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Agricultural wetlands as potential hotspots for mercury bioaccumulation: Experimental evidence using caged fish

Wetlands provide numerous ecosystem services, but also can be sources of methylmercury (MeHg) production and export. Rice agricultural wetlands in particular may be important sites for MeHg bioaccumulation due to their worldwide ubiquity, periodic flooding schedules, and high use by wildlife. We assessed MeHg bioaccumulation within agricultural and perennial wetlands common to California’s Central Valley during summer, when the majority of wetland habitats are shallowly flooded rice fields. We introduced caged western mosquitofish ( Gambusia affinis ) within white rice ( Oryza sativa ), wild rice ( Zizania palustris ), and permanent wetlands at water inlets, centers, and outlets. Total mercury (THg) concentrations and body burdens in caged mosquitofish increased rapidly, exceeding baseline values at introduction by 135% to 1197% and 29% to 1566% among sites, respectively, after only 60 days. Mercury bioaccumulation in caged mosquitofish was greater in rice fields than in permanent wetlands, with THg concentrations at wetland outlets increasing by 12.1, 5.8, and 2.9 times over initial concentrations in white rice, wild rice, and permanent wetlands, respectively. In fact, mosquitofish caged at white rice outlets accumulated 721 ng Hg/fish in just 60 days. Mercury in wild mosquitofish and Mississippi silversides ( Menidia audens ) concurrently sampled at wetland outlets also were greater in white rice and wild rice than permanent wetlands. Within wetlands, THg concentrations and body burdens of both caged and wild fish increased from water inlets to outlets in white rice fields, and tended to not vary among sites in permanent wetlands. Fish THg concentrations in agricultural wetlands were high, exceeding 0.2 μg/g ww in 82% of caged fish and 59% of wild fish. Our results indicate that shallowly flooded rice fields are potential hotspots for MeHg bioaccumulation and, due to their global prevalence, suggest that agricultural wetlands may be important contributors to MeHg contamination.

California↗

Redox transformations and transport of cesium and iodine (-1, 0, +5) in oxidizing and reducing zones of a sand and gravel aquifer

Tracer tests were performed in distinct biogeochemical zones of a sand and gravel aquifer in Cape Cod, MA, to study the redox chemistry (I) and transport (Cs, I) of cesium and iodine in a field setting. Injection of iodide (I - ) into an oxic zone of the aquifer resulted in oxidation of I - to molecular iodine (I 2 ) and iodate (IO 3 - ) over transport distances of several meters. Oxidation is attributed to Mn-oxides present in the sediment. Transport of injected IO 3 - and Cs + was retarded in the mildly acidic oxic zone, with retardation factors of 1.6-1.8 for IO 3 - and 2.3-4.4for Cs. Cs retardation was likely due to cation exchange reactions. Injection of IO 3 - into a Fe-reducing zone of the aquifer resulted in rapid and complete reduction to I - within 3 m of transport. The nonconservative behavior of Cs and I observed during the tracer tests underscores the necessity of taking the redox chemistry of I as well as sorption properties of I species and Cs into account when predicting transport of radionuclides (e.g., 129 I and 137 Cs) in the environment.

Massachusetts↗

Relationship and variation of qPCR and culturable enterococci estimates in ambient surface waters are predictable

The quantitative polymerase chain reaction (qPCR) method provides rapid estimates of fecal indicator bacteria densities that have been indicated to be useful in the assessment of water quality. Primarily because this method provides faster results than standard culture-based methods, the U.S. Environmental Protection Agency is currently considering its use as a basis for revised ambient water quality criteria. In anticipation of this possibility, we sought to examine the relationship between qPCR-based and culture-based estimates of enterococci in surface waters. Using data from several research groups, we compared enterococci estimates by the two methods in water samples collected from 37 sites across the United States. A consistent linear pattern in the relationship between cell equivalents (CCE), based on the qPCR method, and colony-forming units (CFU), based on the traditional culturable method, was significant (P < 0.05) at most sites. A linearly decreasing variance of CCE with increasing CFU levels was significant (P < 0.05) or evident for all sites. Both marine and freshwater sites under continuous influence of point-source contamination tended to reveal a relatively constant proportion of CCE to CFU. The consistency in the mean and variance patterns of CCE versus CFU indicates that the relationship of results based on these two methods is more predictable at high CFU levels (e.g., log 10 CFU > 2.0/100 mL) while uncertainty increases at lower CFU values. It was further noted that the relative error in replicated qPCR estimates was generally higher than that in replicated culture counts even at relatively high target levels, suggesting a greater need for replicated analyses in the qPCR method to reduce relative error. Further studies evaluating the relationship between culture and qPCR should take into account analytical uncertainty as well as potential differences in results of these methods that may arise from sample variability, different sources of pollution, and environmental factors.

Environmental Science & Technology↗

Zn and Cu isotopes as tracers of anthropogenic contamination in a sediment core from an urban lake

In this work, we use stable Zn and Cu isotopes to identify the sources and timing of the deposition of these metals in a sediment core from Lake Ballinger near Seattle, Washington, USA. The base of the Lake Ballinger core predates settlement in the region, while the upper sections record the effects of atmospheric emissions from a nearby smelter and rapid urbanization of the watershed. δ 66 Zn and δ 65 Cu varied by 0.50‰ and 0.29‰, respectively, over the 500 year core record. Isotopic changes were correlated with the presmelter period (∼1450 to 1900 with δ 66 Zn = +0.39‰ ± 0.09‰ and δ 65 Cu = +0.77‰ ± 0.06‰), period of smelter operation (1900 to 1985 with δ 66 Zn = +0.14 ± 0.06‰ and δ 65 Cu = +0.94 ± 0.10‰), and postsmelting/stable urban land use period (post 1985 with δ 66 Zn = 0.00 ± 0.10‰ and δ 65 Cu = +0.82‰ ± 0.12‰). Rapid early urbanization during the post World War II era increased metal loading to the lake but did not significantly alter the δ 66 Zn and δ 65 Cu, suggesting that increased metal loads during this time were derived mainly from mobilization of historically contaminated soils. Urban sources of Cu and Zn were dominant since the smelter closed in the 1980s, and the δ 66 Zn measured in tire samples suggests tire wear is a likely source of Zn.

Washington↗

Response of a macrotidal estuary to changes in anthropogenic mercury loading between 1850 and 2000

Methylmercury (MeHg) bioaccumulation in marine food webs poses risks to fish-consuming populations and wildlife. Here we develop and test an estuarine mercury cycling model for a coastal embayment of the Bay of Fundy, Canada. Mass budget calculations reveal that MeHg fluxes into sediments from settling solids exceed losses from sediment-to-water diffusion and resuspension. Although measured methylation rates in benthic sediments are high, rapid demethylation results in negligible net in situ production of MeHg. These results suggest that inflowing fluvial and tidal waters, rather than coastal sediments, are the dominant MeHg sources for pelagic marine food webs in this region. Model simulations show water column MeHg concentrations peaked in the 1960s and declined by almost 40% by the year 2000. Water column MeHg concentrations respond rapidly to changes in mercury inputs, reaching 95% of steady state in approximately 2 months. Thus, MeHg concentrations in pelagic organisms can be expected to respond rapidly to mercury loading reductions achieved through regulatory controls. In contrast MeHg concentrations in sediments have steadily increased since the onset of industrialization despite recent decreases in total mercury loading. Benthic food web MeHg concentrations are likely to continue to increase over the next several decades at present-day mercury emissions levels because the deep active sediment layer in this system contains a large amount of legacy mercury and requires hundreds of years to reach steady state with inputs.

Environmental Science & Technology↗

Isotopic composition and origin of indigenous natural perchlorate and co-occurring nitrate in the southwestern United States

Perchlorate (ClO 4 − ) has been detected widely in groundwater and soils of the southwestern United States. Much of this ClO 4 − appears to be natural, and it may have accumulated largely through wet and dry atmospheric deposition. This study evaluates the isotopic composition of natural ClO 4 − indigenous to the southwestern U.S. Stable isotope ratios were measured in ClO 4 − (δ 18 O, Δ 17 O, δ 37 Cl) and associated NO 3 − (δ 18 O, Δ 17 O, δ 15 N) in groundwater from the southern High Plains (SHP) of Texas and New Mexico and the Middle Rio Grande Basin (MRGB) in New Mexico, from unsaturated subsoil in the SHP, and from NO 3 − -rich surface caliche deposits near Death Valley, California. The data indicate natural ClO 4 − in the southwestern U.S. has a wide range of isotopic compositions that are distinct from those reported previously for natural ClO 4 − from the Atacama Desert of Chile as well as all known synthetic ClO 4 − . ClO 4 − in Death Valley caliche has a range of high Δ 17 O values (+8.6 to +18.4 ‰), overlapping and extending the Atacama range, indicating at least partial atmospheric formation via reaction with ozone (O 3 ). However, the Death Valley δ 37 Cl values (−3.1 to −0.8 ‰) and δ 18 O values (+2.9 to +26.1‰) are higher than those of Atacama ClO 4 − . In contrast, ClO 4 − from western Texas and New Mexico has much lower Δ 17 O (+0.3 to +1.3‰), with relatively high δ 37 Cl (+3.4 to +5.1 ‰) and δ 18 O (+0.5 to +4.8 ‰), indicating either that this material was not primarily generated with O 3 as a reactant or that the ClO 4 − was affected by postdepositional O isotope exchange. High Δ 17 O values in ClO 4 − (Atacama and Death Valley) are associated with high Δ 17 O values in NO 3 − , indicating that both compounds preserve characteristics of O 3 -related atmospheric production in hyper-arid settings, whereas both compounds have low Δ 17 O values in less arid settings. Although Δ 17 O variations in terrestrial NO 3 − can be attributed to mixing of atmospheric (high Δ 17 O) and biogenic (low Δ 17 O) NO 3 − , variations in Δ 17 O of terrestrial ClO 4 − are not readily explained in the same way. This study provides important new constraints for identifying natural sources of ClO 4 − in different environments by multicomponent isotopic characteristics, while presenting the possibilities of divergent ClO 4 − formation mechanisms and(or) ClO 4 − isotopic exchange in biologically active environments.

Environmental Science & Technology↗

Tet and sul antibiotic resistance genes in livestock lagoons of various operation type, configuration, and antibiotic occurrence

Although livestock operations are known to harbor elevated levels of antibiotic resistant bacteria, few studies have examined the potential of livestock waste lagoons to reduce antibiotic resistance genes (ARGs). The purpose of this study was to determine the prevalence and examine the behavior of tetracycline [tet(O) and tet(W)] and sulfonamide [sul(I) and su/(II)] ARGsin a broad cross-section of livestock lagoons within the same semiarid western watershed. ARGs were monitored for one year in the water and the settled solids of eight lagoon systems by quantitative polymerase chain reaction. In addition, antibiotic residues and various bulk water quality constituents were analyzed. It was found that the lagoons of the chicken layer operation had the lowest concentrations of both tet and sul ARGs and low total antibiotic concentrations, whereas su ARGs were highest in the swine lagoons, which generally corresponded to the highest total antibiotic concentrations. A marginal benefit of organic and small dairy operations also was observed compared to conventional and large dairies, respectively. In all lagoons, su ARGs were observed to be generally more recalcitrant than tet ARGs. Also, positive correlations of various bulk water quality constituents were identified with tet ARGs but not sul ARGs. Significant positive correlations were identified between several metals and tet ARGs, but Pearson's correlation coefficients were mostly lower than those determined between antibiotic residues and ARGs. This study represents a quantitative characterization of ARGs in lagoons across a variety of livestock operations and provides insight into potential options for managing antibiotic resistance emanating from agricultural activities.

Environmental Science & Technology↗

Linear solvation energy relationship of the limiting partition coefficient of organic solutes between water and activated carbon

A linear solvation energy relationship has been found for 353 values of the limiting adsorption coefficients of diverse chemicals: log K = −0.37 + 0.0341 V i − 1.07β + D + 0.65 P with R = 0.951, s = 0.51, n = 353, and F = 818.0, where V i is the intrinsic molar volume; β is a measure of the hydrogen bond acceptor strength of the solute; D is an index parameter for the research group which includes the effects of the different types of carbon used, the temperature, and the length of time allowed for the adsorption equilibrium to be established; and P is an index parameter for the flatness of the molecule. P is defined to be unity if there is an aromatic system in the molecule or if there is a double bond or series of conjugated double bonds with no more that one non-hydrogen atom beyond the double bond and zero otherwise. A slightly better fit is obtained if the two-thirds power of V i is used as a measure of the surface area in place of the volume term: log K = −1.75 + 0.227 V 2/3 − 1.10β + D + 0.60 P with R = 0.954, s = 0.49, n = 353, and F = 895.39. This is the first quantitative measure of the effect of the shape of the molecule on its tendency to be adsorbed on activated carbon.

Environmental Science & Technology↗

Fate of linear alkylbenzene sulfonate in the Mississippi River

The 2 800-km reach of the Mississippi River between Minneapolis, MN, and New Orleans, LA, was examined for the occurrence and fate of linear alkylbenzene sulfonate (LAS), a common anionic surfactant found in municipal sewage effluents. River water and bottom sediment were sampled in the summer and fall of 1991 and in the spring of 1992. LAS was analyzed using solid-phase extraction/derivatization/ gas chromatography/mass spectrometry. LAS was present on all bottom sediments at concentrations ranging from 0.01 to 20 mg/kg and was identified in 21% of the water samples at concentrations ranging from 0.1 to 28.2 μg/L. The results indicate that LAS is a ubiquitous contaminant on Mississippi River bottom sediments and that dissolved LAS is present mainly downstream from the sewage outfalls of major cities. The removal of the higher LAS homologs and external isomers indicates that sorption and biodegradation are the principal processes affecting dissolved LAS. Sorbed LAS appears to degrade slowly.

Environmental Science & Technology↗

Comparison of the in situ and desorption sediment-water partitioning of polycyclic aromatic hydrocarbons and polychlorinated biphenyls

In situ sediment−porewater partitioning of polycyclic aromatic hydrocarbons (PAHs) measured in three cores from Boston Harbor, MA, has led us to suggest that only a fraction of the total measured sediment PAH concentration is a vailable for e quilibrium p artitioning (AEP fraction). To test this, aqueous PAH concentrations were measured in laboratory desorption experiments using subsamples of the same Boston Harbor sediments. The observed concentrations were consistent with what we predicted from the field-derived AEP values: C aqueous = ( C sediment × AEP)/( f oc × K oc ) where f oc is the fraction organic carbon in the sediment and K oc is the organic carbon normalized sediment−water partition coefficient. Equilibrium partitioning models based on the total measured sediment PAH concentrations overestimated the measured aqueous PAH concentrations by as much as 100 times in some cases. Only a small fraction of the sediment phenanthrene and pyrene concentrations (1−40%) appeared to be available for equilibrium partitioning. Both in situ and laboratory desorption aqueous polychlorinated biphenyl (PCB) concentrations were consistent with equilibrium partitioning models and the assumption that 100% of these compounds was available for equilibrium partitioning. These results are particularly important to efforts to predict the environmental mobility and bioavailability of the PAHs.

Massachusetts↗

Glutathione conjugation and contaminant transformation

The recent identification of a novel sulfonated metabolite of alachlor in groundwater and metolachlor in soil is likely the result of glutathione conjugation. Glutathione conjugation is an important biochemical reaction that leads, in the case of alachlor, to the formation of a rather difficult to detect, water-soluble, and therefore highly mobile, sulfonated metabolite. Research from weed science, toxicology, and biochemistry is discussed to support the hypothesis that glutathione conjugation is a potentially important detoxification pathway carried out by aquatic and terrestrial plants and soil microorganisms. A brief review of the biochemical basis for glutathione conjugation is presented. We recommend that multidisciplinary research focus on the occurrence and expression of glutathione and its attendant enzymes in plants and microorganisms, relationships between electrophilic substrate structure and enzyme activity, and the potential exploitation of plants and microorganisms that are competent in glutathione conjugation for phytoremediation and bioremediation.

Environmental Science & Technology↗

Air pollutant intrusion into the Wieliczka Salt Mine

The Wieliczka Salt Mine World Cultural Heritage Site contains many rock salt sculptures that are threatened by water vapor condensation from the mine ventilation air. Gaseous and particulate air pollutant concentrations have been measured both outdoors and within the Wieliczka Salt Mine, along with pollutant deposition fluxes to surfaces within the mine. One purpose of these measurements was to determine whether or not low deliquescence point ionic materials (e.g., NH4NO3) are accumulating on surfaces to an extent that would exacerbate the water vapor condensation problems in the mine. It was found that pollutant gases including SO2 and HNO3 present in outdoor air are removed rapidly and almost completely from the air within the mine by deposition to surfaces. Sulfur isotope analyses confirm the accumulation of air pollutant-derived sulfur in liquid dripping from surfaces within the mine. Particle deposition onto interior surfaces in the mine is apparent, with resulting soiling of some of those sculptures that have been carved from translucent rock salt. Water accumulation by salt sculpture surfaces was studied both experimentally and by approximate thermodynamic calculations. Both approaches suggest that the pollutant deposits on the sculpture surfaces lower the relative humidity (RH) at which a substantial amount of liquid water will accumulate by 1% to several percent. The extraordinarily low SO2 concentrations within the mine may explain the apparent success of a respiratory sanatorium located deep within the mine.

Environmental Science & Technology↗

Dietary exposure of mink to carp from Saginaw Bay. 3. Characterization of dietary exposure to planar halogenated hydrocarbons, dioxin equivalents, and biomagnification

Mink are known to be very sensitive to the toxic effects of planar polychlorinated biphenyls (pPCBs), polychlorinated dibenzo- p -dioxins (PCDDs), and polychlorinated dibenzofurans (PCDFs), collectively known as planar halogenated hydrocarbons (PHHs). Previously, we reported the reproductive effects in mink fed a diet containing 10, 20, or 40% fish taken from Saginaw Bay, Lake Huron. The present study reports the chemical characterization of the diets and the adult mink livers, along with a comparison of an additive model of toxicity with the results of the H4IIE bioassay on these samples. The assessment of dietary or tissue-based exposure of the mink to 2,3,7,8-tetrachlorodibenzo- p -dioxin (TCDD) and related compounds revealed that TCDD equivalents of the PHH mixtures largely followed an additive model of toxicity as compared with the H4IIE bioassay. Consistent dietary and liver tissue-based threshold concentrations for reproductive toxicity in mink were determined regardless of whether PHHs were quantified as TEQs (additive toxicity) or TCDD-EQs (H4IIE bioassay). Significant reproductive effects were observed in the lowest treatment group (10% fish or 19.4 pg of H4IIE bioassay-derived TCDD-EQs/g). Consumption-normalized mink liver biomagnification factors (BMFs) were 6.4−74.2 for PCDDs, <1−75.8 for PCDFs, <1−15.9 for PCBs, and in general, increased with degree of chlorination within each class. Based on TEQs or TCDD-EQ, this study confirms that mink are among the most, if not the most, sensitive mammalian species to the reproductive toxicity of TCDD and related compounds.

Environmental Science & Technology↗

Acetochlor in the hydrologic system in the midwestern United States, 1994

The herbicide acetochlor [2-chloro- N -(ethoxymethyl)- N -(2-ethyl-6-methylphenyl)acetamide] was given conditional registration in the United States by the U.S. Environmental Protection Agency in March 1994. This registration provided a rare opportunity to investigate the occurrence of a pesticide during its first season of extensive use in the midwestern United States. Water samples collected and analyzed by the U.S. Geological Survey during 1994 documented the distribution of acetochlor in the hydrologic system; it was detected in 29% of the rain samples from four sites in Iowa, 17% of the stream samples from 51 sites across nine states, and 0% of the groundwater samples from 38 wells across eight states. Acetochlor exhibited concentration increases in rain and streams following its application to corn in the midwestern United States, with 75% of the rainwater and 35% of the stream samples having acetochlor detected during this time period. Acetochlor concentrations in rain decreased as the growing season progressed. Based on the limited data collected for this study, it is anticipated that acetochlor concentrations will have a seasonal pattern in rain and streams similar to those of other acetanilide herbicides examined. Possible explanations for the absence of acetochlor in groundwater for this study include the rapid degradation of acetochlor in the soil zone, insufficient time for this first extensive use of acetochlor to have reached the aquifers sampled, and the possible lack of acetochlor use in the recharge areas for the wells examined.

Environmental Science & Technology↗

Occurrence of alachlor and its sulfonated metabolite in rivers and reservoirs of the midwestern United States: The importance of sulfonation in the transport of chloroacetanilide herbicides

Alachlor and its metabolite, 2-[(2',6'-diethylphenyl)- (methoxymethyl)amino]-2-oxoethanesulfonate (ESA), were identified in 76 reservoirs in the midwestern United States using immunoassay, liquid chromatography, and gas chromatography/mass spectrometry. The median concentration of ESA (0.48 ??g/L) exceeded the median concentration of alachlor (<0.05 ??g/L), with highest values in the upper Midwest. ESA also was detected in the Mississippi River from the mouth to the headwaters at concentrations of 0.2-1.5 ??g/L, exceeding the concentration of alachlor. In a field runoff study, alachlor rapidly formed ESA. It is hypothesized that a glutathione conjugate forms, which later oxidizes in soil to ESA. The removal of the chlorine atom lessens the toxicity of the parent compound and increases runoff potential. It is hypothesized further that sulfonic acid metabolites of other chloroacetanilides, including acetochlor, butachlor, metolachlor, and propachlor, also occur in surface water.

Midwest↗

Effects of sampling strategies on estimates of annual mean herbicide concentrations in midwestern rivers

The effects of 10 sampling strategies on estimates of annual mean concentrations of the herbicides atrazine, alachlor, and cyanazine in selected midwestern rivers were tested. The accuracy of the strategies was computed by comparing time-weighted annual mean herbicide concentrations calculated from water samples collected from 17 locations on midwestern rivers, with simulated annual mean concentrations calculated for each sampling strategy, using Monte Carlo simulations. Monthly sampling was the most accurate strategy tested. The U.S. Environmental Protection Agency requires quarterly sampling for municipalities using surface water as a source of drinking water. Due to the seasonality of herbicide occurrence and transport, quarterly sampling underestimates annual mean herbicide concentrations in over 40% of the simulations. Three of the strategies tested showed that, relative to quarterly sampling, a more accurate representation of annual mean concentrations could be obtained by sampling more frequently during spring and early summer runoff and assuming zero herbicide concentration during late summer and winter months.

Environmental Science & Technology↗

Pesticides in streams draining agricultural and urban areas in Colorado

A study was conducted from April 1993 through April 1994 to describe and compare the occurrence and distribution of pesticides in streams in a small agricultural and a small urban area in Colorado. Twenty-five water samples collected at least monthly at the mouths of two tributary streams of the South Plate River were analyzed for 47 pesticides. The results indicate that both agricultural and urban areas are probable sources for pesticides in streams. In the agricultural area, 30 pesticides were detected, and in the urban area, 22 pesticides were detected in one or more samples. Most often, the more frequently detected pesticides in both areas also were some of the more commonly used pesticides. In both areas, pesticide concentrations were higher during the summer (application period) with maximum concentrations generally occurring in storm runoff. The year-round detection of some pesticides in both areas at consistently low concentrations, regardless of season or streamflow volume, could indicate that these compounds persist in the shallow alluvial aquifer year-round.

Environmental Science & Technology↗