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.

Calibration and Application of PUF Disk Passive Air Samplers To Assess Chlorinated Paraffins in Ambient Air in Australia, China, and Vietnam.

Ambient air samples were collected in Brisbane (Australia), Dalian (China), and Hanoi (Vietnam) during Mar 2013-Feb 2018 using polyurethane foam based passive air samplers. A sampling rate calibration experiment was conducted for chlorinated paraffins (CPs, i.e., short-chain, medium-chain, and long-chain CPs), where the sampling rates were 4.5 ± 0.7, 4.8 ± 0.3, and 4.8 ± 2.1 m3 day-1 for SCCPs, MCCPs, and LCCPs, respectively. The atmospheric concentration of CPs was then calculated and the medians of ∑CPs were 0.079, 1.0, and 0.89 ng m-3 in Brisbane, Dalian, and Hanoi, respectively. The concentration of CPs in Brisbane's air remained at low levels, with no significant differences observed between the city background site and the city center site, indicating limited usage and production of CPs in this city. The highest concentration of MCCPs was detected in Dalian, while the highest concentration of SCCPs was detected in Hanoi. A decrease of SCCP concentration and an increase of MCCPs' were found in Brisbane's air from 2016 to 2018, while increasing trends for both SCCPs and MCCPs were observed in Dalian. These results indicated impacts from different sources of CPs in the investigated cities.

Novel Per- and Polyfluoroalkyl Substances Discovered in Cattle Exposed to AFFF-Impacted Groundwater.

The leaching of per- and polyfluoroalkyl substances (PFASs) from Australian firefighting training grounds has resulted in extensive contamination of groundwater and nearby farmlands. Humans, farm animals, and wildlife in these areas may have been exposed to complex mixtures of PFASs from aqueous film-forming foams (AFFFs). This study aimed to identify PFAS classes in pooled whole blood (n = 4) and serum (n = 4) from cattle exposed to AFFF-impacted groundwater and potentially discover new PFASs in blood. Thirty PFASs were identified at various levels of confidence (levels 1a-5a), including three novel compounds: (i) perfluorohexanesulfonamido 2-hydroxypropanoic acid (FHxSA-HOPrA), (ii) methyl((perfluorohexyl)sulfonyl)sulfuramidous acid, and (iii) methyl((perfluorooctyl)sulfonyl)sulfuramidous acid, belonging to two different classes. Biotransformation intermediate, perfluorohexanesulfonamido propanoic acid (FHxSA-PrA), hitherto unreported in biological samples, was detected in both whole blood and serum. Furthermore, perfluoroalkyl sulfonamides, including perfluoropropane sulfonamide (FPrSA), perfluorobutane sulfonamide (FBSA), and perfluorohexane sulfonamide (FHxSA) were predominantly detected in whole blood, suggesting that these accumulate in the cell fraction of blood. The suspect screening revealed several fluoroalkyl chain-substituted PFAS. The results suggest that targeting only the major PFASs in the plasma or serum of AFFF-exposed mammals likely underestimates the toxicological risks associated with exposure. Future studies of AFFF-exposed populations should include whole-blood analysis with high-resolution mass spectrometry to understand the true extent of PFAS exposure.

Improving Wastewater-Based Tobacco Use Estimates Using Anabasine.

In wastewater-based epidemiology (WBE), nicotine metabolites have been used as biomarkers for monitoring tobacco use. Recently, the minor tobacco alkaloids anabasine and anatabine have been suggested as more specific biomarkers for tobacco use since nicotine use can be from both tobacco and non-tobacco sources. This study aimed to provide an in-depth evaluation of the suitability of anabasine and anatabine as WBE biomarkers of tobacco and subsequently estimate their excretion factors for WBE applications. Pooled urine (n = 64) and wastewater samples (n = 277), collected between 2009 and 2019 in Queensland, Australia, were analyzed for nicotine and its metabolites (cotinine and hydroxycotinine), as well as anabasine and anatabine. Anabasine performed as the better biomarker, showing a similar per capita load in pooled urine (2.2 ± 0.3 µg/day/person) and wastewater samples (2.3 ± 0.3 µg/day/person), while the per capita load of anatabine in wastewater was 50% higher than its load in urine. It is estimated that 0.9 µg of anabasine was excreted per cigarette smoked. Triangulation of tobacco sales data and tobacco use estimated from either anabasine or cotinine showed that anabasine-based estimates were 5% higher than sales data, while cotinine-based estimates were between 2 and 28% higher. Our results provided concrete evidence to confirm the suitability of anabasine as a specific biomarker for monitoring tobacco use by WBE.

Increased Nicotine Consumption in Australia During the First Months of the COVID-19 Pandemic.

INTRODUCTION: Mixed findings have been reported about the impact of the COVID-19 pandemic on smoking behavior in different populations. AIMS AND METHODS: In this study, we aimed to quantify changes in smoking prevalence through the proxy of nicotine consumption in the Australian population from 2017 to 2020 inclusive. Estimates of nicotine consumption between 2017 and 2020 were retrieved from a national wastewater monitoring program that covers up to 50% of the Australian population. National sales data for nicotine replacement therapy (NRT) products from 2017 to 2020 were also acquired. Linear regression and pairwise comparison were conducted to identify data trends and to test differences between time periods. RESULTS: The average consumption of nicotine in Australia decreased between 2017 and 2019 but increased in 2020. Estimated consumption in the first half of 2020 was significantly higher (~30%) than the previous period. Sales of NRT products increased gradually from 2017 to 2020 although sales in the first half of the year were consistently lower than in the second half. CONCLUSION: Total nicotine consumption increased in Australia during the early stage of the pandemic in 2020. Increased nicotine consumption may be due to people managing higher stress levels, such as from loneliness due to control measures, and also greater opportunities to smoke/vape while working from home and during lockdowns in the early stage of the pandemic. IMPLICATIONS: Tobacco and nicotine consumption have been decreasing in Australia but the COVID-19 pandemic may have temporarily disrupted this trend. In 2020, the higher impacts of lockdowns and working from home arrangements may have led to a temporary reversal of the previous downward trend in smoking during the early stage of the pandemic.

Apparent Half-Lives of Chlorinated-Perfluorooctane Sulfonate and Perfluorooctane Sulfonate Isomers in Aviation Firefighters.

Elevated levels of perfluorooctane sulfonate (PFOS) and elevated detection frequency of chloro-substituted PFOS have been reported in Australian firefighters with historical exposure to aqueous-film forming foam (AFFF). The aim of this study is to estimate the apparent half-lives of Cl-PFOS and PFOS isomers in firefighters following the end of exposure to 3M-AFFF. Paired serum samples from 120 firefighters, collected approximately five years apart, were analyzed for 8-Cl-PFOS (8-chloroperfluoro-1-octanesulfonic acid) and PFOS isomers via targeted LC-MS/MS. Apparent half-life was estimated by assuming a first order-elimination model. Cl-PFOS was detected in 93% of all initial serum samples (

Semiquantitative Characterization of Bromo-chloro Paraffins and Olefins in the Australian Environment.

A semiquantitative high-resolution mass spectrometry method was developed and applied to assess the occurrence of bromo-/chloro paraffins (BCPs) and olefins (BCOs) in the environment. More than 400 possible BCPs and BCO congener groups were detected in dust, air, and sewage sludge samples collected from Australia. Median chain analytes with the number of halogen atoms <7 (CnHmClxBry, 14 ≤ n ≤ 17, x + y < 7) prevailed in the dust and sludge samples, while short chain analytes (CnHmClxBry, 10 ≤ n ≤ 13, x + y < 7) predominated the air samples. The estimated concentrations of ∑BCPs and ∑BCOs in dust and sludge were approximately 20% that of the chlorinated paraffins (CPs) present, with the median concentrations of 5.4 µg/g (dust) and 0.18 µg/g (sludge) for ∑BCPs and 22 µg/g (in dust) and 0.50 µg/g (sludge) for BCOs. In the air samples, the concentrations of BCPs (0.020 pg/m3) and BCOs (0.032 pg/m3) were 3-4 orders of magnitudes lower than the concentrations of CPs (790 pg/m3). Significant correlations (P < 0.001) were found between the concentration of CPs, BCPs, and BCOs in all the matrices.

Assessment of Mobilization Potential of Per- and Polyfluoroalkyl Substances for Soil Remediation.

This study investigated the mobilization of a wide range of per- and polyfluoroalkyl substances (PFASs) present in aqueous film-forming foams (AFFFs) in water-saturated soils through one-dimensional (1-D) column experiments with a view to assessing the feasibility of their remediation by soil desorption and washing. Results indicated that sorption/desorption of most of the shorter-carbon-chain PFASs (C ≤ 6) in soil reached greater than 99% rapidly─after approximately two pore volumes (PVs) and were well predicted by an equilibrium transport model, indicating that they will be readily removed by soil washing technologies. In contrast, the equilibrium model failed to predict the mobilization of longer-chain PFASs (C ≥ 7), indicating the presence of nonequilibrium sorption/desorption (confirmed by a flow interruption experiment). The actual time taken to attain 99% sorption/desorption was up to 5 times longer than predicted by the equilibrium model (e.g., ∼62 PVs versus ∼12 PVs predicted for perfluorooctane sulfonate (PFOS) in loamy sand). The increasing contribution of hydrophobic interactions over the electrostatic interactions is suggested as the main driving factor of the nonequilibrium processes. The inverse linear relationship (R2 = 0.6, p < 0.0001) between the nonequilibrium mass transfer rate coefficient and the Freundlich sorption coefficient could potentially be a useful means for preliminary evaluation of potential nonequilibrium sorption/desorption of PFASs in soils.

Comparing the Leaching Behavior of Per- and Polyfluoroalkyl Substances from Contaminated Soils Using Static and Column Leaching Tests.

Soil contaminated with aqueous film-forming foams (AFFFs) containing per- and polyfluoroalkyl substances (PFASs) at firefighting training sites has become a major concern worldwide. To date, most studies have focused on assessing soil-water partitioning behavior of PFASs and the key factors that can affect their sorption, whereas PFASs leaching from contaminated soils have not yet been widely investigated. This study evaluated the leaching and desorption of a wide range of PFASs from twelve contaminated soils using the Australian Standard Leaching Procedure (ASLP), the U.S. EPA Multiple Extraction Procedure (MEP), and Leaching Environmental Assessment Framework (LEAF). All three leaching tests provided a similar assessment of PFAS leaching behavior. Leaching of PFASs from soils was related to C-chain lengths and their functional head groups. While short-chain (CF2 ≤ 6) PFASs were easily desorbed and leached, long-chain PFASs were more difficult to desorb. PFASs with a carboxylate head group were leached more readily and to a greater extent than those with a sulfonate or sulfonamide head group. Leaching of long-chain PFASs was pH-dependent where leaching increased at high pH, while leaching of short-chain PFASs was less sensitive to pH. Comparing different leaching tests showed that the results using the alkaline ASLP were similar to the cumulative MEP data and the former might be more practical for routine use than the MEP. No single soil property was adequately able to describe PFAS leaching from the soils. Overall, the PFAS chemical structure appeared to have a greater effect on PFAS leaching from soil than soil physicochemical properties.

Associations between serum perfluoroalkyl acid (PFAA) concentrations and health related biomarkers in firefighters.

OBJECTIVES: Firefighters who used aqueous film forming foam in the past have experienced elevated exposures to perfluoroalkyl acids (PFAAs). The objective of this study was to examine the associations between clinical chemistry endpoints and serum concentrations of perfluorooctanoic acid (PFOA), perfluorohexane sulfonate (PFHxS), perfluoroheptane sulfonate (PFHpS) and perfluorooctane sulfonate (PFOS) in firefighters. Multiple linear regression was used to assess relationships between PFAA serum concentrations and biochemical markers for cardiovascular disease, kidney-, liver- and thyroid function, in a cross-sectional survey of 783 firefighters with elevated levels of PFHxS, PFHpS and PFOS in relation to the most recently reported levels in the general Australian population. Linear logistic regression was used to assess the odds ratios for selected self-reported health outcomes. Repeated measures linear mixed models were further used to assess relationships between PFAAs and biomarkers for cardiovascular disease and kidney function longitudinally in a subset of the firefighters (n = 130) where serum measurements were available from two timepoints, five years apart. In the cross-sectional analysis, higher levels of all PFAAs were significantly associated with higher levels of biomarkers for cardiovascular disease (total-cholesterol, and LDL-cholesterol). For example, doubling in PFOS serum concentration were associated with increases in total cholesterol (ß:0.111, 95% confidence interval (95%CI): 0.026, 0.195 mmol/L) and LDL-cholesterol (ß: 0.104, 95%CI:0.03, 0.178 mmol/L). Doubling in PFOA concentration, despite not being elevated in the study population, were additionally positively associated with kidney function marker urate (e.g., ß: 0.010, 95%CI; 0.004, 0.016 mmol/L) and thyroid function marker TSH (e.g., ß: 0.087, 95%CI: 0.014, 0.161 mIU/L). PFAAs were not associated with any assessed self-reported health conditions. No significant relationships were observed in the longitudinal analysis. Findings support previous studies, particularly on the association between PFAAs and serum lipids.

Social, demographic, and economic correlates of food and chemical consumption measured by wastewater-based epidemiology.

Wastewater is a potential treasure trove of chemicals that reflects population behavior and health status. Wastewater-based epidemiology has been employed to determine population-scale consumption of chemicals, particularly illicit drugs, across different communities and over time. However, the sociodemographic or socioeconomic correlates of chemical consumption and exposure are unclear. This study explores the relationships between catchment specific sociodemographic parameters and biomarkers in wastewater generated by the respective catchments. Domestic wastewater influent samples taken during the 2016 Australian census week were analyzed for a range of diet, drug, pharmaceutical, and lifestyle biomarkers. We present both linear and rank-order (i.e., Pearson and Spearman) correlations between loads of 42 biomarkers and census-derived metrics, index of relative socioeconomic advantage and disadvantage (IRSAD), median age, and 40 socioeconomic index for area (SEIFA) descriptors. Biomarkers of caffeine, citrus, and dietary fiber consumption had strong positive correlations with IRSAD, while tramadol, atenolol, and pregabalin had strong negative correlation with IRSAD. As expected, atenolol and hydrochlorothiazide correlated positively with median age. We also found specific SEIFA descriptors such as occupation and educational attainment correlating with each biomarker. Our study demonstrates that wastewater-based epidemiology can be used to study sociodemographic influences and disparities in chemical consumption.

Multisite Calibration of a Microporous Polyethylene Tube Passive Sampler for Quantifying Drugs in Wastewater.

Passive sampling approaches to monitor licit and illicit drugs of concern in wastewater shows promise as a supplementary sampling technique to grab sampling when conventional composite autosampling may not be possible. Recent studies have assessed the applicability of passive sampling at a single wastewater treatment plant (WWTP). However, it remains unknown whether a single-site calibration can be applied to other WWTPs. This study evaluated the in situ calibration of microporous polyethylene tube passive samplers (MPTs) against simultaneously collected composite samples for 22 different WWTPs. Samples were analyzed for methylamphetamine, amphetamine, hydroxycotinine, cotinine, benzoylecgonine, 3,4-methylenedioxymethamphetamine, and noroxycodone. Estimated rates of chemical uptake (sampling rates) were calculated using the mass accumulated in the samplers, the concentration measured in composite samples, and the duration of deployment. The estimated sampling rates were consistent between WWTPs (>90% within a factor of two) and ranged from 5 mL day-1 (amphetamine) to 9 mL day-1 (noroxycodone). The samplers were effective at estimating analyte concentrations, with 77% of results having a normalized difference to 24 h composite samples of below 30%. Our study suggests that MPT passive samplers provide a tool for the spatiotemporal monitoring of drug use where automated integrative sampling techniques may not be feasible.

Postflood Monitoring in a Subtropical Estuary and Benchmarking with PFASs Allows Measurement of Chemical Persistence on the Scale of Months.

Measurements of chemical persistence in natural environments can provide insight into behavior not easily replicated in laboratory studies. However, it is difficult to find environmental situations suitable for such measurements, particularly for substances with half-lives exceeding several weeks. The objective of this study was to demonstrate that a strategic postflood monitoring campaign can be used to quantify transformation half-lives on the scale of months in a real aquatic system. Water samples were collected in the upper Brisbane River estuary on 36 occasions over 37 weeks and analyzed for 127 pharmaceuticals and personal care products (PPCPs), pesticides, and perfluoroalkyl substances (PFASs). High quality time trend data were obtained for 41 substances. For many of these, data on the input of a wastewater treatment plant to the upper estuary were also obtained. A mass balance model of the estuary stretch was formulated and parametrized using PFASs as persistent benchmarking chemicals. Transformation half-life estimates were obtained for 10 PPCPs and 7 pesticides ranging from 18 to 260 days. Furthermore, insight was obtained into dominant transformation processes as well as the magnitude of chemical inputs to the estuary and their sources. The approach developed shows that under certain conditions, estuaries can be used to quantify the persistence of organic contaminants with half-lives of the order of several months.

Effects of pH, Temperature, Suspended Solids, and Biological Activity on Transformation of Illicit Drug and Pharmaceutical Biomarkers in Sewers.

In-sewer stability of biomarkers is a critical factor for wastewater-based epidemiology, as it could affect the accuracy of the estimated prevalence of substances in the community. The spatiotemporal variations of environmental and biological conditions in sewers can influence the transformation of biomarkers. To date, the relationship between environmental variables and biomarker stability in sewers is poorly understood. Therefore, this study evaluated the transformation of common illicit drug and pharmaceutical biomarkers in laboratory sewer reactors with different levels of pH, temperature, and suspended solids. The correlations between degradation rates of 14 biomarkers, 3 controlled environmental variables (pH, temperature, and suspended solids concentration), and 3 biological activity indicators (sulfide production rate, methane production rate, and the removal rate of soluble chemical oxygen demand (SCOD)) were assessed using correlation matrix, stepwise regression method, and principal component analysis. The consistent results affirmed the dominant effects of biological activities and pH on biomarker transformation in sewers, particularly for labile compounds, whereas the impact of temperature or suspended solids was less significant. This study enhances the understanding of factors affecting the fate of micropollutants in sewer systems and facilitates the interpretation of WBE results for assessing drug use and public health in communities.

Assessing decontamination and laundering processes for the removal of polycyclic aromatic hydrocarbons and flame retardants from firefighting uniforms.

Firefighter uniforms protect firefighters from exposure to potentially harmful chemicals including a range of semi-volatile organic compounds (SVOCs). Contaminated uniforms can become a secondary source of firefighters' exposure to these chemicals. There is inconsistency on the removal efficiency of SVOCs during the cleaning, laundering and field decontamination of firefighting uniforms. Therefore, this study aims to assess how effective decontamination and laundering processes are in reducing firefighter uniforms as a vector for transport and exposure to SVOCs. Firefighters who had attended a controlled house fire and simulated container burns had their uniforms sampled pre- and post-laundering. Clean station wear was laundered with contaminated uniforms and after a load of contaminated uniforms to assess inter and intra load contamination. Surface wipes were collected from uniforms across 12 fire stations, after they had returned from a laundering provider. Concentrations of 13 polycyclic aromatic hydrocarbons (PAHs), six organophosphate flame retardants (OPFRs) and seven polybrominated diphenyl ethers (PBDEs) were measured in the collected samples. The concentrations of ∑13 PAHs in firefighters uniforms ranged between 0.063 and 43 µg g-1, while concentration of ∑6 OPFRs were between 0.061 and 90 µg g-1 with ∑7 PBDEs concentrations being measured between 0.00054 and 0.97 µg g-1.The highest concentrations of ∑13 PAHs were measured on the outer layers of gloves at an average of 19 µg g-1, with the highest ∑6 OPFRs concentrations being measured in the middle layers of gloves at an average of 31 µg g-1. The highest ∑7 PBDEs concentrations were measured on the shell layers of turnout jackets at 0.42 µg g-1. The significant reduction in ∑13 PAHs after laundering or decontamination was only found in 3 of the 16 sampled areas from firefighting uniforms. No significant differences were found in the between pre- and post-laundering concentrations of ∑6 OPFRs or ∑7 PBDEs in firefighting uniforms. The current laundering techniques do not appear to effectively remove PAHs, OPFRs and PBDEs at the measured concentrations from firefighters' uniforms. Further research is required to assess if chemical exposure though firefighting uniforms poses a health risk to firefighters and to develop methods for the removal of SVOCs from firefighting uniforms.

Intraday variability of indicator and pathogenic viruses in 1-h and 24-h composite wastewater samples: Implications for wastewater-based epidemiology.

We monitored the concentration of indicator viruses crAssphage and pepper mild mottle virus (PMMoV) and human pathogen adenovirus (HAdV) in influent from a wastewater treatment plant in Brisbane, Australia in 1-h and 24-h composite samples. Over three days of sampling, the mean concentration of crAssphage gene copies (GC)/mL in 24-h composite samples did not differ significantly (p = 0.72-0.92), while for PMMoV GC/mL (p value range: 0.0002-0.0321) and HAdV GC/mL (p value range: 0.0028-0.0068) significant differences in concentrations were observed on one day of sampling compared to the other two. For all three viruses, the variation observed in 1-h composite samples was greater than the variation observed in 24-h composite samples. For crAssphage, in 54.1% of 1-h composite samples, the concentration was less than that observed in 24-h composite samples; whereas for PMMoV and HAdV the concentration was less in 79.2 and 70.9% of 1-h composite samples, respectively, compared to the relevant 24-h composite samples. Similarly, the concentration of crAssphage in 1-h compared to 24-h composite samples did not differ (p = 0.1082) while the concentrations of PMMoV (p < 0.0001) and HAdV (p < 0.0001) in 1-h composite samples were significantly different from 24-h composite samples. These results suggest that 24-h composite samples offer increased analytical sensitivity and decreased variability compared to 1-h composite samples when monitoring wastewater, especially for pathogenic viruses with low infection rates within a community. Thus, for wastewater-based epidemiology applications, 24-h composite samples are less likely to produce false negative results and erroneous public health information.

Transformation of Illicit Drugs and Pharmaceuticals in Sewer Sediments.

In-sewer stability of human excreted biomarkers is a critical factor of wastewater-based epidemiology in back-estimating illicit drug and pharmaceutical use in the community. Biomarker stability has been investigated in sewers with the presence of biofilms, but the understanding in sewer sediments is still lacking. This study for the first time employed a laboratory sediment reactor to measure 18 illicit drug and pharmaceutical biomarkers under gravity sewer environments with the presence of sediments. Biomarkers exhibited various stability patterns due to transformation processes occurring in the bulk wastewater and sediments. The attenuation of a biomarker by sediments is driven by complex processes involving biodegradation, diffusion, and sorption, which is directly proportional to the ratio of sediment surface area against wastewater volume. The sediment-driven transformation coefficients of biomarkers are higher than the accordingly biofilm-mediated rates because of stronger microbial activities in sediments. Additionally, the stability of most biomarkers was insensitive to the natural pH variation in sewers, except for a few compounds (e.g., methadone, ketamine, and paracetamol) susceptible to pH changes. In general, this study delineates the stability data of various biomarkers in gravity sewers with sediments, which are novel and long-missing information for wastewater-based epidemiology and improve the reliability of back-estimation in complex sewer networks.

Urinary Concentrations of Bisphenols in the Australian Population and Their Association with the Per Capita Mass Loads in Wastewater.

Health concerns and related regulation of bisphenol A (BPA) in some countries have led to an increase in the production and use of unregulated and poorly understood BPA analogues, including bisphenol S (BPS), bisphenol F (BPF), bisphenol B (BPB), and bisphenol AF (BPAF). To assess the temporal trends of human exposure to BPA analogues, urine and wastewater samples were collected from South East Queensland, Australia between 2012 and 2017 and analyzed for five bisphenols using validated isotope dilution liquid chromatography tandem mass spectrometry methods. BPA and BPS were the predominant bisphenols detected in both urine and wastewater samples, with median concentrations of 2.5 and 0.64 µg/L in urine and 0.94 and 1.1 µg/L in wastewater, respectively. BPB, BPF, and BPAF had low detection frequencies in both urine and wastewater samples. Concentrations of BPA in both urine and wastewater decreased over the sampling period, whereas concentrations of BPS increased, suggesting that BPS has become a BPA replacement. The contributions of urinary excretion to wastewater were calculated by the ratio of daily per capita urinary excretion to wastewater-based mass loads of bisphenols. Urinary BPA and BPS contributed to less than 1% of the load found in wastewater, indicating that much of the BPA and BPS originates from other sources.

Quantitative Analysis of Selected Plastics in High-Commercial-Value Australian Seafood by Pyrolysis Gas Chromatography Mass Spectrometry.

Microplastic contamination of the marine environment is widespread, but the extent to which the marine food web is contaminated is not yet known. The aims of this study were to go beyond visual identification techniques and develop and apply a simple seafood sample cleanup, extraction, and quantitative analysis method using pyrolysis gas chromatography mass spectrometry to improve the detection of plastic contamination. This method allows the identification and quantification of polystyrene, polyethylene, polyvinyl chloride, polypropylene, and poly(methyl methacrylate) in the edible portion of five different seafood organisms: oysters, prawns, squid, crabs, and sardines. Polyvinyl chloride was detected in all samples and polyethylene at the highest total concentration of between 0.04 and 2.4 mg g-1 of tissue. Sardines contained the highest total plastic mass concentration (0.3 mg g-1 tissue) and squid the lowest (0.04 mg g-1 tissue). Our findings show that the total concentration of plastics is highly variable among species and that microplastic concentration differs between organisms of the same species. The sources of microplastic exposure, such as packaging and handling with consequent transference and adherence to the tissues, are discussed. This method is a major development in the standardization of plastic quantification techniques used in seafood.

Release of Plastics to Australian Land from Biosolids End-Use.

Plastics are contaminants of emerging concern that can enter the environment from multiple sources, including via land application of treated sewage sludge (biosolids). Biosolids samples collected from 82 wastewater treatment plants (WWTPs) across Australia and covering 34% of the population during census week in 2016 were quantitatively analyzed to estimate the release of seven common plastics. Quantitative analysis was performed by pressurized liquid extraction followed by double-shot microfurnace pyrolysis coupled to gas chromatography mass spectrometry. Ninety nine percent of the samples contained plastics (Σ6plastics) at concentrations of between 0.4 and 23.5 mg/g dry weight (median; 10.4 mg/g dry weight), while polycarbonate was not detected in any sample. Per-capita mass loads of plastics (Σ6plastics) released were between 8 and 877 g/person/year across all investigated WWTPs. Polyethylene was the predominant plastic detected, contributing to 69% of Σ6plastics. Based on the concentrations measured, it was projected that around 4700 metric tons (Mt) of plastics are released into the Australian environment through biosolids end-use each year, equating to approximately 200 g/person/year, which represents 0.13% of total plastics use in Australia. Of this, 3700 Mt of plastics are released to agricultural lands and 140 Mt to landscape topsoil. Our results provide a first quantitative per-capita mass loads and emission estimate of plastic types through biosolids end-use.