Micron-size tire tread particles leach organic compounds at higher rates than centimeter-size particles: Compound identification and profile comparison.

Tire tread particles (TTP) are environmentally prevalent microplastics and generate toxic aqueous leachate. We determined the total carbon and nitrogen leachate concentrations and chemical profiles from micron (∼32 µm) and centimeter (∼1 cm) TTP leachate over 12 days. Dissolved organic carbon (DOC) and total dissolved nitrogen (TDN) were used to measure the concentration of leached compounds. Nontargeted chemical analysis by comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (GC×GC/TOF-MS) was used to compare the chemical profiles of leachates. After leaching for 12 days, DOC was 4.0 times higher in the micron TTP leachate than in the centimeter TTP leachate, and TDN was 2.6 times higher. The total GC×GC/TOF-MS chromatographic feature peak area was 2.9 times greater in the micron TTP leachate than the centimeter TTP leachate, and similarly, the total relative abundance of 54 tentatively identified compounds was 3.3 times greater. We identified frequently measured tire-related chemicals, such as 6PPD, N-cyclohexyl-N'-phenylurea (CPU), and hexa(methoxymethyl)melamine (HMMM), but nearly 50% of detected chemicals were not previously reported in tire literature or lacked toxicity information. Overall, the results demonstrate that smaller TTP have a greater potential to leach chemicals into aquatic systems, but a significant portion of these chemicals are not well-studied and require further risk assessment.

Genotoxicity effects on Geophagus brasiliensis fish exposed to Doce River water after the environmental disaster in the city of Mariana, MG, Brazil / Efeitos da genotoxicidade em peixes da espécie Geophagus brasiliensis expostos a água do Rio Doce após o desastre ambiental na cidade de Marina, MG, Brasil

Abstract The Doce River basin has suffered the largest environmental accident ever occurred in Brazil with the influx of tailings from Fundão and Santarém, belonging to Samarco mining company, due to the disaster in Mariana. A spill between 50 and 60 million m3 of tailings was estimated by the company. According to Samarco, the wastewater was composed mainly of clay, silt and heavy metals like iron, copper and manganese. Thereby, the objective of the present study was evaluated the genotoxic damage in juvenile of Geophagus brasiliensis (Quoy e Gaimard, 1824) exposed to Doce river water before (DRWBA - Doce River water before acident) and after (DRWAA - Doce River water after acident) the influx of tailings from the Germano and Santarém Dam disasters in Mariana, MG, Brazil. For this, 24 individuals of the species G. brasiliensis (obtained on IFES/ALEGRE fish culture) were submitted to a bioassay with three treatments and eight replicates. The treatments were: 1) Control water (water from the urban water supply system, filtered with a 0.45 µm membrane), 2) DRBA and 3) DRAA. After 96 h, these fishes were anesthetized to remove blood for evaluation of genotoxic damage (micronucleus and comet). For the bioassay, a total of 80 L of The Doce River water were collected before the influx of tailings and after the influx and then submitted to metal quantification analysis. Fish exposed to DRWBA and DRWAA treatments showed a significant increase in both the number of erythrocyte micronuclei and the DNA damage index in relation to the control fish; however, they did not present any differences between the two treatments. The results demonstrate that the DRWBA treatment was already genotoxic for the fish, mainly due to dissolved Cu concentrations in the water. The DRWAA treatment probably presented genotoxicity due to the increase in the dissolved fraction and synergistic effects of several metals found in the tailings of the Mariana accident.

Resumo A bacia do Rio Doce sofreu o maior acidente ambiental com o influxo de rejeitos de Fundão e Santarém, pertencentes à empresa de mineração Samarco, devido ao desastre em Mariana. Um derramamento entre 50 e 60 milhões de m3 de rejeitos foi estimado pela empresa. De acordo com a Samarco, o rejeito despejado era composto principalmente de argila, silte e alguns metais pesados como ferro, cobre e manganês. Com isso, o presente estudo teve como objetivo avaliar os danos genotóxicos em juvenis de Geophagus brasilienses expostos a água do rio Doce antes (DRWAA - água do Rio Doce antes do acidente) e depois (DRWBA- água do Rio Doce depois do acidente) da chegada dos rejeitos do rompimento das barragens de Germano e Santarém em Mariana, MG, Brasil. Para isso, 24 indivíduos da espécie G. brasilienses (obtidos na piscicultura do IFES/ALEGRE) foram submetidos a um bioensaio com três tratamentos e oito réplicas. Os tratamentos eram: 1) Controle (com água do abastecimento urbano, filtrada com filtro analítico de 0,45 µm); 2) DRWBA e 3) DRWAA. Após um período de 96 h, esses peixes foram anestesiados para retirada de sangue para avaliação dos danos genotóxicos (micronúcleo e cometa). Para a realização do bioensaio, um total de 80 L de água do Rio Doce foram coletados antes da chegada dos rejeitos e outros 80 L foram coletados depois da chegada dos rejeitos e ambas foram submetidas a análises de quantificação de metal. Os peixes expostos ao DRWBA e ao DRWAA apresentaram um aumento significativo na quantidade de micronúcleos eritrocitários e no índice de danos do DNA em relação aos peixes controle, no entanto não apresentaram diferenças entre si. Os resultados obtidos demonstram que a DRWBA já era genotóxica para os peixes, principalmente, em função das concentrações de Cu dissolvido na água. A DRWAA apresentou genotixicidade, provavelmente, em função do aumento da fração dissolvida e do efeito sinérgico de diversos metais presentes nos rejeitos do acidente de Mariana.

A critical review of synthetic chemicals in surface waters of the US, the EU and China.

There is a wide concern that emerging organic pollutants (EOPs) in surface water could adversely affect human health and wildlife. However, the geographic distribution, exposure pattern and ecological risk of emerging organic pollutants are poorly understood at a global scale. This paper provides a comprehensive survey on the exposure level of EOPs in China, the US and the EU based on the published literature. The hazard level of three categories of EOPs, namely pharmaceuticals and personal care products (PPCPs), pesticides and industrial chemicals was further evaluated by adopting a novel Aquatic HazPi index that jointly accounts for the persistence, bioaccumulation, toxicity and bioactivity. Furthermore, a correlation analysis of land use with the surface water exposure status regarding the synthetic chemicals was conducted. According to the published data reported between 2010 and 2016, the concentration of pesticides in the US was higher than in the EU and China. The concentration of PPCPs in the EU was generally lower than in both the US and China, while the concentration of industrial chemicals in China was higher than in the EU and the US. Among the chemicals whose median concentration in surface water was >10 ng/L, the antiretroviral Efavirenz, the pesticide Fipronil, and octocrylene, an industrial chemical and cosmetic ingredient, were found with the highest aquatic HazPi value. Lastly, the spatial distribution and concentration of hazardous EOPs was shown to depend on local landscape and land usages. Our study provides the first broad overview on the geographic distribution, exposure pattern of hazardous EOPs in the three major economic entities: China, the US and the EU.

Abundance, morphology and chemical composition of microplastics in sand and sediments from a protected coastal area: The Mar Menor lagoon (SE Spain).

This paper presents the abundance and ubiquitous presence of microplastics in a protected coastal zone located in the southeast of Spain: The Mar Menor lagoon, an important tourist destination in this region. Seventeen sampling sites, corresponding to both intertidal and backshore points, were collected during winter 2017 and 2018, being situated in different protected areas according to international, European and Spanish environmental policies. The main objectives of the study were to examine microplastics in both protected and non-protected areas, and to test the importance of local activities on their presence. Northwest samples reported higher average microplastic concentrations than samples collected in the southeastern part of the coastal lagoon, likely due to the extensive use of sludge from wastewater treatment plants besides the fragmentation of low density polyethylene from plastic greenhouses, being microplastic films also higher for northwest than for southeast samples. Moreover, large inter-site differences observed in microplastic concentrations also demonstrated that local activities, mainly tourism and fishery, may play an important role as microplastic sources. The extensive amount of 17 different polymer types identified in this paper, much higher than most reported in similar studies, together with the variety of colors of microplastics most of them in a fragmented form (59.4%) and mainly detected in urban beaches, should be related to the geographical situation of this coastal lagoon, together with enormous environmental passives accumulated over the past 50 years. Only polyvinyl ester resins proved to be statistically higher in non-protected than in protected zones, probably related to their use in manufacturing boat hulls, although sources and pathways for microplastics are always difficult to assess. Measures to avoid microplastic pollution should be taken through educational programs, with also a clear commitment from plastic producers and transformers.

Weight-of-Evidence Approach for Assessing Removal of Metals from the Water Column for Chronic Environmental Hazard Classification.

The United Nations and the European Union have developed guidelines for the assessment of long-term (chronic) chemical environmental hazards. This approach recognizes that these hazards are often related to spillage of chemicals into freshwater environments. The goal of the present study was to examine the concept of metal ion removal from the water column in the context of hazard assessment and classification. We propose a weight-of-evidence approach that assesses several aspects of metals including the intrinsic properties of metals, the rate at which metals bind to particles in the water column and settle, the transformation of metals to nonavailable and nontoxic forms, and the potential for remobilization of metals from sediment. We developed a test method to quantify metal removal in aqueous systems: the extended transformation/dissolution protocol (T/DP-E). The method is based on that of the Organisation for Economic Co-operation and Development (OECD). The key element of the protocol extension is the addition of substrate particles (as found in nature), allowing the removal processes to occur. The present study focused on extending this test to support the assessment of metal removal from aqueous systems, equivalent to the concept of "degradability" for organic chemicals. Although the technical aspects of our proposed method are different from the OECD method for organics, its use for hazard classification is equivalent. Models were developed providing mechanistic insight into processes occurring during the T/DP-E method. Some metals, such as copper, rapidly decreased (within 96 h) under the 70% threshold criterion, whereas others, such as strontium, did not. A variety of method variables were evaluated and optimized to allow for a reproducible, realistic hazard classification method that mimics reasonable worst-case scenarios. We propose that this method be standardized for OECD hazard classification via round robin (ring) testing to ascertain its intra- and interlaboratory variability. Environ Toxicol Chem 2019;38:1839-1849. © 2019 SETAC.

Preliminary study of the source apportionment and diversity of microplastics: Taking floating microplastics in the South China Sea as an example.

At present, the study of microplastic sources is in a relatively preliminary stage due to the complexity of microplastic features in the environment. Based on a literature review, we developed a source-specific classification system for the quantitative analysis of microplastic sources. The classification system includes ten types of microplastics based on morphology and composition and can identify their main sources and the associated probabilities. To reflect the complexity of types and sources in the regional combination of microplastics, we first propose a microplastic diversity index (D1-D'(MP)). We use the South China Sea as an example to carry out quantitative source analysis and calculate the diversity index. Eight types of microplastics were found, mainly consisting of maritime coatings (type "Gran_coat") (33.0%) and synthetic fibers (type "Fib_thin") (29.6%). We also found that the diversity increased with offshore distance. In addition, we partitioned surface microplastics globally according to a two-dimensional microplastic abundance-diversity index. We believe that these indicators can effectively reflect pollution status and ultimately lead to different types of control measures. In the future, additional indicators for the characterization of microplastics must be included in the classification system to establish a one-to-one source analysis system for microplastic characteristics and source apportionment. In general, our study may provide new insights into the establishment of more accurate and quantitative source apportionment techniques and effective pollution control.

Target site model: Predicting mode of action and aquatic organism acute toxicity using Abraham parameters and feature-weighted k-nearest neighbors classification.

A database of 1480 chemicals with 47 associated modes of action compiled from the literature encompasses a wide range of chemical classes (alkanes, polycyclic aromatic hydrocarbons, pesticides, and polar compounds) and includes toxicity data for 79 different aquatic genera. The data were split into a calibration group and a validation group (80/20) to apply k-nearest neighbors (k-NN) methodology to predict the toxic mode of action for the compound. Other approaches were tested (support vector machines and linear discriminant analysis) as well as variations in the k-NN technique (distance weighting, feature weighting). Best-prediction results were found with k = 3, in a voting platform with optimized feature weighting. Using the predicted mode of action, the appropriate polyparameter target site model for that mode of action is applied to calculate the 50% lethal concentration (LC50). Predicted LC50s for the validation database resulted in a root-mean squared error (RMSE) of 0.752. This can be compared to an RMSE of 0.655 for the same validation set using the reference mode of action labels. The complete database resulted in an RMSE of 0.793 for reference mode of action labels. This confirms that the classification model has sufficient accuracy for predicting the mode of action and for determining toxicity using the target site model. Environ Toxicol Chem 2019;38:375-386. © 2018 SETAC.

Prioritizing anthropogenic chemicals in drinking water and sources through combined use of mass spectrometry and ToxCast toxicity data.

Advancements in high-resolution mass spectrometry based methods have enabled a shift from pure target analysis to target, suspect and non-target screening analyses to detect chemicals in water samples. The multitude of suspect chemicals thereby detected needs to be prioritized for further identification, prior to health risk assessment and potential inclusion into monitoring programs. Here, we compare prioritization of chemicals in Dutch water samples based on relative intensities only to prioritization including hazard information based on high-throughput in vitro toxicity data. Over 1000 suspects detected in sewage treatment plant effluent, surface water, groundwater and drinking water samples were ranked based on their relative intensities. Toxicity data availability and density in the ToxCast database were determined and visualized for these suspects, also in regard to water relevant mechanisms of toxicity. More than 500 suspects could be ranked using occurrence/hazard ratios based on more than 1000 different assay endpoints. The comparison showed that different prioritization strategies resulted in significantly different ranking, with only 2 suspects prioritized based on occurrence among the top 20 in the hazard ranking. We therefore propose a novel scheme that integrates both exposure and hazard data, and efficiently prioritizes which features need to be confidently identified first.

Microplastic ingestion ubiquitous in marine turtles.

Despite concerns regarding the environmental impacts of microplastics, knowledge of the incidence and levels of synthetic particles in large marine vertebrates is lacking. Here, we utilize an optimized enzymatic digestion methodology, previously developed for zooplankton, to explore whether synthetic particles could be isolated from marine turtle ingesta. We report the presence of synthetic particles in every turtle subjected to investigation (n = 102) which included individuals from all seven species of marine turtle, sampled from three ocean basins (Atlantic [ATL]: n = 30, four species; Mediterranean (MED): n = 56, two species; Pacific (PAC): n = 16, five species). Most particles (n = 811) were fibres (ATL: 77.1% MED: 85.3% PAC: 64.8%) with blue and black being the dominant colours. In lesser quantities were fragments (ATL: 22.9%: MED: 14.7% PAC: 20.2%) and microbeads (4.8%; PAC only; to our knowledge the first isolation of microbeads from marine megavertebrates). Fourier transform infrared spectroscopy (FT-IR) of a subsample of particles (n = 169) showed a range of synthetic materials such as elastomers (MED: 61.2%; PAC: 3.4%), thermoplastics (ATL: 36.8%: MED: 20.7% PAC: 27.7%) and synthetic regenerated cellulosic fibres (SRCF; ATL: 63.2%: MED: 5.8% PAC: 68.9%). Synthetic particles being isolated from species occupying different trophic levels suggest the possibility of multiple ingestion pathways. These include exposure from polluted seawater and sediments and/or additional trophic transfer from contaminated prey/forage items. We assess the likelihood that microplastic ingestion presents a significant conservation problem at current levels compared to other anthropogenic threats.

Genotoxicity effects on Geophagus brasiliensis fish exposed to Doce River water after the environmental disaster in the city of Mariana, MG, Brazil.

The Doce River basin has suffered the largest environmental accident ever occurred in Brazil with the influx of tailings from Fundão and Santarém, belonging to Samarco mining company, due to the disaster in Mariana. A spill between 50 and 60 million m3 of tailings was estimated by the company. According to Samarco, the wastewater was composed mainly of clay, silt and heavy metals like iron, copper and manganese. Thereby, the objective of the present study was evaluated the genotoxic damage in juvenile of Geophagus brasiliensis (Quoy e Gaimard, 1824) exposed to Doce river water before (DRWBA - Doce River water before acident) and after (DRWAA - Doce River water after acident) the influx of tailings from the Germano and Santarém Dam disasters in Mariana, MG, Brazil. For this, 24 individuals of the species G. brasiliensis (obtained on IFES/ALEGRE fish culture) were submitted to a bioassay with three treatments and eight replicates. The treatments were: 1) Control water (water from the urban water supply system, filtered with a 0.45 µm membrane), 2) DRBA and 3) DRAA. After 96 h, these fishes were anesthetized to remove blood for evaluation of genotoxic damage (micronucleus and comet). For the bioassay, a total of 80 L of The Doce River water were collected before the influx of tailings and after the influx and then submitted to metal quantification analysis. Fish exposed to DRWBA and DRWAA treatments showed a significant increase in both the number of erythrocyte micronuclei and the DNA damage index in relation to the control fish; however, they did not present any differences between the two treatments. The results demonstrate that the DRWBA treatment was already genotoxic for the fish, mainly due to dissolved Cu concentrations in the water. The DRWAA treatment probably presented genotoxicity due to the increase in the dissolved fraction and synergistic effects of several metals found in the tailings of the Mariana accident.

Toxicological risk assessment and prioritization of drinking water relevant contaminants of emerging concern.

Toxicological risk assessment of contaminants of emerging concern (CEC) in (sources of) drinking water is required to identify potential health risks and prioritize chemicals for abatement or monitoring. In such assessments, concentrations of chemicals in drinking water or sources are compared to either (i) health-based (statutory) drinking water guideline values, (ii) provisional guideline values based on recent toxicity data in absence of drinking water guidelines, or (iii) generic drinking water target values in absence of toxicity data. Here, we performed a toxicological risk assessment for 163 CEC that were selected as relevant for drinking water. This relevance was based on their presence in drinking water and/or groundwater and surface water sources in downstream parts of the Rhine and Meuse, in combination with concentration levels and physicochemical properties. Statutory and provisional drinking water guideline values could be derived from publically available toxicological information for 142 of the CEC. Based on measured concentrations it was concluded that the majority of substances do not occur in concentrations which individually pose an appreciable human health risk. A health concern could however not be excluded for vinylchloride, trichloroethene, bromodichloromethane, aniline, phenol, 2-chlorobenzenamine, mevinphos, 1,4-dioxane, and nitrolotriacetic acid. For part of the selected substances, toxicological risk assessment for drinking water could not be performed since either toxicity data (hazard) or drinking water concentrations (exposure) were lacking. In absence of toxicity data, the Threshold of Toxicological Concern (TTC) approach can be applied for screening level risk assessment. The toxicological information on the selected substances was used to evaluate whether drinking water target values based on existing TTC levels are sufficiently protective for drinking water relevant CEC. Generic drinking water target levels of 37 µg/L for Cramer class I substances and 4 µg/L for Cramer class III substances in drinking water were derived based on these CEC. These levels are in line with previously reported generic drinking water target levels based on original TTC values and are shown to be protective for health effects of the majority of contaminants of emerging concern evaluated in the present study. Since the human health impact of many chemicals appearing in the water cycle has been studied insufficiently, generic drinking water target levels are useful for early warning and prioritization of CEC with unknown toxicity in drinking water and its sources for future monitoring.

Proposal for MSW contaminant classification applied to a tropical aquifer.

Groundwater is a natural resource exploited worldwide causing danger due to the lixiviation of waste deposited, which presents high potential degradation. Internationally, regulation aims for the maintenance of the quality of this resource. But the local lithology, mainly in countries with tropical weather, was not considered. This paper has an objective to propose two methodologies of contaminant identification of municipal solid waste (MSW) considering the Brazilian regulation, the local lithology and the temporal aspect. The study site is located in the midwest of São Paulo, at the Marília Formation, Bauru Aquifer, which presents sandstone rich in calcite. At first, the historic monitoring data accumulated between 2002 and 2015 were statistically organized. Then, methodologies of classification of major constituents and contamination method were developed. After these analyses, the compounds that possibly cause anomaly in the local environment are Al, As, Ba, Ca, Cd, Co, Cr, Cu, phosphatic, nitrogenous, and sulfated compounds, Fe, K, Mn, Ni, and Pb. Some of these have lithogenic genesis typical of tropical environment, and others come from the disposed waste. Despite different approaches, both methods demonstrate efficiency in identifying the pollutants presenting distinctions among themselves in conjunction with actual local regulation and the lithogenic source of certain compounds.

Prioritization of substances for national ambient monitoring of sediment in Switzerland.

In Switzerland, surface waters are protected by the Swiss Water Protection Ordinance (OEaux; OFEV 1998), which stipulates that the water quality shall be such that the water, suspended matter, and sediments contain no persistent synthetic substances to ensure the protection of aquatic life. Local agencies are in charge of water quality monitoring, using a set of validated methods. Several lists of priority substances have been developed for aquatic microcontaminants for surface water monitoring but not for sediments. Some local agencies have established sediment monitoring programs, but to date, there exists no harmonized methodology for sediment quality assessment in Switzerland. Within the main goal of developing and providing methodologies for monitoring sediment quality in Switzerland, a screening was performed to help prioritize sediment-relevant microcontaminants. The screening approach was largely based on the NORMAN (network of reference laboratories, research centers, and related organizations for monitoring emerging environmental substances) system and was carried out in four steps: (1) identification of candidate substances, (2) selection of sediment relevant substances, (3) classification of substances into different categories based on identified data gaps and envisaged actions, and (4) ranking within each action category. This paper describes the methodology used in the prioritization process for sediment-relevant substances and provides recommendations for monitoring strategies in Switzerland.

A new four-step hierarchy method for combined assessment of groundwater quality and pollution.

A new four-step hierarchy method was constructed and applied to evaluate the groundwater quality and pollution of the Dagujia River Basin. The assessment index system is divided into four types: field test indices, common inorganic chemical indices, inorganic toxicology indices, and trace organic indices. Background values of common inorganic chemical indices and inorganic toxicology indices were estimated with the cumulative-probability curve method, and the results showed that the background values of Mg2+ (51.1 mg L-1), total hardness (TH) (509.4 mg L-1), and NO3- (182.4 mg L-1) are all higher than the corresponding grade III values of Quality Standard for Groundwater, indicating that they were poor indicators and therefore were not included in the groundwater quality assessment. The quality assessment results displayed that the field test indices were mainly classified as grade II, accounting for 60.87% of wells sampled. The indices of common inorganic chemical and inorganic toxicology were both mostly in the range of grade III, whereas the trace organic indices were predominantly classified as grade I. The variabilities and excess ratios of the indices were also calculated and evaluated. Spatial distributions showed that the groundwater with poor quality indices was mainly located in the northeast of the basin, which was well-connected with seawater intrusion. Additionally, the pollution assessment revealed that groundwater in well 44 was classified as "moderately polluted," wells 5 and 8 were "lightly polluted," and other wells were classified as "unpolluted."

Probability of misclassifying biological elements in surface waters.

Measurement uncertainties are inherent to assessment of biological indices of water bodies. The effect of these uncertainties on the probability of misclassification of ecological status is the subject of this paper. Four Monte-Carlo (M-C) models were applied to simulate the occurrence of random errors in the measurements of metrics corresponding to four biological elements of surface waters: macrophytes, phytoplankton, phytobenthos, and benthic macroinvertebrates. Long series of error-prone measurement values of these metrics, generated by M-C models, were used to identify cases in which values of any of the four biological indices lay outside of the "true" water body class, i.e., outside the class assigned from the actual physical measurements. Fraction of such cases in the M-C generated series was used to estimate the probability of misclassification. The method is particularly useful for estimating the probability of misclassification of the ecological status of surface water bodies in the case of short sequences of measurements of biological indices. The results of the Monte-Carlo simulations show a relatively high sensitivity of this probability to measurement errors of the river macrophyte index (MIR) and high robustness to measurement errors of the benthic macroinvertebrate index (MMI). The proposed method of using Monte-Carlo models to estimate the probability of misclassification has significant potential for assessing the uncertainty of water body status reported to the EC by the EU member countries according to WFD. The method can be readily applied also in risk assessment of water management decisions before adopting the status dependent corrective actions.

Characteristics and sources of anthropogenic and biogenic hydrocarbons in sediments from the coast of Qatar.

Surface sediment samples from the coastal zone of Qatar were collected and analyzed to determine the characteristics, and sources of anthropogenic and biogenic hydrocarbons. The main compounds in these surface sediments included n-alkanes, methyl n-alkanoates, diterpenoids, hopanes, steranes, phthalate esters, polycyclic aromatic hydrocarbons (PAHs) and unresolved complex mixture (UCM). Their total concentrations ranged from 18.7±3.7-81.1±7.5ng/g (3.7±0.6-10.4±4.8%) for n-alkanes, 8.3±2.3-51±3.4ng/g (3.0±2.0-5.6±2.0%) for methyl n-alkanoates, 1.8±0.1-10.5±1.0ng/g (1.0±0.5-0.4±0.1%) for diterpenoids, 0.0-79.3±7.4ng/g (0.0-7.9±0.6%) for hopanes, 0.0-32.9±7.9ng/g (0.0-6.5±1.0%) for steranes, 0.7±0.1-36.3±3.4ng/g (0.1±0.1-1.9±3.4%) for phthalates, 0.30±0.2-7.8±0.7ng/g (0.02±0.04-0.42±0.72%) for PAHs, and 38±9-609±57ng/g (38.5±13.4-56.5±13.4%) for UCM. The major sources of these lipids were anthropogenic petroleum residues and plasticizers (80-89%), with lesser amounts from natural higher plants and microbial residues (11-20%). Petroleum residues and plasticizer inputs to the coastal sediments of Qatar likely affect the marine ecosystems and associated species groups as well as shallow coastal nursery and spawning areas.

Risk-based prioritization method for the classification of groundwater pesticide pollution from agricultural regions.

Agricultural regions are a significant source of groundwater pesticide pollution. To ensure that agricultural regions with a significantly high risk of groundwater pesticide contamination are properly managed, a risk-based ranking method related to groundwater pesticide contamination is needed. In the present paper, a risk-based prioritization method for the classification of groundwater pesticide pollution from agricultural regions was established. The method encompasses 3 phases, including indicator selection, characterization, and classification. In the risk ranking index system employed here, 17 indicators involving the physicochemical properties, environmental behavior characteristics, pesticide application methods, and inherent vulnerability of groundwater in the agricultural region were selected. The boundary of each indicator was determined using K-means cluster analysis based on a survey of a typical agricultural region and the physical and chemical properties of 300 typical pesticides. The total risk characterization was calculated by multiplying the risk value of each indicator, which could effectively avoid the subjectivity of index weight calculation and identify the main factors associated with the risk. The results indicated that the risk for groundwater pesticide contamination from agriculture in a region could be ranked into 4 classes from low to high risk. This method was applied to an agricultural region in Jiangsu Province, China, and it showed that this region had a relatively high risk for groundwater contamination from pesticides, and that the pesticide application method was the primary factor contributing to the relatively high risk. The risk ranking method was determined to be feasible, valid, and able to provide reference data related to the risk management of groundwater pesticide pollution from agricultural regions. Integr Environ Assess Manag 2017;13:1052-1059. © 2017 SETAC.

Ranking REACH registered neutral, ionizable and ionic organic chemicals based on their aquatic persistency and mobility.

The contaminants that have the greatest chances of appearing in drinking water are those that are mobile enough in the aquatic environment to enter drinking water sources and persistent enough to survive treatment processes. Herein a screening procedure to rank neutral, ionizable and ionic organic compounds for being persistent and mobile organic compounds (PMOCs) is presented and applied to the list of industrial substances registered under the EU REACH legislation as of December 2014. This comprised 5155 identifiable, unique organic structures. The minimum cut-off criteria considered for PMOC classification herein are a freshwater half-life >40 days, which is consistent with the REACH definition of freshwater persistency, and a log Doc < 4.5 between pH 4-10 (where Doc is the organic carbon-water distribution coefficient). Experimental data were given the highest priority, followed by data from an array of available quantitative structure-activity relationships (QSARs), and as a third resort, an original Iterative Fragment Selection (IFS) QSAR. In total, 52% of the unique REACH structures made the minimum criteria to be considered a PMOC, and 21% achieved the highest PMOC ranking (half-life > 40 days, log Doc < 1.0 between pH 4-10). Only 9% of neutral substances received the highest PMOC ranking, compared to 30% of ionizable compounds and 44% of ionic compounds. Predicted hydrolysis products for all REACH parents (contributing 5043 additional structures) were found to have higher PMOC rankings than their parents, due to increased mobility but not persistence. The fewest experimental data available were for ionic compounds; therefore, their ranking is more uncertain than neutral and ionizable compounds. The most sensitive parameter for the PMOC ranking was freshwater persistency, which was also the parameter that QSARs performed the most poorly at predicting. Several prioritized drinking water contaminants in the EU and USA, and other contaminants of concern, were identified as PMOCs. This identification and ranking procedure for PMOCs can be part of a strategy to better identify contaminants that pose a threat to drinking water sources.

Prioritization of pharmaceuticals based on risks to aquatic environments in Kazakhstan.

Over the last 20 years, there has been increasing interest in the occurrence, fate, effects, and risk of pharmaceuticals in the natural environment. However, we still have only limited or no data on ecotoxicological risks of many of the active pharmaceutical ingredients (APIs) currently in use. This is partly due to the fact that the environmental assessment of an API is an expensive, time-consuming, and complicated process. Prioritization methodologies, which aim to identify APIs of most concern in a particular situation, could therefore be invaluable in focusing experimental work on APIs that really matter. The majority of approaches for prioritizing APIs require annual pharmaceutical usage data. These methods cannot therefore be applied to countries, such as Kazakhstan, that have very limited data on API usage. The present paper therefore offers an approach for prioritizing APIs in surface waters in information-poor regions such as Kazakhstan. Initially data were collected on the number of products and active ingredients for different therapeutic classes in use in Kazakhstan and on the typical doses. These data were then used alongside simple exposure modeling approaches to estimate exposure indices for active ingredients (about 240 APIs) in surface waters in the country. Ecotoxicological effects data were obtained from the literature or predicted. Risk quotients were then calculated for each pharmaceutical based on the exposure and the substances were ranked in order of risk quotient. Highest exposure indices were obtained for benzylpenicillin, metronidazole, sulbactam, ceftriaxone, and sulfamethoxazole. The highest risk was estimated for amoxicillin, clarithromycin, azithromycin, ketoconazole, and benzylpenicillin. In the future, the approach could be employed in other regions where usage information is limited. Integr Environ Assess Manag 2017;13:832-839. © 2017 SETAC.

Simultaneous in-vial acetylation solid-phase microextraction followed by gas chromatography tandem mass spectrometry for the analysis of multiclass organic UV filters in water.

UV filters are a class of emerging contaminants that are widely used in personal care products (PCPs) and that can be detected at low concentrations in the aquatic environment (ngL-1). Sensitive modern analytical methods are then mandatory to accurately analyze them. A methodology based on solid-phase-microextraction (SPME), considered as a 'Green Chemistry' technique, followed by gas chromatography-tandem mass spectrometry (GC-MS/MS) has been developed for the simultaneous analysis of 14 UV filters of different chemical nature in environmental and recreational waters. In-vial low-cost derivatization was carried out to improve chromatographic performance of phenolic compounds. The extraction parameters (fiber coating, extraction mode, and salt addition) were optimized by means of experimental designs in order to achieve reliable conditions. Finally, the SPME-GC-MS/MS method was validated in terms of linearity, accuracy and precision with LODs in the low ngL-1 level. Its application to the analysis of 28 different samples including sea, river, spa, swimming pool, and aquapark waters, enabled the detection of 11 target UV filters at concentration levels up to 540µgL-1, highlighting the presence of OCR in all analyzed samples and of 2EHMC (proposed to be considered as priority pollutant) in 79% of them.