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GEOCHEMISTRY of URANIUM in the CARIACO Trencht

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GEOCHEMISTRY of URANIUM in the CARIACO Trencht GEOCHEMISTRY OF URANIUM IN THE CARIACO TRENCHt CLARA C. DORTA AND ELIZABETH RONA University of Miami, Rosenstiel School of Marine and Atmospheric Science ABSTRACT During a cruise (P6603) of the R/V PILLSBURY of the University of Miami, several cores were taken from the Cariaco Trench. The concen- trations of thorium, protactinium, and uranium have been studied. A layer of oxidized clay is present below a few meters of reduced sediments. Anal- yses show high concentration of uranium to be associated with the organic- rich reducing sediments. In one core, a fivefolddecrease in uranium content is found in the oxidized layer, whereas the thorium and protactinium re- main the same. Aeration of the sediment at the end of the last glaciation dissolved uranium in the oxidized layer. In the reducing layers, uranium concentrations are higher than in sediments of the open sea. INTRODUCTION The Cariaco Trench is a depression about 1390 meters deep on the Con- tinental Shelf off the Venezuelan coast, 100 miles long in the east-west direction, and 40 miles wide in the north-south direction. It is separated from the Caribbean Sea by a ridge which includes a line of islands. The sill is nowhere deeper than 150 meters, thus shutting off the deeper water from that of the Caribbean. Above sill depth, the waters of the trench are in free communication with the Caribbean Sea, while below, an isolated marine environment undisturbed by mixing exists. The Cariaco Trench offers an opportunity to study the geochemistry of uranium in an anaerobic environ- ment, and the stratigraphy of Recent marine deposits. The chemistry of the waters of the Cariaco Trench has been studied extensively by Richards & Vaccaro (1956). The oxygen content of the water below sill depth decreases to zero at about 475 meters (Fig. 1); here hydrogen sulfide can first be detected. Below this depth the concentration of hydrogen sulfide increases. At 700 meters, nitrogen as nitrate disappears, and the only inorganic nitrogen is ammonia. This situation is similar to that of other euxinic basins, such as the Norwegian Fjords and the Black Sea. The sediments are rich in "black mud" of relatively high organic con- tent. The sediments from the Cariaco Trench have been investigated by Heezen et at. (1959), Broecker et at. (1960), and Lidz et at. (1969). The upper 5 or 10 meters of the cores are composed of dark greenish gray laminated 1 Contribution No. 1400 from the University of Miami, Rosenstiel School of Marine and Atmos- pheric Science. 1971] Dorta & Rona: Geochemistry of Uranium, Cariaco Trench 755 DISSOLVED OXYGEN AND TOTAL REDOX REACTANTS MIL L I REACTANTS OR mg AIL 0.0 0.1 0.2 0.3 0.4 0.5 0.6 -tt, ":t!..' I , I I I , , I I I ~ 100 .••...••..•. r,1) __ .•.,.," f \ r \ i + ~ ~\.\ \ . en v VII a: + , w 600 t I- W v~ ++ ~ IV . \ r I ffl I- \ a.. 800 w o Jz 1++ 'v\ CARIACO TRENCH ~ T • DISSOLVED OXYGEN 1 1000 I v SULFIDE CONCENTRATION + vf + TOTAL REDOX REACTANTS I v I, CARIBBEAN , 1200 o DISSOLVED OXYGEN + ,, v A 1400 0.00 0.05 5 CONC., mg AIL FIGURE 1. Dissolved oxygen in the Cariaco Trench and the nearby Caribbean; sulphide concentrations and total oxygen and sulphate consumed in the Cariaco Trench. (After Richard & Vaccaro, 1956.) lutite, deposited under reducing conditions. A layer of oxidized clay is present beneath this organic layer (an indication that aeration occurred sometime in the past) and is followed below by another laminated layer (cf., Fig. 3). A radiocarbon date on organic material from the base of the 756 Bulletin of Marine Science [21 (3) 61° 66° 65° VENEZUELA 66" . Lo"t;on of C.,;a ". ,~ FIGURE 2 Navy H. O. Cha" ~ 0.2319,TeenehApriland hidrographic statio s .~ upper anacrob' I 917. 13th Ed., 195 0iMler u.s. 11,000 years ~ :yer indicates that sta . belowd' must have. .bc(Heezend el a.,l 1959)gnahon of the trench b an .m'eropaleonlo eo eposited dnrin . Therefore th eg~n.abruptly P,gure 2 show log,eal analyses by Lgdthe last glacia;;o e ox.,d,zctl day 'he cores were ta~:n map of lhe Cariae~ ~ et al. (1969) s~' M,""~logieal Melh d . Table 1 gives 1 . rench and the I pp.ort this view o s.-P oea',o oeat.o . 2-5) have b our cores from th . n, water dep'h, and ns at which een analyzed f ~ Canaco Tre h core length. or maJor', mmor, andnctrace(seeel F Ig. 2 and Tables ements , usmg. effilS-. DATA FOR C TABLE 1 ORES FROM THE CARIACO T Latitude RENCH (N) Longitude Water depth Core length Core No. (W) (m) (em) P6603-1 10°28' 64°39' 1346 790 P6603-2 10°35' 64°38' 940 820 P6603-4 10°48.6' 65°21' 1124 210 P6603-7 10°42.5' 65°50' 1339 504 1971 ] Dorta & Rona: Geochemistry of Uranium, Cariaco Trench 757 TABLE 2 ELEMENTALANALYSESOF CORE P6603-2 -_ .. ~----- ,----- ~-~--- Depth (em) 4-8 254-259 354-359 504-509 --- -----~- p~O.; (%) 0.163 0.231 0.189 0.121 SiO~ ('70) 31.53 50.76 42.68 33.33 AI ('70) 5.93 2.80 6.24 5.56 Fe ('70) 2.9 1.5 3.1 2.9 Na ('7~) 0.519 1.63 2.22 1.63 Mn (%) 0.019 0.009 0.029 0.032 Ca ('70) 4.07 1.64 4.15 5.07 Mg (%) 0.84 0.72 0.78 1.20 K ('70) 1.16 0.664 1.16 1.08 TABLE 3 ELEMENTALANALYSESOF CORE P6603-1 Depth (em) 0-7 50-54 103-109 357 TiO~ ('70) 0.70 0.80 0.70 0.75 Fe ('70) 3.75 3.72 3.60 3.90 AI~O:l ('70) 13.4 13.2 13.0 13.6 MnO ('70) 0.028 0.018 0.030 0.033 P~O~ ('70) 0.18 0.20 0.25 0.25 MgO ('/'0) 2.05 1.95 1.85 1.90 CaO ('70) 8.60 9.25 9.15 9.70 Na~O ('70) 2.75 2.75 2.60 2.45 K~O (70) 1.80 1.80 1.72 1.62 B (ppm) 100 130 115 110 Ba (ppm) 400 350 400 350 Co (ppm) 12 5 5 10 Cr (ppm) 95 85 95 100 Cu (ppm) 25 30 25 30 La (ppm) 25 30 35 40 Ni (ppm) 80 85 70 80 Sc (ppm) 12 14 13 13 V (ppm) 200 250 190 200 Y (ppm) 20 25 25 25 Zr (ppm) 90 95 105 105 Mo (ppm) 75 90 85 85 --- 758 Bulletin at Marine Science [21(3) TABLE 4 ELEMENTAL ANALYSES OF CORE P6603-4 Depth (em) 6 53 74 Ti02 (%) 0.40 0.40 0.45 Fe (%) 2.45 2.70 2.80 AI203 (%) 9.0 10.0 10.0 MnO (%) 0.025 0.035 0.022 P205 (%) 0.17 0.20 0.30 MgO (%) 1.85 1.95 1.80 CaO (%) 21.2 19.8 18.0 Na20 (0/0) 2.65 2.85 3.00 K20 (%) 1.80 1.25 1.45 B (ppm) 95 110 120 Ba (ppm) 250 400 450 Co (ppm) 5 10 5 Cr (ppm) 80 90 80 Cu (ppm) 20 18 13 La (ppm) 20 20 16 Ni (ppm) 70 80 75 Sc (ppm) 9 10 10 V (ppm) 180 145 190 Y (ppm) 16 18 13 Zr (ppm) 40 60 50 Mo (ppm) 110 60 40 sion spectroscopy and atomic absorption. Uranium, thorium isotopes, and protactinium were separated by ion exchange and solvent extraction tech- niques. The concentrations of the radio elements were determined by alpha particle spectrometry (Rona, 1969) (Tables 6-9). Uranium concentrations are high in all cores, compared to the Caribbean cores (cf., Rona & Emiliani, 1969; Rona, Emiliani & Dorta, 1970)-up to 30 p.g/g sediment in trench cores compared to 1 to 2 p.g/g in the Carib- bean cores. Anoxic environments are rich in organic material which decom- poses slowly, utilizing all the oxygen available. Uranium forms complexes with organic matter and is released after decomposition. In the reducing environment of the sediment interface, uranium is immobilized as insoluble sulfide or hydroxide. In all cores, high concentrations of uranium show correlation with organic matter and with molybdenum and vanadium. These elements are also scavenged by organic matter. The presence of Ti02 indi- cates the intrusion of detrital material in some sediment profiles. 1971] Dorta & Rona: Geochemistry of Uranium, Cariaco Trench 759 TABLE 5 ELEMENTAL ANALYSES OF CORE P6603-7 Depth (em) 2-6 50-54 100-104 320 Ti02 ('fa) 0.70 0.65 0.85 0.55 Fe ('70) 4.00 3.55 4.20 3.15 AI203 ('fa) 13.8 13.0 13.6 13.2 MnO ('fa) 0.054 0.038 0.069 0.024 P205 ('fa) 0.20 0.14 0.30 0.14 MgO ('fa) 2.33 1.85 2.20 4.20 CaO ('fa) 10.5 15.0 8.3 13.5 Na20 ('fa) 3.40 2.00 2.55 1.70 K20 ('fa) 1.50 2.00 1.82 1.90 B (ppm) 105 100 60 120 Ba (ppm) 200 300 300 300 Co (ppm) 12 11 16 5 Cr (ppm) 90 80 90 70 Cu (ppm) 20 25 25 20 La (ppm) 30 30 35 30 Ni (ppm) 70 70 75 50 Sc (ppm) 14 13 16 12 V (ppm) 185 180 135 140 Y (ppm) 20 25 30 20 Zr (ppm) 95 95 55 80 Mo (ppm) 50 30 19 60 TABLE 6 ISOTOPIC ANALYSES OF URANIUM, THORIUM, AND PROTACTINIUM OF CORE P6603-2 U-23S* Depth U-234" U-234 Th-232 Th-230"t Pa-231*t Th-230 CaCO.
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