Calibration of a microporous polyethylene tube passive sampler for polar organic compounds in wastewater effluent.

Water resources are vulnerable to contamination from polar organic compounds (POCs) originating from sources such as wastewater effluent. Two configurations of a microporous polyethylene tube (MPT) passive sampler were investigated for the time-integrative detection and quantification of POCs in effluent. One configuration contained the polymeric reversed phase sorbent Strata-X (SX) and the other Strata-X suspended in agarose gel (SX-Gel). These were deployed for up to 29 days and analysed for forty-nine POCs including pesticides, pharmaceuticals and personal care products (PPCPs) together with illicit drugs. Complementary composite samples were collected on days 6, 12, 20 and 26 representing the previous 24 h. Thirty-eight contaminants were detected in composite samples and MPT extracts, with MPT sampling rates (Rs) for 11 pesticides and 9 PPCPs/drugs ranging from 0.81 to 10.32 mL d-1 in SX and 1.35-32.83 mL d-1 in SX-Gel. Half-times to equilibrium of contaminants with the SX and SX-Gel equipped samplers ranged from two days to >29 days. MPT (SX) samplers were also deployed at 10 wastewater treatment effluent discharge sites across Australia for 7 days (again with complementary composite samples), to validate the sampler performance under varying conditions. Extracts from these MPTs detected 48 contaminants in comparison with 46 in composite samples, with concentrations ranging from 0.1 to 138 ng mL-1. An advantage of the MPT was preconcentration of contaminants, resulting in extract levels often markedly above instrument analytical detection limits. The validation study demonstrated a high correlation between accumulated contaminant mass in the MPTs and wastewater concentrations from composite samples (r2 > 0.70, where concentrations in composite samples were > 3× LOD). The MPT sampler shows promise as a sensitive tool for detecting POCs at trace levels in wastewater effluent and also quantifying these levels if temporal concentration variations are not significant.

Identification and Quantification of Micro-Bioplastics in Environmental Samples by Pyrolysis-Gas Chromatography-Mass Spectrometry.

Bioplastics are materials that are biobased and/or biodegradable, but not necessarily both. Concerns about environmental plastic pollution are constantly growing with increasing demand for substituting fossil-based plastics with those made using renewable resource feedstocks. For many conventional bioplastics to completely decompose/degrade, they require specific environmental conditions that are rarely met in natural ecosystems, leading to rapid formation of micro-bioplastics. As global bioplastic production and consumption/use continue to increase, there is growing concern regarding the potential for environmental pollution from micro-bioplastics. However, the actual extent of their environmental occurrence and potential impacts remains unclear, and there is insufficient mass concentration-based quantitative data due to the lack of quantitative analytical methods. This study developed and validated an analytical method coupling pressurized liquid extraction and pyrolysis-gas chromatography-mass spectrometry combined with thermochemolysis to simultaneously identify and quantify five targeted micro-bioplastics (i.e., polylactic acid (PLA), polyhydroxyalkanoate, polybutylene succinate, polycaprolactone, and polybutylene adipate terephthalate (PBAT)) in environmental samples on a polymer-specific mass-based concentration. The recovery of spiked micro-bioplastics in environmental samples (biosolids) ranged from 74 to 116%. The limits of quantification for the target micro-bioplastics were between 0.02 and 0.05 mg/g. PLA and PBAT were commonly detected in wastewater, biosolids, and sediment samples at concentrations between 0.07 and 0.18 mg/g. The presented analytical method enables the accurate identification, quantification, and monitoring of micro-bioplastics in environmental samples. This study quantified five micro-bioplastic types in complex environmental samples for the first time, filling in gaps in our knowledge about bioplastic pollution and providing a useful methodology and important reference data for future research.

Influence of surface oxidation on the quantification of polypropylene microplastics by pyrolysis gas chromatography mass spectrometry.

The influence of photo-oxidation on the quantification of isotactic polypropylene by Pyrolysis Gas Chromatography/Mass Spectrometry (Pyr-GC/MS) was assessed. Beads (oval shape, ~5 mm) and fragments (irregular shaped, 250-50 µm and 500-1000 µm) were subjected to relatively harsh simulated accelerated weathering conditions (using a filtered xenon-arc reproducing sunlight's full spectrum) for up to 37 and 80 days, respectively. Samples collected (n = 10 replicates for each treatment) at increasing number of weathering days were analysed by Fourier-transform infrared spectroscopy with Attenuated Total Reflection (FTIR-ATR), scanning electron microscopy, and differential scanning calorimetry in order to assess the extent and the rate of degradation. The rate of surface oxidation occurred faster for fragments compared to beads, probably due to their higher surface area. Quantification of the polypropylene trimer (2,4-dimethyl-1-heptene) via double shot Pyr-GC/MS, showed that the signal of the trimer relative to the mass of polypropylene was reduced through weathering with a degradation rate of 1:3 faster for fragments over beads. Signal reduction and carbonyl index were correlated to show that polypropylene with a carbonyl index of ≥13 has a significantly reduced 2,4-dimethyl-1-heptene signal when compared to virgin material. Consequently, the quantification of polypropylene subjected to weathering under harsh conditions may be underestimated by 42% (fragments, carbonyl index: 18) to 49% (beads, carbonyl index: 30) when quantified by Pyr-GC/MS and using virgin polypropylene calibration standards. Pyrolysis at a lower temperature (350 °C) identified six degradation specific markers (oxidation products) that increased in concentration with weathering. Further comparisons between virgin and weathered microplastics may need to be considered to avoid underestimation of microplastic concentrations in future studies.

Plastics contamination of store-bought rice.

This study investigated mass concentrations of selected plastics in store-bought rice, the staple of more than half the world's population. Polyethylene, polyethylene terephthalate, poly-(methyl methacrylate), polypropylene, polystyrene and polyvinyl chloride were quantified using pressurized liquid extraction coupled to double-shot pyrolysis gas chromatography/mass spectrometry. Polyethylene, polypropylene and polyethylene terephthalate were quantifiable in the rice samples with polyethylene the most frequently detected (95%). There was no statistical difference between total plastic concentration in paper and plastic packaged rice. Shaking the rice in its packaging had no significant difference on the concentration of plastics. Washing the rice with water significantly reduced plastic contamination. Instant (pre-cooked) rice contained fourfold higher levels of plastics, suggesting that industrial processing potentially increases contamination. A preliminary estimate of the intake of plastic through rice consumption for Australians established 3.7 mg per serve (100 g) if not washed and 2.8 mg if washed. Annual consumption was estimated around 1 g/person.

The legacy and drivers of groundwater nutrients and pesticides in an agriculturally impacted Quaternary aquifer system.

Nutrient and pesticide pollution are among the major threats to groundwater quality in agriculturally impacted aquifers. Understanding their legacy effects and drivers are important to protect aquifers from exposures to contamination. However, the complexities of groundwater flowpaths make it difficult to predict the time-scales of groundwater flow and contaminant transport. To determine these controls of groundwater nutrient and pesticides in an aquifer system underlying an intensive agricultural area in the Great Barrier Reef catchment, Australia, we sampled tritium (3H) to estimate groundwater-age, nutrient and pesticide concentrations to investigate groundwater contamination, and nitrogen (ẟ15N-NO3-) and oxygen (ẟ18O-NO3-) isotopes to determine groundwater nitrate dynamics. We, then, constructed high-resolution 3D geological and groundwater flow models of the aquifer system to determine the role of the geologic heterogeneity on the observed nutrient and pesticide concentrations. Groundwater 3H derived ages, and nutrient and pesticide concentrations did not follow distinct spatial trends. ẟ15N-NO3- and ẟ18O-NO3- values indicated that nitrification and denitrification processes influenced nitrate dynamics in the aquifer system; however, they were not solely able to explain the entire 3D variability. The 3D geologic modelling identified possible preferential flowpaths and perched systems, which helped to explain the observed groundwater-age, nutrient and pesticide variabilities. Old-groundwater (~100-years) was found in shallow depths (<15 m) where perched systems were identified. In areas with preferential flowpaths, young-groundwater (⁓1-year) with significant nitrate (~12 mg-N/L) and pesticides (up to 315 ng/L) concentrations were detected at deeper depths (>25 m), below perched and locally confined systems. Downward increasing groundwater-age, and decreasing nutrient and pesticide concentrations were detected in the unconfined aquifer, while old-groundwater (~160-years) and lower nitrate (<3 mg-N/L) and pesticides (<2 ng/L) concentrations were detected in the confined systems. This study demonstrates the importance of understanding both the geology and the hydrogeology of an area before deploying monitoring studies and/or making conclusions from tritium, nutrient and pesticide data alone.

Can SPEcies At Risk of pesticides (SPEAR) indices detect effects of target stressors among multiple interacting stressors?

Pesticides are increasingly recognised as a threat to freshwater biodiversity, but their specific ecological effects remain difficult to distinguish from those of co-occurring stressors and environmental gradients. Using mesocosms we examined the effects of an organophosphate insecticide (malathion) on stream macroinvertebrate communities concurrently exposed to a suite of stressors typical of streams in agricultural catchments. We assessed the specificity of the SPEcies At Risk index designed to determine pesticide effects in mesocosm trials (SPEARmesocosm). This index determines the log abundance proportion of taxa that are considered physiologically sensitive to pesticides. Geographic variation in pesticide sensitivity within taxa, coupled with variation between pesticides and the effects of co-occurring stressors may decrease the accuracy of SPEARmesocosm. To examine this, we used local pesticide sensitivity assessments based on rapid toxicity tests to develop two new SPEAR versions to compare to the original SPEARmesocosms index using mesocosm results. We further compared these results to multivariate analyses and community indices (e.g. richness, abundance, Simpson's diversity) commonly used to assess stressor effects on biota. To assess the implications of misclassifying species sensitivity on SPEAR indices we used a series of simulations using artificial data. The impacts of malathion were detectable using SPEARmesocosm, and one of two new SPEAR indices. All three of the SPEAR indices also increased when exposed to other agricultural non-pesticide stressors, and this change increased with greater pesticide concentrations. Our results support that interactions between other non-pesticide stressors with pesticides can affect SPEAR performance. Multivariate analysis and the other indices used here identified a significant effect of malathion especially at high concentrations, with little or no evidence of effects from the other agricultural stressors.

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.

Calibration and validation of a microporous polyethylene passive sampler for quantitative estimation of illicit drug and pharmaceutical and personal care product (PPCP) concentrations in wastewater influent.

Wastewater-based epidemiology (WBE), the per capita normalised measurement of drugs, chemicals or metabolites in wastewater influent, relies on sampling and quantitative analysis to evaluate temporal and spatial trends of chemical consumption. Continuous, high-resolution, flow proportional composite sampling is optimal for accurate representations of chemical mass loads, but is rarely implemented, with conventional autosamplers providing relatively low frequency time or volume proportional samples. However, due to equipment or resource constraints at many wastewater treatment plants (WWTPs), even this may not be feasible. Passive sampling may provide an alternative sampling strategy. To investigate this, samplers comprising hollow, cylindrical Microporous Polyethylene Tubes (MPTs) containing polymeric sorbent phases of Strata-X and Strata-X in agarose were simultaneously deployed in a municipal WWTP influent stream. Samplers were extracted, analysed and evaluated for a range of illicit drugs and pharmaceuticals and personal care products (PPCPs) after 4, 7, 15, 21, and 29 day deployments. The MPT samplers were calibrated against 24-hour time proportional composite grab samples that were collected in parallel. Diffusion through the MPT governed uptake, reducing or eliminating the influence of external flow rates that may fluctuate unpredictably in a WWTP environment. Calibration data for six illicit drugs and fourteen PPCPs, including methamphetamine, benzoylecgonine, MDMA, codeine and carbamazepine, demonstrated linear accumulation in the samplers (R2 ≥ 0.84). Derived sampling rates for these analytes ranged from 0.25 to 17 mL d-1 for ibuprofen and verapamil, respectively. A validation study using this sampling rate data showed the MPT could effectively quantify concentrations (≥0.1 ng mL-1) of a range of amphetamine-type stimulants, opioids and metabolites as well as nicotine, accounting for 95% of the variance in parallel composite grab sample concentrations of these compounds. The MPT sampler shows promise for providing essential monitoring data for WBE, informing future intervention and research strategies.

Current-use pesticides in New Zealand streams: Comparing results from grab samples and three types of passive samplers.

New Zealand uses more than a ton of pesticides each year; many of these are mobile, relatively persistent, and can make their way into waterways. While considerable effort goes into monitoring nutrients in agricultural streams and programs exist to monitor pesticides in groundwater, very little is known about pesticide detection frequencies, concentrations, or their potential impacts in New Zealand streams. We used the 'Polar Organic Chemical Integrative Sampler' (POCIS) approach and grab water sampling to survey pesticide concentrations in 36 agricultural streams in Waikato, Canterbury, Otago and Southland during a period of stable stream flows in Austral summer 2017/18. We employed a new approach for calculating site-specific POCIS sampling rates. We also tested two novel passive samplers designed to reduce the effects of hydrodynamic conditions on sampling rates: the 'Organic-Diffusive Gradients in Thin Films' (o-DGT) aquatic passive sampler and microporous polyethylene tubes (MPTs) filled with Strata-X sorbent. Multiple pesticides were found at most sites; two or more were detected at 78% of sites, three or more at 69% of sites, and four or more at 39% of sites. Chlorpyrifos concentrations were the highest, with a maximum concentration of 180 ng/L. Concentrations of the other pesticides were generally below 20 ng/L. Mean concentrations of individual pesticides were not correlated with in-stream nutrient concentrations. The majority of pesticides were detected most frequently in POCIS, presumably due to its higher sampling rate and the relatively low concentrations of these pesticides. In contrast, chlorpyrifos was most frequently detected in grab samples. Chlorpyrifos concentrations at two sites were above the 21-day chronic 'No Observable Effect Concentration' (NOEC) values for fish and another two sites had concentrations greater than 50% of the NOEC. Otherwise, concentrations were well-below NOEC values, but close to the New Zealand Environmental Exposure Limits in several cases.

Assessment of drugs and personal care products biomarkers in the influent and effluent of two wastewater treatment plants in Ho Chi Minh City, Vietnam.

Wastewater samples were collected at the influent and effluent of two wastewater treatment plants (WWTPs) in Ho Chi Minh City, Vietnam and then pooled to daily samples over multiple days using 6 hourly grab samples. The aim was to provide a first assessment of the occurrence, consumption, removal and release of a range of organic chemicals including pharmaceuticals and personal care products (PPCPs), illicit drugs, an artificial sweetener, tobacco and its metabolites and alcohol biomarkers (referred to here as DPCPBs). Nineteen DPCPBs were detected via direct measurement of filtered wastewater on LC-MS/MS with a concentration range of 0.05-38µg/L. Caffeine and paracetamol were the most prominent compounds detected in the influent, while acesulfame was found at the highest concentration in the effluent of both WWTPs. Mean concentrations of metabolites of tobacco (nicotine: 7.6µg/L, cotinine: 1.4µg/L and hydroxycotinine: 1.7µg/L) and alcohol (ethyl sulphate: 3.3µg/L) were lower than those of European countries. Consumption rates based on daily mass loads and catchment population data obtained from the WWTPs were <10g/d/1000 pp for the majority of selected PPCPs, except for caffeine (300g/d/1000 pp) and paracetamol (320g/d/1000 pp). Consumption rates for codeine and methamphetamine were 0.05g/d/1000 pp and 0.17g/d/1000 pp, respectively. Consistently across the two WWTPs most of the chemicals (10) showed >80% apparent removal rate from the wastewater, three chemicals showed apparent removal efficiency of approximately 50%; and the removal efficiency could not be assessed for 5 compounds due to their low concentrations in the influent. Based on the fraction of treated and untreated wastewater (10:90) that is released into the receiving environment we estimated a total discharge of approximately 170kg per day of DPCPBs in Ho Chi Minh City.

Development and calibration of a passive sampler for N-nitrosodimethylamine (NDMA) in water.

N-Nitrosamines such as N-nitrosodimethylamine (NDMA) are organic compounds of environmental concern in groundwater, wastewater and potable water due to their potent carcinogenicity in laboratory animal studies and probable human carcinogenicity. While passive sampling techniques have become a widely used tool for providing time-averaged estimates of trace pollutant concentration, for chemicals such as NDMA that have relatively high water solubility, the selection of a suitable sorbent is difficult. This work is a proof of principle study that investigated for the first time the use of coconut charcoal as a passive sampler sorbent. Apparent charcoal/water sorption coefficients for NDMA were >551 mL g(-1) at environmentally relevant aqueous concentrations of less than 1 µg L(-1). Under the experimental conditions employed, a sampling rate of 0.45 L d(-1) was determined and for an aqueous concentration of 1000 ng L(-1), it is predicted that the sampler remains in the linear uptake stage for approximately 4d, while equilibrium attainment would require about 26 d. The presence of humic acid, used as a surrogate for DOC, enhanced NDMA sorption on the coconut charcoal.

Detection of s-triazine pesticides in natural waters by modified large-volume direct injection HPLC.

There is a need for simple and inexpensive methods to quantify potentially harmful persistent pesticides often found in our water-ways and water distribution systems. This paper presents a simple, relatively inexpensive method for the detection of a group of commonly used pesticides (atrazine, simazine and hexazinone) in natural waters using large-volume direct injection high performance liquid chromatography (HPLC) utilizing a monolithic column and a single wavelength ultraviolet-visible light (UV-vis) detector. The best results for this system were obtained with a mobile phase made up of acetonitrile and water in a 30:70 ratio, a flow rate of 2.0 mL min(-1), and a detector wavelength of 230 nm. Using this method, we achieved retention times of less than three minutes, and detection limits of 5.7 microg L(-1) for atrazine, 4.7 microg L(-1) for simazine and 4.0 microg L(-1) for hexazinone. The performance of this method was validated with an inter-laboratory trial against a National Association of Testing Authorities (NATA) accredited liquid chromatography-mass spectrometry/mass spectrometry (LC-MS/MS) method commonly used in commercial laboratories.