Contaminants of Emerging Concern: Mass Balance and Comparison of Wastewater Effluent and Upstream Sources in a Mixed-Use Watershed.

Understanding the sources, transport, and spatiotemporal variability of contaminants of emerging concern (CECs) is important for understanding risks and developing monitoring and mitigation strategies. This study used mass balances to compare wastewater treatment plant (WWTP) and upstream sources of 16 CECs to a mixed-use watershed in Minnesota, under different seasonal and hydrological conditions. Three distinct CEC groups emerged with respect to their source proportionality and instream behavior. Agricultural herbicides and daidzein inputs were primarily via upstream routes with the greatest loadings and concentrations during high flows. Trimethoprim, mecoprop, nonprescription pharmaceuticals, and personal care products entered the system via balanced/mixed pathways with peak loadings and concentrations in high flows. Carbaryl, 4-nonylphenol, and the remaining prescription pharmaceuticals entered the system via WWTP effluent with relatively stable loadings across sampling events. Mass balance analysis based on multiple sampling events and sites facilitated CEC source comparisons and may therefore prove to be a powerful tool for apportioning sources and exploring mitigation strategies.

Reproductive responses of male fathead minnows exposed to wastewater treatment plant effluent, effluent treated with XAD8 resin, and an environmentally relevant mixture of alkylphenol compounds.

On-site, continuous-flow experiments were conducted during August and October 2002 at a major metropolitan wastewater treatment plant (WWTP) to determine if effluent exposure induced endocrine disruption as manifested in the reproductive competence of sexually mature male fathead minnows (Pimephales promelas). The fathead minnows were exposed in parallel experiments to WWTP effluent and WWTP effluent treated with XAD8 macroreticular resin to remove the hydrophobic-neutral fraction which contained steroidal hormones, alkylphenolethoxylates (APEs), and other potential endocrine disrupting compounds (EDCs). The effluent composition varied on a temporal scale and the continuous-flow experiments captured the range of chemical variability that occurred during normal WWTP operations. Exposure to WWTP effluent resulted in vitellogenin induction in male fathead minnows, with greater response in October than in August. Concentrations of ammonia, APEs, 17beta-estradiol, and other EDCs also were greater in October than in August, reflecting a change in effluent composition. In the October experiment, XAD8 treatment significantly reduced vitellogenin induction in the male fathead minnows relative to the untreated effluent, whereas in August, XAD8 treatment had little effect. During both experiments, XAD8 treatment removed greater than 90% of the APEs. Exposure of fish to a mixture of APEs similar in composition and concentration to the WWTP effluent, but prepared in groundwater and conducted at a separate facility, elicited vitellogenin induction during both experiments. There was a positive relation between vitellogenin induction and hepatosomatic index (HSI), but not gonadosomatic index (GSI), secondary sexual characteristics index (SSCI), or reproductive competency. In contrast to expectations, the GSI and SSCI increased in males exposed to WWTP effluent compared to groundwater controls. The GSI, SSCI, and reproductive competency were positively affected by XAD8 treatment of the WWTP effluent.

Changes in antibacterial activity of triclosan and sulfa drugs due to photochemical transformations.

Sulfa drugs and triclosan represent two classes of antibacterials that have been found in natural waters and for which photodegradation is anticipated to be a significant loss process. Parent antibacterial compounds and the products of photolysis reactions were compared for three sulfa drugs and triclosan to determine the extent to which photolysis affects their antibacterial potency on Escherichia coli DH5alpha. Sulfathiazole (median effective concentration [EC50] = 20.0 microM), sulfamethoxazole (EC50 = 12.3 microM), and sulfachloropyridazine (EC50 = 6.9 microM) inhibited bacterial growth but did not affect respiratory activity. Photolysis products of these sulfa drugs did not retain any measurable ability to inhibit growth. Triclosan inhibited both the growth (EC50 = 0.24 microM) and respiratory activity of E. coli DH5alpha. Triclosan photolysis products also exhibited no measurable effect on growth or respiratory activity. These experiments indicate that the products of triclosan and sulfa drug photolysis are unlikely to possess antibacterial activity in natural waters. The rapid screening method used for these two classes of compounds will be useful for helping to identify photolabile antibacterial compounds, for which photoproducts could require further investigation.

Sources and transport of contaminants of emerging concern: A two-year study of occurrence and spatiotemporal variation in a mixed land use watershed.

The occurrence and spatiotemporal variation of 26 contaminants of emerging concern (CECs) were evaluated in 68 water samples in 2011-2012 in the Zumbro River watershed, Minnesota, U.S.A. Samples were collected across a range of seasonal/hydrological conditions from four stream sites that varied in associated land use and presence of an upstream wastewater treatment plant (WWTP). Selected CECs included human/veterinary pharmaceuticals, personal care products, pesticides, phytoestrogens, and commercial/industrial compounds. Detection frequencies and concentrations varied, with atrazine, metolachlor, acetaminophen, caffeine, DEET, and trimethoprim detected in more than 70% of samples, acetochlor, mecoprop, carbamazepine, and daidzein detected in 30%-50% of samples, and 4-nonylphenol, cotinine, sulfamethoxazole, erythromycin, tylosin, and carbaryl detected in 10%-30% of samples. The remaining target CECs were not detected in water samples. Three land use-associated trends were observed for the detected CECs. Carbamazepine, 4-nonylphenol, erythromycin, sulfamethoxazole, tylosin, and carbaryl profiles were WWTP-dominated, as demonstrated by more consistent loading and significantly greater concentrations downstream of the WWTP and during low-flow seasons. In contrast, acetaminophen, trimethoprim, DEET, caffeine, cotinine, and mecoprop patterns demonstrated both seasonally-variable non-WWTP-associated and continual WWTP-associated influences. Surface water studies of CECs often target areas near WWTPs. This study suggests that several CECs often characterized as effluent-associated have additional important sources such as septic systems or land-applied biosolids. Finally, agricultural herbicide (atrazine, acetochlor, and metolachlor) profiles were strongly influenced by agricultural land use and seasonal application-runoff, evident by significantly greater concentrations and loadings at upstream sites and in early summer when application and precipitation rates are greatest. Our results indicate that CEC monitoring studies should consider a range of land uses, seasonality, and transport pathways in relation to concentrations and loadings. This knowledge can augment CEC monitoring programs to result in more accurate source, occurrence, and ecological risk characterizations, more precisely targeted mitigation initiatives, and ultimately, enhanced environmental decision-making.

Partitioning of polychlorinated biphenyls in octanol/water, triolein/water, and membrane/water systems.

The use of the octanol/water partition constant (Kow) as a surrogate parameter for lipid/water partitioning of persistent organic pollutants (POPs) was reassessed by comparing the measured Kow of 12 selected polychlorinated biphenyl congeners (PCBs) with partition constants in triolein/water (Ktw) and membrane/water (Kmw) systems. Kow and Ktw were measured by the slow-stirring method. Kmw was measured by an adaptation of the slow-stirring method using suspensions of phosphatidylcholine and phosphatidylserine liposomes. Partitioning of POPs to octanol, triolein, and liposomes is similar but not equal. The log-log correlation for Kow and Ktw is excellent (r2 = 0.982) and that for Kow and Kmw is somewhat weaker (r2 = 0.856). Ktw values are greater than Kow by a factor of 1.6. Kmw of some PCB congeners exceed both Kow and Ktw by an order of magnitude. The differences are attributed to different PCB activity coefficients in the different lipid phases. The results imply that Kow can be used as a reasonable conservative estimate of lipid/water partitioning. But the observed differences between Kow and Kmw also indicate that using Kow to predict accumulation of POPs, particularly highly hydrophobic ones, in the polar lipids of organisms will underestimate their concentrations at equilibrium.

Sediment-water distribution of contaminants of emerging concern in a mixed use watershed.

This study evaluated the occurrence and distribution of 15 contaminants of emerging concern (CECs) in stream water and sediments in the Zumbro River watershed in Minnesota and compared these with sub-watershed land uses. Sixty pairs of sediment and water samples were collected across all seasons from four stream sites for over two years and analyzed for selected personal care products, pesticides, human and veterinary medications, and phytoestrogens. Spatial and temporal analyses indicate that pharmaceuticals and personal care products (urban/residential CECs) are significantly elevated in water and/or sediment at sites with greater population density (>100 people/km(2)) and percentage of developed land use (>8% of subwatershed area) than those with less population density and land area under development. Significant spatial variations of agricultural pesticides in water and sediment were detectable, even though all sites had a high percentage of agricultural land use. Seasonality in CEC concentration was observed in water but not in sediment, although sediment concentrations of three CECs did vary between years. Average measured non-equilibrium distribution coefficients exceeded equilibrium hydrophobic partitioning-based predictions for 5 of the 7 detected CECs by at least an order of magnitude. Agreement of measured and predicted distribution coefficients improved with increasing hydrophobicity and in-stream persistence. The more polar and degradable CECs showed greater variability in measured distributions across different sampling events. Our results confirm that CECs are present in urban and agricultural stream sediments, including those CECs that would typically be thought of as non-sorptive based on their log Kow values. These results and the observed patterns of sediment and water distributions augment existing information to improve prediction of CEC fate and transport, leading to more accurate assessments of exposure and risk to surface water ecosystems.

Influence of suspended solids on acute toxicity of carbofuran to Daphnia magna: I. Interactive effects.

This study explored the effects on Daphnia magna from exposure to the pesticide carbofuran in combination with stress from suspended solids exposure. Our objective was to assess whether suspended solids affects the toxicodynamic response of D. magna to carbofuran. A series of laboratory experiments was performed where animals were exposed to carbofuran concentrations ranging from 0 to 160 microg/l in combination with suspended solids concentrations ranging from 0 to 10000 mg/l. In the absence of suspended solids, effects of carbofuran were dose dependent and resulted in an EC(50) of 92 microg/l. Exposure to suspended solids, up to extreme levels that may be encountered in the environment and in the absence of carbofuran, showed no measurable toxicity. When D. magna were exposed to a constant carbofuran concentration, the numbers of affected organisms increased with increasing suspended solids concentrations. At a suspended solids concentration of 1000 mg/l, the EC(50) for carbofuran was reduced by half to 45 microg/l. The relationship between the toxicity of carbofuran (microg/l) and the concentration of suspended solids (mg/l) can be described with the following equation: carbofuran EC(50)=72 exp(-0.00014 [suspended solids]). An analysis of the data indicates that this relationship is consistent with a potentiated toxicity mechanism rather than an additive model.

Influence of suspended solids on acute toxicity of carbofuran to Daphnia magna: II. An evaluation of potential interactive mechanisms.

It has been demonstrated that simultaneous exposure of Daphnia magna to suspended solids and a carbamate pesticide potentiates the toxic response to the pesticide. The toxicodynamics between these stressors were investigated to determine possible mechanisms of interaction. Three experimental series were conducted with D. magna to determine: the effect of food availability on carbofuran toxicity; the effect of food availability on jointly administered carbofuran and suspended solids; and changes in the magnitude of effects which can occur with suspended solids of different composition. These experiments demonstrated that both carbofuran toxicity and the joint toxicity of carbofuran and suspended solids to D. magna can be modulated by food availability. While it is clear that food dilution could contribute to energy stress, it appears likely that additional interactive processes also contribute to the observed synergism between carbofuran and suspended solids. Additionally, decomposed peat was shown to be less of a stressor to these pelagic invertebrates than inorganic subsoil.

Subcellular accumulation of polychlorinated biphenyls in the green alga Chlamydomonas reinhardtii.

In this study, the subcellular accumulation of 13 polychlorinated biphenyl (PCB) congeners was investigated in the green alga Chlamydomonas reinhardtii. Two main arguments pertaining to the mechanism of bioaccumulation of persistent bioaccumulative toxic chemicals (PBTs) in phytoplankton were evaluated, including the controversy of whether the limitation of uptake of ultra-hydrophobic pollutants is kinetic or due to a physical barrier presented by the membrane that prevents transfer into the internal parts of the cell, and second, the role of surface adsorption for the bioaccumulation process. The first argument was addressed by studying the time-dependent subcellular uptake of PCBs into thylakoids (photosynthetic membranes) as representative internal membranes. The second issue was addressed by investigating the role of the algal cell wall as a potential extracellular sorbate. Accumulation of PCBs in thylakoids was found to be limited kinetically and slow compared to total accumulation in the alga. Super-hydrophobic PCBs with Kow > 6 were not restricted from entering the cell. Sorption to the cell wall was found to be less than 10% and insignificant compared to total bioaccumulation in C. reinhardtii. To our knowledge, this is the first study in which the subcellular uptake of a class of PBTs was investigated directly. The results offer a mechanistic framework for improving kinetic modeling of PBT bioaccumulation in phytoplankton.

Preferential biomagnification of aryl hydrocarbon hydroxylase-inducing polychlorinated biphenyl congeners in the Lake Michigan, USA, lower food web.

Preferential biomagnification of 14 dioxin-like polychlorinated biphenyls (PCBs) was determined in lower-trophic-level organisms of the Lake Michigan, USA, food web. Bioaccumulation of these coplanar, aryl hydrocarbon hydroxylase (AHH)-inducing PCB congeners and total PCBs in phytoplankton, zooplankton, Mysis relicta, and Diporeia sp. were studied for two locations in Lake Michigan over time. The results indicate that both total PCB and AHH-inducing PCBs biomagnify with increasing food web trophic level, with biomagnification of the AHH-inducing PCBs occurring to a greater degree. The biomagnification factors (BMFs) of the AHH-inducing PCBs suggest that they are highly conserved relative to other PCB congeners. The concentrations expressed as dioxin toxic equivalencies (TEQ concentrations) indicate that the biomagnification of AHH PCBs causes greater concentrations, and thus greater toxicity risk, with increasing trophic level.

Identifying sources of emerging organic contaminants in a mixed use watershed using principal components analysis.

Principal components analysis (PCA) was used to identify sources of emerging organic contaminants in the Zumbro River watershed in Southeastern Minnesota. Two main principal components (PCs) were identified, which together explained more than 50% of the variance in the data. Principal Component 1 (PC1) was attributed to urban wastewater-derived sources, including municipal wastewater and residential septic tank effluents, while Principal Component 2 (PC2) was attributed to agricultural sources. The variances of the concentrations of cotinine, DEET and the prescription drugs carbamazepine, erythromycin and sulfamethoxazole were best explained by PC1, while the variances of the concentrations of the agricultural pesticides atrazine, metolachlor and acetochlor were best explained by PC2. Mixed use compounds carbaryl, iprodione and daidzein did not specifically group with either PC1 or PC2. Furthermore, despite the fact that caffeine and acetaminophen have been historically associated with human use, they could not be attributed to a single dominant land use category (e.g., urban/residential or agricultural). Contributions from septic systems did not clarify the source for these two compounds, suggesting that additional sources, such as runoff from biosolid-amended soils, may exist. Based on these results, PCA may be a useful way to broadly categorize the sources of new and previously uncharacterized emerging contaminants or may help to clarify transport pathways in a given area. Acetaminophen and caffeine were not ideal markers for urban/residential contamination sources in the study area and may need to be reconsidered as such in other areas as well.

Toward identifying the next generation of superfund and hazardous waste site contaminants.

BACKGROUND: This commentary evolved from a workshop sponsored by the National Institute of Environmental Health Sciences titled "Superfund Contaminants: The Next Generation" held in Tucson, Arizona, in August 2009. All the authors were workshop participants. OBJECTIVES: Our aim was to initiate a dynamic, adaptable process for identifying contaminants of emerging concern (CECs) that are likely to be found in future hazardous waste sites, and to identify the gaps in primary research that cause uncertainty in determining future hazardous waste site contaminants. DISCUSSION: Superfund-relevant CECs can be characterized by specific attributes: They are persistent, bioaccumulative, toxic, occur in large quantities, and have localized accumulation with a likelihood of exposure. Although still under development and incompletely applied, methods to quantify these attributes can assist in winnowing down the list of candidates from the universe of potential CECs. Unfortunately, significant research gaps exist in detection and quantification, environmental fate and transport, health and risk assessment, and site exploration and remediation for CECs. Addressing these gaps is prerequisite to a preventive approach to generating and managing hazardous waste sites. CONCLUSIONS: A need exists for a carefully considered and orchestrated expansion of programmatic and research efforts to identify, evaluate, and manage CECs of hazardous waste site relevance, including developing an evolving list of priority CECs, intensifying the identification and monitoring of likely sites of present or future accumulation of CECs, and implementing efforts that focus on a holistic approach to prevention.

On the rate of decline of persistent organic contaminants in lake trout (Salvelinus namaycush) from the Great Lakes, 1970-2003.

Thirty-four years of data from the Great Lakes Fish Monitoring Program (GLFMP) show significant changes in the behavior of most contaminants in lake trout over time consistent with changes in contaminant inputs following regulation and remediation. Polybrominated diphenyl ethers (PBDEs) show positive apparent first-order rate constants falling to near zero. Dieldrin shows relatively unchanging half-lives of around 10 years except in Lake Superior (approximately 25 years). Mirex, consistently detected only in Lake Ontario fish, shows a slow decrease until the 1990s, when remediation of a source site occurred, after which half-lives are 2-3 years. Half-lives of oxychlordane, polychlorinated biphenyls (PCBs), and dichloro-diphenyl-trichlorethane (DDT) and its metabolites were typically 3-6 years until the mid 1980s; since then, the newest data confirm half-lives are usually around 15-30 years. For PCBs, an increasing half-life is found in other media as well. Changes in food web structure, fishery dynamics, and climate undoubtedly affect concentrations but cannot explain observed long-term trends across several media. Concentrations of legacy contaminants in the Great Lakes are likely to continue to decline only slowly and pose a health concern for decades without identifying and containing remaining sources.

Use of measurement data in evaluating exposure of humans and wildlife to POPs/PBTs.

The Stockholm Convention on Persistent Organic Pollutants (POPs) recognized that POPs resist degradation, undergo long-range transport, and accumulate in remote ecosystems. The Stockholm Convention also acknowledged that indigenous communities, particularly in the Arctic, were at risk because of the biomagnification of POPs and contamination of their traditional foods. This recognition was largely based on environmental monitoring data and demonstrates the need to have adequate guidance on data collection and use. Although long-range transport, persistence, and bioaccumulation models are important for screening potential POPs and for assessing human exposure, environmental measurement data are needed to confirm predictions. Indeed the Stockholm Convention (Annex E) requires monitoring data for assessing "exposure in local areas and, in particular, as a result of long-range environmental transport". However, there is relatively little guidance available on the most appropriate environmental measurement approaches, particularly for new candidate POPs, and on how to create a weight of evidence based on such data. We provide guidance on how to assess existing data that have been generated by monitoring programs and individual studies on the exposure of top predators and humans to candidate or potential POPs, as well as considerations for collecting new additional data. Our overall recommendation for assessing exposure in humans and top predators is to use or obtain direct measurements of the compound of concern from a significantly and uniquely exposed population (indigenous populations, remote populations), as well as data demonstrating biomagnification within food webs and time trends if possible. These data must be from the appropriate sample matrix type, collected and analyzed using accepted methodologies, reviewed for quality assurance, and interpreted correctly in order to be used to assess exposure.

EPA at 40: bringing environmental protection into the 21st century.

Sustainability science suggests that effective environmental protection requires an integrated systems approach.

Partitioning and bioaccumulation of PBDEs and PCBs in Lake Michigan.

Water from Lake Michigan and fish from all five Great Lakes have been sampled and analyzed for a suite of six polybrominated diphenyl ether (PBDE) congeners and 110 polychlorinated biphenyl congeners (PCBs). The Lake Michigan dissolved phase PBDE congener concentrations (0.2 to 10 pg/L) are similar to dissolved phase PCB congener concentrations (nondetected to 13 pg/L). Partitioning of PBDEs between the particulate and dissolved phases exhibits behavior similar to that of PCBs. Organic-carbon-normalized water-particle partition coefficients (log K(OC)s) ranged from 6.2 to 6.5. Lake trout are depleted in BDE-99 relative to dissolved phase concentrations, and in contrast to what is expected from the PCB congener patterns. This reflects suspected debromination of BDE-99 in the food web of Lake Michigan. A regression of the log of the bioaccumulation factor (BAF) and the log of the octanol-water partition coefficent (K(OW)) indicated a positive relationship for both PCB congeners and PBDE congeners. BDE-99 does not appear to followthe same trend, a further indication that it is subject to biotransformation. Using the PBDE BAFs for Lake Michigan and the PBDE fish concentrations from the other Great Lakes it is expected that the dissolved phase concentrations of congeners in the other lakes would range from 0.04 to approximately 3 pg/L.

Effect of microbes on contaminant transfer in the Lake Superior food web.

The partitioning of PCBs to natural populations of aquatic heterotrophic bacteria from Lake Superior was measured in both field and laboratory studies to better understand the role of bacteria and the microbial food web in persistent, bioaccumulative, toxic organic contaminant (PBT) transfer. A filtration method that separated material >1 microm from that <1 microm was used to collect and measure PCB concentrations in the bacterial fraction. We used bacterial biovolume and a conversion factor to calculate bacterial carbon, which was used to normalize PCB concentrations. The range of total PCB concentrations in the bacterial fraction (61-337 ng/g organic carbon; OC) was similar, but generally higher than that of the total particulate fraction (36-324 ng/g OC). Measured log bioaccumulation factors (BAFoc, bacterial fraction; Koc, total particulate) were significantly greater in the bacterial fraction than in the total particulate fraction (bacterial range 6.7-7.3, total particulate range 5.8-7.0). Laboratory experiments demonstrated that a hexachlorobiphenyl reached steady state with a natural community of Lake Superior bacteria within 48 h and had a mean log BAFoc of 7.5 +/- 1.9. The octanol/ water partition coefficient (Kow) consistently under-predicted BAFoc, however, the magnitude of the under-prediction was still within the range of uncertainty in food web modeling (factors of 3-9). Food web modeling and risk assessment of PBT bioaccumulation in aquatic systems could be improved by considering the microbial food web (bacteria and its protozoan grazers) as a previously unaccounted for pathway of contaminant transfer.