Evidence that watershed nutrient management practices effectively reduce estrogens in environmental waters.

We evaluate the impacts of different nutrient management strategies on the potential for co-managing estrogens and nutrients in environmental waters of the Potomac watershed of the Chesapeake Bay. These potential co-management approaches represent agricultural and urban runoff, wastewater treatment plant effluent, and combined sewer overflow replacements. Twelve estrogenic compounds and their metabolites were analysed by gas chromatography-mass spectrometry. Estrogenic activity (E2Eq) was measured by in vitro bioassay. We detected estrone E1 (0.05-6.97 ng L-1) and estriol E3 (below detection-8.13 ng L-1) and one conjugated estrogen (estrone-3-sulfate E1-3S; below detection-8.13 ng L-1). E1 was widely distributed and positively correlated with E2Eq, water temperature, and dissolved organic carbon (DOC). Among nonpoint sources, E2Eq, and concentrations of E1, soluble reactive phosphorus (SRP) and total dissolved nitrogen (TDN) decreased by 51-61%, 77-82%, 62-64%, 4-16% in restored urban and agricultural streams with best management practices (BMPs) relative to unrestored streams without BMPs. In a wastewater treatment plant (Blue Plains WWTP), >94% of E1, E1-3S, E3, E2Eq and TDN were removed while SRP increased by 305% during nitrification/denitrification as a part of advanced wastewater treatment. Consequently, E1 and TDN concentrations in WWTP effluents were comparable or even lower than those observed in the receiving stream or river waters, and the effects of wastewater discharges on downstream E1 and TDN concentrations were minor. Highest E2Eq value and concentrations of E1, E3, and TDN were detected in combined sewer overflow (CSO). This study suggests that WWTP upgrades with biological nutrient removal, CSO management, and certain agricultural and urban BMPs for nutrient controls have the potential to remove estrogens from point and nonpoint sources along with other contaminants in streams and rivers.

Spatial distribution of pesticides, organochlorine compounds, PBDEs, and metals in surface marine sediments from Cartagena Bay, Colombia.

Cartagena Bay is an estuarine system located in the Caribbean Sea (Colombia, South America), that receives fresh water from Canal del Dique, which is connected to the Magdalena River, the most important river of Colombia, with some of the most prominent Colombian cities located in its watershed, which has a high sediment yield. An analysis of persistent organic pollutants and heavy metals was carried out on marine sediments from Cartagena Bay. Cartagena Bay sediments deployed the occurrence of total levels of pesticides (thiocarbamates, bromacil, triazines, organochlorines, and organophosphorus), polybrominated diphenyl ethers (PBDEs), and polychlorinated biphenyls (PCBs), in sediments ranging from 0.83-33.67 ng/g dry-weight, 0.05-0.34 ng/g dry-weight, and 0.06-19.58 ng/g dry-weight, respectively. Their concentrations were lower than those reported in NOAA Screening Quick Reference Tables. DDTs and PCBs are banned organochlorine compounds, since, even at low levels, their presence in sediments represents a threat to aquatic organisms and, therefore, to human health through the trophic chain. Sediments showed high concentrations of strontium (50-959.6 mg/kg). All metals evaluated in the marine sediments were found in the S6 sampling point; this was near tannery and hydrocarbon industries (Pb 37.1 mg/kg, Cr 137.2 mg/kg, Cd 1.7 mg/kg, Cu 64.4 mg/kg, As 13.1 mg/kg, Sr 318.9 mg/kg); these results exceeded the accepted values of threshold effect levels (TEL) used as an indicator of their potential risk on marine life.

Toxicity profile of organic extracts from Magdalena River sediments.

The Magdalena River, the main river of Colombia, receives contaminated effluents from different anthropogenic activities along its path. However, the Magdalena River is used as drinking water source for approximately 30 million inhabitants, as well as a major source of fish for human consumption. Only a few studies have been conducted to evaluate the environmental and toxicological quality of the Magdalena River. To evaluate sediment toxicity, wild-type and GFP transgenic Caenorhabditis elegans were exposed to methanolic extracts, and effects on lethality, locomotion, growth, and gene expression were determined based on fluorescence spectroscopy. These biological and biochemical parameters were correlated with measured pollutant concentrations (PAHs and trace elements), identifying patterns of toxicity along the course of the river. Effects on lethality, growth, and locomotion were observed in areas influenced by industrial, gold mining, and petrochemical activities. Changes in gene expression were evident for cyp-34A9, especially in the sampling site located near an oil refinery, and at the seaport, in Barranquilla City. Body bend movements were moderately correlated with Cr and As concentrations. The expression of mtl-1, mtl-2, hsp-6, and hsp-70 were significantly associated with Pb/U, Pb, Sr, and As/Sr/Pb/U, respectively. Interestingly, toxicity of methanolic as well as aqueous extracts were more prone to be dependent on Cd, Zn, and Th. In general, ecological risk assessment showed sediments display low environmental impact in terms of evaluated metals and PAHs. Different types of waste disposal on the Magdalena River, as a result of mining, domestic, agricultural, and industrial activities, incorporate toxic pollutants in sediments, which are capable of generating a toxic response in C. elegans.

Lessons learned from more than two decades of research on emerging contaminants in the environment.

In the last twenty years, thousands of research papers covering different aspects of emerging contaminants have been published, ranging from environmental occurrence to treatment and ecological effects. Emerging contaminants are environmental pollutants that have been investigated widely only in the last two decades and include anthropogenic and naturally occurring chemicals such as pharmaceuticals and personal care products and their metabolites, illicit drugs, engineered nanomaterials, and antibiotic resistance genes. The advancement in our knowledge on emerging contaminants has been the result of the appearance of highly sensitive and powerful analytical instrumentation that rapidly developed, allowing identification and trace quantification of unknown contaminants in complex environmental matrices. High efficiency chromatographic separations coupled to high-resolution mass spectrometers have become more common in environmental laboratories and are the pillars of environmental research, increasing our awareness and understanding of the presence of emerging contaminants in the environment, their transformation and fate, and the complex ecological consequences that they pose on exposed biological systems. This introductory paper for the Virtual Thematic Issue on Emerging Contaminants presents a brief literature overview on key research milestones in the area of emerging contaminants, focusing on pharmaceuticals and personal care products and endocrine disrupting compounds, and highlighting selected research papers previously published in the Journal of Hazardous Materials during the period of January 2012 to December 2015.

Chemical and biological assessment of endocrine disrupting chemicals in a full scale dairy manure anaerobic digester with thermal pretreatment.

Concentrated animal feeding operations are important sources of estrogens and their conjugates, which are introduced into the environment through manure land application. In this study, concentrations of estrogens were measured in an anaerobic co-digestion system with thermal pasteurization pretreatment. Free estrogens (estrone (E1), 17α-estradiol (E2α), 17ß-estradiol (E2ß), estriol (E3)) were analyzed by gas chromatography with mass spectrometry (GC/MS), and conjugated estrogens (sulfate- and glucuronide-conjugates) were analyzed by liquid chromatography with tandem mass spectrometry (LC/MS/MS). Additionally, yeast estrogen screen assay was used to determine the estrogenic potential of the manure. The total hormone concentrations (mainly E1, E2α, E2ß, and sulfated estrogens) were observed at concentrations up to a total of 7100ng/L in the liquid fraction, while free estrogen levels were 630ng/kg in the solid fraction of the untreated manure. The total hormone concentration did not decrease significantly during digestion, however, the relative composition of the estrogens changed from E2α (65%) being the predominant species before digestion to mostly E1 (72%) after digestion. This conversion process has important implications because E1 is more estrogenic than E2α. Total E2 equivalents associated with E1, E2α and E2ß concentrations as determined by GC/MS indicate that E1 is the most important contributor to the endocrine-disruption activity of the treated manure.

Quantum dots exhibit less bioaccumulation than free cadmium and selenium in the earthworm Eisenia andrei.

The present study addresses the bioaccumulation behavior of cadmium selenide quantum dots by Eisenia andrei earthworms in a terrestrial environment. Earthworms were exposed to quantum dot-treated soil for up to 4 wk and analyzed for cadmium and selenium concentration using inductively coupled plasma mass spectrometry. Results were compared with those from earthworms exposed to cadmium nitrate and selenious acid, as positive controls, and those exposed in untreated soil (negative control). Earthworms exposed to quantum dots showed significant bioaccumulation of cadmium and selenium (5.3- and 1.5-fold higher concentration over negative controls, respectively) after 4 wk. Over the same 4 wk, positive control earthworms accumulated 9.2- and 2.2-fold higher cadmium and selenium, respectively, than negative controls for a much more substantial final body burden of the 2 elements. The concentrations also increased with exposure time; cadmium concentrations increased from 3600 ± 310 ng/g to 8080 ± 660 ng/g, from 1 to 4 wk, suggesting that further bioaccumulation may take place with even longer exposure time. The molar ratio of cadmium to selenium in the quantum dot-exposed worms (6.2) is closer to the ratios seen in positive control worms (7.2) than to the pure quantum dots (1.8), which implies that quantum dots are taken up predominantly in the degraded form. The results suggest that chemical modification of quantum dots to protect them from environmental degradation could potentially reduce bioaccumulation of the nanoparticles by earthworms.