Pharmaceutical Personal Care Products Research Articles

Fungal-Based Remediation in the Treatment of Anthropogenic Activities and Pharmaceutical-Pollutant-Contaminated Wastewater

Pharmaceutical personal care products (PPCPs) have increased in consumption due to the worldwide post-pandemic situation, marking them as chemical and pathogenic pollutants in significantly higher concentrations than ever in the ecosystem. Considering the inexplicable levels of these chemical residues discharged into the environment, concerns have been raised regarding their probable ecotoxicity to marine and terrestrial life. A further concern is the potential for developing and spreading antibiotic-resistant microorganisms and genes in aquatic ecosystems due to antibiotic exposure. Hence, knowing how these compounds impact aquatic ecosystem functioning is imperative, and thus is a critical area of research. The ecological risk analysis of PPCPs in aquatic ecosystems has been carried out using various strategies. Previous studies have reported numerous approaches for eliminating these PPCPs, including conventional treatment methods, activated sludge processes, generated wetlands, biological remediation, sequencing batch reactors, phytoremediation, and membrane bioreactors. In terms of green biotechnology approaches, the current research aims to discover effective procedures for removing PPCPs and their emerging resources as pollutants. Therefore, this review focuses on the over-extensive utilization of PPCPs and their emergent sources responsible for the contamination and environmental threat for future wastewater purposes. Further, as fungi and their enzymes and derivatives can remove pharmaceuticals and personal care products from wastewater through oxidation and several processes, they have attracted the attention of the scientific community due to their ability to remove PPCPs as pollutants and their status as emerging resources in wastewater. This review examines the fundamental approach and progress of the bioremediation of pharmaceutical- and personal-care-contaminated wastewater using fungal-based systems. It also discusses mechanistic approaches through hybridizing cultures and other biological systems with fungal strains, current technologies, and prospects for future research on PPCPs in wastewater treatment.

Work along both lines: The p-chloro-m-cresol achieved stable and long-term partial nitrification and inhibited the enrichment of resistance genes

The p-chloro-m-cresol (PCMC) is a versatile preservative with extensive appliance in various pharmaceutical personal care products. In this study, PCMC in-situ anaerobic soaking of activated sludge was implemented to initiate, maintain and restore partial nitrification (PN). The optimal treatment condition was 80 mg/L PCMC and 30 h exposure time, which stably sustained PN for up to 157 days. Results showed that PCMC had a great influence on the content and secondary structures of extracellular polymeric substances, thus enhanced the aggregation and tolerance of bacteria to PCMC. The molecular docking simulation illustrated that PCMC achieved long-term PN by inhibiting nitrite oxidoreductase. The microbial community results showed that PCMC had a stronger inhibitory effect on nitrite oxidizing bacteria, and ammonia oxidizing bacteria was enriched in both quantity and oligotypes which could adapt to PCMC. Meanwhile, PCMC can obviously block the enrichment of some resistance genes without increasing resistance gene transmission burden of system. PCMC is a novel and promising PN inhibitor.

The interaction mechanism of polystyrene microplastics with pharmaceuticals and personal care products

Microplastics (MPs) have been detected in the hydrosphere, with hazardous implications in transporting coexisting water pollutants. Our knowledge about the interaction mechanisms that MPs establish with organic pollutants are still growing, which is essential to understand the adsorption properties of MPs and their relative stability with adsorbates. Here, we used classical (force field methods) and ab-initio (density functional theory) computational chemistry tools to characterize the interaction mechanisms between Polystyrene-MPs (PS-MPs) and pharmaceuticals/personal care products (PPCPs). Adsorption conformations and energies, thermochemistry, binding, and energy decomposition analyses were performed to obtain the quantitative mechanistic information. Our results show that PS-MPs have permanent dipoles, increasing the interaction with neutral PPCPs while repelling the charged pollutants; in all cases, a stable physisorption takes place. Moreover, PS-MPs increase their solubility upon pollutant adsorption due to an increase in the dipole moment, increasing their co-transport ability in aqueous environments. The stability of the PS-MPs/PPCPs complexes is further confirmed by thermochemical and molecular dynamics trajectory analysis as a function of temperature and pressure. The interaction mechanism of high pKa pollutants (pKa > 5) is due to a balanced contribution of electrostatic and dispersion forces, while the adsorption of low pKa pollutants (pKa < 5) maximizes the electrostatic forces, and steric repulsion effects explain their relative lower adsorption stability. In this regard, several pairwise intermolecular interactions are recognized as a source of stabilization in the PS-MPs/PPCPs binding: hydrogen bonding, π-π, OH⋯π, and CH⋯π, CCl⋯CH and CH⋯CH interactions. The ionic strength in solution slightly affects the adsorption stability of neutral PPCPs, while the sorption of charged pollutants is enhanced. This mechanistic information provides quantitative data for a better understanding of the interactions between organic pollutants and MPs, serving as valuable information for sorption/kinetic studies.

Screening of pesticides and emerging contaminants in eighteen Greek lakes by using target and non-target HRMS approaches: Occurrence and ecological risk assessment

Lakes, albeit ecosystems of vital importance, are insufficiently investigated with respect to the degradation of water quality due to the organic micropollutants load. As regards Greece, screening of lake waters is scarce and concerns a limited number of contaminants. However, understanding the occurrence of contaminants of emerging concern (CECs) and other micropollutants in lakes is essential to appraise their potential ecotoxicological effects. The aim of this study was to deploy a multiresidue screening approach based on liquid chromatography−high-resolution mass spectrometry (HRMS) to get a first snapshot for >470 target CECs, including pesticides, pharmaceuticals, personal care products (PPCPs), per- and polyfluoroalkyl substances (PFASs), as well as organophosphate flame retardants (OPFRs) in eighteen Greek lakes in Central, Northern and West Northern Greece. The omnipresent compounds were DEET (N,N-diethyl-meta-toluamide), caffeine and TCPP (tris (1-chloro-2-propyl) phosphate). Maximum concentrations varied among the different classes. DEET was detected at a maximum average concentration of >1000 ng/L in Lake Orestiada, while its mean concentration was estimated at 233 ng/L. The maximum total concentrations for pesticides, PPCPs, PFASs, and OPFRs were 5807, 2669, 33.1, and 1214 ng/L, respectively, indicating that Greek lakes are still threatened by the intense agricultural activity. Besides, HRMS enabled a non-target screening by exploiting the rich content of the full-scan raw data, allowing the ‘discovery’ of tentative candidates, such as surfactants, pharmaceuticals, and preservatives among others, without reference standards. The potential ecotoxicity was assessed by both the risk quotient method and ECOSAR (Ecological Structure Activity Relationships) revealing low risk for most of the compounds.

Risk Assessment of Personal Care Products, Pharmaceuticals, and Stimulants in Mgeni and Msunduzi Rivers, KwaZulu-Natal, South Africa

In this work, environmental occurrence and risk assessment of pharmaceuticals, personal care products (PPCPs), and stimulants are presented. A quantitative technique is described for ultrasonic-assisted solid-phase extraction (SPE) followed by GC-MS after derivatization of PPCPs; propylparaben, triclosan, carbamazepine, chloramphenicol, and stimulant caffeine. Ultrasonic-assisted extraction together with centrifugation were used to extract sediment samples collected from the Mgeni and Msunduzi rivers. An SPE procedure was used for cleanup and to concentrate selected compounds from diluted aqueous extracts. The final extracts were derivatized and analyzed with GC-MS in selected ion monitoring (SIM) mode. The recoveries of the analytes ranged from 66 to 108%. The method detection limits were (0.08–1.82 ng g−1 for solid and 0.08–10 μg L−1 for liquid) and quantification limits (0.42–5.51 ng g−1 for solid and 0.25–25 μg L−1 for liquid). The optimized method was applied in the evaluation of two rivers over 3 months in KwaZulu-Natal, South Africa. All targeted compounds were present in the environment at concentration levels between not detected to 174 ng g−1 and not detected to 30 μg L−1 for solids and aqueous environmental samples, respectively. A comparison of predicted no environmental effect concentration (PNECs) with measured environmental concentration (MECs) showed that these PPCPs present a high ecological risk to the receiving environment (agricultural lands and households). Our work is close to reality because we used MECs as opposed to using predicted environmental concentration (PECs) values, which are normally calculated from consumption, production of compound per year, and various estimated factors.

Honeycomb-like holey Co3O4 membrane triggered peroxymonosulfate activation for rapid degradation of organic contaminants

Heterogeneous advanced oxidation processes (AOPs) are commonly employed for the degradation of recalcitrant contaminants, however, practical application of heterogeneous AOPs has been limited by their low activation efficiency and inefficient utilization of radicals. Herein, this study demonstrates for the first time that 2D honeycomb-like holey membranes assembled by Co3O4 nanosheets, serve as an excellent activator for peroxymonosulfate (PMS) and aid in rapid pollutant removal. The Co3O4 membrane achieved 100% target pollutant ranitidine removal and a membrane retention time of only ~385 ms with the degradation rate 3–5 orders of magnitude faster than that achieved by conventional heterogeneous catalysis. Ranitidine degradation was maintained at >90% for 13 h of continuous-flow operation at a high flux of 176 L m−2 h−1 bar−1. Furthermore, the Co3O4 membrane could also effectively degrade several recalcitrant pollutants, including pharmaceutical personal care products, phenols, and dyes. SO4•– and •OH were identified as the primary reactive oxygen species in the Co3O4 membrane/PMS system, with Co providing the active site for PMS activation. This strategy of membrane-based AOP treatment offers helpful guidance for the design of other efficient heterogeneous catalytic systems and presents a novel approach to overcoming the limitations of conventional heterogeneous catalysis.

Chloroxylenol at environmental concentrations can promote conjugative transfer of antibiotic resistance genes by multiple mechanisms

The intergeneric conjugative transfer of antibiotic resistance genes (ARGs) is recognized as an important way to the dissemination of antibiotic resistance. However, it is unknown whether the extensive use of chloroxylenol (para-chloro-meta-xylenol, PCMX) in many pharmaceutical personal care products will lead to the spread of ARGs. In this study, the abilities and mechanisms of PCMX to accelerate the intergeneric conjugative transfer were investigated. Results showed that exposure of bacteria to environmental concentrations of PCMX (0.20–1.00 mg/L) can significantly stimulate the increase of conjugative transfer by 8.45–9.51 fold. The phenotypic experiments and genome-wide RNA sequencing revealed that 0.02–5.00 mg/L PCMX exposure could increase the content of alkaline phosphatase and malondialdehyde, which are characteristic products of cell wall and membrane damage. In addition, PCMX could lead to excessive production of reactive oxygen species (ROS) by 1.26–2.00 times, the superoxide dismutase and catalase produced by bacteria in response to oxidative stress were not enough to neutralize the damage of ROS, thus promoting the conjugative transfer. Gene Ontology enrichment analysis indicated that cell membrane permeability, pili, some chemical compounds transport and energy metabolism affected conjugative transfer. This study deepened the understanding of PCMX in promoting propagation of ARGs, and provided new perspectives for use and treatment of personal care products.

Fabrication of thermoresponsive metal-organic nanotube sponge and its application on the adsorption of endocrine-disrupting compounds and pharmaceuticals/personal care products: Experiment and molecular simulation study.

Thermoresponsive metal-organic nanotube modified (MONT-pNIPAM, pNIPAM=poly N-isopropylacrylamide) sponge was synthesized using the dip-coating method and served as an adsorbent for endocrine-disrupting compounds (EDCs) and pharmaceuticals/personal care products (PPCPs) removal. The material was characterized using Fourier transform infrared spectroscopy, scanning electron microscopy, X-ray diffraction, and N2 sorption-desorption. Nonlinear regression-based equations were derived to optimize pH and ionic strength during process. Though thermoresponsive polymer phase transition between dissolve and aggregate, realizing the adsorption tunnel "ON-OFF" under the temperature control. Adsorption kinetics and isotherms were investigated on the basis of a static experiment. The pseudo-second-order kinetic model and the Langmuir isotherm were fitted well to characterize adsorption. At an initial concentration of 50mgL-1, maximum adsorption capacity were 128mg/g, 184mg/g and partition coefficient were 1.09mgg-1 μM-1, 1.13mgg-1 μM-1 for dibutyl phthalate (DBP) and parachlorometaxylenol (PCMX), respectively. The density-functional theory (DFT) was applied to calculate the interaction energy and investigate the possible mechanism. Combining the experimental data with theoretical calculation, results demonstrated that the MONT-pNIPAM sponge was a highly efficient adsorbent material that was suitable for the removal of EDCs/PPCPs from water.

Comparison of life cycle toxicity assessment methods for municipal wastewater treatment with the inclusion of direct emissions of metals, PPCPs and EDCs

The occurrence of various micropollutants such as pharmaceuticals personal care products, endocrine disrupting chemicals (PPCPs/EDCs) and metals in municipal wastewater, and their poor removal efficiencies can lead to toxicity impact on humans, and freshwater and terrestrial ecosystems. Life cycle assessment is an efficient and effective tool to evaluate the environmental impact of wastewater treatment plants, but guidelines for toxicity assessment are lacking due to the complexity. This study aims to evaluate both life cycle inventory by including metals and PEC, and life cycle toxicity assessment (LCIA) methods namely CML-IA, Recipe, USEtox, EDIP 2003 and IMPACT 2002+ in midpoint category with a large centralised wastewater treatment plant in Malaysia as a case study. The removal efficiencies of metals and PPCPs/EDCs in the wastewater ranged from 9% to 99% and no clear patterns were found about occurrence and removal efficiencies of metals and PPCPs/EDCs in developing and developed countries. The inclusion of metals and PPCPs/EDCs in effluent resulted in 76% increase in freshwater ecotoxicity potential (FEP) and 88% increase in terrestrial ecotoxicity potential (TEP) while only 4% increase in human toxicity potential (HTP). The results indicate the importance of including direct emissions such as metals and PPCPs/EDCs even in low-strength municipal wastewater for environmental toxicity assessment. The comparison of five LCIA methods suggests that HTP assessment is more challenging due to inconsistency between five LCIA methods while CML-IA, Recipe, and IMPACT 2002+ achieved consistent human toxicity and ecotoxicity assessment results in the WWTP. The results highlight the importance of sampling and inclusion of metals and PPCPs/EDCs data especially prioritised micropollutants for life cycle toxicity assessment and recommends LCIA methods for ecotoxicity assessment of WWTPs in the current scientific development situation on toxicity studies, which can provide guidance to researchers for life cycle toxicity assessment of wastewater treatment.

MBR-UV/Cl2 system in treating polluted surface water with typical PPCP contamination

This study proposed the membrane bioreactor–ultraviolet/chlorine (MBR-UV/Cl2) process for treating polluted surface water with pharmaceutical personal care product (PPCP) contamination. Results showed that MBR-UV/Cl2 effectively removed the organic matters and ammonia at approximately 80% and 95%. MBR-UV/Cl2 was used in the removal of sulfadiazine(SDZ), sulfamethoxazole(SMZ), tetracycline(TC), oxytetracycline(OTC), ciprofloxacin(CIP), ofloxacin(OFX), erythromycin(ERY), roxithromycin(ROX), ibuprofen(IBU) and, naproxen(NAX) at 12.18%, 95.61%, 50.50%, 52.97%, 33.56%, 47.71%, 87.57%, 93.38%, 93.80%, and 71.46% in which their UV/Cl2 contribution was 12.18%, 95.61%, 29.04%, 38.14%, 25.94%, 7.20%, 80.28%, 33.79%, 73.08%, and 23.05%, respectively. The removal of 10 typical PPCPs using UV/Cl2 obtained higher contributions than those of the MBR process, except OTC, ROX, and IBU. The UV/Cl2 process with 3-min hydraulic retention time and chlorine concentration at 3 mg/L effectively removed the trace of PPCPs. MBR-UV/Cl2 has the potential to be developed as an effective technology in treating polluted surface water with PPCP contamination.

An efficient resin for solid-phase extraction and determination by UPLCMS/MS of 44 pharmaceutical personal care products in environmental waters

In this study, a hydrophilic resin named GCHM was fabricated based on poly(N-vinyl pyrrolidone-co-divinylbenzene), characterized, and applied as a solid-phase extraction (SPE) material. Up to 44 pharmaceuticals and personal care products (PPCPs) belonging to 10 classes were recovered in environmental water samples. Different variables affecting extraction, such as adsorbent amount, sample pH, and loading speed, were optimized. Under optimal conditions, the average absolute recovery of 44 PPCPs was 75.6% using GCHM, indicating a better performance than the commercial Oasis® HLB. SPE with home-made hydrophilic polymeric sorbent followed by ultra-performance liquid chromatography and tandem mass spectrometry was validated, and the method achieved good linearity (r2 >0.991, for all analytes). In addition, the method detection limits of target compounds ranged from 0.03 to 0.6 ng/L. The developed method was applied to determine PPCPs in 10 environmental water samples taken from the Yangtze River, Huaihe River, and Taihu Lake, 1 groundwater sample from Changzhou in Jiangsu Province, 1 wastewater sample from Xiamen and 2 seawater samples from the Jiulong River in Fujian Province, China. In these samples, 22 compounds were determined at levels ranging from 0.5 to 1590 ng/L.

Occurrence and risk assessment of organic micropollutants in freshwater systems within the Lake Victoria South Basin, Kenya

The unintended release of chemicals to the environment has led to global concern on water quality prompting widespread research on the occurrence of these compounds in water. While increasing information on organic micropollutants (OMPs) in European water resources is available, there is still limited information on the occurrence of OMPs in African water systems. In this study, a multi-residue analysis covering 428 chemicals using liquid chromatography coupled to high resolution mass spectrometry (LC-HRMS) was performed on water samples collected from 48 surface water sites within the Lake Victoria South Basin, Kenya. A total of 75 compounds including pharmaceuticals, personal care products (PPCPs), pesticides, and industrial chemicals were detected and an additional three compounds (nevirapine, lamivudine and adenosine) were identified through suspect screening. Four compounds including diphenhydramine, simazine, triethylphosphate and acetyl-sulfamethoxazole (A-SMX) were detected in >80% of the sites showing their ubiquitous nature in the study area. Individual compound concentrations were detected up to 24 μg L−1. Concentrations above 1 μg L−1 were also reported for triethylcitrate, N-ethyl-o-toluenesulfonamide, hexazinone, nevirapine, adenosine and carbendazim. While crustaceans were potentially the taxon at risk for acute toxicity (toxic unit (TU) up to 2) with diazinon driving this risk, lower but substantial acute risk (TU 0.5) was observed for algae. Chronic risks were observed in 11 sites for algae (TU > 0.02) and in 5 sites for fish (TU > 0.01). A total of 16 compounds were prioritized based on frequency and extent of the exceedance of thresholds for acute and chronic risks to algae, crustaceans and fish and another 7 compounds prioritized by applying lowest Predicted No-Effect Concentrations (PNEC). Based on these indicators, this study provides candidate priority compounds for monitoring, assessment and abatement in western Kenya.

Determination of acid dissociation constants and reaction kinetics of dimethylamine-based PPCPs with O3, NaClO, ClO2 and KMnO4

Dimethylamine-based pharmaceutical personal care products (DMA-based PPCPs) are a group of N-nitrosodimethylamine (NDMA) precursors. The acid dissociation constant (pKa) values of four DMA-based PPCPs were determined by potentiometric titration over the pH range of 3–11. The pKa values of ranitidine, nizatidine, doxylamine and carbinoxamine corresponding to the DMA moiety were 8.4, 6.8, 9.4 and 9.1, respectively. Competition reaction kinetics and pseudo-first-order reaction kinetics were used to determine the reaction rate constant (k) of the DMA-based PPCPs with O3, NaClO, ClO2 and KMnO4. Comparing the degradation rate constants of the four DMA-based PPCPs, the results of ClO2 oxidation were close, and for the other three oxidants, the order was kranitidine ≈ knizatidine > kdoxylamine ≈ kcarbinoxamine. Comparing the reaction rate of the four oxidants, for ranitidine and nizatidine, the order was kNaClO > kO3 > kKMnO4 > kClO2, and for doxylamine and carbinoxamine, the order was kO3 > kNaClO > kClO2 > kKMnO4.

Health and ecological risk assessment of emerging contaminants (pharmaceuticals, personal care products, and artificial sweeteners) in surface and groundwater (drinking water) in the Ganges River Basin, India

Pharmaceuticals, personal care products (PPCPs), and artificial sweeteners (ASWs) are contaminants of emerging concern commonly found in the aquatic environments. In India, studies reporting environmental occurrence of these contaminants are scarce. In this study, we investigated the occurrence and distribution of 15 PPCPs and five ASWs in the river and groundwater (used untreated as drinking water) at several sites along the Ganges River. Based on the measured groundwater concentrations, we estimated the life-long human health risk from exposure to PPCPs through drinking. In addition, we estimated the risk of exposure to PPCPs and ASWs in the river water for aquatic organisms. The sum of detected PPCPs in the river water ranged between 54.7-826 ng/L, with higher concentrations in the severely anthropogenically influenced middle and lower reaches of the Ganges. The highest concentration among the PPCPs in the river water was of caffeine (743 ng/L). The sum of detected ASWs in river water ranged between 0.2–102 ng/L. Similar to PPCPs, the sum of ASWs in the river water was higher in the middle and lower reaches of the Ganges. In groundwater, the sum of detected PPCPs ranged between 34–293 ng/L, whereas of ASWs ranged between 0.5-25 ng/L. Negligible risk for humans was estimated from PPCPs in the drinking groundwater sources along the Ganges River, whereas moderate risks to PPCPs and ASWs (namely: caffeine, sulfamethoxazole, triclocarban, triclosan, and sucralose) were estimated for aquatic organisms in the Ganges River.

Occurrence, fate and removal of pharmaceuticals, personal care products and pesticides in wastewater stabilization ponds and receiving rivers in the Nzoia Basin, Kenya

Although there is increased global environmental concern about emerging organic micropollutants (EOMPs) such as pharmaceuticals, personal care products (PPCPs) and polar pesticides, limited information is available on their occurrence in Africa. This study presents unique data on concentrations and loads of 31 PPCPs and 10 pesticides in four wastewater stabilization ponds (WSPs) and receiving rivers (flowing through urban centres) in Kenya. The WSPs indicate a high potential to remove pharmaceutically active compounds (PhACs) with removals by up to >4 orders of magnitude (>99.99% removal), mainly occurring at the facultative stage. However, there are large differences in removal among the different classes, and a shift in the relative PhACs occurrence is observed during wastewater treatment. Whereas the influent is dominated by high-consumption PhACs like anti-inflammatory drugs (e.g. paracetamol and ibuprofen, up to 1000 μg L−1), the most recalcitrant PhACs including mainly antibiotics (e.g. sulfadoxin and sulfamethoxazole) and antiretrovirals (e.g. lamivudine and nevirapine) are largely abundant (up to 100 μg L−1) in treated effluent.Overall, concentrations of EOMPs in the Nzoia Basin rivers are the highest in dry season (except pesticides) and in small tributaries. They are of the same order of magnitude as those measured in the western world, but clearly lower than what we recently measured in the Ngong River, Nairobi region. Based on the specific consumption patterns and recalcitrant behavior, high concentrations (>1000 ng L−1) are observed in the rivers for PPCPs like lamivudine, zidovudine, sulfamethoxazole and methylparaben. Concentration levels of pesticides are in general one order of magnitude lower (<250 ng L−1). Our data suggest a continuous input of EOMPs to the rivers from both point (WSPs) and diffuse (urban centres) sources. To better understand and manage the impact of both sources, EOMP removal mechanisms in WSPs and their attenuation in rivers merit further research.

Spatial (bio)accumulation of pharmaceuticals, illicit drugs, plasticisers, perfluorinated compounds and metabolites in river sediment, aquatic plants and benthic organisms.

Organic contaminants such as pharmaceuticals, personal care products (PPCPs) and other emerging contaminants (ECs) are known to persist in the aquatic environment and many are indicated as endocrine, epigenetic, or other toxicants. Typically, the study of PPCPs/ECs in the aquatic environment is limited to their occurrence dissolved in river water. In this study, accumulation and spatial distribution of thirteen PPCPs/ECs were assessed in aquatic sediment (n=23), periphyton (biofilm, n=8), plants Callitriche sp. (n=8) and Potamogeton sp. (n=7) as well as amphipod crustaceans (Gammarus pulex, n=10) and aquatic snails (Bithynia tentaculata, n=9). All samples (n=65) were collected from the Hogsmill, Blackwater and Bourne Rivers in southern England. Targeted PPCPs/ECs included pharmaceuticals, plasticisers, perfluorinated compounds, illicit drugs and metabolites. Extraction from solid matrices occurred using ultrasonic-assisted extraction followed by an in-house validated method for solid-phase extraction and subsequent liquid-chromatography tandem mass-spectrometry. Field-derived bioconcentration-factors and biota-sediment accumulation-factors were determined for all studied biota. Residues of studied contaminants were found in all sediment and biota. Concentrations of contaminants were generally higher in biota than sediment. Evidence suggests that the studied aquatic plants may effectively degrade bisphenol-A into its main transformation product hydroxyacetophenone, potentially mediated by cytochrome p450 and internalisation of contaminants into the cellular vacuole. A positive association between both hydrophobicity and PFC chain length and contaminant accumulation was observed in this work. Only PFCs, plasticisers and HAP were classified as either 'bioaccumulative' or 'very bioaccumulative' using BCF criteria established by guidelines of four governments. Contaminants appeared to be differentially bioaccumulative in biota, indicating there may be a need for a species-specific BCF/BSAF classification system. These data form a detailed accounting of PPCP/EC fate and distribution in the aquatic environment highlighting accumulation at lower trophic levels, a potential source for higher organisms.

Spatial distribution of organic contaminants in three rivers of Southern England bound to suspended particulate material and dissolved in water

The spatial distribution of pharmaceuticals, personal care products (PPCPs) and other emerging contaminants (ECs) such as plasticisers, perflourinated compounds (PFCs) and illicit drug metabolites in water and bound to suspended particulate material (SPM) is not well-understood. Here, we quantify levels of thirteen selected contaminants in water (n=88) and their partition to suspended particulate material (SPM, n=16) in three previously-unstudied rivers of Greater London and Southern England during a key reproduction/spawning period. Analysis was conducted using an in-house validated method for Solid Phase Extraction followed by High-Performance Liquid Chromatography-Tandem Mass-Spectrometry. Analytes were extracted from SPM using an optimised method for ultrasonic-assisted solvent extraction. Detection frequencies of contaminants dissolved in water ranged from 3% (ethinylestradiol) to 100% (bisphenol-A). Overall mean concentrations in the aqueous-phase ranged from 14.7ng/L (benzoylecgonine) to 159ng/L (bisphenol-A). Sewage treatment works (STW) effluent was the predominant source of pharmaceuticals, while plasticisers/perfluorinated compounds may additionally enter rivers via other sources. In SPM, detection frequencies ranged from 44% (PFOA) to 94% (hydroxyacetophenone). Mean quantifiable levels of analytes bound to SPM ranged from 13.5ng/g dry SPM (0.33ng bound/L water) perfluorononanoic acid to 2830ng/g dry SPM (14.3ng bound/L water) perfluorooctanesulfonic acid. Long chain (>C7) amphipathic and acidic PFCs were found to more preferentially bind to SPM than short chain PFCs and other contaminants (Kd=34.1–75.5 vs <5 respectively). Per capita daily contributions of studied contaminants entering rivers ranged from 0.157μg/person/day of benzoylecgonine (cocaine metabolite) to 58.6μg/person/day of bisphenol-A. The large sample size of this work (n=104) enabled ANOVA followed by Tukey HSD post-hoc tests to establish significant trends in PPCP/EC spatial distribution from headwaters through downstream stretches of studied rivers. Novel findings include environmental Kd calculations, the occurrence of contaminants in river headwaters, increases in contaminant metabolite concentrations downstream of STW effluents revealing possible in-river degradation or de-conjugation, the influence of polarity and acidity in the partition of contaminants to particulate-material, among others.

Contaminants of emerging concern in a large temperate estuary

This study was designed to assess the occurrence and concentrations of a broad range of contaminants of emerging concern (CECs) from three local estuaries within a large estuarine ecosystem. In addition to effluent from two wastewater treatment plants (WWTP), we sampled water and whole-body juvenile Chinook salmon (Oncorhynchus tshawytscha) and Pacific staghorn sculpin (Leptocottus armatus) in estuaries receiving effluent. We analyzed these matrices for 150 compounds, which included pharmaceuticals, personal care products (PPCPs), and several industrial compounds. Collectively, we detected 81 analytes in effluent, 25 analytes in estuary water, and 42 analytes in fish tissue. A number of compounds, including sertraline, triclosan, estrone, fluoxetine, metformin, and nonylphenol were detected in water and tissue at concentrations that may cause adverse effects in fish. Interestingly, 29 CEC analytes were detected in effluent and fish tissue, but not in estuarine waters, indicating a high potential for bioaccumulation for these compounds. Although concentrations of most detected analytes were present at relatively low concentrations, our analysis revealed that overall CEC inputs to each estuary amount to several kilograms of these compounds per day. This study is unique because we report on CEC concentrations in estuarine waters and whole-body fish, which are both uncommon in the literature. A noteworthy finding was the preferential bioaccumulation of CECs in free-ranging juvenile Chinook salmon relative to staghorn sculpin, a benthic species with relatively high site fidelity.

Development of sample extraction and clean-up strategies for target and non-target analysis of environmental contaminants in biological matrices

Recently, there has been an increasing trend towards multi-targeted analysis and non-target screening methods as a means to increase the number of monitored analytes. Previous studies have developed biomonitoring methods which specifically focus on only a small number of analytes with similar physico-chemical properties. In this paper, we present a simple and rapid multi-residue method for simultaneous extraction of polar and non-polar organic chemicals from biological matrices, containing up to 5% lipid content. Our method combines targeted multi-residue analysis using gas chromatography triple quadrupole mass spectrometry (GC-QqQ-MS/MS) and a multi-targeted analysis complemented with non-target screening using liquid chromatography coupled to a quadrupole time of flight mass spectrometry (LC-QTOF-MS/MS). The optimization of the chemical extraction procedure and the effectiveness of different clean-up methods were evaluated for two biological matrices: fish muscle (lipid content ∼2%) and breast milk (∼4%). To extract a wide range of chemicals, the partition/extraction procedure used for the QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) approach was tested as the initial step for the extraction of 77 target compounds covering a broad compound domain. All the target analytes have different physico-chemical properties (log Kow ranges from −0.3 to 10) and cover a broad activity spectrum; from polar pesticides, pharmaceuticals, personal care products (PPCPs) to highly lipophilic chemicals such as polybrominated diphenyl ethers (PBDEs), polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs) and organochloride pesticides (OCPs). A number of options were explored for the clean-up of lipids, proteins and other impurities present in the matrix. Zirconium dioxide-based sorbents as dispersive solid-phase extraction (d-SPE) and protein-lipid removal filter cartridges (Captiva ND Lipids) provided the best results for GC-MS and LC-MS analysis respectively. The method was fully validated for samples of fish muscle and breast milk through the evaluation of recoveries, matrix effects, limit of quantification, linearity and precision (inter-day and intra-day). Mean recoveries (n=5) were between 70 and 120% with relative standard deviations (RSD) less than 20% in most of the cases. GC-MS/MS LOQs ranged from 0.08 to 3μg/kg and LC-QTOF-MS/MS LOQs ranged from 0.2 to 9μg/kg. The developed strategy was successfully applied for analysis of real samples; 22 target analytes were found in the breast milk samples and 10 in the fish samples. Non-target analysis allowed the detection and identification of an additional 14 contaminants and metabolites in the samples.

Occurrence of halogenated transformation products of selected pharmaceuticals and personal care products in secondary and tertiary treated wastewaters from southern California.

Final effluent samples from 10 southern California (United States) wastewater treatment facilities, employing four distinct treatment schemes, were surveyed for selected pharmaceuticals, personal care products (PPCPs), alkylphenols, and 21 of their halogenated disinfection byproducts. Chlorinated and brominated standards and isotopically labeled internal standards were synthesized and purified to confirm and more accurately quantify selected disinfection byproducts of salicylic acid, bisphenol A, gemfibrozil, naproxen, diclofenac, technical 4-nonylphenol, and 4-tert-octylphenol using high-performance liquid chromatography and tandem mass spectrometry. Concentrations of parent compounds ranged from <10 to 3830 ng/L (gemfibrozil), and those of chloro/bromo byproducts ranged from <4 to 370 ng/L (dibromo nonylphenol). The highest concentrations of parent compounds were measured in effluent that was not subjected to tertiary treatment. The chlorinated and brominated byproduct concentration may be affected by the influent concentration of parent compounds, hydraulic retention times, and chlorine contact times. Salicylic acid was readily halogenated, which is evident from the ratio of halogenated to nonhalogenated species. There were no measured chlorinated byproducts of bisphenol A despite occasionally high concentrations of the parent compound. Not surprisingly, higher concentrations of most brominated species were measured in the treatment plant with the highest bromide concentrations. These results demonstrate the occurrence of novel halogenated byproducts of PPCPs that have limited toxicological data and significant uncertainty with regard to their risk to ecological systems.