Analysis of environmental endocrine disrupting chemicals using the E-screen method and stir bar sorptive extraction in wastewater treatment plant effluents

Endocrine disrupting chemicals (EDCs) have become a major issue in the field of environmental science due to their ability to interfere with the endocrine system. Recent studies show that surface water is contaminated with EDCs, many released from wastewater treatment plants (WWTP). This pilot study used biological (E-screen assay) and chemical (stir bar sorptive extraction-GC-MS) analyses to quantify estrogenic activity in effluent water samples from a municipal WWTP and in water samples of the recipient river, upstream and downstream of the plant.The E-screen assay was performed on samples after solid phase extraction (SPE) to determine total estrogenic activity; the presence of estrogenic substances can be evaluated by measuring the 17-β-estradiol equivalency quantity (EEQ). Untreated samples were also assayed with an acute toxicity test (Vibrio fischeri) to study the correlation between toxicity and estrogenic disruption activity.Mean EEQs were 4.7 ng/L (± 2.7 ng/L) upstream and 4.4 ng/L (± 3.7 ng/L) downstream of the plant, and 11.1 ng/L (± 11.7 ng/L) in the effluent. In general the WWTP effluent had little impact on estrogenicity nor on the concentration of EDCs in the river water. The samples upstream and downstream of the plant were non-toxic or weakly toxic (0 < TU < 0.9) while the effluent was weakly toxic or toxic (0.4 < TU < 7.6). Toxicity and estrogenic activity were not correlated.At most sites, industrial mimics, such as the alkylphenols and phthalates, were present in higher concentrations than natural hormones. Although the concentrations of the detected xenoestrogens were generally higher than those of the steroids, they accounted for only a small fraction of the EEQ because of their low estrogenic potency. The EEQs resulting from the E-screen assay and those calculated from the results of chemical analyses using estradiol equivalency factors were comparable for all samples and closely correlated.     

Pharmaceuticals and personal care products (PPCPs) and endocrine disrupting chemicals (EDCs) in stormwater canals and Bayou St. John in New Orleans, Louisiana, USA

Samples were collected from two stormwater canals and a recreational urban waterway known as Bayou St. John in New Orleans, Louisiana, USA and analyzed for a range of pharmaceuticals and personal care products (PPCPs) and endocrine disrupting chemicals (EDCs). Concentrations of 7 PPCPs and EDCs were measured by a method that provides for simultaneous extraction and quantification of the following compounds: clofibric acid, naproxen, ibuprofen, fluoxetine, clorophene, triclosan, bisphenol A. The method also was used as an indicator of the occurrence of estrogenic compounds by targeting estrone and 17beta-estradiol. The two canals (Orleans and London) are used to drain a portion of the city's stormwater directly into the Mississippi River or Lake Pontchartrain. Bayou St. John is located between the two canals and supplied with water from Lake Pontchartrain. Results from the 6-month sampling period indicated the following concentration ranges for the two stormwater canals: naproxen (ND - 145 ng/l), ibuprofen (ND - 674 ng/l), triclosan (ND - 29 ng/l) and bisphenol A (1.9-158 ng/l). Concentrations of these target analytes increased with cumulative rainfall. For bayou waters, only naproxen (2.1-4.8 ng/l) and bisphenol A (0.9-44 ng/l) were detected. Estrone was detected but determined non-quantifiable for multiple sampling events at the 3 sites. None of the other target analytes (clofibric acid, fluoxetine, clorophene, and 17beta-estradiol) were detected above their method detection levels. Results of this study demonstrate the occurrence of PPCPs and EDCs in New Orleans stormwater canals and Bayou St. John. Results also demonstrate the use of this analytical technique as an indicator of non-point source sewage contamination in New Orleans stormwater canals.     

Organochlorine pesticides in colostrums in case of normal and preterm labor (IASI, Romania)

Assessment of organochlorine pesticides (OCPs) in human body is important for human health because they have weak estrogenic or antiestrogenic effects and are considered endocrine disrupters. We used colostrum of women as indicator for levels of OCPs in human body for mothers with normal and preterm labor from eastern part of Romania. Sixty- three samples of colostrum were extracted by solid-phase extraction. Analyses were carried out using gas chromatography coupled to mass spectrometry (GC-MS). OCPs have been detected in all samples, with p,p’-dichlorodiphenyldichloroethylene (p,p’-DDE) and γ-hexachlorocyclohexane (γ-HCH) being at the highest concentrations. Of the organochlorines measured in clostrum samples from women in preterm labor, median levels of DDTs (470 ng/g) and HCHs (99 ng/g) were higher than for the same compounds from women in normal labor (median of DDTs = 268 ng/g and median of HCHs = 96 ng/g). Normal labor had higher median concentrations of HCB (19.5 ng/g) versus preterm labor (14 ng/g). Statistical data show high Spearman correlation coefficients between various OCPs. We found a good correlation between α-, γ-, β- and δ- HCH isomers (p < 0.001) for both normal and preterm labor. The most abundant target compound was p,p’-DDE (median value 96 ng/g, and 137 ng/g for mother with normal and preterm labor, respectively) in all colostrum samples. The estimated daily intakes of HCHs by infants exceeded corresponding Health Canada guidelines.     

Determination of phenolic endocrine disrupting chemicals and acidic pharmaceuticals in surface water of the Pearl Rivers in South China by gas chromatography-negative chemical ionization-mass spectrometry

An analytical method for phenolic endocrine disrupting chemicals and acidic pharmaceuticals in river water was developed using gas chromatography mass spectrometry (GC-MS) coupled with negative chemical ionization (NCI) technique, and used for the determination of these compounds in the Pearl Rivers (Liuxi, Zhujiang and Shijing Rivers). Derivatization using pentafluorobenzoyl chloride (PFBOCl) and pentafluorobenzyl bromide (PFBBr) before GC-MS analysis were applied and optimized for phenolic compounds and acidic compounds, respectively. The target compounds were analyzed for river waters from the upstream to downstream of the Pearl Rivers. Phenolic compounds 4-tert-octylphenol (4-t-OP), 4-nonylphenol (4-NP), bisphenol-A (BPA), estrone (E1), estradiol (E2) and triclosan (TCS) were detected at trace or low levels in the water samples from Liuxi River and Zhujiang River. Diethylstilbestrol (DES) was not detected in the Pearl Rivers. The highest concentrations of the phenolic compounds were found in Shijing River, and they were 3150 ng/L for 4-t-OP, 11,300 ng/L for 4-NP, 1040 ng/L for BPA, 79 ng/L for E1, 7.7 ng/L for E2 and 355 ng/L for TCS, respectively. Only a few acidic pharmaceuticals were detected at low concentrations in water from Liuxi River and Zhujiang River, but the highest concentrations for the acidic pharmaceuticals were also found in Shijing River. The highest concentrations detected for clofibric acid, ibuprofen, gemfibrozil, naproxen, mefenamic acid and diclofenac were 17 ng/L, 685 ng/L, 19.8 ng/L, 125 ng/L, 24.6 ng/l and 150 ng/L, respectively. The results suggest Liuxi and Zhujiang Rivers are only slightly contaminated and can be used as drinking water sources, but Shijing River is heavily polluted by the wastewater from nearby towns.     

The removal of pharmaceuticals, personal care products, endocrine disruptors and illicit drugs during wastewater treatment and its impact on the quality of receiving waters

A 5-month monitoring program was undertaken in South Wales in the UK to determine the fate of 55 pharmaceuticals, personal care products, endocrine disruptors and illicit drugs (PPCPs) in two contrasting wastewater plants utilising two different wastewater treatment technologies: activated sludge and trickling filter beds. The impact of treated wastewater effluent on the quality of receiving waters was also assessed.PPCPs were found to be present at high loads reaching 10 kg day⁻¹ in the raw sewage. Concentrations of PPCPs in raw sewage were found to correlate with their usage/consumption patterns in Wales and their metabolism. The efficiency of the removal of PPCPs was found to be strongly dependent on the technology implemented in the wastewater treatment plant (WWTP). In general, the WWTP utilising trickling filter beds resulted in, on average, less than 70% removal of all 55 PPCPs studied, while the WWTP utilising activated sludge treatment gave a much higher removal efficiency of over 85%. The monitoring programme revealed that treated wastewater effluents were the main contributors to PPCPs concentrations (up to 3 kg of PPCPs day⁻¹) in the rivers studied. Bearing in mind that in the cases examined here the WWTP effluents were also major contributors to rivers' flows (dilution factor for the studied rivers did not exceed 23 times) the effect of WWTP effluent on the quality of river water is significant and cannot be underestimated.     

Identification of estrogen-like effects and biologically active compounds in river water using bioassays and chemical analysis

The Nackdong River is the longest river in South Korea and passes through major cities that have several industrial complexes, including chemical, electric, and petrochemical complexes, and municipal characteristics such as apartment complexes. Along the river, the Gumi region has an electric industrial complex and an apartment complex that may be possible point sources of xenoestrogens such as phenolic compounds. To identify the causative chemicals for estrogenic activity in the river water of this region, bioassay-directed chemical analysis was performed. All samples from six sampling sites (an upstream point: S1; hot spot points: S2-1, S2-2, and S2-3; and downstream points: S3, and S4) showed estrogenic activity in the E-screen assay, with bio-EEQs (17β-E₂-equivalent quantities) ranging from 25.35-677.15 pg/L. Samples from S2-2, the sampling point downstream of the junction of stream water, and domestic and industrial wastewater, contained the highest estrogenic activity. Since the bio-EEQ of the organic acid fraction (F2) of the S2-2 sample had the highest activity (823.25 pg-EEQ/L) and F2 may contain phenolic compounds, GC-MS analyses for phenolic xenoestrogens were conducted with the organic acid fractions of the river water samples. Six estrogenic phenolic chemicals, 4-NP, BPA, 4-t-OP, 4-t-BP, 4-n-OP, and 4-n-HTP, were detected, with the highest concentrations (I-EEQ) found in S2-2 (231.80 pg/L). Among these phenolic chemicals, 4-NP was the most potent estrogen (bio-EEF; 8.12 × 10^− 5) and acted as a full agonist. Furthermore, 4-NP was present at levels (2.0 µg/L in S2-2) that can induce VTG induction in fish (>1 µg/L). In addition, we confirmed that river water (S2-2) significantly increased serum VTG levels in crucian carp (Carassius auratus) in a fish exposure experiment under laboratory conditions. Therefore, phenolic xenoestrogens, especially 4-NP, may be the main causative compounds responsible for the estrogenic effect on the Nackdong River.     

Perfluorinated contaminants in fur seal pups and penguin eggs from South Shetland, Antarctica

Perfluorinated compounds (PFCs) have emerged as a new class of global environmental pollutants. In this study, the presence of perfluorochemicals (PFCs) in penguin eggs and Antarctic fur seals was reported for the first time. Tissue samples from Antarctic fur seal pups and penguin eggs were collected during the 2003/04 breeding season. Ten PFC contaminants were determined in seal and penguin samples. The PFC concentrations in seal liver were in the decreasing order, PFOS > PFNA > PFHpA > PFUnDA while in Adélie penguin eggs were PFHpA > PFUnDA > PFDA > PFDoDA, and in Gentoo penguin eggs were PFUnDA > PFOS > PFDoDA > PFHpA. The PFC concentrations differed significantly between seals and penguins (p < 0.005) and a species-specific difference was found between the two species of penguins (p < 0.005). In our study we found a mean concentration of PFOS in seal muscle and liver samples of 1.3 ng/g and 9.4 ng/g wet wt, respectively, and a mean concentration in Gentoo and Adélie penguin eggs of 0.3 ng/g and 0.38 ng/g wet wt, respectively. PFCs detected in penguin eggs and seal pups suggested oviparous and viviparous transfer of PFOS to eggs and off-springs.     

Sediment mercury dynamics and historical trends of mercury deposition in the St. Lawrence River area of concern near Cornwall, Ontario, Canada

The St. Lawrence River near Cornwall, Ontario was designated an Area of Concern by the International Joint Commission in 1985. Sediments from this area have historically been contaminated with mercury (Hg), and although concentrations have decreased since the 1970s, they still remain high. Nine sediment cores were collected from three sites within the Area of Concern in 2004/05 to determine the variability in historical profiles of Hg deposition to the river. Sediment and pore water phases were analyzed for total mercury (THg) and methyl mercury (MeHg) and cores were analyzed for ²¹⁰Pb to determine chronologies of sedimentation at these sites. Mercury diffusion rates in pore waters within the sediment column were determined to be very low (between 0 and 2.15 ng cm^− 2 year^− 1, n = 3) compared to the recent Hg sedimentation rates at these sites (183 ± 30 ng cm^− 2 year^− 1 SE, n = 9) determined by multiplying surface Hg concentrations with ²¹⁰Pb-derived sedimentation rates. These results indicate that Hg profiles in these cores accurately depict historical releases of Hg to the river bed. The influence of federal regulations in the early 1970s to restrict Hg emissions to the river was apparent in these dated sediment cores, as were the closures of several local industries in the mid 1990s. Mercury accumulation rates prior to 1970 were 60 times higher than those occurring after 1995. Methyl mercury showed surface enrichment in most of these sediment cores providing evidence that mercury methylation occurred most rapidly near the sediment surface.     

Selected personal care products and endocrine disruptors in biosolids: an Australia-wide survey

Personal care products (PCPs) and endocrine disrupting compounds (EDCs) are groups of organic contaminants that have been detected in biosolids around the world. There is a shortage of data on these types on compounds in Australian biosolids, making it difficult to gain an understanding of their potential risks in the environment following land application. In this study, 14 biosolids samples were collected from 13 Australian wastewater treatment plants (WWTPs) to determine concentrations of eight compounds that are PCPs and/or EDCs: 4-t-octylphenol (4tOP), 4-nonylphenol (4NP), triclosan (TCS), bisphenol A (BPA), estrone (E1), 17β-estradiol (E2), estriol (E3) and 17α-ethinylestradiol (EE2). Concentration data were evaluated to determine if there were any differences between samples that had undergone anaerobic or aerobic treatment. The concentration data were also compared to other Australian and international data. Only 4tOP, 4NP, TCS, and BPA were detected in all samples and E1 was detected in four of the 14 samples. Their concentrations ranged from 0.05 to 3.08 mg/kg, 0.35 to 513 mg/kg, < 0.01 to 11.2 mg/kg, < 0.01 to 1.47 mg/kg and < 45 to 370 μg/kg, respectively. The samples that were obtained from WWTPs that used predominantly anaerobic treatment showed significantly higher concentrations of the compounds than those obtained from WWTPs that used aerobic treatment. Overall, 4NP, TCS and BPA concentrations in Australian biosolids were lower than global averages (by 42%, 12% and 62%, respectively) and 4tOP concentrations were higher (by 25%), however, of these differences only that for BPA was statistically significant. The European Union limit value for NP in biosolids is 50 mg/kg, which 4 of the 14 samples in this study exceeded.     

Elimination and fate of selected micro-organic pollutants in a full-scale anaerobic/anoxic/aerobic process combined with membrane bioreactor for municipal wastewater reclamation

The occurrence and elimination of 19 micro-organic pollutants including endocrine disrupting chemicals (EDCs) and pharmaceuticals and personal care products (PPCPs) in a full-scale anaerobic/anoxic/aerobic-membrane bioreactor process was investigated. The investigated process achieved over 70% removal of the target EDCs and 50%–100% removal of most of the PPCPs, with influent concentration ranging from ng/L to μg/L. Three PPCPs, carbamazepine, diclofenac and sulpiride were not well removed, with the removal efficiency below 20%. A rough mass balance suggests that the targets were eliminated through sludge-adsorption and/or biodegradation, the former of which was particularly significant for the removal of hydrophobic compounds. The two-phase fate model was employed to describe the kinetics of sludge-adsorption and biodegradation. It was found that the fast sludge adsorption (indicated by mass-transfer rates greater than 10 for most compounds) is responsible for the rapid decline of the aqueous concentration of the targets in the first compartment of the treatment process (i.e. in the anaerobic tank). In contrast, the slow biodegradation proved to be the rate-determining step for the entire degradation process, and the rates are generally positively related to the dissolved oxygen level. On the other hand, this study showed that the removal rates of most targets can reach a quasi-plateau in 5 h under aerobic conditions, indicating that hydraulic retention time of ca. 5 h in aerobic tanks should be sufficient for the elimination of most targets.