Contamination Pattern and Risk Assessment of Polar Compounds in Snow Melt: An Integrative Proxy of Road Runoffs.

To assess the contamination and potential risk of snow melt with polar compounds, road and background snow was sampled during a melting event at 23 sites at the city of Leipzig and screened for 489 chemicals using liquid chromatography high-resolution mass spectrometry with target screening. Additionally, six 24 h composite samples were taken from the influent and effluent of the Leipzig wastewater treatment plant (WWTP) during the snow melt event. 207 compounds were at least detected once (concentrations between 0.80 ng/L and 75 µg/L). Consistent patterns of traffic-related compounds dominated the chemical profile (58 compounds in concentrations from 1.3 ng/L to 75 µg/L) and among them were 2-benzothiazole sulfonic acid and 1-cyclohexyl-3-phenylurea from tire wear and denatonium used as a bittern in vehicle fluids. Besides, the analysis unveiled the presence of the rubber additive 6-PPD and its transformation product N-(1.3-dimethylbutyl)-N'-phenyl-p-phenylenediamine quinone (6-PPDQ) at concentrations known to cause acute toxicity in sensitive fish species. The analysis also detected 149 other compounds such as food additives, pharmaceuticals, and pesticides. Several biocides were identified as major risk contributors, with a more site-specific occurrence, to acute toxic risks to algae (five samples) and invertebrates (six samples). Ametryn, flumioxazin, and 1,2-cyclohexane dicarboxylic acid diisononyl ester are the main compounds contributing to toxic risk for algae, while etofenprox and bendiocarb are found as the main contributors for crustacean risk. Correlations between concentrations in the WWTP influent and flow rate allowed us to discriminate compounds with snow melt and urban runoff as major sources from other compounds with other dominant sources. Removal rates in the WWTP showed that some traffic-related compounds were largely eliminated (removal rate higher than 80%) during wastewater treatment and among them was 6-PPDQ, while others persisted in the WWTP.

Mixture Risk Drivers in Freshwater Sediments and Their Bioavailability Determined Using Passive Equilibrium Sampling.

The identification of mixture risk drivers is a great challenge for sediment assessment, especially when taking bioavailability into consideration. The bioavailable portion, which comprises the organic contaminants in pore water and the ones bound to organic carbon, was accessed by equilibrium partitioning to polydimethylsiloxane (PDMS). The exhaustive solvent and PDMS extracts were toxicologically characterized with a battery of in vitro reporter gene assays and chemically analyzed with liquid and gas chromatography coupled to high-resolution mass spectrometry. The bioavailable fractions of mixture effects and individual chemicals were mostly lower than 0.1, indicating that more than 90% of the substances are strongly bound and would not pose an immediate risk but could potentially be remobilized in the long term. Despite 655 organic chemicals analyzed, only 0.1-28% of the observed biological effects was explained by the detected compounds in whole sediments, while 0.009-3.3% was explained by bioavailable chemicals. The mixture effects were not only dominated by legacy pollutants (e.g., polycyclic aromatic hydrocarbons (PAHs) in the bioassay for activation of the aryl-hydrocarbon receptor (AhR) and oxidative stress response (AREc32)) but also by present-use chemicals (e.g., plastic additives for binding to the peroxisome proliferator-activated receptor γ (PPARγ)), with different fingerprints between whole sediments and bioavailable extracts. Our results highlight the necessity to involve different bioassays with diverse effect profiles and broader selection of contaminants along with bioavailability for the risk assessment of chemical mixtures in sediments.

Assessing the Mixture Effects in In Vitro Bioassays of Chemicals Occurring in Small Agricultural Streams during Rain Events.

Rain events may impact the chemical pollution burden in rivers. Forty-four small streams in Germany were profiled during several rain events for the presence of 395 chemicals and five types of mixture effects in in vitro bioassays (cytotoxicity; activation of the estrogen, aryl hydrocarbon, and peroxisome proliferator-activated receptors; and oxidative stress response). While these streams were selected to cover a wide range of agricultural impacts, in addition to the expected pesticides, wastewater-derived chemicals and chemicals typical for street runoff were detected. The unexpectedly high estrogenic effects in many samples indicated the impact by wastewater or overflow of combined sewer systems. The 128 water samples exhibited a high diversity of chemical and effect patterns, even for different rain events at the same site. The detected 290 chemicals explained only a small fraction (<8%) of the measured effects. The experimental effects of the designed mixtures of detected chemicals that were expected to dominate the mixture effects of detected chemicals were consistent with predictions for concentration addition within a factor of two for 94% of the mixtures. Overall, the burden of chemicals and effects was much higher than that previously detected in surface water during dry weather, with the effects often exceeding proposed effect-based trigger values.

Mapping chemical footprints of organic micropollutants in European streams.

There is increasing awareness that chemical pollution of freshwater systems with complex mixtures of chemicals from domestic sources, agriculture and industry may cause a substantial chemical footprint on water organisms, pushing aquatic ecosystems outside the safe operating space. The present study defines chemical footprints as the risk that chemicals or chemical mixtures will have adverse effects on a specific group of organisms. The aim is to characterise these chemical footprints in European streams based on a unique and uniform screening of more than 600 chemicals in 445 surface water samples, and to derive site- and compound-specific information for management prioritisation purposes. In total, 504 pesticides, biocides, pharmaceuticals and other compounds have been detected, including frequently occurring and site-specific compounds with concentrations up to 74 µg/L. Key finding is that three-quarter of the investigated sites in 22 European river basins exceed established thresholds for chemical footprints in freshwater, leading to expected acute or chronic impacts on aquatic organisms. The largest footprints were recorded on invertebrates, followed by algae and fish. More than 70 chemicals exceed thresholds of chronic impacts on invertebrates. For all organism groups, pesticides and biocides were the main drivers of chemical footprints, while mixture impacts were particularly relevant for invertebrates. No clear significant correlation was found between chemical footprints and the urban discharge fractions, suggesting that effluent-specific quality rather than the total load of treated wastewater in the aquatic environment and the contribution of diffuse sources, e.g. from agriculture, determine chemical footprints.

Reference Electrode Reveals Insights on Sodium Metal/Solid Electrolyte Interface Cycling and Voiding Behaviors at High Current Densities and Areal Capacities.

Plating and stripping processes at solid metal electrode/solid electrolyte interfaces are of great significance for high-energy, solid-state batteries. Here, we introduce a Na metal reference electrode to a symmetric Na metal/sodium ß″ alumina/Na metal cell and study both cycling and unidirectional protocols with a focus on high current density and areal capacity. For example, in a current ramp test at 5 mAh cm-2 we find a shift from stable to unstable interfacial polarization during stripping at ≳3 mA cm-2, and at 7.5 mA cm-2 we measure 100s of mV of voltage magnitude rise at the stripping electrode and 10s of mV of voltage changes at the plating electrode. In unidirectional testing (i.e., passing current in a single direction until cell failure), at 1.2 mA cm-2 we find only ∼40% of the initial Na foil could be transferred through the solid electrolyte and again observe 100s of mV (and larger) voltage magnitude rise at the stripping electrode and 10s of mV of voltage change at the plating electrode. This test also shows that the 100s of mV of interfacial polarization can be sustained for hours (at 1.2 mA cm-2) to tens of hours (in a test at 0.3 mA cm-2). Hence, across several test protocols we find a Na metal reference electrode provides quantitative insights on electrochemical interfacial behavior that are not revealed in two-electrode testing. We also built a two-dimensional model of our three-electrode symmetric cell to quantify the link between the measured interfacial potentials in our testing and changes in electrochemically active interfacial contact and find that 100s of mV of interfacial potential rise indicates loss of electrochemically active contact area of >80%. Our work provides a promising approach to clarify the coupled interfacial electrochemical and contact mechanics processes at solid metal electrode/solid electrolyte interfaces.

MCDA-DEA approach to construct a composite indicator for effluents from WWTPs considering the influence of PPCPs.

Considering current water situation, reuse is an effective solution to meet water demand and reduce pressure on conventional water sources. However, pharmaceutical and personal care products (PPCPs) in effluents from wastewater treatment plants (WWTPs) decrease their quality and suitability. With the aim of identifying and monitoring both the influence of PPCPs and the suitability of effluents to be reused, this study proposes the development of a composite indicator (CI) related to PPCP presence in WWTPs, through the common weight multi-criteria decision analysis (MCDA)-data envelopment analysis (DEA) model. Obtaining a CI for PPCPs is a novel approach in the published literature, showing a new perspective in PPCP management and their influence in wastewater treatment. Furthermore, this study proposes an improvement on MCDA-DEA model which maintains the initial hierarchy obtained for the units analyzed. The development of CI is based on information about the technological, environmental, social, and biological issues of WWTPs. Results show that 4 of the 33 WWTPs analysed had the best CI values, meaning that their effluents have lower environmental impact. The development of a CI related to PPCPs in WWTPs suggests that further steps are needed to manage the WWTP effluents. Hence, the need to implement preventive measures in WWTPs has been shown, even though the removal of PPCPs is not yet part of European law. This work highlights the importance of considering PPCPs as priority pollutants in wastewater management and reuse frameworks, to guarantee low environmental impact and adapt wastewater reuse based on a circular economy approach. HIGHLIGHTS: Emerging contaminants (PPCPs) are used as effluent quality indicators. A composite indicator for PPCPs performance has been developed through MCDA-DEA model. Indicator obtained allow decision makers implementing concrete actions to assess effluent quality. Results show the improvement capacity of the effluents quality through PPCPs removing.

A dataset of organic pollutants identified and quantified in recycled polyethylene pellets.

Plastics are produced with a staggering array of chemical compounds, with many being known to possess hazardous properties, and others lacking comprehensive hazard data. Furthermore, non-intentionally added substances can contaminate plastics at various stages of their lifecycle, resulting in recycled materials containing an unknown number of chemical compounds at unknown concentrations. While some national and regional regulations exist for permissible concentrations of hazardous chemicals in specific plastic products, less than 1 % of plastics chemicals are subject to international regulation [1]. There are currently no policies mandating transparent reporting of chemicals throughout the plastics value chain or comprehensive monitoring of chemicals in recycled materials. The dataset presented here provides the chemical analysis of 28 samples of recycled High-Density Polyethylene (HDPE) pellets obtained from various regions of the Global South, along with a reference sample of virgin HDPE. The analysis comprises both Target and Non-Targeted Screening approaches, employing Liquid Chromatography-High-Resolution Mass Spectrometry (LC-HRMS) and Gas Chromatography-High-Resolution Mass Spectrometry (GC-HRMS). In total, 491 organic compounds were detected and quantified, with an additional 170 compounds tentatively annotated. These compounds span various classes, including pesticides, pharmaceuticals, industrial chemicals, plastic additives. The results highlight the prevalence of certain chemicals, such as N-ethyl-o-Toluesulfonamide, commonly used in HDPE processing, found in high concentrations. The paper provides a dataset advancing knowledge of the complex chemical composition associated with recycled plastics.

Complex chemical cocktail, containing insecticides diazinon and permethrin, drives acute toxicity to crustaceans in mountain lakes.

Mountain lakes have long been perceived as pristine environments. However, atmospheric deposition of persistent organic pollutants (POPs) have been shown to expose these sensitive ecosystems to chemical pollution. Little is known on how this pollution impacts aquatic ecosystems at high altitudes. We combined passive sampling with liquid and gas chromatography high resolution mass spectrometry (LC- and GC-HRMS) to screen the water of eight lakes in three different regions of the French Pyrenees. In total, we screened for 479 organic chemicals including POPs, polycyclic aromatic hydrocarbons (PAHs), legacy and current-use pesticides, biocides, and musk fragrances. We detected a complex cocktail of 151 individual chemicals and used their toxic unit summation (ΣTU) to assess toxicity for crustaceans and algae. While risks for algae never reached chronic risks, this was always the case for crustaceans. Acute toxic risk thresholds for crustaceans were even exceeded in several of our sites. At sites with acute toxic risk levels (> 0.1 ΣTU) crustaceans were completely absent or showed a low abundance. We conclude that crustaceans were at least partly impacted by the high toxic risks driven by the insecticides diazinon and permethrin. These drugs are widely used to protect livestock from blue tongue disease transmitted by sucking insects, suggesting free roaming livestock as local source. Our results provide important evidence on toxic chemical pollution in relatively remote mountain areas, with important consequences for aquatic mountain ecosystems.

A risk based assessment approach for chemical mixtures from wastewater treatment plant effluents.

In this study, 56 effluent samples from 52 European wastewater treatment plants (WWTPs) were investigated for the occurrence of 499 emerging chemicals (ECs) and their associated potential risks to the environment. The two main objectives were (i) to extend our knowledge on chemicals occurring in treated wastewater, and (ii) to identify and prioritize compounds of concern based on three different risk assessment approaches for the identification of consensus mixture risk drivers of concern. Approaches include (i) PNEC and EQS-based regulatory risk quotients (RQs), (ii) species sensitivity distribution (SSD)-based hazard units (HUs) and (iii) toxic units (TUs) for three biological quality elements (BQEs) algae, crustacean, and fish. For this purpose, solid-phase extracts were analysed with wide-scope chemical target screening via liquid chromatography high-resolution mass spectrometry (LC-HRMS), resulting in 366 detected compounds, with concentrations ranging from < 1 ng/L to > 100 µg/L. The detected chemicals were categorized with respect to critical information relevant for risk assessment and management prioritization including: (1) frequency of occurrence, (2) measured concentrations, (3) use groups, (4) persistence & bioaccumulation, and (5) modes of action. A comprehensive assessment using RQ, HU and TU indicated exceedance of risk thresholds for the majority of effluents with RQ being the most sensitive metric. In total, 299 out of the 366 compounds were identified as mixture risk contributors in one of the approaches, while 32 chemicals were established as consensus mixture risk contributors of high concern, including a high percentage (66%) of pesticides and biocides. For samples which have passed an advanced treatment using ozonation or activated carbon (AC), consistently much lower risks were estimated.

Enabling "lithium-free" manufacturing of pure lithium metal solid-state batteries through in situ plating.

The coupling of solid-state electrolytes with a Li-metal anode and state-of-the-art (SOA) cathode materials is a promising path to develop inherently safe batteries with high energy density (>1000 Wh L-1). However, integrating metallic Li with solid-electrolytes using scalable processes is not only challenging, but also adds extraneous volume since SOA cathodes are fully lithiated. Here we show the potential for "Li-free" battery manufacturing using the Li7La3Zr2O12 (LLZO) electrolyte. We demonstrate that Li-metal anodes >20 µm can be electroplated onto a current collector in situ without LLZO degradation and we propose a model to relate electrochemical and nucleation behavior. A full cell consisting of in situ formed Li, LLZO, and NCA is demonstrated, which exhibits stable cycling over 50 cycles with high Coulombic efficiencies. These findings demonstrate the viability of "Li-free" configurations using LLZO which may guide the design and manufacturing of high energy density solid-state batteries.

Identification of effective parameters for anti-inflammatory concentration in València City's wastewater using fuzzy-set qualitative comparative analysis.

The current literature about pharmaceutical and personal care compounds (PPCPs) focuses on identifying their concentration and toxicological risk both in surface water and in wastewater. However, the influence of urban areas (population ageing, income level, hospitals and others) has not yet been analysed. Knowing how a population (and its facilities) affects PPCPs' presence in wastewater is important to identify the conditions that are responsible for their presence. In this work, the influence of water consumption, population ageing, income level, hospitals and nursing homes on the anti-inflammatory concentration have been analysed. To fill the gap between the quantitative data on PPCPs' concentration and the qualitative reasoning of the influence of urban areas on the anti-inflammatory concentration, the use of fuzzy-set qualitative comparative analysis (fsQCA) is proposed. The fsQCA results are presented as recipes that show the different causal combinations of conditions that explain the presence of anti-inflammatories in wastewater. Using fsQCA for urban wastewater management with the aim of explaining the presence of anti-inflammatories in wastewater treatment plants (WWTPs) is a novelty in the literature. The results obtained here show the influence of water consumption (WATCON), hospitals (HOSP) and population ageing (POPAG) as the main conditions for the anti-inflammatory concentration in Valèncian wastewater. Specifically, these conditions are present in all the recipes obtained with consistency of 99%. Through the results obtained, it would be possible to identify that HOSP are the main facilities that discharge anti-inflammatories into urban wastewater. Hence, the necessity of preventive measures to avoid the anti-inflammatory discharge into water bodies has been showed. Furthermore, under a methodological point of view, this work highlights the eligibility of fsQCA as a wastewater cycle management tool.

The Use of Chromatographic Methods Coupled to Mass Spectrometry for the Study of Emerging Pollutants in the Environment.

The consumption of compounds that improve the human health and wellness is increasing, and as a result, the residues of these substances reach the environment or food chain. For this reason, the scientific community is looking for new analytical methods that are more accurate and can detect the greatest number of compounds in different matrices. This manuscript compares different studies in abiotic and biotic matrices, where most of them (92%) uses Liquid Chromatography to separate the compounds. For the detection, most of the studies for both matrices uses, coupled to the chromatograph, a triple quadrupole mass spectrometer (50%) due to the precision to quantify the concentration of these compounds. Time of Flight (QToF) mass spectrometer is used in 24% of the manuscripts reviewed, in both matrices. It is possible to quantify the concentration of these compounds with the instrument but do not provide as high accuracy as the triple quadrupole.

Monetary valuation of salicylic acid, methylparaben and THCOOH in a Mediterranean coastal wetland through the shadow prices methodology.

The presence of pharmaceutical and personal care products and drugs of abuse (PPCPs) in wastewater treatment plants (WWTPs) indicates discharge of the effluent may not be suitable for the ecological balance of water ecosystems, such as wetlands. These PPCPs degrade water quality, considered as an ecosystem service (ES), provoking serious environmental impacts. Assessing the monetary value of PPCPs can be used as a proxy for environmental status of the ES of water quality (ESWQ). Considering PPCPs as non-desirable outputs of WWTPs, the shadow prices methodology has been implemented using directional distance function to measure the environmental avoided cost of removing salicylic acid (SA), methylparaben (MP), and THCOOH from WWTPs effluents discharged to Albufera Natural Park (Spain). The SA shows the highest shadow price (138.16 €/µg), followed by THCOOH (48.15 €/µg), and MP (30.66 €/µg). These values are interpreted as the environmental cost that would be avoided if SA, MP, and THCOOH were removed from WWTPs effluents. The non-parametric tests show that wastewater treatment technology, together with population equivalent (as a proxy of the size of urban areas) and seasonality are factors that influence shadow prices obtained. The approach used in this study highlights the use of PPCPs as status indicators of ESWQ quantified in monetary units. As a way to synthesize the essential concepts to implement the shadow prices approach, this study proposes a flow diagram to represent the relationship between all the factors involved in this work. The use of shadow prices methodology proves that removing SA, MP, and THCOOH is associated with a measurable improvement in the ESWQ of Albufera Natural Park. The findings of this study will be useful for plant managers in order to make decisions about the removal of PPCPs in WWTPs effluents.

Multi-residue determination of 47 organic compounds in water, soil, sediment and fish-Turia River as case study.

A sensitive and reliable method based on solid-liquid extraction (SLE) using McIlvaine-Na2EDTA buffer (pH=4.5)-methanol and solid-phase extraction (SPE) clean up prior to ultra-high-performance liquid chromatography coupled to tandem mass spectrometry (UHPLC-MS/MS) was applied to determine 47 organic contaminants in fish, soil and sediments. The SPE procedure to clean-up the extracts was also used as extraction method to determine these compounds in water. Recoveries ranged from 38 to 104% for all matrices with RSDs<30%. Limits of Quantification for the target compounds were in the range of 10-50ng/g for soil, 2-40ng/g for sediment, 5-30ng/g for fish and 0.3-26ng/L for water. Furthermore, the proposed method was compared to QuEChERS (widely used for environmental matrices) that involves extraction with buffered acetonitrile (pH 5.5) and dispersive SPE clean-up. The results obtained (recoveries>50% for 36 compounds in front of 9, matrix effect<20% for 31 compounds against 21, and LOQs <25ngg-1 for 38 compounds against 22) indicates that the proposed method is more efficient than QuEChERS, The method was applied to monitoring these compounds along the Turia River. In river waters, Paracetamol (175ngL-1), ibuprofen (153ngL-1) and bisphenol A (41ngL-1) were the compounds most frequently detected while in sediments were vildagliptin (7ngg-1) and metoprolol (31ngg-1) and in fish, bisphenol A (33ngg-1) or sulfamethoxazole (13ngg-1).

Universal method to determine acidic licit and illicit drugs and personal care products in water by liquid chromatography quadrupole time-of-flight.

Pharmaceuticals, illicit drugs and personal care products are emerging contaminants widely distributed in water. Currently, a number of solid-phase extraction (SPE) procedures followed by liquid chromatography tandem mass spectrometry (LC-MS/MS) have been reported. However, target analysis of selected compounds is commonly used whereas other related contaminants present in the sample remain invisible. Carmona et al. [1] described a method for determining 21 emerging contaminants by LC-MS/MS with improved mobile phases. We tested this protocol in combination with high resolution mass spectrometry using a quadrupole time-of-flight (QqTOF) instrument to get a wide non-target screening approach in order to have a broader scope and more practical method for detecting licit and illicit drugs and personal care products than traditional target methods. The essential points in the method are: •The screening capabilities of QqTOF (ABSciex Triple TOF™) are used for detecting and identifying non-target pharmaceuticals and a large number of other emerging contaminants in water.•The quantitative features of the instrument, the Achilles heel of the QqTOF mass spectrometers, are established for few selected compounds.•The method may be applied to identify a large number of emerging contaminants in water. However, pre-validation will be needed to quantify them.

Occurrence of acidic pharmaceuticals and personal care products in Turia River Basin: from waste to drinking water.

The occurrence of 21 acidic pharmaceuticals, including illicit drugs, and personal care products (PPCPs) in waste, surface and drinking water and in sediments of the Turia River Basin (Valencia, Spain) was studied. A liquid chromatography tandem mass spectrometry (LC-MS/MS) method was developed for the determination of these PPCPs with electrospray (ESI) in negative ionization (NI) mode. Ammonium fluoride in the mobile phase improved ionization efficiency by an average increase in peak area of 5 compared to ammonium formate or formic acid. All studied compounds were detected and their concentration was waste water>surface water>drinking water. PPCPs were in waste water treatment plants (WWTPs) influents up to 7.26µgL(-1), dominated by ibuprofen, naproxen and 11-nor-9-carboxy-Δ9-tetrahydrocannabinol (THCOOH). WWTPs were highly effective in removing most of them, with an average removal rate of >90%. PPCPs were still detected in effluents in the 6.72-940ngL(-1) range, with the THCOOH, triclocarban, gemfibrozil and diclofenac as most prevalent. Similarly, diclofenac, gemfibrozil, ibuprofen, naproxen and propylparaben were detected quite frequently from the low ngL(-1) range to 7µgL(-1) in the surface waters of Turia River. Ibuprofen, methylparaben, salicylic acid and tetrahydrocannabinol (THC) were at concentrations up to 0.85ngg(-1) d.w. in sediments. The discharge of WWTP as well as of non-treated waters to this river is a likely explanation for the significant amount of PPCPs detected in surface waters and sediments. Mineral and tap waters also presented significant amounts (approx. 100ngL(-1)) of ibuprofen, naproxen, propylparaben and butylparaben. The occurrence at trace levels of several PPCPs in drinking water raises concerns about possible implications for human health.