URANIUM PRECIPITATION IN BLACK SEA SEDIMENTS

R. F. ANDERSON and M. Q. FLEISHER

Lamont-Doherty Geological Observatory
of Columbia University
Palisades, New York 10964 USA

ABSTRACT. Previous studies have shown that organic-rich sediments of anoxic marine
basins like the Black Sea are enriched in uranium, and that the seawater itself is the
source of the uranium. An earlier study of uranium in the water column of the Black Sea
showed that the processes of uranium precipitation are not occurring in the water column,
from which it was inferred that the precipitation process occurs in the sediments.
Concentrations of U in sediments and associated pore waters were measured at three sites
in the Black Sea: an abyssal plain site in the central eastern basin, and two sites on the
shelf along a transect out from the Bay of Sinop: one shallow site underlying oxygenated
bottom waters and one deeper site underlying sulfidic bottom waters. Similar pore water
uranium profiles were found at all three sites, indicating that similar processes of U
precipitation are occurring at all of these sites. Authigenic U contents of the sediments
are highest in the abyssal sediments, lowest in sediments from the outer shelf, and
intermediate at the inner shelf site. Chemically reducing conditions of the sediments
themselves, rather than the condition of the bottom waters or the composition of the
sediments, lead to precipitation of uranium. The concentration of authigenic uranium that
builds up in the sediments is inversely related to sediment accumulation rate.

1. Introduction
Organic-rich sediments of anoxic marine basins like the Black Sea are enriched in
uranium by more than an order of magnitude compared to open-ocean pelagic clays and
oozes (e.g., Koczy, 1957; Kochenov et aI., 1965; Dorta and Rona, 1971; Kolodny and
Kaplan, 1973; Mo et al., 1973; Rona and Joensu, 1974; Degens et aI., 1977; Huh et aI.,
1987; Anderson, 1987). The isotopic composition of the authigenic uranium present in
these sediments indicates that it has a seawater origin (uranium dissolved in open-ocean
seawater is enriched in 234U relative to secular equilibrium with 238U by 14%; Turekian
and Chan, 1971; Ku et aI., 1977; Chen et aI., 1986).
Four general mechanisms for the deposition of U in sediments have been
proposed: 1) active biological uptake of U by organisms whose remains are incorporated
into organic-rich sediments; 2) chemical adsorption or complexation of dissolved U by
particulate organic matter which eventually settles to the sea floor, where the U-organic
complex is preserved after burial by the anoxic conditions in the sediments; 3) chemical
reduction in anoxic water columns of the soluble U(VI) carbonate complex to insoluble
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E. Izdar and J. W. Murray (eds.), Black Sea Oceanography, 443-458.
© 1991 KilMer Academic Publishers.
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U(IV) which is subsequently removed to the sediments by chemical scavenging

processes; and 4) diffusion of dissolved U(VI) into anoxic sediments where it is reduced
and precipitated. Any of these mechanisms may operate under certain environmental
conditions; however, each of these mechanisms has only been inferred from indirect
evidence, and there has been little rigorous testing of any of these proposed processes.
These processes, and evidence in support of each, are discussed in detail by Anderson et
aI. (1989A&B).
A previous study (Anderson et aI., 1989A) ofU dissolved in the water column and of
U associated with particulate matter settling through the water column showed that
uranium exists in its soluble U(VI) form in the deep water of the Black Sea. Dissolved
U(VI) occurs as a chemically-reducible species which has a residence time in the deep
waters of about 1000 years. Biogeochemical processes in the water column, including
uptake by plankton, complexation by POC, and chemical reduction to insoluble U(IV)
followed by scavenging onto settling particulate matter, contribute negligibly to the
deposition of U in Black Sea sediments. From these findings it was inferred that
deposition of authigenic U in the sediments of the Black Sea, and by analogy in
sediments of other anoxic marine basins, must involve precipitation ofU within the
sediments themselves, rather than removal processes occurring in the water column.
At the time of the earlier study there were no measurements of concentrations of U in
pore waters and sediments of sufficient detail and/or sufficient reliability to substantiate
this conclusion. The purpose of this paper is to follow up the earlier study and present
results for the distributions of U in pore waters and sediments of the Black Sea. Sites
from both the abyssal plain and the continental shelf are examined to better understand the
locations, as well as the mechanisms, of U deposition in the sediments of anoxic marine
basins.

2. Sampling Locations and Sample Processing Methods

Sample locations are shown in Table 1. Stations 15 and 17 were occupied during a
transect across the shelf running out of the Bay of Sinop on the north central coast of
Turkey. Water overlying the sediments at Station 17 is well oxygenated whereas sulfide
was easily detected by smell in the bottom waters at Station 15. Sediments at Station 15
consisted of grey and black bands, the coloring being inferred to come from varying
amounts ofFeS and pyrite. Sediments at Station 17 were more consolidated, lacked the
black-colored bands, and contained shell hash material. Station 18A is in the central
abyssal plain of the eastern basin of the Black Sea. Sediments at Station 18A were
laminated to a depth of 15 cm, below which occurred a homogeneous grey turbidite.
Table 1. Locations of stations occupied during Leg 4 of the 1988
Black Sea expedition from which sediment samples were used in:
this study.
Station Latitude Longitude Water
Depth (m)
17 Inner Shelf 41 ° 46.80'N 35° 36.50'E 97
15 Outer Shelf 41 ° 51.67'N 35° 41.63'E 198
18A Abyssal Plain 42° 28.15'N 37° 35.30'E 2149