A millennial-scale record of Pb and Hg contamination in peatlands of the Sacramento-San Joaquin Delta of California, USA.

In this paper, we provide the first record of millennial patterns of Pb and Hg concentrations on the west coast of the United States. Peat cores were collected from two micro-tidal marshes in the Sacramento-San Joaquin Delta of California. Core samples were analyzed for Pb, Hg, and Ti concentrations and dated using radiocarbon and (210)Pb. Pre-anthropogenic concentrations of Pb and Hg in peat ranged from 0.60 to 13.0µgg(-1)and from 6.9 to 71ngg(-1), respectively. For much of the past 6000+ years, the Delta was free from anthropogenic pollution, however, beginning in ~1425CE, Hg and Pb concentrations, Pb/Ti ratios, Pb enrichment factors (EFs), and HgEFs all increased. Pb isotope compositions of the peat suggest that this uptick was likely caused by smelting activities originating in Asia. The next increases in Pb and Hg contamination occurred during the California Gold Rush (beginning ~1850CE), when concentrations reached their highest levels (74µgg(-1) Pb, 990ngg(-1) Hg; PbEF=12 and HgEF=28). Lead concentrations increased again beginning in the ~1920s with the incorporation of Pb additives in gasoline. The phase-out of lead additives in the late 1980s was reflected in changes in Pb isotope ratios and reductions in Pb concentrations in the surface layers of the peat. The rise and subsequent fall of Hg contamination was also tracked by the peat archive, with the highest Hg concentrations occurring just before 1963CE and then decreasing during the post-1963 period. Overall, the results show that the Delta was a pristine region for most of its ~6700-year existence; however, since ~1425CE, it has received Pb and Hg contamination from both global and regional sources.

Mercury cycling in agricultural and managed wetlands, Yolo Bypass, California: spatial and seasonal variations in water quality.

The seasonal and spatial variability of water quality, including mercury species, was evaluated in agricultural and managed, non-agricultural wetlands in the Yolo Bypass Wildlife Area, an area managed for multiple beneficial uses including bird habitat and rice farming. The study was conducted during an 11-month period (June 2007 to April 2008) that included a summer growing season and flooded conditions during winter. Methylmercury (MeHg) concentrations in surface water varied over a wide range (0.1 to 37ngL(-1) unfiltered; 0.04 to 7.3ngL(-1) filtered). Maximum MeHg values are among the highest ever recorded in wetlands. Highest MeHg concentrations in unfiltered surface water were observed in drainage from wild rice fields during harvest (September 2007), and in white rice fields with decomposing rice straw during regional flooding (February 2008). The ratio of MeHg to total mercury (MeHg/THg) increased about 20-fold in both unfiltered and filtered water during the growing season (June to August 2007) in the white and wild rice fields, and about 5-fold in fallow fields (July to August 2007), while there was little to no change in MeHg/THg in the permanent wetland. Sulfate-bearing fertilizer had no effect on Hg(II) methylation, as sulfate-reducing bacteria were not sulfate-limited in these agricultural wetlands. Concentrations of MeHg in filtered and unfiltered water correlated with filtered Fe, filtered Mn, DOC, and two indicators of sulfate reduction: the SO4(2-)/Cl(-) ratio, and δ(34)S in aqueous sulfate. These relationships suggest that microbial reduction of SO4(2-), Fe(III), and possibly Mn(IV) may contribute to net Hg(II)-methylation in this setting.

Lagrangian mass-flow investigations of inorganic contaminants in wastewater-impacted streams.

Understanding the potential effects of increased reliance on wastewater treatment plant (WWTP) effluents to meet municipal, agricultural, and environmental flow requires an understanding of the complex chemical loading characteristics of the WWTPs and the assimilative capacity of receiving waters. Stream ecosystem effects are linked to proportions of WWTP effluent under low-flow conditions as well as the nature of the effluent chemical mixtures. This study quantifies the loading of 58 inorganic constituents (nutrients to rare earth elements) from WWTP discharges relative to upstream landscape-based sources. Stream assimilation capacity was evaluated by Lagrangian sampling, using flow velocities determined from tracer experiments to track the same parcel of water as it moved downstream. Boulder Creek, Colorado and Fourmile Creek, Iowa, representing two different geologic and hydrologic landscapes, were sampled under low-flow conditions in the summer and spring. One-half of the constituents had greater loads from the WWTP effluents than the upstream drainages, and once introduced into the streams, dilution was the predominant assimilation mechanism. Only ammonium and bismuth had significant decreases in mass load downstream from the WWTPs during all samplings. The link between hydrology and water chemistry inherent in Lagrangian sampling allows quantitative assessment of chemical fate across different landscapes.

Anthropogenic tracers, endocrine disrupting chemicals, and endocrine disruption in Minnesota lakes.

Concentrations of endocrine disrupting chemicals and endocrine disruption in fish were determined in 11 lakes across Minnesota that represent a range of trophic conditions and land uses (urban, agricultural, residential, and forested) and in which wastewater treatment plant discharges were absent. Water, sediment, and passive polar organic integrative samplers (POCIS) were analyzed for steroidal hormones, alkylphenols, bisphenol A, and other organic and inorganic molecular tracers to evaluate potential non-point source inputs into the lakes. Resident fish from the lakes were collected, and caged male fathead minnows were deployed to evaluate endocrine disruption, as indicated by the biological endpoints of plasma vitellogenin and gonadal histology. Endocrine disrupting chemicals, including bisphenol A, 17ß-estradiol, estrone, and 4-nonylphenol were detected in 90% of the lakes at part per trillion concentrations. Endocrine disruption was observed in caged fathead minnows and resident fish in 90% of the lakes. The widespread but variable occurrence of anthropogenic chemicals in the lakes and endocrine disruption in fish indicates that potential sources are diverse, not limited to wastewater treatment plant discharges, and not entirely predictable based on trophic status and land use.

Evaluation of statistical treatments of left-censored environmental data using coincident uncensored data sets: I. Summary statistics.

The main classes of statistical treatment of below-detection limit (left-censored) environmental data for the determination of basic statistics that have been used in the literature are substitution methods, maximum likelihood, regression on order statistics (ROS), and nonparametric techniques. These treatments, along with using all instrument-generated data (even those below detection), were evaluated by examining data sets in which the true values of the censored data were known. It was found that for data sets with less than 70% censored data, the best technique overall for determination of summary statistics was the nonparametric Kaplan-Meier technique. ROS and the two substitution methods of assigning one-half the detection limit value to censored data or assigning a random number between zero and the detection limitto censored data were adequate alternatives. The use of these two substitution methods, however, requires a thorough understanding of how the laboratory censored the data. The technique of employing all instrument-generated data--including numbers below the detection limit--was found to be less adequate than the above techniques. At high degrees of censoring (greater than 70% censored data), no technique provided good estimates of summary statistics. Maximum likelihood techniques were found to be far inferior to all other treatments except substituting zero or the detection limit value to censored data.

Chemical loading into surface water along a hydrological, biogeochemical, and land use gradient: a holistic watershed approach.

Identifying the sources and impacts of organic and inorganic contaminants at the watershed scale is a complex challenge because of the multitude of processes occurring in time and space. Investigation of geochemical transformations requires a systematic evaluation of hydrologic, landscape, and anthropogenic factors. The 1160 km2 Boulder Creek Watershed in the Colorado Front Range encompasses a gradient of geology, ecotypes, climate, and urbanization. Streamflow originates primarily as snowmelt and shows substantial annual variation. Water samples were collected along a 70-km transect during spring-runoff and base-flow conditions, and analyzed for major elements, trace elements, bulk organics, organic wastewater contaminants (OWCs), and pesticides. Major-element and trace-element concentrations were low in the headwaters, increased through the urban corridor, and had a step increase downstream from the first major wastewater treatment plant (WWTP). Boron, gadolinium, and lithium were useful inorganic tracers of anthropogenic inputs. Effluent from the WWTP accounted for as much as 75% of the flow in Boulder Creek and was the largest chemical input. Under both hydrological conditions, OWCs and pesticides were detected in Boulder Creek downstream from the WWTP outfall as well as in the headwater region, and loads of anthropogenic-derived contaminants increased as basin population density increased. This report documents a suite of potential endocrine-disrupting chemicals in a reach of stream with native fish populations showing indication of endocrine disruption.

Accumulation of contaminants in fish from wastewater treatment wetlands.

Increasing demands on water resources in arid environments make reclamation and reuse of municipal wastewater an important component of the water budget. Treatment wetlands can be an integral part of the water-reuse cycle providing both water-quality enhancement and habitat functions. When used for habitat, the bioaccumulation potential of contaminants in the wastewater is a critical consideration. Water and fish samples collected from the Tres Rios Demonstration Constructed Wetlands near Phoenix, Arizona, which uses secondary-treated wastewater to maintain an aquatic ecosystem in a desert environment, were analyzed for hydrophobic organic compounds (HOC) and trace elements. Semipermeable membrane devices (SPMD) were deployed to investigate uptake of HOC. The wetlands effectively removed HOC, and concentrations of herbicides, pesticides, and organic wastewater contaminants decreased 40-99% between inlet and outlet. Analysis of Tilapia mossambica and Gambusia affinis indicated accumulation of HOC, including p,p'-DDE and trans-nonachlor. The SPMD accumulated the HOC detected in the fish tissue as well as additional compounds. Trace-element concentrations in whole-fish tissue were highly variable, but were similar between the two species. Concentrations of HOC and trace elements varied in different fish tissue compartments, and concentrations in Tilapia liver tissue were greater than those in the whole organism or filet tissue. Bioconcentration factors for the trace elements ranged from 5 to 58,000 and for the HOC ranged from 530 to 150,000.

Aqueous stability of gadolinium in surface waters receiving sewage treatment plant effluent, Boulder Creek, Colorado.

In many surface waters, sewage treatment plant (STP) effluent is a substantial source of both regulated and unregulated contaminants, including a suite of complex organic compounds derived from household chemicals, pharmaceuticals, and industrial and medical byproducts. In addition, STP effluents in some urban areas have also been shown to have a positive gadolinium (Gd) anomaly in the rare earth element (REE) pattern, with the Gd derived from its use in medical facilities. REE concentrations are relatively easy to measure compared to many organic wastewater compounds and may provide a more widely utilized tracer of STP effluents. To evaluate whether sewage treatment plant-associated Gd is a useful tracer of treatment plant effluent, an investigation of the occurrence, fate, and transport of rare earth elements was undertaken. The rare earth element patterns of four of five STP effluents sampled display positive Gd anomalies. The one site that did not have a Gd anomaly serves a small community, population 1200, with no medical facilities. Biosolids from a large metropolitan STP are not enriched in Gd even though the effluent is, suggesting that a substantial fraction of Gd remains in the aqueous phase through routine treatment plant operation. To evaluate whether STP-derived Gd persists in the fluvial environment, a 14-km study reach downstream of an STP was sampled. Gadolinium anomalies were present at all five downstream sites, but the magnitude of the anomaly decreased. Effluent from STPs is a complex mixture of organic and inorganic constituents, and to better understand the chemical interactions and their effect on REEs, the aqueous speciation was modeled using comprehensive chemical analyses of water samples collected downstream of STP input. These calculations suggest that the REEs will likely remain dissolved because phosphate and carbonate complexes dominate over free REE ions. This study supports the application of Gd anomalies as a useful tracer of urban wastewater.