George R. Southworth

Whole-ecosystem study shows rapid fish-mercury response to changes in mercury deposition

Methylmercury contamination of fisheries from centuries of industrial atmospheric emissions negatively impacts humans and wildlife worldwide. The response of fish methylmercury concentrations to changes in mercury deposition has been difficult to establish because sediments/soils contain large pools of historical contamination, and many factors in addition to deposition affect fish mercury. To test directly the response of fish contamination to changing mercury deposition, we conducted a whole-ecosystem experiment, increasing the mercury load to a lake and its watershed by the addition of enriched stable mercury isotopes. The isotopes allowed us to distinguish between experimentally applied mercury and mercury already present in the ecosystem and to examine bioaccumulation of mercury deposited to different parts of the watershed. Fish methylmercury concentrations responded rapidly to changes in mercury deposition over the first 3 years of study. Essentially all of the increase in fish methylmercury concentrations came from mercury deposited directly to the lake surface. In contrast, <1% of the mercury isotope deposited to the watershed was exported to the lake. Steady state was not reached within 3 years. Lake mercury isotope concentrations were still rising in lake biota, and watershed mercury isotope exports to the lake were increasing slowly. Therefore, we predict that mercury emissions reductions will yield rapid (years) reductions in fish methylmercury concentrations and will yield concomitant reductions in risk. However, a full response will be delayed by the gradual export of mercury stored in watersheds. The rate of response will vary among lakes depending on the relative surface areas of water and watershed.

The role of volatilization in removing polycyclic aromatic hydrocarbons from aquatic environments

The movement of organic contaminants from water to the atmosphere can be important in reducing concentrations of foreign substances in aquatic ecosystems (HILL et al. 1976, DILLING 1977, MACKAY and LEINONEN 1975). Polycyclic aromatic hydrocarbons (PAH), a class of chemical produced in the combustion and pyrolysis of organic fuels, possess properties which suggest that their volatility in solution may be significant (MACKAY and WOLKOFF 1973). Since many PAH are potent carcinogens, a knowledge of their persistence, transport, and fate in aquatic environments is critical. The objective of this paper is to determine the relative volatility of two to five ring PAH structures in water, and estimate the importance of the volatilization process in removing PAH from aquatic environments. The theoretical basis for describing the transfer of vola: tile substances across an air-water interface has been succinctc}y detailed (LISS 1973, LISS and SLATER 1974). The rate of the process under a given set of conditions is described as a simple first order exponential decay with rate constant KL/depth. K L, the overall mass transfer coefficient, has units of distance time (such as cm/hr) and three components: kg, k I and H, related by the expression

Bioaccumulation potential of polycyclic aromatic hydrocarbons in Daphnia pulex

Abstract The bioaccumulation potentials by aquatic biota from aqueous solution were determined for seven polycyclic aromatic hydrocarbons (PAH). The PAH were tested using Daphnia pulex and consisted of the following compounds: naphthalene, anthracene, phenanthrene, pyrene, 9-methylanthracene, benz(a)anthracene and perylene. Bioaccumulation kinetics were described as a first order approach to equilibrium in a two-compartment model (water and Daphnia), using a two-stage technique to estimate uptake and elimination rates, while accounting for decreasing aqueous concentrations. Estimates of equilibrium concentration factors were obtained by two methods: (1) evaluating the kinetic model as t tends to infinity and (2) direct measurement of concentration factor at t =24 h. Estimations of equilibrium concentration factors obtained by the two methods were in good agreement, and increased dramatically with increasing molecular weight within the series of compounds. The calculated n-octanol-water partition coefficient was shown to be a good predictor of bioaccumulation potential of PAH in Daphnia. PAH were concentrated from a high of about 10,000-fold for benz(a)anthracene to a low of about 100-fold for naphthalene.

Mercury and other heavy metals influence bacterial community structure in contaminated Tennessee streams

ABSTRACT High concentrations of uranium, inorganic mercury [Hg(II)], and methylmercury (MeHg) have been detected in streams located in the Department of Energy reservation in Oak Ridge, TN. To determine the potential effects of the surface water contamination on the microbial community composition, surface stream sediments were collected 7 times during the year, from 5 contaminated locations and 1 control stream. Fifty-nine samples were analyzed for bacterial community composition and geochemistry. Community characterization was based on GS 454 FLX pyrosequencing with 235 Mb of 16S rRNA gene sequence targeting the V4 region. Sorting and filtering of the raw reads resulted in 588,699 high-quality sequences with lengths of >200 bp. The bacterial community consisted of 23 phyla, including Proteobacteria (ranging from 22.9 to 58.5% per sample), Cyanobacteria (0.2 to 32.0%), Acidobacteria (1.6 to 30.6%), Verrucomicrobia (3.4 to 31.0%), and unclassified bacteria. Redundancy analysis indicated no significant differences in the bacterial community structure between midchannel and near-bank samples. Significant correlations were found between the bacterial community and seasonal as well as geochemical factors. Furthermore, several community members within the Proteobacteria group that includes sulfate-reducing bacteria and within the Verrucomicrobia group appeared to be associated positively with Hg and MeHg. This study is the first to indicate an influence of MeHg on the in situ microbial community and suggests possible roles of these bacteria in the Hg/MeHg cycle.

Kinetic controls on the complexation between mercury and dissolved organic matter in a contaminated environment.

The interaction of mercury (Hg) with dissolved natural organic matter (NOM) under equilibrium conditions is the focus of many studies but the kinetic controls on Hg-NOM complexation in aquatic systems have often been overlooked. We examined the rates of Hg-NOM complexation both in a contaminated Upper East Fork Poplar Creek (UEFPC) in Oak Ridge, Tennessee, and in controlled laboratory experiments using reducible Hg (Hg(R)) measurements and C(18) solid phase extraction techniques. Of the filterable Hg at the headwaters of UEFPC, >90% was present as Hg(R) and this fraction decreased downstream but remained >29% of the filterable Hg at all sites. The presence of higher Hg(R) concentrations than would be predicted under equilibrium conditions in UEFPC and in experiments with a NOM isolate suggests that kinetic reactions are controlling the complexation between Hg and NOM. The slow formation of Hg-NOM complexes is attributed to competitive ligand exchange among various moieties and functional groups in NOM with a range of binding strengths and configurations. This study demonstrates the need to consider the effects of Hg-NOM complexation kinetics on processes such as Hg methylation and solid phase partitioning.

History of mercury use and environmental contamination at the Oak Ridge Y-12 Plant.

Between 1950 and 1963 approximately 11 million kilograms of mercury (Hg) were used at the Oak Ridge Y-12 National Security Complex (Y-12 NSC) for lithium isotope separation processes. About 3% of the Hg was lost to the air, soil and rock under facilities, and East Fork Poplar Creek (EFPC) which originates in the plant site. Smaller amounts of Hg were used at other Oak Ridge facilities with similar results. Although the primary Hg discharges from Y-12 NSC stopped in 1963, small amounts of Hg continue to be released into the creek from point sources and diffuse contaminated soil and groundwater sources within Y-12 NSC. Mercury concentration in EFPC has decreased 85% from ∼2000 ng/L in the 1980s. In general, methylmercury concentrations in water and in fish have not declined in response to improvements in water quality and exhibit trends of increasing concentration in some cases.

Long-term increased bioaccumulation of mercury in largemouth bass follows reduction of waterborne selenium.

Average mercury concentrations in largemouth bass from Rogers Quarry in east Tennessee were found to increase steadily following the elimination of selenium-rich discharges of fly ash to the quarry in 1989. From 1990 to 1998, mean mercury concentrations (adjusted to compensate for the covariance between individual fish weight and mercury concentration) in bass rose from 0.02 to 0.61 mg/kg. There was no indication that the rate increase was slowing or that mercury concentrations in fish were approaching a plateau or steady state. Mean selenium concentrations in bass declined from 3 to 1 mg/kg over the first five years of the study, but remained at 1-1.5 mg/kg (about twice typical concentrations in bass from local reference sites) for the last three years of the study. Gross physical abnormalities were common in fish from the site in the first three years after elimination of fly ash discharges but disappeared after two more years. Although it remains possible that other chemical or physical changes related to fly ash disposal in the system were associated with increased mercury bioaccumulation, the most likely explanation is that selenium played a critical role. It appears as though aqueous selenium enrichment was capable of having a profound effect on mercury bioaccumulation in this system but at the cost of causing a high incidence of gross abnormalities in fish. However, it is possible that selenium concentrations between the national ambient water quality criterion for the protection of aquatic life, 5 microg/l, and that now found in Rogers Quarry (<2 microg/l) could reduce mercury bioaccumulation without causing adverse effects on aquatic biota and fish-eating wildlife.

Roles of dissolved organic matter in the speciation of mercury and methylmercury in a contaminated ecosystem in Oak Ridge, Tennessee

Environmental context. Mercury (Hg) presents an environmental concern owing to its transformation to the potent neurotoxin methylmercury (CH3Hg+). The environmental factors that control bacterial methylation of mercury are poorly understood, but we know that methylmercury is bioaccumulated and biomagnified in aquatic food webs. We show that, even at low concentrations (~3 mg L–1), natural dissolved organic matter strongly complexes with ionic Hg2+ and CH3Hg+, thereby influencing biological uptake and methylation of Hg in aquatic environments. Abstract. Complexation of the mercuric ion (Hg2+) and methylmercury (CH3Hg+) with organic and inorganic ligands influences mercury transformation and bioaccumulation in aquatic environments. Using aqueous geochemical modelling, we show that natural dissolved organic matter (DOM), even at low concentrations (~3 mg L–1), controls the Hg speciation by forming strong Hg-DOM and CH3Hg-DOM complexes through the reactive sulfur or thiol-like functional groups in DOM in the contaminated East Fork Poplar Creek at Oak Ridge, Tennessee. Concentrations of neutral Hg(OH)2, Hg(OH)Cl, CH3HgCl, and CH3HgOH species are negligible. Of the coexisting metal ions, only Zn2+, at concentrations of 1.6–2.6 × 10–7 M, competes with Hg2+ for binding with DOM, causing decrease in Hg-DOM complexation but having little impact on CH3Hg-DOM complexation. DOM may thus play a dominant role in controlling the transformation, biological uptake, and methylation of Hg in this contaminated ecosystem.

Potential and realized bioconcentration. A comparison of observed and predicted bioconcentration of azaarenes in the fathead minnow (Pimephales promelas).

Many potentially hazardous organic compounds associated with synthetic-fuel production possess physicochemical properties that suggest a high potential for bioconcentration in aquatic organisms. Some of these compounds have been found to be metabolized by fish and other aquatic organisms. In this study, the bioconcentration of four polycyclic bases, or azaarenes, in fathead minnows was compared with predicted bioconcentration behavior estimated from octanolwater partitioning and with observed bioconcentration of azaarenes in Daphnia pulex. Bioconcentration in fish of those azaarenes with moderate to high (?lOOO-fold) predicted bioconcentration factors was found to be far lower than predicted or observed in D. pulex, where the bioconcentration factor is the ratio of concentration of contaminant in an organism to the aqueous concentration of the contaminant a t equilibrium. This deviation was shown to be due to the rapid metabolic alteration of the azaarenes within the fish, demonstrating that the rates of such processes are fast enough to play a large role in determining bioconcentration of organics.

Form of mercury in stream fish exposed to high concentrations of dissolved inorganic mercury

The form of mercury predominating in mercury-contaminated fish from both pristine and industrialized waters in North America and Europe has almost universally been methylmercury. Sunfish (Lepomis auritus) living in a stream contaminated with 0.5-1 micrograms/L dissolved inorganic mercury accumulated greater concentrations of total mercury at headwater sites, where the dissolved mercury concentrations were greatest, than they did at downstream sites. However, despite evidence from laboratory studies that dissolved inorganic mercury is rapidly accumulated by fish without transformation to methylmercury, methylmercury constituted 85% or more of the total mercury concentration in fish at all sites.