Municipal wastewater treatment plant (WWTP) effluent is a primary source of pharmaceuticals and personal care products (PPCPs) to the marine environment, as most of these compounds are not fully ...removed during the treatment process. Continual discharge from WWTPs into coastal areas may act as a stressor by continually exposing organisms to a suite of PPCPs. To quantify organismal exposure to PPCP mixtures, we conducted a 12-week lab experiment that exposed Pacific oysters to effluent from two Oregon coastal WWTPs of different discharge capacities (permitted as <1 million gallons/day and >1 million gallons/day; or < or >3.785 million liters/day) at a dilution of 25 %. Composite samples of weekly collected effluent and a subset of freeze-dried oysters from experiment week 12 were analyzed for PPCPs. Though challenges with food availability inhibited our ability to confidently identify effects of the contaminants on growth and fitness, the experiment allowed us to examine uptake of contaminants from effluent into an estuarine bivalve of commercial importance. We detected 30 PPCPs and three alkylphenols in effluent and 13 PPCPs and four alkylphenols in oyster tissue, indicating high rates of release from secondary treatment and significant potential for marine organism exposure to and uptake of PPCPs in rural coastal areas.
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•30 PPCPs and three alkylphenols detected in rural coastal wastewater effluent•13 PPCPs and four alkylphenols detected in oyster tissue post exposure to effluent•Carbamazepine, diphenhydramine, diltiazem, fluoxetine, thiabendazole, trimethoprim in all samples•Diphenhydramine had the highest concentrations overall in oysters post exposure.•Two coastal wastewater treatment plants contained similar PPCPs and concentrations
The continuous use of household and personal care products (HPCPs) produces an immense amount of chemicals, such as parabens, bisphenols, benzophenones and alkylphenol ethoxylates, which are of great ...concern due to their well-known endocrine-disrupting properties. These chemicals easily enter the environment through man-made activities, thus contaminating the biota, including soil, water, plants and animals. Thus, on top of the direct exposure on account of their presence in HPCPs, humans are also susceptible to secondary indirect exposure attributed to the ubiquitous environmental contamination. The aim of this review was therefore to examine the sources and occurrence of these noteworthy contaminants (i.e. parabens, bisphenols, benzophenones, alkylphenol ethoxylates), to summarise the available research on their environmental presence and to highlight their bioaccumulation potential. The most notable environmental contaminants appear to be MeP and PrP among parabens, BPA and BPS among bisphenols, BP-3 among benzophenones and NP among alkylphenols. Their maximum detected concentrations in the environment are mostly in the range of ng/L, while in human tissues, their maximum concentrations achieved μg/L due to bioaccumulation, with BP-3 and nonylphenol showing the highest potential to bioaccumulate. Finally, of another great concern is the fact that even the unapproved parabens and benzophenones have been detected in the environment.
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Although the levels of micropollutants in landfill leachate and municipal wastewater are well-established, the individual removal mechanisms and the fate of micropollutants throughout a landfill ...leachate treatment plant (LTP) were seldom investigated. Therefore, the determination of the removal efficiencies and the fates of micropollutants in a full-scale leachate treatment plant located in the largest city of Turkey were aimed in this study. Some important processes, such as equalization pond, bioreactor, ultrafiltration (UF) and nanofiltration (NF), are being operated in the treatment plant. Landfill leachate was characterized as an intense pollution source of macro and micropollutants compared to other water types. Chemical oxygen demand (COD), NH3, suspended solids (SS) and electrical conductivity (EC) values of the landfill leachate (and their removal efficiencies in the treatment plant) were determined as 18,656 ± 12,098 mg/L (98%), 3090 ± 845 mg/L (99%), 4175 ± 1832 mg/L (95%) and 31 ± 2 mS/cm (51%), respectively. Within the scope of the study, the most frequently and abundantly detected micropollutants in the treatment plant were found as heavy metals (8 ± 1.7 mg/L), VOCs (38 ± 2 μg/L), alkylphenols (9 ± 3 μg/L) and phthalates (8 ± 3 μg/L) and the overall removal efficiencies of these micropollutants ranged from −11% to 100% in the treatment processes. The main removal mechanism of VOCs in the aerobic treatment process has been found as the volatilization due to Henry constants greater than 100 Pa·m3/mol. However, the molecular weight cut off restriction of UF membrane has caused to less or negative removal efficiencies for some VOCs. The biological treatment unit which consists of sequential anoxic and oxic units (A/O) was found effective on the removal of PAHs (62%) and alkylphenols (87%). It was inferred that both NO3 accumulation in anoxic reactor, high hydraulic retention time (HRT) and sludge retention time (SRT) in aerobic reactor provide higher biodegradation and volatilization efficiencies as compared to the literature. Membrane processes were more effective on the removal of alkylphenols (60–80%) and pesticides (59–74%) in terms of influent and effluent loads of each unit. Removal efficiencies for Cu, Ni and Cr, which were the dominant heavy metals, were determined as 92, 91 and 51%, respectively and the main removal mechanism for heavy metals has thought to be coprecipitation of suspended solids by microbial biopolymers in the bioreactor and the separation of colloids during membrane filtration. Total effluent loads of the LTP for VOCs, semi volatiles and heavy metals were 1.0 g/day, 5.2 g/day and 1.5 kg/day, respectively. It has been concluded that the LTP was effectively removing both conventional pollutants and micropollutants with the specific operation costs of 0.27 $/(kg of removed COD), 0.13 $/(g of removed VOCs), 0.35 $/(g of removed SVOCs) and 2.6 $/(kg of removed metals).
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•The full-scale and largest leachate treatment plant of Turkey was investigated.•BTEX were significantly removed in the bioreactor between 81 and 100%.•Membrane processes were found more effective on the removal of SVOCs unlike VOCs.•The volatility of PAHs was found as the main removal mechanism in the bioreactor.•Loads of the LTP for VOCs, SVOCs and heavy metals were 1.0, 5.2 g/day and 1.5 kg/day.
Alkyl-substituted benzoquinones serve as versatile building blocks for a variety of biologically active compounds. In this work, we present an approach for the environmentally benign synthesis of ...alkyl-p-benzoquinones, in particular trimethyl-p-benzoquinone (TMBQ, vitamin E precursor), which employs aqueous hydrogen peroxide as oxidant and a divanadium-substituted γ-Keggin polyoxotungstate, γ-PW10O38V2(μ-O)(μ–OH)4– (V2-POM), immobilized on nitrogen-doped carbon nanotubes (N-CNTs) as heterogeneous catalyst. A series of supported catalysts V2-POM/N-CNTs containing 5–25 wt % of V2-POM and 0–4.8 atom % of N has been prepared and characterized by elemental analysis, N2 adsorption, SEM, TEM, XPS, and FTIR techniques. The catalytic performance of V2-POM/N-CNTs was assessed in the selective oxidation of 2,3,6-trimethylphenol (TMP) with H2O2 under mild reaction conditions (60 °C, MeCN). The presence of nitrogen in the support ensures strong adsorption and molecular dispersion of V2-POM on the carbon surface, leading to highly active and selective heterogeneous catalysts, which do not suffer from metal leaching and can be used repeatedly without loss of the catalytic performance. By application of the optimal catalyst V2-POM/N-CNTs enclosing 15 wt % of V2-POM and 1.8 atom % of N, TMBQ could be obtained with 99% yield and 80% oxidant utilization efficiency. The catalyst demonstrated the truly heterogeneous nature of the catalysis and high turnover frequencies (500 h–1) and space–time yield (450 g L–1 h–1). FTIR and XPS techniques confirmed the stability of V2-POM and N-CNT support under the turnover conditions.
The distribution of per- and polyfluoroalkyl substances (PFAS), alkylphenols, organotin compounds, phthalates, alkylated polycyclic aromatic hydrocarbons, current-use pesticides (CUPs) and personal ...care products (PCPs) was characterized in 29 surface sediments from two Spanish Iberian continental shelf areas (14 on the Atlantic and 15 on the Mediterranean coasts). Concretely, 115 organic contaminants were determined and a specific methodology was used for each contaminant group, including contaminants of emerging concern (CECs) and traditional ones, such as polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and organochlorinated pesticides (OCPs). PAHs, alkylated PAHs, alkylphenols and phthalates were found in all samples, showing mean concentrations per group higher than 20 ng/g (16–4974 ng/g d.w.) in the subregions under consideration (Galician, Cantabrian, Levantine-Balearic and Strait-Alboran). CUPs and PCPs were found in the majority of samples at very low concentrations of ng/g (1.4–46.8 ng/g d.w.), whereas organotins and PFAS were found principally in sediments from the Mediterranean subregions (2.5–3.9 ng/g d.w.). Different distribution patterns were observed for the contaminant groups and subregions under consideration as a consequence of the diverse predominant sources (industrial, urban, transport and agricultural activities) and environmental behavior (mainly hydrophobicity and persistence). Risk assessment confirmed the impact of phthalates, alkylphenols, PAHs and PCBs on Atlantic ecosystems and of alkylphenols, chlorpyrifos, phthalates, TBT, PAHs, OCPs and PCBs on the Mediterranean ones. Furthermore, the presence of CUPs, PCPs and PFAS in sediments from the Spanish continental shelf located between 2 and 31 km from the coast suggested that those contaminants may also provoke adverse effects on coastal marine ecosystems between their sources and their depositional areas.
Alkylphenols, phthalates and organotins may provoke adverse effects on Spanish coastal marine ecosystems from their sources to the sediment depositional areas.
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•Alkylated PAHs, alkylphenols and phthalates were found in all sediment samples.•Organotins and PFAS were mainly found in Mediterranean sediments.•Alkylphenols, phthalates and organotins may provoke adverse effects in sediments.•CUPs, PCPs and PFAS were also present in continental shelf sediments.
Selective oxidation of aliphatic C–H bonds in alkylphenols serves significant roles not only in generation of functionalized intermediates that can be used to synthesize diverse downstream chemical ...products, but also in biological degradation of these environmentally hazardous compounds. Chemo-, regio-, and stereoselectivity; controllability; and environmental impact represent the major challenges for chemical oxidation of alkylphenols. Here, we report the development of a unique chemomimetic biocatalytic system originated from the Gram-positive bacterium Corynebacterium glutamicum. The system consisting of CreHI (for installation of a phosphate directing/anchoring group), CreJEF/CreG/CreC (for oxidation of alkylphenols), and CreD (for directing/anchoring group offloading) is able to selectively oxidize the aliphatic C–H bonds of p- and m-alkylated phenols in a controllable manner. Moreover, the crystal structures of the central P450 biocatalyst CreJ in complex with two representative substrates provide significant structural insights into its substrate flexibility and reaction selectivity.
•The conditions of derivatization of alkylphenols with dansyl chloride were tested.•Improved method provides more reproducible results and lower limits of quantitation.•The high levels of ...alkylphenols in blank samples affect the result of analysis.•Comparison of the level of alkylphenols in drinking and wastewater was carried out.
The present study describes an effect of reaction condition of pre-column derivatization of alkylphenols (APs): bisphenol A (BPA), 4-tert-octylphenol (4-t-OP), 4-octylphenol (4-OP), 4-n-nonylphenol (4-n-NP), and isomers of 4-nonylphenol (iso-NP) with 5-(dimethylamino) naphthalene-1-sulfonyl chloride (dansyl chloride, DNSC) on their LC–ESI–MS/MS determination in water samples. Chemical derivatization improves the sensitivity and selectivity of LC–MS/MS analysis. In principle, alkylphenols can be analyzed by LC–MS/MS without derivatization. However, pre-column derivatization of APs increases the sensitivity up to 1000 times in comparison with the analysis of underivatized alkylphenols. Reaction conditions affecting formation of the DNSC-derivatives, such as various solvent, reaction temperature, reaction time, DNSC concentration and pH values were tested. The most suitable conditions, in terms of achieving a high sensitivity, resulting from this study are: acetonitrile as reaction solvent, 60min as reaction time, 60°C as reaction temperature, pH values 10.5, 0.5mgmL−1 as DNSC concentration. Calibration curves are linear at least in the range of 1–1000ngmL−1, limits of detection (LOD) and limits of quantification (LOQ) ranging from 0.02 to 0.25pg/injection and from 0.08 to 0.83pg/injection, respectively. The improved procedure was successfully applied for the analysis of APs and BPA in real water samples. The median concentration of BPA and iso-NP obtained in bottled waters was 4.7ngL−1 and 33.5ngL−1, respectively. The median concentration of 4-t-OP was 1.3ngL−1.
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•Target PAHs, APs, and SOs were detected in all sediments from Yellow and Bohai seas.•Industrial and municipal activities significantly correlated to increased PAHs pollution.•Sources ...of PAHs in China shifted from multiple to diesel and gasoline combustion recently.•Great potential ecological risk was found in Nantong, Huludao, and Qinhuangdao in China.•Chemicals and/or sites of concern varied between China and South Korea and across regions.
The Yellow and Bohai seas comprise one of the most rapidly developing regions in the world, but efforts to assess coastal pollution by persistent toxic substances (PTSs) on wide spatial scale are lacking. The present study aimed to (1) measure the concentrations of PTSs, such as polycyclic aromatic hydrocarbons (PAHs), alkylphenols (APs), and styrene oligomers (SOs) via large-scale sediment monitoring (total of 125 locations), (2) assess potential ecological risk of PTSs in sediments to coastal ecosystems, (3) estimate various sources and fresh inputs of PTSs, (4) determine distribution patterns of PTSs by human activities and land-use type, and (5) address decadal (2008–2018) changes in distributions of PTSs. The high concentrations of PAHs > 7000 ng g−1 dry weight (dw) in sediments were detected in Nantong in the Yellow Sea of China (YSC) and Huludao and Qinhuangdao in the Bohai Sea (BS), whereas lesser concentrations (< 200 ng g−1 dw) were detected in the Yellow Sea of Korea (YSK). We found relatively high concentrations of sedimentary APs and SOs in Nantong, Huludao, and Qinhuangdao from the YSC and BS regions, but corresponding concentrations were generally below < 100 ng g−1 dw in other locations. Concentrations of PAHs at 38 locations (30% of YSC and BS) posed a potential risk to aquatic ecosystems, whereas relatively low risk concentrations occurred in all locations of YSK. The main source of PAHs (concentrated in YSC and BS) were by-products of diesel and gasoline combustion (42% of total concentration), whereas biomass combustion (24%) dominated in YSK. Fresh inputs of PTSs indicated that the generation and use of PTSs continue across all regions and locations. Among PTSs, concentrations of PAHs were significantly associated with location (p < 0.05) relative to land-use within a given region, whereas concentrations of APs and SOs showed no significant relationships (p > 0.05) among or within regions. Over time, concentrations of PAHs have generally declined, but sediment contamination has increased at some locations in China, with sources shifting from a mixture of PAHs types to those linked to diesel and gasoline combustion. Additional studies are needed on the fate and potential ecological risk posed by certain PTSs in hotspots. This is one of the first efforts providing backgrounds on PTS pollution in the large marine ecosystem of the Yellow and Bohai seas.
Water contamination by emerging contaminants is increasing in the context of rising urbanization, industrialization, and agriculture production. Emerging contaminants refers to contaminants for which ...there is currently no regulation requiring monitoring or public reporting of their presence in our water supply or wastewaters. There are many emerging contaminants such as pesticides, pharmaceuticals, drugs, cosmetics, personal care products, surfactants, cleaning products, industrial formulations and chemicals, food additives, food packaging, metalloids, rare earth elements, nanomaterials, microplastics, and pathogens. The main sources of emerging contaminants are domestic discharges, hospital effluents, industrial wastewaters, runoff from agriculture, livestock and aquaculture, and landfill leachates. In particular, effluents from municipal wastewater treatment plants are major contributors to the presence of emerging contaminants in waters. Although many chemicals have been recently regulated as priority hazardous substances, conventional plants for wastewater and drinking water treatment were not designed to remove most emerging contaminants. Here, we review key examples of contamination in China, Portugal, Mexico, Colombia, and Brazil. Examples include persistent organic pollutants such as polychlorinated biphenyls, dibenzofurans, and polybrominated diphenyl ethers, in lake and ocean ecosystems in China; emerging contaminants such as alkylphenols, natural and synthetic estrogens, antibiotics, and antidepressants in Portuguese rivers; and pharmaceuticals, hormones, cosmetics, personal care products, and pesticides in Mexican, Brazilian, and Colombian waters. All continents are affected by these contaminants. Wastewater treatment plants should therefore be upgraded, e.g., by addition of tertiary treatment systems, to limit environmental pollution.
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