Assessing the Fate of Benzophenone-Type UV Filters and Transformation Products during Soil Aquifer Treatment: The Biofilm Compartment as Bioaccumulator and Biodegrader in Porous Media.

The fate of selected UV filters (UVFs) was investigated in two soil aquifer treatment (SAT) systems, one supplemented with a reactive barrier containing clay and vegetable compost and the other as a traditional SAT reference system. We monitored benzophenone-3 (BP-3) and its transformation products (TPs), including benzophenone-1 (BP-1), 4,4'-dihydroxybenzophenone (4DHB), 4-hydroxybenzophenone (4HB), and 2,2'-dihydroxy-4-methoxybenzophenone (DHMB), along with benzophenone-4 (BP-4) and avobenzone (AVO) in all involved compartments (water, aquifer sediments, and biofilm). The reactive barrier, which enhances biochemical activity and biofilm development, improved the removal of all detected UVFs in water samples. Among monitored UVFs, only 4HB, BP-4, and AVO were detected in sediment and biofilm samples. But the overall retained amounts were several orders of magnitude larger than those dissolved. These amounts were quantitatively reproduced with a specifically developed simple analytical model that consists of a mobile compartment and an immobile compartment. Retention and degradation are restricted to the immobile water compartment, where biofilm absorption was simulated with well-known compound-specific Kow values. The fact that the model reproduced observations, including metabolites detected in the biofilm but not in the (mobile) water samples, supports its validity. The results imply that accumulation ensures significant biodegradation even if the degradation rates are very low and suggest that our experimental findings for UVFs and TPs can be extended to other hydrophobic compounds. Biofilms act as accumulators and biodegraders of hydrophobic compounds.

Efficient removal of toxicity associated to wastewater treatment plant effluents by enhanced Soil Aquifer Treatment.

The regeneration of wastewater has been recognized as an effective strategy to counter water scarcity. Nonetheless, Wastewater Treatment Plant (WWTP) effluents still contain a wide range of contaminants of emerging concern (CECs) even after water depuration. Filtration through Soil Aquifer Treatment (SAT) systems has proven efficient for CECs removal although the attenuation of their associated biological effects still remains poorly understood. To evaluate this, three pilot SAT systems were monitored, two of them enhanced with different reactive barriers. SATs were fed with secondary effluents during two consecutive campaigns. Fifteen water samples were collected from the WWTP effluent, below the barriers and 15 m into the aquifer. The potential attenuation of effluent-associated biological effects by SATs was evaluated through toxicogenomic bioassays using zebrafish eleutheroembryos and human hepatic cells. Transcriptomic analyses revealed a wide range of toxic activities exerted by the WWTP effluents that were reduced by more than 70% by SAT. Similar results were observed when HepG2 hepatic cells were tested for cytotoxic and dioxin-like responses. Toxicity reduction appeared partially determined by the barrier composition and/or SAT managing and correlated with CECs removal. SAT appears as a promising approach to efficiently reduce effluent-associated toxicity contributing to environmental and human health preservation.

Factors driving PPCPs uptake by crops after wastewater irrigation and human health implications.

Currently, water scarcity affects more than three billion people. Nevertheless, the volume of treated wastewater discharged into the environment is estimated to exceed 100 m3 per inhabitant/year. These water resources are regularly used in agriculture worldwide to overcome water shortages. Such a practice, however, entails the uptake of waterborne pollutants, such as pharmaceuticals and personal care products (PPCPs), by crops and their further access to the food web, constituting an additional route of human exposure to PPCPs, with potential health outcomes. In this study, the occurrence of 56 PPCPs in tomatoes, lettuce, and carrot, together with soil and irrigation water, was evaluated using a QuEChERS-based methodology for extraction and LC-MS/MS for analysis. The influence of the selected cultivation conditions on the plant uptake levels of PPCPs was assessed. Two irrigation water qualities (secondary and tertiary treatment effluents), two soil compositions (sandy and clayey), two irrigation systems (dripping and sprinkling), and three crop types (lettuce, tomato, and carrot) were tested. Carrots showed the highest load of PPCPs (7787 ng/g dw), followed by tomatoes (1692 ng/g dw) and lettuces (1248 ng/g dw). The most translocated PPCPs were norfluoxetine (fluoxetine antidepressant main metabolite) (521 ng/g dw), and the anti-inflammatory diclofenac (360 ng/g dw). Nine PPCPs, are reported to be accumulated in crops for the first time. Water quality was the most important factor for reducing PPCPs' plant uptake. Overall, the best conditions for reducing PPCP uptake by crops were irrigation with reclaimed water by sprinkling in soils with higher clay content. The risk assessment performed revealed that the crops' consumption posed no risk to human health. This study serves as the first comprehensive assessment of the relevance of diverse cultivation factors on PPCPs' plant uptake under field agricultural practices.

Target analysis and suspect screening of UV filters, parabens and other chemicals used in personal care products in human cord blood: Prenatal exposure by mother-fetus transfer.

Prenatal exposure to certain organic chemicals like pesticides and phenols has been lifelong associated with birth outcomes and health disorders. Many personal care product (PCP) ingredients have similar properties or structures to those chemicals. Previous studies have documented the occurrence of UV filters (UVFs) and paraben preservatives (PBs) in the placenta, but observational studies concerning PCPs chemicals and foetal exposure are particularly scarce. Thus, this work aimed to assess the presence of a wide range of PCPs chemicals using target and suspect screening in the umbilical cord blood of new born babies to evaluate their potential transfer to the fetus. To do so, we analysed 69 umbilical cord blood plasma samples from a mother-child cohort from Barcelona (Spain). We quantified 8 benzophenone-type UVFs and their metabolites, and 4 PBs using validated analytical methodologies based on target screening using liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). Then, we screened for additional 3246 substances using high-resolution mass spectrometry (HRMS) and advanced suspect analysis strategies. Six UVFs and three parabens were detected in the plasma with frequencies between 1.4% and 17.4% and concentrations up to 53.3 ng/mL (benzophenone-2). Thirteen additional chemicals were tentatively identified in the suspect screening, and ten were further confirmed with the corresponding standards. Among them, we found the organic solvent N-methyl-2-pyrrolidone, the chelating agent 8-hydroxyquinoline, and the antioxidant 2,2'-methylenebis(4-methyl-6-tert-butylphenol), which have been demonstrated to display reproductive toxicity. UVFs and PBs presence in the umbilical cord blood demonstrates mother-fetus transfer through the placental barrier and prenatal exposure to these PCPs chemicals, which may lead to adverse effects in the early stages of fetal development. Considering the small cohort used in this study, the reported results should be interpreted as a preliminary reference for the background umbilical cord transfer levels of the target PCPs chemicals. Further research is needed to determine the long-term consequences of prenatal exposure to PCPs chemicals.

Distribution in marine fish and EDI estimation of contaminants of emerging concern by vortex-assisted matrix solid-phase dispersion and HPLC-MS/MS.

Due to their persistence or continuous discharge, toxic substances are present in the aquatic environment, and can bioaccumulate and biomagnify in the food web, generating a significant ecological risk and a threat to human health. The present study assess the occurrence and tissue (muscle, liver, stomach and gills) distribution of 59 anthropogenic contaminants of emerging concern (CECs) in marine fish from Brazil. A simpler and faster analytical methodology based on vortex-assisted matrix solid-phase dispersion (VA-MSPD) and liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) was developed and validated. Limits of quantification ranged from 3.31 to 114 ng g-1 dw with recovery rates between 60 and 140 % and relative standard deviation below 20 %. The ultraviolet filters 4-hydroxybenzophenone (4HB) (benzophenone-3 metabolite) and benzocaine (Et-PABA), and the antibacterial salicylic acid were frequently accumulated in muscle and liver at concentrations between 39.5 and 21.0 ngg-1 dw. The determined concentrations resulted to be lower than the tolerable daily intake recommended by the European Food Safety Authority (EFSA).

Occurrence and fate of contaminants of emerging concern and their transformation products after uptake by pak choi (Brassica rapa subsp. chinensis).

Recovery and reuse of nutrients is a major challenge in agriculture. A new process contributing to a circular economy is the anaerobic digestion of food waste, which is a sustainable way of recycling nutrients as the digestate can be used as fertiliser in agriculture and horticulture. However, the digestate may be polluted with contaminants of emerging concern (CECs) that can be circulated back into the food chain, posing a risk to the environment and human health. In this work, the nutrient solution was spiked with 18 selected CECs frequently detected in food waste biogas facilities, and subsequent uptake and fate of these CECs were evaluated in pak choi grown in two different nutrient solutions (mineral and organic). All spiked compounds except two (propylparaben, fenbendazole) were taken up by pak choi plants, with perfluorobutanoic acid (PFBA) and sertraline displaying the highest concentrations (270 and 190 µg/kg fresh weight, respectively). There were no statistically significant differences in uptake between mineral and organic nutrient solutions. Uptake of per- and polyfluoroalkyl substances (PFAS) was negatively correlated with perfluorocarbon chain length and dependent on the functional group (r = -0.73). Sixteen transformation products (TPs) were tentatively identified using suspect screening, most of which were Phase II or even Phase III metabolites. Six of these TPs were identified for the first time in plant metabolism and their metabolic pathways were considered.

Using integrative samplers to estimate the removal of pharmaceuticals and personal care products in a WWTP and by soil aquifer treatment enhanced with a reactive barrier.

The need and availability of freshwater is a major environmental issue, aggravated by climate change. It is necessary to find alternative sources of freshwater. Wastewater could represent a valid option but requires extensive treatment to remove wastewater-borne contaminants, such as contaminants of emerging concern (CECs). It is urgent to develop not only sustainable and effective wastewater treatment techniques, but also water quality assessment methods. In this study, we used polar organic chemical integrative samplers (POCIS) to investigate the presence and abatement of contaminants in an urban wastewater treatment plant (WWTP) and in soil aquifer treatment (SAT) systems (a conventional one and one enhanced with a reactive barrier). This approach allowed us to overcome inter-day and intraday variability of the wastewater composition. Passive sampler extracts were analyzed to investigate contamination from 56 pharmaceuticals and personal care products (PPCPs). Data from the POCIS were used to estimate PPCPs' removal efficiency along the WWTP and the SAT systems. A total of 31 compounds, out of the 56 investigated, were detected in the WWTP influent. Removal rates along WWTP were highly variable (16-100 %), with benzophenone-3, benzophenone-1, parabens, ciprofloxacin, ibuprofen, and acetaminophen as the most effectively removed chemicals. The two SAT systems yielded much higher elimination rates than those achieved through the primary and secondary treatments together. The SAT system that integrated a reactive barrier, based on sustainable materials to promote enhanced elimination of CECs, was significantly more efficient than the conventional one. The removal of the recalcitrant carbamazepine and its epoxy- metabolite was especially remarkable in this SAT, with removal rates between 69-81 % and 63-70 %, respectively.

Contaminants of emerging concern in marine areas: First evidence of UV filters and paraben preservatives in seawater and sediment on the eastern coast of Tunisia.

UV filters (UVFs) and paraben preservatives (PBs) are widely used components in many personal care products. However, there has been a rising concern for their endocrine-disrupting effects on wildlife once they reach aquatic ecosystems via recreative activities and wastewater treatment plants effluents. This study addresses UVFs and PBs occurrence in seawater and sediment impacted by tourism and sewage discharges along the coast of Mahdia, center East Tunisia. Samples of water and sediment were collected for 6 months from 3 coastal areas. Among the 14 investigated UVFs, 8 were detected in seawater and 4 were found in sediment. All PBs were present in seawater and only methylparaben (MePB) was detected in sediment. Benzophenone-3 (oxybenzone, BP3), benzocaine (EtPABA), and MePB were present in all water samples with concentrations in the ranges 16.4-66.9, 7.3-37.7, and 17.6-222 ng/L, respectively. However, the highest value, 1420 ng/L, corresponded to octinoxate (EHMC). In sediments, avobenzone (AVO), 4-methyl benzylidene camphor (4MBC), EHMC, 5-methyl-1-H-benzotriazole (MeBZT), and MePB were detected at concentrations within the range 1.1-17.6 ng/g dw, being MePB the most frequently detected (89%). MePB and MBZT presented the highest sediment-water partition coefficients and MePB also showed a positive correlation with total suspended solids' water content. Overall, pollutants concentrations remained rather constant along the sampling period, showing little seasonal variation. This study constitutes the first monitoring of UVFs and PBs on the Tunisian coastline and provides occurrence data for reference in further surveys in the country.

Mediterranean seagrass Posidonia oceanica accumulates sunscreen UV filters.

Certain ultra-violet filter (UVF) components of solar creams have negative impacts on coral reefs and have been prohibited in international tourism destinations (i.e., Hawaii, Florida, and Palau) to protect coral reefs. In the Mediterranean coasts which are also hotspots of international tourism and where endemic seagrass Posidonia oceanica forms extensive meadows, the accumulation of UVF components have not been studied. We report for the first time, that the rhizomes of P. oceanica internally accumulated UVFs BP3, BP4, AVO, 4MBC and MeBZT and the paraben preservative MePB. The components BP4 and MePB occurred in higher concentrations reaching up to 129 ng g-1 dw and 512 ng g-1 dw, respectively. This work emphasizes the need for more experimental studies on the effects of UVFs on seagrasses and check if we should follow suit to prohibit certain UVFs to protect this species as what has been done in other regions to protect corals.

Oxybenzone contamination from sunscreen pollution and its ecological threat to Hanauma Bay, Oahu, Hawaii, U.S.A.

Hanauma Bay is a 101-acre bay created by the partial collapse of a volcanic cone and once supported a vibrant coral reef system. It is the most popular swimming area in the Hawaiian Islands and has been reported to have averaged between 2.8 and 3.5 million visitors a year between the 1980s and the 2010s, with visitors averaging between 3000-4000 a day and peaking around 10,000-13,000 per day. Concentrations of oxybenzone and other common UV filters were measured in subsurface water samples and in sands from the beach-shower areas in Hanauma Bay. Results demonstrate that beach showers also can be a source of sunscreen environmental contamination. Hydrodynamic modeling indicates that oxybenzone contamination within Hanauma Bay's waters could be retained between 14 and 50 h from a single release event period. Focusing on only oxybenzone, two different Hazard and Risk Assessment analyses were conducted to determine the danger of oxybenzone to Hanauma Bay's coral reef system. Results indicate that oxybenzone contamination poses a significant threat to the wildlife of Hanauma Bay. To recover Hanauma Bay's natural resources to a healthy condition and to satisfactorily conserve its coral reef and sea grass habitats, effective tourism management policies need to be implemented that mitigate the threat of sunscreen pollution.

Development of a sensitive analytical method for the simultaneous analysis of Benzophenone-type UV filters and paraben preservatives in umbilical cord blood.

UV filters and parabens are compounds used in large quantities in modern societies and have become ubiquitous in the environment. They are considered compounds of emerging concern due to the unwanted effects they cause in the environment and their bioaccumulation potential in humans. Considering their endocrine disrupting activity and their so far unknown effects in newborns, a continuous monitoring of these substances is required. In this work, we developed and validated a new sensitive methodology for the analysis of 8 UV filters and metabolites, and 4 parabens in umbilical cord blood samples. The method consisted of a liquid-liquid extraction and phase separation by freezing. Then, the organic extract was further analyzed at alkaline pH using liquid chromatography coupled to tandem-mass spectrometry (LC-MS/MS) using a QqLIT hybrid mass spectrometer as analyzer. The low limits of detection achieved (0.01-0.42 ng/mL) allowed the reliable simultaneous quantification of UV filters and parabens in this complex biological matrix.•Simple, fast and sensitive analysis of UV filters and parabens in cord blood samples.•First simultaneous analysis of UV filters and parabens in cord blood.•Allows the evaluation of perinatal transfer of UV filters and parabens from the mother to the fetus.

Development of a QuEChERS-based method for the analysis of pharmaceuticals and personal care products in lettuces grown in field-scale agricultural plots irrigated with reclaimed water.

The use of reclaimed water for agricultural irrigation is an increasingly common practice, which recently has found its own European regulatory frame. However, the partial removal of organic contaminants together with other xenobiotic substances in current wastewater treatment plants leads to the occurrence of residues of such pollutants in the treated effluents. Wastewater reclamation techniques are thus required to provide reclaimed water fitting the minimum quality standards set up for irrigation of crops intended for human consumption. This work describes the development and validation of a simple QuEChERS-based extraction and liquid chromatography quadrupole-linear ion trap mass spectrometry (LC-QqLIT-MS/MS) method for the simultaneous quantitative analysis of 55 pharmaceuticals and personal care products (PPCPs) in lettuces irrigated with treated wastewater and reclaimed water. The method showed good recovery rates (80-120%) and low detection limits (0.04-0.8 ng/g dw). In comparison with previous analytical methodologies, this method was simpler, faster and, in most cases, more sensitive. Moreover, is the first one analysing selected personal care products in lettuces. The proposed method was applied to assess the potential transfer of contaminants of urban origin in the use of reclaimed water in agriculture. The case study consisted in the evaluation of the lettuce uptake of the selected contaminants at field scale under two irrigation systems, two soil compositions, and two water types. Benzophenone-2, 4-hydroxybenzophenone, 1H-benzotriazole, 2-(2-Benzotriazol-2-yl)-p-cresol, nalidixic acid, diclofenac, carbamazepine 10,11-epoxy, N-des-methylvenlafaxine, and salicylic acid were transferred to all samples. Highest detected values corresponded to 4-hydroxybenzophenone (84.1 ng/g dw), benzophenone-2 (54.4 ng/g dw), and salicylic acid (53.8 ng/g dw). The best combination to minimize the transfer of the target contaminants from the irrigation water to the lettuces was sprinkling irrigation with water reclaimed by soil infiltration through reactive barriers, and clayey soil.

Rapid and cost-effective multiresidue analysis of pharmaceuticals, personal care products, and antifouling booster biocides in marine sediments using matrix solid phase dispersion.

Currently, there are many contaminants of concern that need to be accurately determined to help assess their potential environmental hazard. Despite their increasing interest, yet few environmental occurrence data exist, likely because they are present at low levels and in very complex matrices. Therefore, multiresidue analytical methods for their determination need to be highly sensitive, selective, and robust. Particularly, due to the trace levels of these chemicals in the environment, an extensive extraction procedure is required before determination. This work details the development of a fast and cheap vortex-assisted matrix solid-phase dispersion-high performance liquid chromatography tandem-mass spectrometry (VA-MSPD-HPLC-MS/MS) method for multiresidue determination of 59 contaminants of emerging concern (CECs) including pharmaceuticals, personal care products, and booster biocides, in sediment. The validated method provided high sensitivity (0.42-36.8 ngg-1 dw quantification limits), wide and good linearity (r2 > 0.999), satisfactory accuracy (60-140%), and precision below 20% for most target analytes. In comparison with previous methods, relying on traditional techniques, the proposed method demonstrated to be more environmentally friendly, cheaper, simpler, and faster. The method was applied to monitor the occurrence of these compounds in sediments collected in Brazil, using only 2 g dw sediment samples, free-solid support, and 5 mL methanol as extraction solvent. The UV filter avobenzone, the UV stabilizer and antifreeze methylbenzotriazole, the preservative methylparaben, the fluoroquinolone antibiotic ciprofloxacin, and the biocides irgarol and 4,5-dichloro-2-octyl-4-isothiazolin-3-one were determined at concentrations in the range 1.44-69.7 ngg-1 dw.

Bioremediation of emerging micropollutants in irrigation water. The alternative of microalgae-based treatments.

The present study evaluated the efficiency of a semi-closed horizontal tubular photobioreactor (PBR) at demonstrative scale to remove a total of 35 target compounds, including benzotriazoles, benzophenones, antibiotics and different pharmaceuticals present in irrigation water in a peri-urban rural area. This water run through an open channel and was a mixture of reclaimed wastewater from a nearby wastewater treatment plant (WWTP) and run-off from the different agricultural fields in the area. Most of the compounds studied are usually not fully eliminated during conventional wastewater treatment, which justifies the need to investigate alternative treatment strategies. A total of 21 of these compounds were detected in the irrigation water. Benzotriazoles were only partially removed after the microalgae treatment, with elimination rates similar to those of conventional WWTPs. The UV filter benzophenone-3 (BP3) showed variable removals, ranging from no elimination to 51%, whereas 4-methylbenzilidenecamphor (4MBC) was completely eliminated. Regarding pharmaceuticals, average removals were higher, in the range of 60-100%, with the exception of the antibiotics sulfamethoxazole (46%) and sulfapyridine, which was not removed. Despite the low biomass productivity of the PBR, parameters such as the size of the reactors, the specific mixed cultures developed and the high temperatures and pH in the closed system may account for the overall good results, The efficiency and sustainability of these systems make them a solid, feasible treatment choice.