Unscrambling why plastics aren't detectable in chicken eggs.

Several food groups have been reported to contain varying concentrations of plastics. This study was designed to quantitatively investigate for the first time in Australia the presence of plastics in store-bought chicken eggs. Three commonly consumed brands of free-range, free-range organic, barn-laid and backyard (home-laid) chicken egg samples were analyzed for seven common polymers (i.e., polypropylene, polyethylene, polyvinyl chloride, polyethylene terephthalate, polystyrene, poly-(methylmethacrylate) and polycarbonate)). Samples were extracted by enzyme digestion and pressurized liquid extraction, followed by quantitative analysis through double-shot microfurnace pyrolysis coupled to gas chromatography-mass spectrometry. No plastics were detected at concentrations >limit of detection (LOD) (from 0.04 µg/g for PS to 0.22 µg/g for PVC) in the egg samples analyzed, regardless of brand and category, suggesting limited exposure of Australians to plastics from consuming eggs This study provides valuable baseline data and underscores the importance of continued monitoring to ensure the safety and integrity of food supplies in the face of rising environmental plastic pollution.

Fluoropolymer sorbent for efficient and selective capturing of per- and polyfluorinated compounds.

Per- and poly-fluoroalkyl substances (PFAS) have gained widespread attention due to their adverse effects on health and environment. Developing efficient technology to capture PFAS from contaminated sources remains a great challenge. In this study, we introduce a type of reusable polymeric sorbent (PFPE-IEX + ) for rapid, efficient, and selective removal of multiple PFAS impurities from various contaminated water sources. The resin achieves >98% removal efficiency ([PFPE-IEX + ] = 0.5-5 mg mL-1, [PFAS]0 = 1-10 ppb in potable water and landfill leachate) and >500 mg g-1 sorption capacity for the 11 types of examined PFAS. We achieve efficient PFAS removal without breakthrough and subsequent resin regeneration and demonstrate good PFAS recovery in a proof-of-concept cartridge setup. The outcomes of this study offer valuable guidance to the design of platforms for efficient and selective PFAS capture from contaminated water, such as drinking water and landfill leachate.

Wastewater-based evaluation of the efficacy of oxycodone regulations in Australia.

BACKGROUND AND AIMS: Between 2018 and 2020, Australia implemented major policy changes to improve the quality and safety of opioid prescribing, with a specific focus on oxycodone. This study used wastewater-based epidemiology to assess the efficacy of Australia's regulatory reforms by measuring change in consumption of oxycodone via exploratory analysis. DESIGN, SETTING, PARTICIPANTS, MEASUREMENTS: Wastewater analysis data on oxycodone consumption was from the National Wastewater Drug Monitoring Program. The program captures data from more than 50 wastewater treatment plant catchments across Australia, equivalent to more than 50% of the national population. Geographic trend analyses were conducted for both major cities and regional areas within all states and territories of Australia over a 6-year period between 2017 and 2023. FINDINGS: Oxycodone consumption showed a statistically significant increase nationally from 78 mg/day/1000 people (95% confidence interval [CI] = 71, 84) in 2017 to 120 mg/day/1000 people in August 2019 (95% CI = 110, 120), an increase of 52% (95% CI = 42, 62, P < 0.0001). From August 2019 to December 2020, there was a statistically significant decrease from 120 to 65 mg/day/1000 people (95% CI = 60, 71), a decrease of 45% (95% CI = 40, 51), followed by a modest 2.4% increase to the end of the study period in April 2023 (95% CI [2.0,2.7]). CONCLUSIONS: A 45% reduction in oxycodone consumption in Australia from 2019 to 2020 coincided with national policy changes that aimed to reduce consumption of prescription opioids. The overall declining trend in consumption was suggestive of the effectiveness of national interventions in reducing pharmaceutical opioid use. Wastewater-based epidemiology provides an effective approach for assessing the effectiveness of controlled substances policy changes.

Evidence of time dependent degradation of polypropylene surgical mesh explanted from the abdomen and vagina of sheep.

The failure of polypropylene mesh is marked by significant side effects and debilitation, arising from a complex interplay of factors. One key contributor is the pronounced physico-mechanical mismatch between the polypropylene (PP) fibres and surrounding tissues, resulting in substantial physical damage, inflammation, and persistent pain. However, the primary cause of sustained inflammation due to polypropylene itself remains incompletely understood. This study comprises a comprehensive, multi-pronged investigation to unravel the effects of implantation on a presumed inert PP mesh in sheep. Employing both advanced and conventional techniques to discern the physical and chemical transformations of the implanted PP. Our analyses reveal a surface degradation and oxidation of polypropylene fibres after 60 days implantation, persisting and intensifying at the 180-day mark. The emergence and accumulation of PP debris in the tissue surrounding the implant also increased with implantation time. We demonstrate observable physical and mechanical alterations in the fibre surface and stiffness. Our study shows surface alterations which indicate that PP is evidently less chemically inert than was initially presumed. These findings underscore the need for a re-evaluation of the biocompatibility and long-term consequences of using PP mesh implants.

Exploring the chemical subspace of RPLC: A data driven approach.

BACKGROUND: The chemical space is comprised of a vast number of possible structures, of which an unknown portion comprises the human and environmental exposome. Such samples are frequently analyzed using non-targeted analysis via liquid chromatography (LC) coupled to high-resolution mass spectrometry often employing a reversed phase (RP) column. However, prior to analysis, the contents of these samples are unknown and could be comprised of thousands of known and unknown chemical constituents. Moreover, it is unknown which part of the chemical space is sufficiently retained and eluted using RPLC. RESULTS: We present a generic framework that uses a data driven approach to predict whether molecules fall 'inside', 'maybe' inside, or 'outside' of the RPLC subspace. Firstly, three retention index random forest (RF) regression models were constructed that showed that molecular fingerprints are able to predict RPLC retention behavior. Secondly, these models were used to set up the dataset for building an RPLC RF classification model. The RPLC classification model was able to correctly predict whether a chemical belonged to the RPLC subspace with an accuracy of 92% for the testing set. Finally, applying this model to the 91 737 small molecules (i.e., ≤1 000 Da) in NORMAN SusDat showed that 19.1% fall 'outside' of the RPLC subspace. SIGNIFICANCE AND NOVELTY: The RPLC chemical space model provides a major step towards mapping the chemical space and is able to assess whether chemicals can potentially be measured with an RPLC method (i.e., not every RPLC method) or if a different selectivity should be considered. Moreover, knowing which chemicals are outside of the RPLC subspace can assist in reducing potential candidates for library searching and avoid screening for chemicals that will not be present in RPLC data.

Exploring the Chemical Space of the Exposome: How Far Have We Gone?

Around two-thirds of chronic human disease can not be explained by genetics alone. The Lancet Commission on Pollution and Health estimates that 16% of global premature deaths are linked to pollution. Additionally, it is now thought that humankind has surpassed the safe planetary operating space for introducing human-made chemicals into the Earth System. Direct and indirect exposure to a myriad of chemicals, known and unknown, poses a significant threat to biodiversity and human health, from vaccine efficacy to the rise of antimicrobial resistance as well as autoimmune diseases and mental health disorders. The exposome chemical space remains largely uncharted due to the sheer number of possible chemical structures, estimated at over 1060 unique forms. Conventional methods have cataloged only a fraction of the exposome, overlooking transformation products and often yielding uncertain results. In this Perspective, we have reviewed the latest efforts in mapping the exposome chemical space and its subspaces. We also provide our view on how the integration of data-driven approaches might be able to bridge the identified gaps.

High throughput and sensitive quantitation of tobacco-specific alkaloids and nitrosamines in wastewater.

Tobacco-specific alkaloids and nitrosamines are important biomarkers for the estimation of tobacco use and human exposure to tobacco-specific nitrosamines that can be monitored by wastewater analysis. Thus far their analysis has used solid phase extraction, which is costly and time-consuming. In this study, we developed a direct injection liquid chromatography-tandem mass spectrometry method for the quantification of two tobacco-specific alkaloids and five nitrosamines in wastewater. The method achieved excellent linearity (R2 > 0.99) for all analytes, with calibration ranging from 0.10 to 800 ng/L. Method limits of detection and quantification were 0.17 ng/L (N-nitrosonornicotine, NNN) and 1.0 ng/L (N-nitrosoanatabine (NAT) and NNN), with acceptable accuracy (100 % ± 20 %) and precision (± 15 %). Analyte loss during filtration was < 15 %, and the relative matrix effect was < 10 %. The method was applied to 43 pooled wastewater samples collected from three wastewater treatment plants in Australia between 2017 and 2021. Anabasine and anatabine were detected in all samples at concentrations of 5.0 - 33 ng/L and 12 - 41 ng/L, respectively. Three of the five tobacco-specific nitrosamines (NAT, NNN, and (4-(methylnitrosamino)-1-(3-pyridyl)-1-butanol) (NNAL)) were detected, in < 50 % of the wastewater samples, with concentrations nearly ten times lower than the tobacco alkaloids (< 1.0 - 6.2 ng/L). In-sewer stability of the nitrosamines was also assessed in this study, with four (NAT, NNAL, NNN, and N-nitrosoanabasine (NAB)) being stable (i.e. < 20 % transformation over 12 h in both control reactor (CR) and rising main reactor (RM) and 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone (NNK) being moderately stable (< 40 % loss over 12 h in RM). This direct injection method provides a high-throughput approach in simultaneous investigation of tobacco use and assessment of public exposure to tobacco-specific nitrosamines.

Seven-years of alcohol consumption in Australia by wastewater analysis: Exploring patterns by remoteness and socioeconomic factors.

BACKGROUND: Wastewater analysis provides a complementary measure of alcohol use in whole communities. We assessed absolute differences and temporal trends in alcohol consumption by degree of remoteness and socioeconomics indicators in Australia from 2016 to 2023. METHODS: Alcohol consumption estimates from 50 wastewater treatment plants (WWTP) in the Australian National Wastewater Drug Monitoring Program were used. Trends were analysed based on 1) site remoteness: Major Cities, Inner Regional and a combined remoteness category of Outer Regional and Remote, and 2) using two socioeconomic indexes from the Australian Bureau of Statistics (ABS) relating to advantage and disadvantage for Income, education, occupation, and housing. RESULTS: Consumption estimates were similar for Major Cities and Inner Regional areas (14.3 and 14.4L/day/1000 people), but significantly higher in Outer Regional and Remote sites (18.6L/day/1000 people). Consumption was decreasing in Major cities by 4.5% annually, Inner Regional by 2.4%, and 3.5% in the combined Outer Regional and Remote category. Consumption estimates were higher in socioeconomically advantaged quartiles than those of lower advantage (0%-25% mean = 13.0, 75%-100% mean = 17.4). Consumption in all quartiles decreased significantly over the 7 year period with annual rates of decrease of 0.9%, 3.7%, 3.6%, and 3.0% for the lowest to highest quartile, respectively. CONCLUSIONS: Declines in Australian alcohol consumption have been steeper in large urban areas than regional and remote areas. There were smaller annual decreases in the most socioeconomically disadvantaged areas. If continued, these trends may increase Australian health inequalities. Policy and prevention work should be appropriately targeted to produce more equitable long-term outcomes.

Limited exposure of captive Australian marsupials to plastics.

The global concern regarding the ubiquitous presence of plastics in the environment has led to intensified research on the impact of these materials on wildlife. In the Australian context, marsupials represent a unique and diverse group of mammals, yet little is known about their exposures to plastics. This study aimed to assess the contamination levels of seven common plastics (i.e., polystyrene (PS), polycarbonate (PC), poly-(methyl methacrylate) (PMMA), polypropylene (PP), polyethylene terephthalate (PET), polyethylene (PE), and polyvinyl chloride (PVC)) in both the diet and faeces of kangaroos, wallabies and koalas sampled from a sanctuary in Northeastern Australia. Quantitative analysis was performed by pressurized liquid extraction followed by double-shot microfurnace pyrolysis coupled to gas chromatography mass spectrometry. Interestingly, the analysis of the food and faeces samples revealed the absence of detectable plastic particles; with this preliminary finding suggesting a relatively limited exposure of captive Australian marsupials to plastics. This study contributes valuable insights into the current state of plastic contamination in Australian marsupials, shedding light on the limited exposures and potential risks, and highlighting the need for continued monitoring and conservation efforts. The results underscore the importance of proactive measures to mitigate plastic pollution and protect vulnerable wildlife populations in Australia's unique ecosystems.

Mass quantification of nanoplastics at wastewater treatment plants by pyrolysis-gas chromatography-mass spectrometry.

Municipal wastewater treatment plants (WWTPs) play a crucial role in the collection and redistribution of plastic particles from both households and industries, contributing to their presence in the environment. Previous studies investigating the levels of plastics in WWTPs, and their removal rates have primarily focused on polymer type, size, shape, colour, and particle count, while comprehensive understanding of the mass concentration of plastic particles, particularly those <1 µm (nanoplastics), remains unclear and lacking. In this study, pyrolysis gas chromatography-mass spectrometry was used to simultaneously determine the mass concentration of nine selected polymers (i.e., polyethylene (PE), polypropylene (PP), polystyrene (PS), poly(ethylene terephthalate) (PET), nylon 6, nylon 66, polyvinylchloride (PVC), poly(methyl methacrylate) (PMMA) and polycarbonate (PC)) below 1 µm in size across the treatment processes or stages of three WWTPs in Australia. All the targeted nanoplastics were detected at concentrations between 0.04 and 7.3 µg/L. Nylon 66 (0.2-7.3 µg/L), PE (0.1-6.6 µg/L), PP (0.1-4.5 µg/L), Nylon 6 (0.1-3.6 µg/L) and PET (0.1-2.2 µg/L), were the predominant polymers in the samples. The mass concentration of the total nanoplastics decreased from 27.7, 18 and 9.1 µg/L in the influent to 1, 1.4 and 0.8 µg/L in the effluent, with approximate removal rates of 96 %, 92 % and 91 % in plants A, B and C, respectively. Based on annual wastewater effluent discharge, it is estimated that approximately 24, 2 and 0.7 kg of nanoplastics are released into the environment per year for WWTPs A, B and C, respectively. This study investigated the mass concentrations and removal rates of nanoplastics with a size range of 0.01-1 µm in wastewater, providing important insight into the pollution levels and distribution patterns of nanoplastics in Australian WWTPs.

Workflow to facilitate the detection of new psychoactive substances and drugs of abuse in influent urban wastewater.

The complexity around the dynamic markets for new psychoactive substances (NPS) forces researchers to develop and apply innovative analytical strategies to detect and identify them in influent urban wastewater. In this work a comprehensive suspect screening workflow following liquid chromatography - high resolution mass spectrometry analysis was established utilising the open-source InSpectra data processing platform and the HighResNPS library. In total, 278 urban influent wastewater samples from 47 sites in 16 countries were collected to investigate the presence of NPS and other drugs of abuse. A total of 50 compounds were detected in samples from at least one site. Most compounds found were prescription drugs such as gabapentin (detection frequency 79%), codeine (40%) and pregabalin (15%). However, cocaine was the most found illicit drug (83%), in all countries where samples were collected apart from the Republic of Korea and China. Eight NPS were also identified with this protocol: 3-methylmethcathinone 11%), eutylone (6%), etizolam (2%), 3-chloromethcathinone (4%), mitragynine (6%), phenibut (2%), 25I-NBOH (2%) and trimethoxyamphetamine (2%). The latter three have not previously been reported in municipal wastewater samples. The workflow employed allowed the prioritisation of features to be further investigated, reducing processing time and gaining in confidence in their identification.

Blueprint for the design, construction, and validation of a plastic and phthalate-minimised laboratory.

Micro and nanosized plastics (MNPs), and a range of associated additive chemicals, have become pervasive contaminants that humans and the environment are exposed to everyday. However, one of the principal challenges in their analysis is adequate strategies to minimise background contamination. Here a blueprint for a specialised plastics and additive-minimised clean room laboratory built for this purpose is presented. Common laboratory construction materials (n = 23) were tested, including acoustic baffles, ceiling materials, floor materials, glazing rubber, and silicone sealant. The % polymer content ranged from 2-76% w/w while the sum concentration of six phthalates ranged from 0.81 (0.73-0.86) to 21000 (15000-27000) mg/kg, assigning many of these materials as inappropriate for use in a clean room environment. The final design of the laboratory consisted of three interconnected rooms, operated under positive pressure with the inner rooms constructed almost entirely of stainless steel. Background concentrations of MNPs and phthalates in the new laboratory were compared to two Physical Containment Level 2 (PC2) laboratory environments, with concentrations of MNPs reduced by > 100 times and phthalates reduced by up to 120 times. This study reports the first known clean room of its kind and provides a blueprint for reference and use by future plastics research.

Plastic pollution in Moreton Bay sediments, Southeast Queensland, Australia.

The mounting issue of plastic waste in the aquatic ecosystem is a growing source of concern. Most plastic waste originates on land and a significant proportion of this eventually finds its way into the marine environment, which is widely regarded as a major repository for plastic debris. Currently, there exists a substantial gap in our understanding of how much plastic, the main polymer types, and the distribution of plastic in the marine environment. This study aimed to provide information on mass concentrations of a range of plastics in the surface sediments in the semi-enclosed Moreton Bay, just offshore the large city of Brisbane, Southeast Queensland, Australia. Surface sediment samples were quantitatively analysed for a suite of 7 common plastic polymer types (i.e., polystyrene (PS), polycarbonate (PC), poly-(methyl methacrylate) (PMMA), polypropylene (PP), polyethylene terephthalate (PET), polyethylene (PE) and polyvinyl chloride (PVC)) using a pressurized liquid extraction (PLE) followed by double-shot microfurnace pyrolysis coupled to gas chromatography mass spectrometry (Pyr-GC/MS). The advantage of this approach is that it can measure plastics below the limit of visual detection. The study revealed that Σ7plastics were consistently present in the samples, although the concentrations displayed a wide range of concentrations from 3.3 to 2194.2 µg/g across different sites. Among the polymers analysed, PE and PVC were found at the highest concentrations, ranging from 2.3 to 1885.9 µg/g and 3.0-979.5 µg/g, respectively. Based on the average concentrations of plastics measured, the dry bulk density and volume of sediments within the top 10 cm of the bay, it was estimated that there is a minimum of 7000 t of plastics stored in the surface sediments of the bay. This study is the first to report the mass concentrations of identified plastics and identify the main polymer types in Moreton Bay. This is important information to develop management plans to reduce the plastic waste entering the coastal marine environment.

Deep dive into the chronic toxicity of tyre particle mixtures and their leachates.

Particles from the tread of vehicle tyres are a global pollutant, which are emitted into the environment at an approximate rate of 1.4 kg.year-1 for an average passenger-car. In this study, popular tyre brands were used to generate a tyre tread microparticle mixture. The chronic toxicity of both particles and chemical leachates were compared on a planktonic test species (Daphnia magna). Over 21 days of exposure, pristine tyre tread microparticles were more toxic (LC50 60 mg.L-1) than chemical lechates alone (LC50 542 mg.L-1). Microparticles and leachates showed distinct effects on reproduction and morphological development at environmentally relevant concentrations, with dose-dependent uptake of particles visible in the digestive tract. Chemical characterization of leachates revealed a metal predominance of zinc, titanium, and strontium. Of the numerous organic chemicals present, at least 54 were shared across all 5 tyre brands, with many classified to be very toxic. Our results provide a critically needed information on the toxicity of tyre tread particles and the associated chemicals that leach from them to inform future mitigation measures. We conclude that tyre particles are hazardous pollutants of particular concern that are close to or possibly above chronic environmental safety limits in some locations.

New PFASs Identified in AFFF Impacted Groundwater by Passive Sampling and Nontarget Analysis.

Monitoring contamination from per- and polyfluoroalkyl substances (PFASs) in water systems impacted by aqueous film-forming foams (AFFFs) typically addresses a few known PFAS groups. Given the diversity of PFASs present in AFFFs, current analytical approaches do not comprehensively address the range of PFASs present in these systems. A suspect-screening and nontarget analysis (NTA) approach was developed and applied to identify novel PFASs in groundwater samples contaminated from historic AFFF use. A total of 88 PFASs were identified in both passive samplers and grab samples, and these were dominated by sulfonate derivatives and sulfonamide-derived precursors. Several ultrashort-chain (USC) PFASs (≤C3) were detected, 11 reported for the first time in Australian groundwater. Several transformation products were identified, including perfluoroalkane sulfonamides (FASAs) and perfluoroalkane sulfinates (PFASis). Two new PFASs were reported (((perfluorohexyl)sulfonyl)sulfamic acid; m/z 477.9068 and (E)-1,1,2,2,3,3,4,5,6,7,8,8,8-tridecafluorooct-6-ene-1-sulfonic acid; m/z 424.9482). This study highlights that several PFASs are overlooked using standard target analysis, and therefore, the potential risk from all PFASs present is likely to be underestimated.

Tracing the origins of plastics in biosolids: The role of sewerage pipe materials and trade waste.

Plastics are ubiquitous in virtually every environment on earth. While the specific sources of plastics entering wastewater are not well known, growing evidence suggests sewage sludge (biosolids) can be a sink for plastics. One potential source could be the sewerage pipe materials used to transport sewage between premises and wastewater treatment plants (WWTPs). To evaluate the significance of sewerage piping as a source of biosolids plastics concentrations, we compared the proportion of the total network (by length and surface area) of polyethylene (PE), polyvinylchloride (PVC), and polypropylene (PP) pipes from 10 WWTPs against their biosolids mass concentrations (mg plastic/g biosolid). Among the 10 catchments, the percentage of the network consisting of PP piping ranged from 0 to 1 %, with 0.8-21 % for PE, and 8-73 % for PVC. Biosolids plastics concentrations ranged from 0.09 to 8.62 mg/g (mg plastic/g biosolid) for PP and PE, respectively. For all three plastics, there was no significant Pearson correlation (r < 0.4) between the biosolids concentration (dry weight mg/g) and the proportion of the network material of the sewerage piping as plastic (either length or surface area). A comparison of trade waste entering a subset of 6 WWTP showed the highest biosolid principal components analysis (PCA) associations between loads of plastics (g/day) and automotive wash bays, general manufacturing, hospitals, laboratories, food manufacturing, laundry and dry cleaning, and cooling towers. A stepwise regression analysis indicated pipe length and surface area, as well as automotive wash bays and food manufacturing may be significant. While our data gave mixed results on the attribution of the sources of plastics entering WWTPs, it suggests that sewerage infrastructure and trade waste may play some role. Future studies should investigate the leachability of sewerage infrastructure and contributions from specific trade waste categories to determine their significance in plastics entering WWTPs.

Associations of sleep duration and daytime sleepiness with plasma amyloid beta and cognitive performance in cognitively unimpaired, middle-aged and older African Americans.

STUDY OBJECTIVES: Given the established racial disparities in both sleep health and dementia risk for African American populations, we assess cross-sectional and longitudinal associations of self-report sleep duration (SRSD) and daytime sleepiness with plasma amyloid beta (Aß) and cognition in an African American (AA) cohort. METHODS: In a cognitively unimpaired sample drawn from the African Americans Fighting Alzheimer's in Midlife (AA-FAiM) study, data on SRSD, Epworth Sleepiness Scale, demographics, and cognitive performance were analyzed. Aß40, Aß42, and the Aß42/40 ratio were quantified from plasma samples. Cross-sectional analyses explored associations between baseline predictors and outcome measures. Linear mixed-effect regression models estimated associations of SRSD and daytime sleepiness with plasma Aß and cognitive performance levels and change over time. RESULTS: One hundred and forty-seven participants comprised the cross-sectional sample. Baseline age was 63.2 ±â€…8.51 years. 69.6% self-identified as female. SRSD was 6.4 ±â€…1.1 hours and 22.4% reported excessive daytime sleepiness. The longitudinal dataset included 57 participants. In fully adjusted models, neither SRSD nor daytime sleepiness is associated with cross-sectional or longitudinal Aß. Associations with level and trajectory of cognitive test performance varied by measure of sleep health. CONCLUSIONS: SRSD was below National Sleep Foundation recommendations and daytime sleepiness was prevalent in this cohort. In the absence of observed associations with plasma Aß, poorer self-reported sleep health broadly predicted poorer cognitive function but not accelerated decline. Future research is necessary to understand and address modifiable sleep mechanisms as they relate to cognitive aging in AA at disproportionate risk for dementia. CLINICAL TRIAL INFORMATION: Not applicable.

In-sewer stability of 31 human health biomarkers and suitability for wastewater-based epidemiology.

Monitoring urinary markers of dietary, disease, and stress by wastewater-based epidemiology (WBE) is a promising tool to better understand population health and wellbeing. However, common urinary biomarkers are subject to degradation in sewer systems and their fates have to be assessed before they can be used in WBE. This study investigated the stability of 31 urinary biomarkers (12 food biomarkers, 8 vitamins, 9 oxidative stress biomarkers, and 1 histamine biomarker) in a laboratory sewer sediment reactor and evaluated their suitability for WBE, considering their detectability in real wastewater and in-sewer stability. These biomarkers showed various transformation patterns, among which 16 compounds had half-lives <2 h while other 15 compounds presented moderate to high stability (2 to >500 h). Thirteen biomarkers showed potential for WBE because of their consistently measurable concentrations in untreated wastewater and sufficient in-sewer stability. Eighteen biomarkers were unsuitable due to their rapid in-sewer degradation and/or undetectable concentration levels in untreated wastewater using previous methods. Transformation rates of these biomarkers showed generally weak relationships with molecular properties but relatively higher correlations with biological activities in sewers. Overall, this study determined in-sewer stability of 31 health-related biomarkers through laboratory experiments, providing new findings to WBE for population health assessment.

Influence of extraction windows for data-independent acquisition on feature annotation during suspect screening.

Non-target analysis (NTA) using high-resolution mass spectrometry is becoming a useful approach to screen for suspect and unknown chemicals. For comprehensive analyses, data-independent acquisition (DIA), like Sequential Windowed Acquisition of all THeoretical Mass Spectra (SWATH-MS) on Sciex instruments, is necessary, usually followed by library matching for feature annotation. The choice of parameters, such as acquisition window number and size, may influence the comprehensiveness of the suspect features detected. The goal of this study was to assess how mass spectrometric DIA settings may influence the ability to obtain confident annotations and identifications of features in environmental (river water, passive sample extract (PSE)), wastewater (unpreserved and acidified) and biological (urine) sample matrices. Each matrix was analysed using 11 different MS methods, with 5-15 variable size acquisition windows. True positive (TP) annotation (i.e., matching experimental and library spectra) rates were constant for PSE (40%) and highest for urine (18%), wastewater (34% and 36%, unpreserved and acidified, respectively) and river water (8%) when using higher numbers of windows (15). The number of annotated features was highest for PSE (12%) and urine (8.5%) when using more acquisition windows (9 and 14, respectively). Less complex matrices (based on average total ion chromatogram intensities) like river water, unpreserved and acidified wastewater have higher annotation rates (7.5%, 8% and 13.2%, respectively) when using less acquisition windows (5-6), indicating matrix dependency of optimum settings. Library scores varied widely for correct (scores between 6 and 100) as well as incorrect annotations (scores between 2 and 100), making it hard to define specific ideal cut-off values. Results highlight the need for properly curated libraries and careful optimization of SWATH-MS and other DIA methods for each individual matrix, finding the best ratio of total annotations to true positive, (i.e., correct) annotations to achieve best NTA results.