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This Feature Article reports general and more specific aspects about microplastic (MP) contamination in continental and marine waters as well as in terrestrial environment. It describes a critical vision of the analytical methods commonly used for MP characterization and determination, including recommendations on green analytical chemistry (GAC) protocols. Insights into MPs as sorption materials and carriers for a variety of emerging contaminants like pharmaceuticals and pesticides are highlighted. Risks to biota living in aquatic and terrestrial environments and human-health-related effects with specific examples of surface and groundwater used for drinking water sources near contaminated sites like landfills are summarized. Lastly, sustainable solutions for how to improve the analysis and comparison of MP detection at the global level is given, including the need for standardized analytical protocols as well as the performance of additional interlaboratory exercises. Additional recommendations include a global database on MP levels made available to all authors to better compare their data qualitatively with that previously published. Policy and remediation actions on how to reduce and mitigate MP pollution may include different types of actions like an improved waste management and reuse system, the development of bioplastics and new plastic materials, as well as legally binding additional funding to cope with increasing plastic pollution at the global scale. [ABSTRACT FROM AUTHOR]

Micro(nano)plastics (MNPs) are pervasive pollutants posing significant environmental and health risks. Selecting appropriate sentinel species to assess MNPs in terrestrial and aquatic environments involves considering factors such as species behavior, habitat, exposure pathways, and the feasibility of sampling. For these reasons, it was imperative to launch a virtual special issue (VSI) in Ecological Indicators. This editorial summarizes the contributions submitted to the VSI, which invited research on bioindicators of MNPs, including sampling protocols, monitoring strategies, and analytical methods, to advance our understanding and management of plastic pollution. The VSI received a total of 12 contributions from four countries, with a significant majority originating from Italy. To present the contributions, we have organized the sections into original articles and reviews. The original articles are further divided into sections on the occurrence of MNPs in biotic and abiotic compartments, the selection of bioindicators, and the effects and risk assessment of MPs. The reviews are categorized based on their focus on aquatic and terrestrial ecosystems. Future ecotoxicology studies should select bioindicators based on exposure to MNPs, conservation status, ecological roles, and human consumption. [ABSTRACT FROM AUTHOR]

Despite their remote locations, high-mountain lakes located in the Alps are vulnerable to chemical pollution. This discussion explores the important aspects of these lakes as repositories of Persistent Organic Pollutants (POPs) and Contaminants of Emerging Concern (CECs), elucidating their sources and implications for both the environment and human health. In terms of the presence of POPs in high-altitude lakes of the Alps, 14 studies have been identified examining the occurrence of polychlorinated biphenyls, dichlorodiphenyltrichloroethane an its metabolites, polybrominated diphenyl ethers, and polycyclic aromatic hydrocarbons. The bulk of research on POPs in high-mountain lakes is concentrated in the Italian Alps (63%), followed by Switzerland (22%), Austria (12%), and France (3%), respectively. Sediment is predominantly investigated (65%), followed by fish (33%) and water (2%). Similarly, in relation to the presence of CECs in high-mountain lakes of the Alps, six studies have been identified investigating the occurrence of musks, perfluorinated compounds, and microplastics. Investigations into CECs predominantly occur in Switzerland (42%), France (33%), and Italy (25%), with fish samples (muscle and liver) being the primary focus (46%), followed by sediment (17%) and water (17%). Other compartments like zooplankton, frog/tadpoles, and snow remain less explored. The discussion also shed light on various pathways through which pollutants reach these remote landscapes, including atmospheric transport, glacial meltwater, and human activities. Protecting these pristine peaks demands concerted efforts encompassing ongoing research, vigilant monitoring, and dedicated conservation initiatives. [Display omitted] • High-mountain lakes located in the Alps are vulnerable to chemical pollution. • The bulk of research on POPs in high-mountain lakes is concentrated in the Italian Alps. • Investigations into CECs predominantly occur in Switzerland. • Sediment is predominantly investigated for POPs while fish for CECs. • Preserving high-mountain lakes needs research, monitoring and conservation measures. [ABSTRACT FROM AUTHOR]

Microplastics (MPs) are acknowledged as emerging contaminants that pose a substantial threat to the environment. The adverse impacts of MP pollution extend across marine, freshwater, and terrestrial ecosystems, covering regions from the Tropics to the Poles. Although our comprehension of MP behavior has progressed in recent years, it is still difficult to predict exposure hotspots or exposure scenarios. Despite a noteworthy increase in data concerning MP occurrence in different environmental compartments and species, there is a noticeable scarcity of experimental data on MP uptake, accumulation, and effects. This Virtual Special Issue (VSI) received a total of 19 contributions from 11 countries, with a significant majority originating from Italy, India, Spain, and China. These contributions were categorized into three main themes: the occurrence and effects of MPs on aquatic and terrestrial organisms, the presence of chemical additives in plastics, and review articles summarizing previously published research on MPs. [ABSTRACT FROM AUTHOR]

Abstract Fish samples of different species (i.e. rainbow trout (Onchorhynchus mykiss), barbel (Barbus barbus) and European chub (Squalius cephalus)) were collected from the Sava River Basin for a preliminary investigation of the levels of PCDD/Fs, PCBs, PBDEs and PFAS as a whole. Concentrations of PCDD/Fs, in terms of pg WHO-TEQ/g ww, were below the maximum limit established at the Commission Regulation (EU) No 1259/2011. On the contrary, when DL-PCBs were also included, levels increase up to 11.7 pg WHO-TEQ PCDD/Fs+DL-PCBs /g ww in a particular case, with two samples out of a total of ten exceeding the maximum set at this EU Regulation and the EQS established at the European Directive regarding priority substances in the field of water policy (0.0065 ng WHO-TEQ PCDD/Fs+DL-PCBs /g ww). A similar trend was also observed for NDL-PCBs, whit the same two samples, from the lower stretch of the river basin, exceeding the maximum limit allowed at the EU Regulation (125 ng/g ww). For PBDEs, levels found in all the samples exceeded the EQS (0.0085 ng/g ww) up to more than a thousand times and 40% of the samples presented PFOS values above the EQS. Data from this study were compared to values reported at the literature for fish from other geographical areas. Graphical abstract Unlabelled Image Highlights • Fish samples from the lower stretch of the river showed PCDD/F+DL-PCB levels above the EQS. • PCDD/Fs+DL-PCBs and NDL-PCBs exceeded the maximum levels for fish (as food product) in 20% of the samples. • PBDE concentrations exceed the EQS up to more than a thousand times. • Data suggest that anthropogenic impact is observed in the Sava River Basin. [ABSTRACT FROM AUTHOR]

Microplastics (MPs) are in all environmental compartments, including atmosphere, terrestrial, and aquatic environments as well as in marine organisms, foods, drinking water, and indoor and outdoor environments. MPs can enter the human body through the food chain and contaminated environment. Ingestion, inhalation, and dermal contact are the routes of their entry into the human body. Recent studies reporting the detection of MPs within the human body have raised concern among the scientific community as the knowledge about human exposure is still very limited and their impact on health is not well-understood yet. In this review article, we briefly cover the reports evidencing MP detection within the human body, e.g., stool, placenta, lungs, liver, sputum, breast milk, and blood. A concise synopsis of sample preparation and analysis of such human matrices is also provided. This article also presents a summary of the effect of MPs on human cell lines and human health. [Display omitted] • Ingestion and inhalation are the main routes for exposure to MPs. • MPs have been found in placenta, feces, colon, lungs, sputum, liver, breast milk, and blood. • Utmost care is required while sample treatment and analysis to avoid contamination. • Some diseases appear to correlate with the presence of MPs. • Human cell line studies and health effects of MPs are briefly presented. [ABSTRACT FROM AUTHOR]

This study evaluates the current situation regarding PBDE and HBCD levels in different river fish species. We collected published data in the last five years in different countries around the world. These levels of pollution were compared with Environmental Quality Standards (EQS) for biota established by the European Directive in the field of water policy. Although HBCD situation is not critical, with only some values exceeding the limit about 5 times, the PBDE levels clearly exceeded the established EQS, with 25% of fish samples exceeding up to ten thousand times. Although it is expected that levels of pollution by PBDEs will decrease over the next years due to the ban in their use, it is not expected that this decrease will reach the EQS values by the end of 2021, as demanded by the European Directive. Hence, it is necessary to implement new strategies in order to minimize the impact of PBDEs on the environment. [ABSTRACT FROM AUTHOR]

Given the rapid advancement of microplastic (MP) contamination studies, we present a comprehensive review in which the studies that identified and characterized MPs in human biological samples, indexed in consulted databases until December 23, 2022, are presented, evaluated, and discussed. Although the studies included in this review report important findings on the presence of MPs in several human biological samples, our know-how in this area still needs to be improved. Thus, we discuss in this review the hot spots and analytical and procedural challenges to be overcome, including the need to expand international collaboration networks, improve volunteer recruitment criteria, and the procedures adopted in the collection and processing stages of samples, detection, and polymeric identification of MPs. Furthermore, we reinforce the importance of adopting more adequate quality assurance/quality control (QA/QC) procedures to generate more robust and reliable data on human contamination by MPs. [Display omitted] • Current studies reveal that our knowledge about MP in humans is limited. • Establishment of collaboration networks is necessary to expand studies on the subject. • Analysis on the collection and processing of human samples is presented in this review. • QA/QC is a critical component in MP studies in human samples. • Suggestions for improving studies related to MPs in human samples are provided. [ABSTRACT FROM AUTHOR]

Ho Chi Minh (HCM) City is the most important urban region of Vietnam, Southeast Asia. In recent times, the quantity of electronic waste (e-waste) has been growing by several thousand tonnes every year. In this research, some of the existing and developing technologies being employed for the recycling of e-waste have been reviewed. Accordingly, the paper has been divided into three sections namely, e-waste treatment technologies in Ho Chi Minh City, the effect of heavy metals on human health and the extraction of metals from e-waste using pyrolysis, hydrometallurgy, bioleaching, mechanical, and air classifier methods, respectively. The extraction of precious metals and heavy metals such as Cd, Cr, Pb, Hg, Cu, Se, and Zn from e-waste can be hazardous to human health. For example, lead causes hazards to the central and peripheral nervous systems, blood system and kidneys; copper causes liver damage; chronic exposure to cadmium ends up causing lung cancer and kidney damage, and mercury can cause brain damage. Thus, this study examines the key findings of many research and review articles published in the field of e-waste management and the health impacts of metal pollution. • The extraction of some precious metals such as Au, Pt and Ag can be performed. • Some of the existing and developing technologies being employed. • E-waste using pyrolysis, hydrometallurgy, biometallurgy, mechanical & air classifier. • Metals cause hazards to the central nervous systems, blood system and kidneys. [ABSTRACT FROM AUTHOR]

Quantitative measurement of drug consumption biomarkers in wastewater can provide objective information on community drug use patterns and trends. This study presents the measurement of alcohol consumption in 20 cities across 11 countries through the use of wastewater-based epidemiology (WBE), and reports the application of these data for the risk assessment of alcohol on a population scale using the margin of exposure (MOE) approach. Raw 24-h composite wastewater samples were collected over a one-week period from 20 cities following a common protocol. For each sample a specific and stable alcohol consumption biomarker, ethyl sulfate (EtS) was determined by liquid chromatography coupled to tandem mass spectrometry. The EtS concentrations were used for estimation of per capita alcohol consumption in each city, which was further compared with international reports and applied for risk assessment by MOE. The average per capita consumption in 20 cities ranged between 6.4 and 44.3 L/day/1000 inhabitants. An increase in alcohol consumption during the weekend occurred in all cities, however the level of this increase was found to differ. In contrast to conventional data (sales statistics and interviews), WBE revealed geographical differences in the level and pattern of actual alcohol consumption at an inter-city level. All the sampled cities were in the “high risk” category (MOE < 10) and the average MOE for the whole population studied was 2.5. These results allowed direct comparisons of alcohol consumption levels, patterns and risks among the cities. This study shows that WBE can provide timely and complementary information on alcohol use and alcohol associated risks in terms of exposure at the community level. [ABSTRACT FROM AUTHOR]

It is crucial to study the presence of transformation products (TPs) of emerging contaminants that can be potentially found in the environment after biological or chemical degradation. This review focuses on the potential and shortcomings of high-resolution mass spectrometry (HRMS) to identify these TPs, with emphasis on recent developments in mass analyzers, data evaluation, and compound identification workflows and applications. Advances in HRMS technologies, including direct introduction or in-line chromatographic separation modes, ionization techniques, mass analyzers, and detection methods, have led to powerful tools to assess the molecular changes and the opening of new horizons to identify unknown molecules. Advances in HRMS pertaining to the generation of analytical data for the main methods to identify TPs, including nontargeted and targeted approaches as they are applied to elucidate the structure of TPs, are also discussed. [ABSTRACT FROM AUTHOR]

Groundwater constitutes the main source of public drinking water supply in many regions. Thus, the contamination of groundwater resources by organic chemicals is a matter of growing concern because of its potential effects on public health. The present manuscript compiles the most recent works related to the study of synthetic organic compounds (SOCs) in groundwater, with special focus on the occurrence of contaminants not or barely covered by previously published reviews, e.g., pesticide and pharmaceutical transformation products, lifestyle products, and industrial chemicals such as corrosion inhibitors, brominated and organophosphate flame retardants, plasticizers, volatile organic compounds (VOCs), and polycyclic aromatic hydrocarbons (PAHs). Moreover, the main challenges in managed aquifer recharge, i.e., reclaimed water injection and infiltration, and riverbank filtration, regarding natural attenuation of organic micropollutants are discussed, and insights into the future chemical quality of groundwater are provided. [ABSTRACT FROM AUTHOR]

Governments all over the world are intensifying their efforts to improve food safety, which are coming in response to an increasing number of food-safety problems and rising consumer concerns. In addition, the variety of toxicant residues in food is increasing continuously as a consequence of industrial development, new agricultural practices, environmental pollution and climate change. This article reviews the new analytical approaches [e.g., coupled chromatography techniques, the use of new extraction materials, multi-dimensional liquid chromatography and novel mass spectrometric methods (e.g., ambient ionization techniques for food analysis)]. We pay special emphasis to reviewing recent literature on analysis of emerging contaminants in food. [ABSTRACT FROM AUTHOR]

A personal narrative is presented which explores the author's experiences as visiting professor at the King Saud University in Riyadh, Saudi Arabia since December 2009.

Abstract: The aim of this study was to test if pharmaceuticals could explain observed responses of field collected and transplanted invertebrate species (Hydropsyche exocellata, Echinogammarus longisetosus, and Daphnia magna). The study was performed in the middle and lower course of Llobregat river basin, which is affected by pharmaceuticals and other pollutants coming from sewage treated effluents. Up to 10 different endpoints including enzyme activities related with detoxication mechanisms (i.e. glutathione S transferase, catalase, esterases), the oxidative stress damage marker (lipid peroxidation), and individual responses (mortality, post-exposure feeding rates) were assessed. Biological responses were complemented with a detailed chemical analysis of metals, detergents, pesticides, pharmaceuticals and other general water quality variables to allow identifying causal abiotic factors. Estimated hazard indexes of measured pollutants indicated that pesticides and metals accounted for most of the predicted toxicity (>95%) in the most contaminated site and that the predicted toxicity of pharmaceuticals was marginal (<5%). The three species showed a clear impact across the studied gradient indicated by higher levels of feeding inhibition and of mortality towards lower reaches. Specific responses such as inhibition of cholinesterase activities were closely related to high and presumable toxic levels of diazinon, whereas unspecific responses such as enhanced levels of antioxidant defensive mechanism and of lipid peroxidation levels were associated with most pollutant classes as well as with high and presumable toxic levels of salt and ammonia. These results indicate that pesticides, salinity, ammonia probably had greater effects on the studied species than pharmaceuticals. [Copyright &y& Elsevier]

Abstract: Multivariate curve resolution alternating least squares (MCR-ALS) is shown to be a powerful chemometric method for the analysis of environmental monitoring data sets. It allows for the investigation, resolution, identification, and description of pollution patterns distributed over a particular geographical area, time and environmental compartment. An integrated interpretation of the main features characterizing pollution patterns of organic contaminants affecting the Ebro River basin (Catalonia, NE Spain) is attempted using the results obtained by MCR-ALS analysis of surface water, groundwater, sediment and soil data sets obtained in a 3-year extensive monitoring study. Agricultural practices were identified as the main source of surface and groundwater diffuse pollution, while sediments and soils appeared mostly polluted by a contamination pattern mainly loaded by polycyclic aromatic hydrocarbons (PAHs) of possible pyrolitic origin. Additionally, a third pollution pattern related to past and ongoing industrial activities was detected to be principally stored in the sediment compartment. Geographical and temporal distributions of these pollution sources are given. [Copyright &y& Elsevier]

Abstract: To date, different water-quality indices (WQIs) categorizing water bodies have flourished in the literature. While this type of index has normally been applied to data sets from manual monitoring programs, we focus attention on the analysis of data from automated sampling networks, from which measurements of a small number of physico-chemical variables are usually obtained from different locations with high temporal resolution. To deal with data of this nature, we compare different indices for the physico-chemical evaluation of water quality. As a result, we select the WQI of the Canadian Council of Ministers of the Environment (CCME WQI) as the most suitable. Our interest in using this WQI rests on its flexibility for selecting parameters as well as the possibility of modifying the objectives to be met by each variable according to the specific end use of the water. We perform a sensitivity analysis for the CCME WQI in order to select the best procedure for calculating it according to input data. Finally, we apply the CCME WQI to simulated data sets describing three different environmental scenarios corresponding to episodes of discharge of urban wastewater, eutrophication and risk to fish. From this comparison and according to the specific objectives we define in this work, we rank sensitivity in CCME WQI performance in the following order: (1) urban wastewater; (2) eutrophication; and, finally, (3) risk to fish. [Copyright &y& Elsevier]

Abstract: A system of recirculating channels was used in this study to examine the long-term effects (29d) of environmentally realistic concentrations of the herbicide diuron (from 0.07 to 7μgL−1) on biofilm communities. The autotrophic activity of biofilms was affected by this herbicide, as reflected by a marked decrease in the photosynthetic efficiency. Diuron exposure also increased chlorophyll-a content and reduced the biovolume of diatom taxa at low concentrations. The effects on bacteria were also remarkable. Bacterial abundance was reduced after a week of exposure to the herbicide at a range of concentrations. Effects were on the number of live bacteria and on the increase in the leucine-aminopeptidase activity. It is suggested that inputs of herbicides to the river ecosystem at low concentrations may cause a chain of effects in the biofilm, which include inhibitory effects on algae but also indirect effects on the relationships between biofilm components. [Copyright &y& Elsevier]

Multivariate curve resolution alternating least squares is shown to he a powerful chemometric tool for investigation of main surface water contamination patterns affecting a particular geographical area over a period of time. When environmental monitoring data tables are analyzed using this method, the identification of the main contamination patterns, and the description of their geographical and temporal distribution profiles, can be obtained. To show the potential of the proposed method, the investigation of the pesticide contamination affecting the Ebro River delta (Catalonia, NE Spain) during the rice-growing season in 2005, in selected an a cane study in thin work. Three different contamination patterns of pesticides with different spatial and temporal behaviors were identified. A method validation using simulated data in then proposed to evaluate the suitability of the proposed multivariate curve resolution method for the analysis of the different possible data structures currently occurring in environmental monitoring studies. In particular, different data structures previously encountered in the experimental study of the Ebro River have been investigated in detail The importance of using either raw or scaled data is contrasted using the simulated data sets. Possible propagation of noise on resolved profiles is also investigated to establish the difference between its effects and the possible ambiguities inherent to multivariate curve resolution methods. [ABSTRACT FROM AUTHOR]

Abstract: A large number of ultraviolet (UV)-absorbing compounds, usually present in personal-care products, textiles exposed to UV radiation and plastics materials, elicit hormonal activity in vitro and in vivo. Induction of vitellogenin, alterations in gonads, decrease in fertility and reproduction, and feminization in sex characteristics of male fish have been associated with frequently-used UV filters, including benzophenones and camphor-related substances. The lowest effect concentrations determined (3μg/L for 3-benzylidene camphor) are generally higher than those measured so far in the environment (ng/L to lower μg/L in water). However, the propensity for rapid accumulation and the potential for mixture effects warrant further research to evaluate the fate and the disposition of UV filters in the aquatic ecosystem. Moreover, the amounts of UV filters added to products are increasing, to date usually 10% (w/w), as a consequence of the higher protection factors demanded, and that requires formulations with higher percentages of UV filters or multi-component mixtures with more UV-absorbing substances. In addition, long-term exposure to UV-absorbing compounds may have negative effects at concentrations much lower than those considered at present. This article provides an overview of the most outstanding findings reported on toxic effects of UV filters in the aquatic environment. We also include environmental levels detected and analytical methodologies applied. [Copyright &y& Elsevier]

Wastewater-based epidemiology (WBE) has become popular to estimate the use of drugs of abuse and recently to establish the incidence of CoVID 19 in large cities. However, its possibilities have been expanded recently as a technique that allows to establish a fingerprint of the characteristics of a city, such as state of health/disease, healthy/unhealthy living habits, exposure to different types of contaminants, etc. with respect to other cities. This has been thanks to the identification of human biomarkers as well as to the fingerprinting and profiling of the characteristics of the wastewater catchment that determine these circumstances. The purpose of this review is to analyze the different methodological schemes that have been developed to perform this biomarker identification as well as the most characteristic analytical techniques in each scheme, their advantages and disadvantages and the knowledge gaps identified. We also discussed the future scope for development. [Display omitted] • Current achievements in biomarker identification for WBE are assessed. • Biomarker identification is done either with a bottom-up or a top-down scheme. • Critical description of each analytical scheme features. • Prospects within the analytical WBE aspects are outlined. [ABSTRACT FROM AUTHOR]

Abstract: Liquid chromatography-mass spectrometry (LC-MS) has contributed significantly in advancing research in the analysis of metabolites and degradation products of food contaminants. Of particular interest is the comprehensive application of LC-MS to discovery of degradation products and metabolites. This review, covering research published between 2003 and 2008, describes how LC-MS has been used in this field, with the majority of work dealing with target-metabolite analysis and only a small fraction using LC-MS comprehensively. In considering the significance of this topic and the potential interest in it, we briefly describe state-of-the art mass analyzers applied for it (QtrAP, QqTOF, and Orbitrap). We detail the challenges and the achievements of LC-MS in this field of analysis, with emphasis on the latest developments in the technique. We also discuss how some of the key features of LC-MS are exploited to identify, to characterize and to determine some metabolites and degradation products of residues and food contaminants. Finally, we critically evaluate the prospects for, and the limitations of, LC-MS in this field, including identification of degradation products, quantitative methods and metabolite profiling. [Copyright &y& Elsevier]

Abstract: This review provides a brief overview on chirality as a structural characteristic of pharmaceuticals. This property has received very little attention in the field of environmental analysis, despite the fact that many drugs are marketed as racemates. The review covers the different methodologies commercially available on chiral liquid chromatography (LC) columns to provide good resolving power. It also reviews recent results obtained in chiral analysis of drugs and their metabolites with an array of modern mass-spectrometric analyzers coupled to an LC system that provides high selectivity and sensitivity. It further covers the occurrence and the fate of chiral drugs in the environment. [Copyright &y& Elsevier]

The two nonsteroidal anti-inflammatory drugs diclofenac (DCF) and aceclofenac (ACE) were monitored for the first time together with their major human phase-I metabolites, namely, 4'-hydroxydiclofenac (4'-OH-DCF) and 4'-hydroxyaceclofenac (4'-OH-ACF), in untreated and treated sewage samples, collected from a municipal wastewater treatment plant which operated a continuous activated sludge (CAS) treatment in parallel with membrane bioreactor (MBR) technology. Mean concentrations of DCF and 4'-OH-DCF in the influent samples amounted to 349 and 237 ng/L, respectively, whereas levels of 4'-OH-ACF (average, 59 ng/L) exceeded those of its parent drug ∼2-fold (31 ng/L). Removal rates of 26 and 56% were achieved for 4'-OH-DCF following CAS and MBR treatment, respectively. The most efficient elimination was observed for 4'-OH-ACF in the MBR with only 4% of the influent concentration remaining in the treated sewage. Biodegradation experiments in batch reactors loaded with mixed liquor demonstrated that ACF underwent rapid ester cleavage to liberate DCF, thus constituting a possible source of DCF release during biological sewage treatment. Studies on the microbial metabolism of DCF (295 Da) in controlled laboratory settings allowed us to identify three novel aerobic biotransformation products. Structure elucidation by means of ultraperformance liquid chromatography-electrospray ionization-hybrid quadrupole-time-of-flight-mass spectrometry in conjunction with H/D-exchange experiments unequivocally identified them as deriving from nitrosation of the hydroxyl group in the carboxylic acid moiety (324 Da) and from nitration of one of the aromatic ring systems (340 Da). A third microbial metabolite emerging in the test medium was assigned as dichlorobenzoic acid (190 Da), possibly formed by N-dealkylalion of DCF and subsequent carboxylation. Taken together, this work constitutes the first report on the occurrence of ACF and the human metabolites 4'-OH-DCF and 4'-OH-ACF in wastewater, underpinning the need of incorporating metabolites excreted by humans in monitoring surveys as part of a risk evaluation for environmentally relevant pharmaceuticals. [ABSTRACT FROM AUTHOR]

Population growth and unpredictable climate changes will pose high demands on water resources in the future. Even at present, surface water is certainly not enough to cope with the water requirement for agricultural, industrial, recreational and drinking purposes. In this context, the usage of ground water has become essential, therefore, their quality and quantity has to be carefully managed. Regarding quantity, artificial recharge can guarantee a sustainable level of ground water, whilst the strict quality control of the waters intended for recharge will minimize contamination of both the ground water and aquifer area. However, all water resources in the planet are threatened by multiple sources of contamination coming from the extended use of chemicals worldwide. In this respect, the environmental occurrence of organic micropollutants such as pesticides, pharmaceuticals, industrial chemicals and their metabolites has experienced fast growing interest. In this paper an overview of the priority and emerging organic micropollutants in the different source waters used for artificial aquifer recharge purposes and in the recovered water is presented. Besides, some considerations regarding fate and removal of such compounds are also addressed. [Copyright &y& Elsevier]

Abstract: Despite some European countries having banned the use of veterinary medicines for non-therapeutic purposes in food-animal agriculture, large amounts of pharmaceutical compounds, mostly antimicrobials, continue to be used for these purposes, as well as being used for the legitimate treatment of animal diseases. The high worldwide consumption of veterinary medicines has alerted scientists and the public in general, and efforts have been made to assess the concentrations levels of such residues (parent compounds, metabolites and degradation products) in the aquatic and terrestrial environments. As a consequence, reliable analytical methods have been developed for the identification and the determination of veterinary pharmaceutical residues in the environment. Probably because of the great complexity of solid environmental samples, only a few studies have been published on their determination in soils, sediments and sludge. Nevertheless, this information is needed to understand and to assess the impact of veterinary medicines on the environment. The important development of liquid chromatography coupled to mass spectrometry (LC-MS) in the environmental field has made this technique a powerful tool for reliable and accurate determination of pharmaceutical residues in the terrestrial environment. We aim to review the latest studies, pointing out the progress achieved in the LC-MS analysis (screening, identification, confirmation and quantification) of veterinary pharmaceutical residues in solid environmental matrices (soil, sediment and sludge), with especial emphasis on sample pretreatment and instrumental detection. [Copyright &y& Elsevier]

Abstract: This overview reviews current knowledge on identification, presence and distribution of drug metabolites in the environment. We compare the metabolic routes of environmentally relevant pharmaceuticals in the human body to those of biotransformations brought about by mixed consortia of microorganisms in natural and engineered wastewaters and surface waters. We describe the characteristics of modern mass-spectrometric instrumentation coupled to liquid-chromatographic separation techniques and review their application in profiling metabolites. We set out analytical methodologies for quantitative analysis of drugs and their degradates in sewage and surface waters and give results of monitoring obtained from their application. [Copyright &y& Elsevier]

Interest in the presence of pharmaceuticals in the environment has recently increased. Despite continuous research efforts there is still a large gap in our knowledge of their fate and effects on the ecosystem. This review covers current information on the occurrence of iodinated X-ray contrast media (ICM) in the environment and developments in the analysis of these highly polar organic micropollutants in aqueous environmental samples. Findings from monitoring surveys conducted on wastewater-treatment plants (WWTP), surface waters, and drinking waters are compiled, and strategies for removal of the compounds in WWTP and waterworks using advanced treatment are reported. Characteristics and advantages of different compound-specific or element-specific mass spectrometric techniques used to monitor ICM in the environment are compared, and applications in elucidation of the structures of biotransformation products, generated in laboratory-scale experiments that simulate sewage treatment or river water/sediment systems, are described. [ABSTRACT FROM AUTHOR]

Abstract: This article is an overview of current methodologies for the analysis of different classes of surfactants by advanced liquid chromatography-mass spectrometry (LC-MS) technologies, including LC-tandem MS (LC-MS 2 ), ion trap, quadrupole-time-of-flight (Q-TOF) and matrix-assisted laser desorption/ionization (MALDI)-TOF. It also discusses the application of LC-MS methods in studies of the fate and the behavior of surfactants during wastewater treatment either using conventional activated sludge (CAS), membrane bioreactor (MBR) or advanced oxidation processes (AOPs). Using advanced LC-MS methodologies, it is possible to detect a variety of polar metabolites, such as carboxylic acids and short-chain sulphonic-acid derivatives of surfactants formed during the biodegradation processes in either the wastewater-treatment plants or the environment. [Copyright &y& Elsevier]

Antimicrobials are used in large quantities in human and veterinary medicine. Their environmental occurrence is of particular concern due to the potential spread and maintenance of bacterial resistance. After intake by the organisms, the unchanged drug and its metabolized forms are excreted and enter wastewater treatment plants where they are mostly incompletely eliminated, and are therefore eventually released into the aquatic environment. The reliable detection of several antimicrobials in different environmental aqueous compartments is the result of great improvements achieved in analytical chemistry. This article provides an overview of the more outstanding analytical methods based on liquid chromatography tandem mass spectrometry, developed and applied to determine antimicrobial residues and metabolites present in surface, waste, and ground waters. [Figure not available: see fulltext.] [ABSTRACT FROM AUTHOR]

Abstract: Identification of the main contamination sources of heavy metals, organic compounds and other physicochemical parameters in Ebro river surface waters and description of their temporal and spatial distributions, are analyzed using chemometrics and geostatistical methods. Historical data available from the Confederación Hidrográfica del Ebro (CHE), which is the organization in charge of the management of the Ebro river basin; covering different years since 1992 for water, sediments and fish samples are investigated. Due to the great amount of data in these databases and to their complexity, chemometrics modelling (using principal components analysis, PCA) coupled to geographical information systems (GIS) is proposed to evaluate the environmental quality of the Ebro river basin. [Copyright &y& Elsevier]

Abstract: A pressurized liquid extraction (PLE) solid-phase extraction (SPE) gas chromatography–mass spectrometry (GC–MS) method was developed for the determination of two model organophosphorus pesticides (OPPs), i.e. chlorpyrifos (CPF, O,O-diethyl-O-[3,5,6-trichloro-2-pyridyl]-phosphorothioate, CAS no. 2921-88-2) and diazinon (DZN, O,O-diethyl-O-2-isopropyl-4-methyl-6-pyrimidyl thiophosphate, CAS no. 333-41-5) and their two more stable metabolites namely, 3,5,6-trichloro-2-pyridinol (TCP, CAS no. 6515-38-4) and 2-isopropyl-6-methyl-4-pyrimidinol (IMHP, CAS no. 28-14-20-2) in sewage sludge and agricultural soil samples was developed. A PLE procedure was optimized as a less time-consuming and cost-effective extraction approach for sewage sludge/soil samples. Derivatization of metabolites was carried out with N-(tert-butyldimethylsilyl)-N-methyltrifluoroacetamide (MTBSTFA) to form stable derivatives. The method was developed using spiked soil samples at 1mg/kg for the intact insecticides and at 2mg/kg for their metabolites. Recovery yields for the target pesticides were>92%, meanwhile for the metabolites the recoveries were somewhat low. Limits of quantification (LOQ) were within the range of 4–62ng/g for the sludge sample and between 3 and 31ng/g for sludge-fertilized soil samples. The method was applied for the determination of both insecticides in some soils fertilized with sludge from municipal wastewater treatment plants (WWTPs) in the proximity of Barcelona (Catalonia, Spain) and in one representative sludge sample used as fertilizer. Results revealed the presence of CPF in all samples at concentrations within the range of 210.32–38.36ng/g. Both major metabolites were also found to be present in all samples. [Copyright &y& Elsevier]

Abstract: We review recent liquid chromatography–tandem mass spectrometry methods using different mass spectrometers (ion-trap, triple-quadrupole and time-of-flight) for the determination of antimicrobials in the environment. Limits of detection as low as 2ng/l can be achieved. Studies show that antimicrobials are present in the aquatic environment at concentrations with maxima ranging from 6ng/l of sulfamethizole in surface water to 12mg/l of chlortetracycline in animal wastewaters. Effluents from wastewater- and sewage-treatment plants have received most attention because of the evidence that their removal of such compounds has been unsuccessful. [Copyright &y& Elsevier]

Surfactants are among the most prevalent organic pollutants of anthropogenic origin with the potential to enter the environment through the discharge of wastewater and sewage sludge. We give an overview of analytical methods currently in use for the determination of different classes of surfactants in sewage sludge and soil. The main focus is on the application of liquid chromatography-mass spectrometry (LC-MS) and gas chromatography-mass spectrometry (GC-MS), discussing various aspects of these two techniques, including sample preparation. We give an overview of data on the occurrence of sludge and sludge-amended soils, and we draw conclusions about the fate of surfactants and their metabolites in sludge-amended soils. Finally, we briefly discuss the current European legislation relating to the use of sludge in agriculture. [Copyright &y& Elsevier]

Toxicity testing has grown steadily in recent years, being a useful tool in environmental risk assessment. This review highlights different bioassays and recently developed biosensors based on acute toxicity measurements. Emphasis is placed on the use of combined approaches involving chemical analysis for the characterization and identification of complex toxic wastewater effluents and sewage sludge. Fractionation schemes that combine sample preparation and chemical analysis with biological measurements are presented and reviewed. Bioassay-directed chemical-analysis protocols involve solid phase extraction (SPE), followed by chromatographic techniques, such as liquid chromatography-mass spectrometry (LC-MS) or gas chromatography-mass spectrometry (GC-MS). Toxicity testing is carried out by either bioluminescence inhibition methods or a whole-cell bacterial biosensor. Other biological toxicity tests are also reviewed. Examples of using different bacterial acute toxicity assays are presented for phenols, polyethoxylate surfactants, linear alkyl benzene sulphonates (LASs), naphthalene and benzene sulphonates, polycyclic aromatic hydrocarbons (PAHs), pesticides and pharmaceutical drugs. [Copyright &y& Elsevier]

A field-test kit (SensioScreen® TR500) for the determination of triazine herbicides in water samples has been evaluated. The test is based on an ELISA method performed on a membrane that allows the visual estimation of the presence of triazine herbicides in <10 min. The kit contains all necessary reagents and equipment, and operates on a very simple protocol. The detection level of this semiquantitative kit has been set at 0.5 μg/l (for the sum of all triazines), although concentration levels of 0.1 μg/l for atrazine can be detected. This is the first time that a commercial field-test kit to control water contamination by herbicides performs in compliance with the EU and USA legislations regarding the limit of detection reached. Evaluation and validation studies have been performed using spiked, certified (AquaCheck) and real environmental samples comparing the results with chromatographic methods. In spite of the semiquantitative–qualitative character of the kit, the results demonstrate that the test SensioScreen® TR500 provides a very good estimation of the atrazine concentration in the sample. This test format could be adapted to the detection of other contaminants of environmental relevance. [Copyright &y& Elsevier]

Concern about the health of aquatic fauna living in waters containing biologically active levels of estrogenic compounds is particularly focused on the effects on their reproductive success. To that end, carp, Cyprinus carpio, a feral fish living in warm waters of Southern Europe (NE Spain), were selected for signs of estrogenicity. The study area covered two tributaries (the Anoia and the Cardener) of the Llobregat River both known to be polluted by estrogenic compounds. The estrogenicity in the carp was measured as vitellogenin (VTG) presence in males and alterations in VTG levels in females, over a 6-month period, embracing both the pre- and post-spawning seasons. VTG content was measured in both the plasma and liver, the latter being the organ that synthesizes it. Also, hepatic 7-ethoxyresorufin O-deethylase (EROD) activity was recorded, as interactions of xenoestrogens and oestradiol have been reported to affect this enzymatic activity. The estrogenicity of these rivers was more evident in the Anoia at the location downstream from the sewage treatment plant (STP), by elevated levels of VTG in males and by the presence of some intersex individuals. In the Cardener, no intersex fish were found and male plasmatic VTG was not so highly elevated. However presence of hepatic VTG, in up to 54% of the male fish analyzed, proved exposure to xenoestrogens. In females, VTG fluctuated according to the biological cycle with a plasmatic peak in May and an earlier maximal in the liver. However, this pattern was altered in the locations with higher xenoestrogens presence. EROD activity showed differences between sexes, with higher activity in males than females, as well as site-related differences (up to one order of magnitude) in the same river. These differences were even greater than those detected between rivers. A seasonal trend was also seen in EROD activity with higher induction towards the summer in both males and females. [Copyright &y& Elsevier]

This critical review paper will discuss the main analytical calibration models as well as the guidelines for their practical use. The main models used to fit a multiple-point calibration dataset are: 1) linear unweighted or ordinary least squares regression (OLSR); 2) quadratic unweighted least squares regression (QLSR); 3) linear weighted least squares regression (WLSR). Unfortunately, there is no standard procedure in analytical chemistry for objectively testing the goodness-of-fit of calibration models. Different proposals were reported in the literature. However, none is more commonly used, and probably not more controversial than R 2 . In this document, a three step simple calibration diagnosis has been proposed. It is based on a combination of different procedures such as graphical plots, statistical significance tests and numerical parameters. Experimental conditions and design of calibration procedures are very relevant for appropriate selection. Finally, some information on the choice of the different models will be reported in four case studies. [Display omitted] • OLSR, QLSR and WLSR are the main analytical calibration models. • Graphical plots, statistical tests and numerical parameters are used to evaluate GoF of calibration models. • %RE values are useful to evaluate bias and therefore to appropriately select the calibration model. • Model selection is dependent on experimental conditions and design of calibration procedures. [ABSTRACT FROM AUTHOR]

Matrix components of a sample can affect the quantitative measurement of the target analytes. This singularity is named "matrix effects" and should be considered for method validation procedure. Two main strategies to overcome matrix effects were suggested in the scientific literature: reducing the presence of components responsible for the effects and compensating the influence of matrix effects in the calibration methodology. It has been recommended that the best option to surpass matrix effects at research level is to establish a systematic optimization by the combination of approaches. On the other hand, from the method validation regulatory viewpoint, the information contained in the different method validation guidelines about matrix effects was uncommon. In fact, only in 54% of the evaluated regulatory documents the term matrix effects was mentioned explicitly in their contents. In addition, in the rest of the guidance documents addressing matrix effects, the subject was typically considered only superficially. Image 1 • Matrix effects are critical for validation of chromatography-mass spectrometry methods. • Detailed evaluation of matrix effects for method validation. • Discrepant information for matrix effects from research versus regulatory points of views. • Contradictory information about matrix effects among different method validation guidelines. [ABSTRACT FROM AUTHOR]

Supramolecular chemistry is the quintessential backbone of all biological processes. It encompasses a wide range from the metabolic network to the self-assembled cytoskeletal network. Combining the chemical diversity with the plethora of functional depth that biological systems possess is a daunting task for synthetic chemists to emulate. The only route for approaching such a challenge lies in understanding the complex and dynamic systems through advanced analytical techniques. The supramolecular complexity that can be successfully generated and analyzed is directly dependent on the analytical treatment of the system parameters. In this review, we illustrate advanced analytical techniques that have been used to investigate various supramolecular systems including complex mixtures, dynamic self-assembly, and functional nanomaterials. The underlying theme of such an overview is not only the exceeding detail with which traditional experiments can be probed but also the fact that complex experiments can now be attempted owing to the analytical techniques that can resolve an ensemble in astounding detail. Furthermore, the review critically analyzes the current state of the art analytical techniques and suggests the direction of future development. Finally, we envision that integrating multiple analytical methods into a common platform will open completely new possibilities for developing functional chemical systems. [ABSTRACT FROM AUTHOR]

Pyrolysis gas chromatography-mass spectrometry (Py-GC-MS) has great potential within environmental analysis. This technique is mainly used for the chemical identification of macromolecules that cannot be characterized by either liquid or gas chromatography due to their big size. Through pyrolysis (controlled thermal degradation), these macromolecules are broken down into simpler molecules that can be separated by gas chromatography and detected by mass spectrometry. This technique has been traditionally used in environmental samples for the characterization of organic matter and humic substances, contaminants, lignins, etc. It attains the identification of the different types of chemical units that integrate the macromolecules. In addition, recently, this technique has experienced an important boom in the chemical characterization of microplastics present in environmental samples. This has triggered its use in this type of matrix. We describe the fundamentals and modalities of Py-GC-MS and outline some of the recent applications for the environmental analysis with special emphasis on humic substances and/or other types of organic matter components as well as microplastics, but reporting also other interesting application of environmental relevance. Image 1 • Recent innovations in Py-GC-MS for environmental analysis are presented. • Advances in the design of currently used pyrolyzers are discussed. • Recently developed working modes within Py-GC-MS are described. • Py-GC-MS applications to organic matter and microplastics are highlighted. • Progresses and promising trends in Py-GC-MS analysis are pointed out. [ABSTRACT FROM AUTHOR]

Image 1 [ABSTRACT FROM AUTHOR]