Mercury and other trace elements in sediment cores from central Texas lakes.

Metals released during fossil fuel use are important atmospheric pollutants. Mercury and other trace metals can be transferred to an aquatic environment through atmospheric deposition. In the work reported here, a number of sediment cores were retrieved from central Texas lakes in the proximity of a coal-fired power plant in search of local anthropogenic effects. Cores were collected along a transient parallel to the prevailing wind direction (S-SE) in the area. Trace element concentrations in the lignite and in effluents from the power plant showed that some elements remained constant (Al, Cu) throughout the different lignite combustion and power production processes. Some (like Cd and Se) showed an affinity for the smaller particles, whereas others (Hg) showed very low concentrations in all the solid wastes, indicating that they probably escaped with the flue gases. Sediment cores from a lake next to the power plant showed higher trace metal concentration in the upper part of the cores (more recent sediment). For example, there was as much as a tenfold increase in Hg concentration between the core bottom (10 ng/g), where the sediment was approximately 100 years old and the surface (100 ng/g). Cd and Se at surface sediments were also found to be as high as 1.6 and 3.45 microg/g, respectively. The excess metal inventory was higher for the lakes located next to the power plant than for two lakes about 30 km away.

Metal concentrations in mussel Crenomytilus grayanus and oyster Crassostrea gigas in relation to contamination of ambient sediments.

The relationship between Zn, Cu, Cd, Pb, and Ni concentrations in soft tissues of mussels and oysters and those in ambient sediments was examined. The study area was the coastal habitats of the northwestern Sea of Japan, which has a broad range of contamination due to urban sewage. Significant increases of all metals, except Ni, were observed in mussel Crenomytilus grayanus at concentrations of easily leachable metals in ambient sediments higher than 2, 100, and 800 microg/g for Cd, Cu, and Zn, respectively. Pb was accumulated by the mussels with no distinct threshold in Pb contamination of sediments. After 2 months, C. grayanus transplanted from a pristine to a contaminated locality increased in Pb up to 12%, and Cu up to 68% of concentrations of these metals in the contaminated local mussels, but Zn and Cd concentrations increased only in the excretory tissue, not in the somatic tissue, or in the soft tissue as a whole. Such regulation of metal accumulation puts limitations on the use of C. grayanus for monitoring of slightly and moderately contaminated localities. On the other hand, the oyster Crassostrea gigas showed definite accumulation of all metals, except Ni, at moderate contamination of ambient sediments. As contamination of sediments increased, increases of Pb, Zn and Cu concentrations in C. gigas slowed, possibly due to physiological control at very high metal concentrations in oyster soft tissue. Thus, the mussel C. grayanus should be used mainly for the monitoring of heavy contaminated localities, and the oyster C. gigas is more suitable as an indicator of low and moderate contamination.

Historical contamination of PAHs, PCBs, DDTs, and heavy metals in Mississippi River Delta, Galveston Bay and Tampa Bay sediment cores.

Profiles of trace contaminant concentrations in sediment columns can be a natural archive from which pollutant inputs into coastal areas can be reconstructed. Reconstruction of historical inputs of anthropogenic chemicals is important for improving management strategies and evaluating the success of recent pollution controls measures. Here we report a reconstruction of historical contamination into three coastal sites along the US Gulf Coast: Mississippi River Delta, Galveston Bay and Tampa Bay. Within the watersheds of these areas are extensive agricultural lands as well as more than 50% of the chemical and refinery capacity of the USA. Despite this pollution potential, relatively low concentrations of trace metals and trace organic contaminants were found in one core from each of the three sites. Concentrations and fluxes of most trace metals found in surface sediments at these three sites, when normalized to Al, are typical for uncontaminated Gulf Coast sediments. Hydrophobic trace organic contaminants that are anthropogenic (polycyclic aromatic hydrocarbons, DDTs, and polychlorinated biphenyls) are found in sediments from all locations. The presence in surface sediments from the Mississippi River Delta of low level trace contaminants such as DDTs, which were banned in the early 1970's, indicate that they are still washed out from cultivated soils. It appears that the DDTs profile in that sediment core was produced by a combination of erosion processes of riverine and other sedimentary deposits during floods. Most of the pollutant profiles indicate that present-day conditions have improved from the more contaminated conditions in the 1950-1970's, before the advent of the Clean Water Act.

The geographic distribution of population health and contaminant body burden in gulf of Mexico oysters.

As part of NOAA's National Status and Trends Mussel Watch Program, oysters were sampled along the Gulf of Mexico coast each winter from 1986 to 1993 (The present analysis deals with 1986-1993 Mussel Watch data; the Mussel Watch project itself continues at this printing) and analyzed for trace metal, polynuclear aromatic hydrocarbons and pesticide body burden, plus a series of biological variables designed to assess population status and health. We identified contaminant and biological variables in which large-scale spatial processes played an important role in establishing population values by examining the likelihood that neighboring bays tended to have populations with body burdens or population attributes more similar than expected by chance. Local or watershed-dependent factors, such as land use and freshwater inflow, are important in controlling the bay-to-bay variation in body burden in most contaminants. However, the bay-to-bay variations in body burden of some metals (As, Cd, Hg, Ni, Se) appear to be principally influenced by larger-scale climatic factors. These metals and the biological variable shell length demonstrated a strong degree of similarity between bays over a large regional area reminiscent of the pattern shown by climatic factors, such as temperature and precipitation. In contrast, among the organics, none of the PAHs showed even a moderately strong climatic signal. Among the pesticides, only two did (dieldrin, total DDTs). These pesticides and the biological variables, reproductive stage and Perkinsus marinus prevalence and infection intensity, had spatial patterns that suggested both a local and a regional influence to their geographic distributions. This same pattern is exhibited by freshwater runoff. Metal contaminants also behaved distinctively compared to organics in the temporal influence of climate in establishing the interannual variability in body burden. For the organics, trends in interannual variability were strongly influenced by climate, whereas spatial trends were not. In contrast, most metals were unaffected by climatic forcing both spatially and temporally. However, all of the metals having a spatial pattern strongly influenced by climate (As, Cd, Hg, Ni, Se) also exhibited interannual variations related to variations in climate.

Concentrations of arsenic, cadmium, copper, lead, mercury, and zinc in human placentas from two cities in Ukraine.

Ukraine is a highly industrialized country with major environmental problems and deteriorating reproductive health. Heavy metals are known reproductive toxins; a study was undertaken to determine whether they were present at sufficient concentrations to be playing a major role in these health problems. Placental concentrations of arsenic, cadmium, copper, lead, mercury, and zinc were determined in 200 women from the general population of two urban areas of Ukraine, Kyiv and Dniprodzerzhinsk. Arsenic was detected in only 5% of the samples, lead in 22%, and mercury in 28%. Cadmium was detected in almost all samples, with a median of 5.2 ng/g. Concentrations of lead, mercury, and cadmium were low compared to those reported elsewhere, while zinc and copper concentrations were comparable.

Spatial and temporal variations of trace metals in bottom sediments of Peter the Great Bay, the Sea of Japan.

New data on trace metal distribution in bottom sediments of Peter the Great Bay (the Sea of Japan) are presented. Much higher concentrations were detected near the most likely anthropogenic sources of trace metal inputs (waste water discharges from Vladivostok and Nakhodka, and the Vladivostok coastal landfill). Sediments in these contaminated areas were up to 700 ppm in Zn, 530 ppm in Pb, 7 ppm in Cd and 3 ppm in Hg. River runoff is of minor importance as a metal source in the investigated areas. The spatial distribution of trace metals outside the areas directly influenced by sewage discharges is regulated by natural processes such as sediment sorting by grain size. Based on radiometric dating of sediment cores, increases in the trace metal content of bottom sediments near Vladivostok begun in approximately 1945.

Trace metals in Gulf of Mexico oysters.

Oysters (Crassostrea virginica) from 50 to 69 locations (sites) along the Gulf of Mexico coastline, collected annually in 1986, 1987 and 1988, have been analyzed for 13 trace metals, including most of the metals of concern from an environmental quality perspective. Essentially the entire U.S. Gulf coastline was sampled, from far south Texas to far south Florida. Pooled samples of 20 oysters from three different stations at each site were analyzed by atomic absorption spectrophotometry. The concentrations found were generally less than or equal to literature values from other parts of the world thought to be uncontaminated by anthropogenic trace metal inputs. A few sites did, however, show apparent trace metal pollution and other sites gave anomalous values that cannot readily be explained by either known anthropogenic or natural causes. The range of values for the overall data set (maximum/minimum) varied from 15-fold for Mn to 624-fold for Pb, whereas the coefficient of variation (standard deviation/mean) was generally in the 50-60% range for most metals. Variations were much greater between stations than between years at a given station. Enrichments usually occurred in suites of three to four elements with Ag, Cd, Cu and Zn being the most common suite, thus several strong inter-element correlations were found. There was, however, little correlation between metal levels in oysters and in sediments from the collection sites even when sediment data were rationed to Al (sediment data are not given here). There was likewise little correlation between oyster metal levels and size, sex or reproductive stage of the oysters (data given elsewhere). Geographically, appreciably elevated (greater than 3 times average) metal levels were generally restricted to single sites within bays or estuaries, implying local control. On the other hand, regionally, Ag, Cd and Se levels were somewhat higher in Texas oysters than in those from Florida, whereas the reverse was true for As and Hg. Concentrations were lower than average for several metals in oysters from central Louisiana, especially Ag, Cd and Cu. Thus, the Mississippi River outflow and extensive offshore oil development do not seem to enrich oysters in trace metals.

Anoxic, hypersaline basin in the northern gulf of Mexico.

A 400-square-kilometer depression in the continental slope of the northern Gulf of Mexico (approximately 27 degrees N, 91 degrees W) has been found to contain anoxic, hypersaline ( approximately 250 grams per kilogram) water in the bottom 200 meters. The interface between the brine and overlying seawater acts as a midwater seismic reflector similar to those seen in the Red Sea. The bulk chemical composition of the brine is similar to that from the Red Sea, but differences between the two in both heat content and geomorphological setting indicate different modes of origin.

Trace metal concentrations and partitioning in zooplankton, neuston, and benthos from the south Texas outer continental shelf.

A variety of marine biota, including zooplankton, sargassum, surface plankton, squid, shrimp, and fish collected along the south Texas Outer Continental Shelf, were analyzed for Cu, Zn, Cd, Pb, Cr, Ni, Fe, and Mn. Although there is a great deal of variation in the chemical content of the various samples, both within species and between species, the variations all fall within the range of values published for similar organisms collected elsewhere. An increase in Pb concentration from north to south, and an increase in Cd concentration from nearshore to further offshore in the zooplankton mirrors the sediment patterns. Statistical analysis of the chemical and biological data for these samples indicates that relatively small percentages of the biological makeup of the sample can markedly affect the concentrations of Pb, Cd, Ni, and Zn. This is particularly true for the larvacea, ostracoda, and mollusca. Chemical analyses of the exoskeletons of shrimp and the skin of both squid and fish indicate that they generally contain higher metal levels in comparison with the flesh from the same organism. This is probably the result of either adsorption from seawater and/or an internal detoxification procedure employed by the organism. The analysis of a composite sample of squid 'pens' indicates that they contain enriched Cu, Cd, Zn, Pb, and Fe levels in comparison with the skin and flesh. These elevated levels are probably the result of an internal detoxification procedure and/or may represent a means of storing necessary metabolites, at least in the case of Cu and Zn, but can not be attributed to adsorption as the chitinous 'pen' is imbedded in tissue and is not directly exposed to seawater.

Manganese and related elements in the interstitial water of marine sediments.

Analyses for manganese, nickel, iron, cobalt, sodium, and lithium in the interstitial water of cores from the southern California borderland and six deep-sea cores in the area of the East Pacific Rise show great variation in concentration of trace elements. Oxidizing near-shore sediments showed a 50-fold enrichment in manganese in contrast to sulfide-rich reducing sediments, which showed no enrichment. Deep-sea sediments were variable in their concentration of the trace metals. All but one core showed a high enrichment in dissolved manganese, with a maximum of 6.6 parts per million. Two cores showed a 100-fold enrichment in nickel and cobalt. The manganese appears to be in solution either as Mn(2+) or as a complex. The results appear to support manganese nodule formation in deep-sea sediments through a diffusion of manganese from depth to the surface.

APDC-MIBK extraction system for the determination of trace elements in saline waters by atomic-absorption spectrophotometry.

A technique has been developed for the determination of "soluble" cobalt, copper, iron, lead, nickel and zinc in saline waters by simultaneous extraction of their complexes with ammonium pyrollidine dithiocarbamate (APDC) into methyl isobutyl ketone (MIBK) and subsequent analysis by atomic-absorption spectrophotometry. Particulate matter is analysed separately by dissolving millipore filters in an acetone-hydrochloric acid mixture. Various analytical and instrumental parameters have been evaluated. The method is selfcompensating in that it makes allowance for any incomplete extraction of the complexes. The technique has been applied to the determination of these elements in sea-water and saline lakes.