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Role for acetotrophic methanogens in methanogenic biodegradation of vinyl chloride

Under methanogenic conditions, stream-bed sediment microorganisms rapidly degraded [1,2-14C]vinyl chloride to 14CH4 and 14CO2. Amendment with 2-bromoethanesulfonic acid eliminated 14CH4 production and decreased 14CO2 recovery by an equal molar amount. Results obtained with [14C]ethene, [14C]acetate, or 14CO2 as substrates indicated that acetotrophic methanogens were responsible for the production of 14CH4 during biodegradation of [1,2-14C]VC.Under methanogenic conditions, stream-bed sediment microorganisms rapidly degraded [1,2-14C]vinyl chloride to 14CH4 and 14CO2. Amendment with 2-bromoethanesulfonic acid eliminated 14CH4 production and decreased 14CO2 recovery by an equal molar amount. Results obtained with [14C]-ethene, [14C]acetate, or 14CO2 as substrates indicated that acetotrophic methanogens were responsible for the production of 14CH4, during biodegradation of [1,2-14C]VC.

Environmental Science & Technology↗

Determination of uptake kinetics (sampling rates) by lipid-containing semipermeable membrane devices (SPMDs) for polycyclic aromatic hydrocarbons (PAHs) in water

The use of lipid-containing semipermeable membrane devices (SPMDs) is becoming commonplace, but very little sampling rate data are available for the estimation of ambient contaminant concentrations from analyte levels in exposed SPMDs. We determined the aqueous sampling rates (R(s)s; expressed as effective volumes of water extracted daily) of the standard (commercially available design) 1-g triolein SPMD for 15 of the priority pollutant (PP) polycyclic aromatic hydrocarbons (PAHs) at multiple temperatures and concentrations. Under the experimental conditions of this study, recovery- corrected R(s) values for PP PAHs ranged from ???1.0 to 8.0 L/d. These values would be expected to be influenced by significant changes (relative to this study) in water temperature, degree of biofouling, and current velocity- turbulence. Included in this paper is a discussion of the effects of temperature and octanol-water partition coefficient (K(ow)); the impacts of biofouling and hydrodynamics are reported separately. Overall, SPMDs responded proportionally to aqueous PAH concentrations; i.e., SPMD R(s) values and SPMD-water concentration factors were independent of aqueous concentrations. Temperature effects (10, 18, and 26 ??C) on Rs values appeared to be complex but were relatively small.The use of lipid-containing semipermeable membrane devices (SPMDs) is becoming commonplace, but very little sampling rate data are available for the estimation of ambient contaminant concentrations from analyte levels in exposed SPMDs. We determined the aqueous sampling rates (Rss; expressed as effective volumes of water extracted daily) of the standard (commercially available design) 1-g triolein SPMD for 15 of the priority pollutant (PP) polycyclic aromatic hydrocarbons (PAHs) at multiple temperatures and concentrations. Under the experimental conditions of this study, recovery-corrected Rs values for PP PAHs ranged from ???1.0 to 8.0 L/d. These values would be expected to be influenced by significant changes (relative to this study) in water temperature, degree of biofouling, and current velocity-turbulence. Included in this paper is a discussion of the effects of temperature and octanol-water partition coefficient (KOW); the impacts of biofouling and hydrodynamics are reported separately. Overall, SPMDs responded proportionally to aqueous PAH concentrations; i.e., SPMD RS values and SPMD-water concentration factors were independent of aqueous concentrations. Temperature effects (10, 18, and 26??C) on RS values appeared to be complex but were relatively small.

Environmental Science & Technology↗

Inhibition of hydroxyl radical reaction with aromatics by dissolved natural organic matter

Reaction of aromatic compounds with hydroxyl radical is inhibited by dissolved natural organic matter (NOM). The degree of inhibition is significantly greater than that expected based on a simple model in which aromatic compound molecules bound to NOM are considered to be unreactive. In this study, hydroxyl radical was produced at steady-state concentrations using Fenton chemistry (H2O2 + Fe2+ ??? Fe3+ + HO- + HO??). Suwannee River fulvic acid and humic acid were used as NOM. The most likely mechanism for the observed inhibition is that hydroxyl radical formation occurs in microenvironmental sites remote from the aromatic compounds. In addition to changes in kinetics, pyrene hydroxyl radical reaction also exhibited a mechanistic change in the presence of fulvic acid. The mechanism changed from a reaction that was apparently firstorder in pyrene to one that was apparently secondorder in pyrene, indicating that pyrene self-reaction may have become the dominant mechanism in the presence of fulvic acid. Dissolved NOM causes significant changes in the rate and mechanism of hydroxyl radical degradation of aromatic compounds. Consequently, literature rate constants measured in pure water will not be useful for predicting the degradation of pollutants in environmental systems. The kinetic and mechanistic information in this study will be useful for developing improved degradation methods involving Fenton chemistry.Reaction of aromatic compounds with hydroxyl radical is inhibited by dissolved natural organic matter (NOM). The degree of inhibition is significantly greater than that expected based on a simple model in which aromatic compounds molecules bounds to NOM are considered to be unreactive. In this study, hydroxyl radical was produced at steady-state concentrations using Fenton chemistry (H2O2 + Fe2+ ??? Fe3+ + HO- + HO??). Suwannee River fulvic acid and humic acid were used as NOM. The most likely mechanisms for the observed inhibition is that hydroxyl radical formation occurs in microenvironmental sites remote from the aromatic compounds. In addition to changes in kinetics, pyrene hydroxyl radical reaction also exhibited a mechanistic change in the presence of fulvic acid. The mechanism changed from a reaction that was apparently first-order in pyrene to one that was apparently second-order in pyrene, indicating that pyrene self-reaction may have become the dominant mechanism in the presence of fulvic acid. Dissolved NOM causes significant changes in the rate and mechanism of hydroxyl radical degradation of aromatic compounds. Consequently, literature rate constants measured in pure water will not be useful for predicting the degradation of pollutants in environmental systems. The kinetic and mechanistic information in this study will be useful for developing improved degradation methods involving Fenton chemistry.

Environmental Science & Technology↗

Negative pH and extremely acidic mine waters from Iron Mountain, California

Extremely acidic mine waters with pH values as low as -3.6, total dissolved metal concentrations as high as 200 g/L, and sulfate concentrations as high as 760 g/L, have been encountered underground in the Richmond Mine at Iron Mountain, CA. These are the most acidic waters known. The pH measurements were obtained by using the Pitzer method to define pH for calibration of glass membrane electrodes. The calibration of pH below 0.5 with glass membrane electrodes becomes strongly nonlinear but is reproducible to a pH as low as -4. Numerous efflorescent minerals were found forming from these acid waters. These extreme acid waters were formed primarily by pyrite oxidation and concentration by evaporation with minor effects from aqueous ferrous iron oxidation and efflorescent mineral formation.

Environmental Science & Technology↗

Anthropogenic platinum and palladium in the sediments of Boston Harbor

Anthropogenic activity has increased recent sediment concentrations of Pt and Pd in Boston Harbor by approximately 5 times background concentrations. Surface sediments and downcore profiles were investigated to evaluate Pt and Pd accumulation and behavior in urban coastal sediments. There is no clear correlation between temporal changes in Pt and Pd consumption and sediment concentration. However, Pt/Pb and Pd/Pb ratios suggest that Pt and Pd flux into the Harbor may not be decreasing with cessation of sludge input as rapidly as other metals. This is supported by the large discrepancy between fluxes associated with sludge and effluent release and those calculated from surface sediment concentrations. This evidence supports catalytic converters as a major source of Pd and Pt to Boston Harbor but cannot preclude other sources. Pd does not exhibit signs of post-burial remobilization below the mixed layer in the sediment cores, although near-surface variability in Pd concentrations may indicate a labile Pd component. Pt displays an inverse correlation with Mn above the oxic/suboxic transition, similar to behavior seen in pristine sediments where Pt is thought to be chemically mobile. This study does not support the use of Pd and Pt as tracers of recent contaminated sedimentation. However, the possibility of a labile Pt and Pd in these sediments highlights the need for further study of the biological uptake of these metals.

Environmental Science & Technology↗

Metolachlor and alachlor breakdown product formation patterns in aquatic field mesocosms

The transformation of metolachlor [2-chloro- N -(2-ethyl-6-methylphenyl)- N -(2-methoxy-1-methylethyl)acetamide] and alachlor [2-chloro- N -(2,6-diethylphenyl)- N -(methoxymethyl)acetamide] in aquatic systems was investigated using outdoor tank mesocosms. Metolachlor and alachlor levels and their ethane sulfonic acid (ESA) and oxanillic acid breakdown products were monitored over time under five experimental treatments (each in quadruplicate). Background water conditions were identical in all treatments with each treatment differing based on the level and type(s) of herbicide present. Treatments included a no-herbicide control, 10 μg/L metolachlor, 25 μg/L metolachlor, 25 μg/L alachlor, and 25 μg/L alachlor plus 25 μg/L metolachlor in combination. The experiment was initiated by adding herbicide(s) to the units to the target concentrations; herbicide and breakdown product levels and other chemical parameters were then monitored for 85 days. In general, metolachlor half-lives were longer than alachlor half-lives under all treatments, although the differences were not statistically significant. Metolachlor half-lives (±95% confidence limits) ranged from 33.0 d (±14.1 d) to 46.2 d (±40.0 d), whereas alachlor half-lives ranged from 18.7 d (±3.5 d) to 21.0 d (±6.5 d) for different treatments. Formation patterns of ESA were similar in all treatments, whereas oxanillic acid formation differed for the two herbicides. Alachlor oxanillic acid was produced in larger quantities than metolachlor oxanillic acid and either ESA under equivalent conditions. Our results suggest that the transformation pathways for alachlor and metolachlor in aquatic systems are similar and resemble the acetochlor pathway in soils proposed by Feng ( Pestic. Biochem. Physiol . 1991 , 34 , 136); however, the oxanillic acid branch of the pathway is favored for alachlor as compared with metolachlor.

Environmental Science & Technology↗

Reactive uptake of trace metals in the hyporheic zone of a mining- contaminated stream, Pinal Creek, Arizona

Significant uptake of dissolved metals occurred by interaction of groundwater and surface water with hyporheic-zone sediments during transport in Pinal Creek, AZ. The extent of trace metal uptake was calculated by mass balance measurements made directly within the hyporheic zone. A conservative solute tracer injected into the stream was used to quantify hydrologic exchange with the stream and groundwater. Fractional reactive uptake of dissolved metals entering the hyporheic zone was determined at 29 sites and averaged 52 ± 25, 27 ± 19, and 36 ± 24% for Co, Ni, and Zn, compared with Mn uptake of 22 ± 19%. First-order rate constants (λ h ) of metal uptake in the hyporheic zone were determined at seven sites using the exchange rate of water derived from tracer arrival in the streambed. Reaction-time constants (1/λ h ) averaged 0.41, 0.84, and 0.38 h for Co, Ni, and Zn, respectively, and 1.3 h for Mn. In laboratory experiments with streambed sediments, metal uptake increased with preexisting Mn oxide concentration, supporting our interpretation that Mn oxides in the hyporheic zone enhance trace metal uptake. Reach-scale mass-balance calculations that include groundwater metal inputs indicated that decreases in metal loads ranged from 12 to 68% over the 7-km perennial reach depending on the metal. The decreases in metal loads are attributed to uptake of trace metals by Mn oxides in the hyporheic zone that is enhanced because of ongoing Mn oxide formation. Analysis of dissolved-metal streambed profiles and conservative solute tracers provide a valuable tool for quantifying metal uptake or release in the hyporheic zone of contaminated streams.

Arizona↗

Carbonate ions and arsenic dissolution by groundwater

Samples of Marshall Sandstone, a major source of groundwater with elevated arsenic levels in southeast Michigan, were exposed to bicarbonate ion under controlled chemical conditions. In particular, effects of pH and redox conditions on arsenic release were evaluated. The release of arsenic from the aquifer rock was strongly related to the bicarbonate concentration in the leaching solution. The results obtained suggest that the carbonation of arsenic sulfide minerals, including orpiment (As2S3) and realgar (As2S2), is an important process in leaching arsenic into groundwater under anaerobic conditions. The arseno-carbonate complexes formed, believed to be As(CO3)2-, As(CO3)(OH)2-, and AsCO3+, are stable in groundwater. The reaction of ferrous ion with the thioarsenite from carbonation process can result in the formation of arsenopyrite which is a common mineral in arsenic-rich aquifers.Samples of Marshall Sandstone, a major source of groundwater with elevated arsenic levels in southeast Michigan, were exposed to bicarbonate ion under controlled chemical conditions. In particular, effects of pH and redox conditions on arsenic release were evaluated. The release of arsenic from the aquifer rock was strongly related to the bicarbonate concentration in the leaching solution. The results obtained suggest that the carbonation of arsenic sulfide minerals, including orpiment (As2S3) and realgar (As2S2), is an important process in leaching arsenic into groundwater under anaerobic conditions. The arseno-carbonate complexes formed, believed to be As(CO3)2-, As(CO3)(OH)2-, and AsCO3+, are stable in groundwater. The reaction of ferrous ion with the thioarsenite from carbonation process can result in the formation of arsenopyrite which is a common mineral in arsenic-rich aquifers.The role of bicarbonate in leaching arsenic into groundwater was investigated by conducting batch experiments using core samples of Marshall Sandstone from southeast Michigan and different bicarbonate solutions. The effects of pH and redox conditions on As dissolution were examined. Results showed that As was not leached significantly out of the Marshall Sandstone samples after 3 d using either deionized water or groundwater, but As was leached efficiently by sodium bicarbonate, potassium bicarbonate, and ferric chloride solutions. The leaching rate with sodium bicarbonate was about 25% higher than that with potassium bicarbonate. The data indicated that bicarbonate ion was involved primarily in As dissolution and that hydroxyl radical ion did not affect As dissolution to any significant degree. The amount of As leached was dependent upon the sodium bicarbonate concentration, increasing with reaction time for each concentration. Significant As leaching was found in the extreme pH ranges of <1.9 and 8.0-10.4. The resulting arseno-carbonate complexes formed were stable in groundwater.

Environmental Science & Technology↗

Silica-coated titania and zirconia colloids for subsurface transport field experiments

Silica-coated titania (TiO 2 ) and zirconia (ZrO 2 ) colloids were synthesized in two sizes to provide easily traced mineral colloids for subsurface transport experiments. Electrophoretic mobility measurements showed that coating with silica imparted surface properties similar to pure silica to the titania and zirconia colloids. Measurements of steady electrophoretic mobility and size (by dynamic light scattering) over a 90-day period showed that the silica-coated colloids were stable to aggregation and loss of coating. A natural gradient field experiment conducted in an iron oxide-coated sand and gravel aquifer also showed that the surface properties of the silica-coated colloids were similar. Colloid transport was traced at μg L - 1 concentrations by inductively coupled plasma-atomic emission spectroscopy measurement of Ti and Zr in acidified samples.

Environmental Science & Technology↗

Urban sprawl leaves its PAH signature

The increasing vehicle traffic associated with urban sprawl in the United States is frequently linked to degradation of air quality, but its effect on aquatic sediment is less well-recognized. This study evaluates trends in PAHs, a group of contaminants with multiple urban sources, in sediment cores from 10 reservoirs and lakes in six U.S. metropolitan areas. The watersheds chosen represent a range in degree and age of urbanization. Concentrations of PAHs in all 10 reservoirs and lakes increased during the past 20-40 years. PAH contamination of the most recently deposited sediment at all sites exceeded sediment-quality guidelines established by Environment Canada, in some cases by several orders of magnitude. These results add a new chapter to the story told by previous coring studies that reported decreasing concentrations of PAHs after reaching highs in the 1950s. Concurrent with the increase in concentrations is a change in the assemblage of PAHs that indicates the increasing trends are driven by combustion sources. The increase in PAH concentrations tracks closely with increases in automobile use, even in watersheds that have not undergone substantial changes in urban land-use levels since the 1970s.The increasing vehicle traffic associated with urban sprawl in the United States is frequently linked to degradation of air quality, but its effect on aquatic sediment is less well-recognized. This study evaluates trends in PAHs, a group of contaminants with multiple urban sources, in sediment cores from 10 reservoirs and lakes in six U.S. metropolitan areas. The watersheds chosen represent a range in degree and age of urbanization. Concentrations of PAHs in all 10 reservoirs and lakes increased during the past 20-40 years. PAH contamination of the most recently deposited sediment at all sites exceeded sediment-quality guidelines established by Environment Canada, in some cases by several orders of magnitude. These results add a new chapter to the story told by previous coring studies that reported decreasing concentrations of PAHs after reaching highs in the 1950s. Concurrent with the increase in concentrations is a change in the assemblage of PAHs that indicates the increasing trends are driven by combustion sources. The increase in PAH concentrations tracks closely with increases in automobile use, even in watersheds that have not undergone substantial changes in urban land-use levels since the 1970s.

Environmental Science & Technology↗

Mobilization and transport of soil particles during infiltration experiments in an agricultural field, Shenandoah Valley, Virginia

Evidence that fine particles mobilized and transported in soils and aquifers can have a profound influence on contaminant migration has spawned much interest recently in understanding colloid transport in natural materials. Repeated infiltration experiments on an initially dry field soil were conducted to evaluate rates of mobilization of fine particles over time and to investigate the importance of transient-flow events on particle transport. Water flow was measured in zero-tension lysimeters at 25 cm depth. For repeated infiltration events and for all plots, water flow sharply increased shortly after initial ponding of water at the soil surface, maintained a relatively steady level during the period of ponding, and decreased gradually thereafter. Particle concentrations measured in the pan lysimeters ranged from 7 mg L - 1 to 265 mg L - 1 and were typically on the order of 10 to 100 mg L - 1 . Greatest particle mass flux was observed during the initial infiltration experiment on each plot. During four subsequent infiltration experiments, all conducted within 250 min of the first event, steady mass fluxes were observed that were approximately 70% of the average value seen in the first flush of water through a dry soil, indicating that the supply of mobile soil particles is only sparingly reduced over closely spaced infiltration events. All peak particle concentrations and mass fluxes occurred near either the rising limb or the falling limb of the water flux hydrograph, presumably reflecting the movement of air−water interfaces during imbibition and drainage.

Virginia↗

Potential for nonenzymatic reduction of Fe(III) via electron shuttling in subsurface sediments

The potential for various substances to serve as electron shuttles between Fe(III)-reducing microorganisms and insoluble Fe(III) oxides in aquifer sediments was evaluated in order to determine whether abiological mechanisms might play a role in the apparent microbial reduction of Fe(III) in subsurface sediments. Humic substances (humics) and the humics analogue, anthraquinone-2,6-disulfonate (AQDS), which were previously found to stimulate microbial reduction of synthetic poorly crystalline Fe(III) oxide under laboratory conditions, were found to also stimulate the reduction of aquifer Fe(III) oxides by indigenous microorganisms. Electron shuttling via biological reduction of U(VI) or S° followed by abiological reduction of Fe(III) by U(IV) or sulfide enhanced the reduction of synthetic Fe(III) oxide in cell suspensions, but these potential electron shuttles did not stimulate Fe(III) reduction when they were added to aquifer sediments. These results emphasize the importance of evaluating potential mechanisms for Fe(III) reduction with natural Fe(III) oxides, under environmentally relevant conditions. The finding that humics and other extracellular quinones can serve as electron shuttles to the Fe(III) oxides found in subsurface environments suggests that some Fe(III) reduction which was previously considered to be the result of direct enzymatic reduction of Fe(III) oxides may instead result from abiotic reduction of Fe(III) by microbially reduced humics or other microbially generated hydroquinones.

Environmental Science & Technology↗

Formation and transport of the sulfonic acid metabolites of alachlor and metolachlor in soil

Alachlor and metolachlor are dechlorinated and transformed into their corresponding ethane sulfonic acid (ESA) metabolites in soil. In a field-disappearance study, it was shown that alachlor ESA was formed at a faster rate and at concentrations 2−4 times higher than metolachlor ESA, conforming with the observed longer disappearance half-life of metolachlor (15.5 d) in the field as compared to alachlor (8 d). Runoff data also showed higher concentrations of alachlor ESA as compared to metolachlor ESA, even though they were applied at the same levels. Data from soil cores showed transport of the ESA compounds in soil to as far down as 75−90 cm below the surface, at concentrations ranging from less than 0.5 μg/L to about 50 μg/L. In contrast, no parent herbicide was detected at these depths. This observation correlates with the higher log K oc values for alachlor (3.33) and metolachlor (3.01) relative to their corresponding ESA metabolites, alachlor ESA (2.26), and metolachlor ESA (2.29).

Environmental Science & Technology↗

Sources and haloacetic acid/trihalomethane formation potentials of aquatic humic substances in the Wakarusa River and Clinton Lake near Lawrence, Kansas

Gram quantities of aquatic humic substances (AHS) were extracted from the Wakarusa River−Clinton Lake Reservoir system, near Lawrence, KS, to support nuclear magnetic resonance (NMR) experimental studies, report concentrations of dissolved organic carbon (DOC) and AHS, define sources of the AHS, and determine if the AHS yield sufficient quantities of haloacetic acids (HAA5) and trihalomethanes (THM4) that exceed U.S. Environmental Protection Agency (EPA) Maximum Contaminant Levels (MCL) in drinking water. AHS from the Wakarusa River and Clinton Lake originated from riparian forest vegetation, reflected respective effects of soil organic matter and aquatic algal/bacterial sources, and bore evidence of biological degradation and photodegradation. AHS from the Wakarusa River showed the effect of terrestrial sources, whereas Clinton Lake humic acid also reflected aquatic algal/bacterial sources. Greater amounts of carbon attributable to tannin-derived chemical structures may correspond with higher HAA5 and THM4 yields for Clinton Lake fulvic acid. Prior to appreciable leaf-fall from deciduous trees, the combined (humic and fulvic acid) THM4 formation potentials for the Wakarusa River approached the proposed EPA THM4 Stage I MCL of 80 μg/L, and the combined THM4 formation potential for Clinton Lake slightly exceeded the proposed THM4 Stage II MCL of 40 μg/L. Finally, AHS from Clinton Lake could account for most (>70%) of the THM4 concentrations in finished water from the Clinton Lake Water Treatment Plant based on September 23, 1996, THM4 results.

Environmental Science & Technology↗

Osmium isotopes demonstrate distal transport of contaminated sediments in Chesapeake Bay

Because the isotopic composition of anthropogenic Os is normally distinctive in comparison to continental crust and is precisely measurable, this platinum-group element is attractive as a tracer of transport pathways for contaminated sediments in estuaries. Evidence herein and elsewhere suggest that biomedical research institutions are the chief source of anthropogenic Os. In the Chesapeake Bay region, uncontaminated sediments bear a crustal 187Os/188Os signature of 0.73 ?? 0.10. Slightly higher 187Os/188Os ratios occur in Re-rich Coastal Plain deposits due to post- Miocene 187Re decay. The upper Susquehanna Basin yields sediments also with higher 187Os/188Os. Beginning in the late 1970s, this signal was overprinted by a low 187Os/188Os (anthropogenic) source in the lower Susquehanna Basin. In the vicinity of Baltimore, which is a major center of heavy industry as well as biomedical research, anthropogenic Os has been found only in sediments impacted by the principal wastewater treatment plant. Surprisingly, a mid-Bay site distant from anthropogenic sources contains the strongest anthropogenic Os signal in the data set, having received anthropogenic Os sporadically since the mid-20th Century. Transport of particles to this site overrode the northward flowing bottom currents. Finding anthropogenic Os at this site cautions that other particle-borne substances, including hazardous ones, could be dispersed broadly in this estuary.Because the isotopic composition of anthropogenic Os is normally distinctive in comparison to continental crust and is precisely measurable, this platinum-group element is attractive as a tracer of transport pathways for contaminated sediments in estuaries. Evidence herein and elsewhere suggest that biomedical research institutions are the chief source of anthropogenic Os. In the Chesapeake Bay region, uncontaminated sediments bear a crustal 187Os/188Os signature of 0.73 ?? 0.10. Slightly higher 187Os/188Os ratios occur in Re-rich Coastal Plain deposits due to post-Miocene 187Re decay. The upper Susquehanna Basin yields sediments also with higher 187Os/188Os. Beginning in the late 1970s, this signal was overprinted by a low 187Os/188Os (anthropogenic) source in the lower Susquehanna Basin. In the vicinity of Baltimore, which is a major center of heavy industry as well as biomedical research, anthropogenic Os has been found only in sediments impacted by the principal wastewater treatment plant. Surprisingly, a mid-Bay site distant from anthropogenic sources contains the strongest anthropogenic Os signal in the data set, having received anthropogenic Os sporadically since the mid-20th Century. Transport of particles to this site overrode the northward flowing bottom currents. Finding anthropogenic Os at this site cautions that other particle-borne substances, including hazardous ones, could be dispersed broadly in this estuary.

Environmental Science & Technology↗