Untargeted analysis of a composite house dust sample has been performed as part of a collaborative effort to evaluate the progress in the field of suspect and nontarget screening and build an ...extensive database of organic indoor environment contaminants. Twenty-one participants reported results that were curated by the organizers of the collaborative trial. In total, nearly 2350 compounds were identified (18%) or tentatively identified (25% at confidence level 2 and 58% at confidence level 3), making the collaborative trial a success. However, a relatively small share (37%) of all compounds were reported by more than one participant, which shows that there is plenty of room for improvement in the field of suspect and nontarget screening. An even a smaller share (5%) of the total number of compounds were detected using both liquid chromatography–mass spectrometry (LC-MS) and gas chromatography–mass spectrometry (GC-MS). Thus, the two MS techniques are highly complementary. Most of the compounds were detected using LC with electrospray ionization (ESI) MS and comprehensive 2D GC (GC×GC) with atmospheric pressure chemical ionization (APCI) and electron ionization (EI), respectively. Collectively, the three techniques accounted for more than 75% of the reported compounds. Glycols, pharmaceuticals, pesticides, and various biogenic compounds dominated among the compounds reported by LC-MS participants, while hydrocarbons, hydrocarbon derivatives, and chlorinated paraffins and chlorinated biphenyls were primarily reported by GC-MS participants. Plastics additives, flavor and fragrances, and personal care products were reported by both LC-MS and GC-MS participants. It was concluded that the use of multiple analytical techniques was required for a comprehensive characterization of house dust contaminants. Further, several recommendations are given for improved suspect and nontarget screening of house dust and other indoor environment samples, including the use of open-source data processing tools. One of the tools allowed provisional identification of almost 500 compounds that had not been reported by participants.
Because of large-scale production and use of an increasing diversity of chemicals in modern society, estuarine and coastal waters may be contaminated with numerous substances. Some of these compounds ...have the potential to affect microalgae at the base of the pelagic food chain. Therefore, we identified the main chemical stressors that negatively affect the effective photosystem II efficiency (ϕPSII) in marine microalgae of the Dutch estuarine and coastal waters. An enhanced effect-directed analysis (EDA) was carried out by combining reversed-phase ultra performance liquid chromatography fractionation of extracts from passive samplers, followed by effect assessment using the pulse amplitude modulation fluorometry assay and chemical analysis of biologically active fractions using high-resolution mass spectrometry. This study focuses on a novel microfractionation technique using 96-well plates to enhance throughput in EDA, structure elucidation, and the analytical and effect confirmation of the compounds that are identified. Although there are numerous unknown compounds present in estuarine and coastal waters, our EDA study shows that atrazine, diuron, irgarol, isoproturon, terbutryn, and terbutylazine are the main contributors to the observed effect on the ϕPSII of marine microalgae.
Due to their specific effect on photosynthesis, herbicides pose a potential threat to coastal and estuarine microalgae. However, comprehensive understanding of the hazard and risk of these ...contaminants is currently lacking. Therefore the aim of the present study was to investigate the toxic effects of four ubiquitous herbicides (atrazine, diuron, Irgarol®1051 and isoproturon) and herbicide mixtures on marine microalgae. Using a Pulse Amplitude Modulation (PAM) fluorometry based bioassay we demonstrated a clear species and herbicide specific toxicity and showed that the current environmental legislation does not protect algae sufficiently against diuron and isoproturon. Although a low actual risk of herbicides in the field was demonstrated, monitoring data revealed that concentrations occasionally reach potential effect levels. Hence it cannot be excluded that herbicides contribute to observed changes in phytoplankton species composition in coastal waters, but this is likely to occur only occasionally.
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•The hazard of herbicides for microalgae is compound and species specific.•In general a low risk although occasional potential effect levels are reached.•Current legislation does not protect marine microalgae sufficiently.
The hazard of herbicides in the coastal waters is compound and species specific and although the general risk in the field is low, occasionally potential effect levels are reached.
Over the past decade, Cell and Gene Therapies (C>) have been an emerging therapeutic area with more than twenty C> drug products approved and over 1000 registered trials. The remarkable progress ...in these modalities brings new challenges for scientists who evaluate manufacturing and storage materials, including risk assessments for extractables and leachables (E&L). Establishing a business process to qualify materials for these applications is an important risk mitigation strategy in support of these assessments. Process validation verifying process performance and product quality requirements using qualified materials also ensures that leachables from the materials do not result in an impact to process and product. The authors provide an overview of available guidelines and publications relevant to E&L risk assessments that can be used to support ex vivo C> products, highlighting gaps and standardization needs in the areas of biocompatibility and extractables conditions. Finally, the authors present leachable testing strategies, relevant to the specific manufacturing and storage conditions of C> products, and safety assessment considerations for organic and inorganic chemical entities.
•Indoor air in buildings of cultural and historical importance had high OCP levels•Cancer risk (CR) from inhalation exposure to OCPs determined for workers•CR from DDE exposure reduced by orders of ...magnitude after theatre restoration•CR for museum workers from γ-HCH exposure were significant as to require mitigation•Museum worker CR was reduced, but still moderate where γ-HCH granules were removed
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Organochlorine pesticides (OCPs) have been used to preserve the integrity of historical buildings or to protect collections of artefacts at potentially large volumes and often without detailed application records. Previous research has focused on the efficiency of remediation at contaminated sites (where identified), as well as improvement of preservation techniques and workplace health and safety. Few studies have assessed the human health risks from occupational exposure to OCPs in buildings of cultural and historical importance. Thus, potential risks may remain unidentified. In the present study, OCPs in indoor air were measured in a baroque theatre and a natural history museum in the Czech Republic, both of which had suspected past indoor application. In the theatre attic p,p′-dichlorodiphenyldichloroethylene (p,p′-DDE) levels in air were up to 190ngm−3, confirming past indoor use of p,p′-dichlorodiphenyltrichloroethane (p,p′-DDT). There was also evidence of γ-hexachlorocyclohexane (γ-HCH) use in the theatre (max γ-HCH in air of 56ngm−3). Yet, the cancer risk (CR) from occupational exposure via inhalation (Expi) to OCPs in the theatre was low (CR<4.0×10−6). γ-HCH was found at elevated levels in air of the museum (max γ-HCH in air of 15,000ngm−3). CR from Expi in the museum was moderate to high (>1×10−4). Our results show the CR through Expi to OCPs in buildings, such as museums can still be significant enough to warrant mitigation measures, e.g., remediation.
In Oman, DDT was sprayed indoors during an intensive malaria eradication program between 1976 and 1992. DDT can remain for years after spraying and is associated with potential health risk. This ...raises the concern for human exposure in areas where DDT was used for indoor spraying. Twelve houses in three regions with a different history of DDT indoor spraying were chosen for a sampling campaign in 2005 to determine p,p′-dichlorodiphenyltrichloroethane (p,p′-DDT), p,p′-dichlorodiphenyldichloroethylene (p,p′-DDE) and p,p′-dichlorodiphenyldichloroethane (p,p′-DDD) levels in indoor air, dust, and outdoor soil. Although DDT was only sprayed indoor, p,p′-DDT, p,p′-DDE and p,p′-DDD were also found in outdoor soil. The results indicate that release and exposure continue for years after cessation of spraying. The predicted cancer risk based on concentrations determined in 2005, indicate that there was still a significant cancer risk up to 13 to 16years after indoor DDT spraying. A novel approach, based on region-specific half-lives, was used to predict concentrations in 2015 and showed that more than 21years after spraying, cancer risk for exposure to indoor air, dust, and outdoor soil are acceptable in Oman for adults and young children. The model can be used for other locations and countries to predict prospective exposure of contaminants based on indoor experimental measurements and knowledge about the spraying time-schedule to extrapolate region-specific half-lives and predict effects on the human population years after spraying.
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•Indoor air and dust are important exposure routes for DDT.•Significant DDT, DDE and DDD levels were found years after indoor spraying.•A novel risk assessment model identified site-specific potential cancer risks in Oman.•Region-specific half-life is important for proper cancer risk assessment.•More data linking indoor exposure to relevant health outcomes are needed.
•We investigated the use of spot water and passive sampling.•SPE and passive sampling are complementary tools used in future EDA studies.•The added value of SPE lies in its suitability for ...quantitative analysis.•Calibration of passive samplers needs further investigation.•The PAM assay can be used as a rapid screening tool for assessing toxic effects.
The extent to which chemical stressors affect primary producers in estuarine and coastal waters is largely unknown. However, given the large number of legacy pollutants and chemicals of emerging concern present in the environment, this is an important and relevant issue that requires further study. The purpose of our study was to extract and identify compounds which are inhibitors of photosystem II activity in microalgae from estuarine and coastal waters. Field sampling was conducted in the Western Scheldt estuary (Hansweert, The Netherlands). We compared four different commonly used extraction methods: passive sampling with silicone rubber sheets, polar organic integrative samplers (POCIS) and spot water sampling using two different solid phase extraction (SPE) cartridges. Toxic effects of extracts prepared from spot water samples and passive samplers were determined in the Pulse Amplitude Modulation (PAM) fluorometry bioassay. With target chemical analysis using LC–MS and GC–MS, a set of PAHs, PCBs and pesticides was determined in field samples. These compound classes are listed as priority substances for the marine environment by the OSPAR convention. In addition, recovery experiments with both SPE cartridges were performed to evaluate the extraction suitability of these methods. Passive sampling using silicone rubber sheets and POCIS can be applied to determine compounds with different structures and polarities for further identification and determination of toxic pressure on primary producers. The added value of SPE lies in its suitability for quantitative analysis; calibration of passive samplers still needs further investigation for quantification of field concentrations of contaminants.
The identity of compounds responsible for estrogenic and dioxin-like activities in sediment from the harbour of the small town Zierikzee in Zeeland, The Netherlands, was investigated using a bioassay ...directed fractionation approach with the
in vitro estrogen and dioxin responsive reporter gene assays ER- and DR-CALUX. For identification of compounds exhibiting activity in the bioassays, either one or two-dimensional GC in combination with quadrupole (MSD), ion trap (ITD) or time-of-flight mass spectrometric detection (ToF-MS) was used, depending on the biological and chemical characteristics and the complexity of the fractions. The natural estrogenic hormone 17-β-estradiol and its metabolite estrone were identified with GC–ITD as the main contributors to the estrogenic activity. After successive rounds of fractionation, the dioxin-like activity could be explained by the presence of various polycyclic aromatic hydrocarbons identified with GC–MSD and two-dimensional comprehensive GC
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GC–ToF-MS. Some estrogenic activity of a relatively non-polar nature remained unidentified.
For several decades now, there has been an increase in the sources and types of chemicals in estuarine and coastal waters as a consequence of anthropogenic activities. This has led to considerable ...concern about the effects of these chemicals on the marine food chain. The fact is that estuarine and coastal waters are the most productive ecosystems with high primary production by microalgae. The toxic pressure of specific phytotoxic chemicals now poses a major threat to these ecosystems.
In a previous study, six herbicides (atrazine, diuron, irgarol, isoproturon, terbutryn and terbutylazine) were identified as the main contaminants affecting photosynthesis in marine microalgae. The purpose of this study is to investigate the toxic pressure of these herbicides in the Dutch estuarine and coastal waters in relation to the effective photosystem II efficiency (ΦPSII) in microalgae. Temporal and spatial variations in the concentrations of these herbicides were analyzed based on monitoring data. Additionally, a field study was carried out in which chemical analysis of water was performed and also a toxicity assessment using the Pulse Amplitude Modulation (PAM) fluorometry assay that measures ΦPSII. The toxic pressure on ΦPSII in microalgae has decreased with 55–82% from 2003 to 2012, with the Western Scheldt estuary showing the highest toxic pressure. By combining toxicity data from the PAM assay with chemical analysis of herbicide concentrations, we have identified diuron and terbutylazine as the main contributors to the toxic pressure on microalgae. Although direct effects are not expected, the toxic pressure is close to the 10% effect level in the PAM assay. A compliance check with the current environmental legislation of the European Union revealed that the quality standards are not sufficient to protect marine microalgae.
•Toxic pressure on effective photosystem II efficiency of marine microalgae•Diuron and terbutylazine are the main contributors to the toxic pressure.•Toxic pressure on microalgae in the Dutch estuarine and coastal waters decreased.•Combine chemical monitoring and bioassay testing to determine toxic pressure•Pulse Amplitude Modulation fluorometry useful for water quality assessment
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