim. Cosmochim. Acta 12, 262-270. PRICEN. B. and CALVERTS. E. (1970) Compositionalvariation in Pacitlc Ocean ferromanganese nodules and its relationshipto sediment accumulation rates. Mar. UeoZ.9, 145-171.

The occurrence and distribution of tin with particular reference to marine environments

629

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