Impacts of Proximity to Primary Source Areas on Concentrations of POPs at Global Sampling Stations Estimated from Land Cover Information

Given the considerable financial and logistical resources supporting long-term monitoring for air pollutants, and the use of these data for performance evaluation of mitigation measures, it is important to account for contributions from primary versus secondary sources. We demonstrate a simple approach for using open source Global land cover raster data from the National Mapping Organization from the Geospatial Information Authority of Japan to assess local source inputs for air measurements of legacy persistent organic pollutants (POPs)polychlorinated biphenyls (PCBs) and organochlorine pesticidesreported under the Global atmospheric passive sampling (GAPS) Network at 119 locations for the time period 2005–2014. The land cover composition within a 10 km radius around the GAPS sites was identified to create source impact indicator (SII) vectors to quantify and rank the remoteness of the sites from human infrastructure. Using principal component analysis, three SII vectors were established to rank sites by impact of (i) general infrastructure/remoteness, (ii) urban infrastructure, and (iii) agricultural infrastructure. General infrastructure describes the combined effects of settlements and agricultural infrastructure. We found significant correlations (p < 0.05) between POP concentrations in air and specific SIIs. PCB levels in air had a statistically significant correlation to the SII ranking urban impacts around the sampling sites, while Endosulfan I, Endosulfan II, and Endosulfan sulfate had a statistically significant correlation with SII ranking agricultural impacts. The complete GAPS data set from 2004–2014 (1040 samples at 119 locations) was standardized based on the SII rankings to assess the global temporal trends of legacy POPs. SIIs were incorporated in the multiple regression analysis to determine global halving times. This includes short-term monitoring data from 79 locations that were previously excluded. Furthermore, the SII approach allows the integration of global monitoring data from different studies for broader global temporal trend analysis. This ability to link the results of independent and small-scale studies can enhance temporal trend analysis in support of the larger scale initiatives, such as inter alia, the Global Monitoring Plan and Effectiveness Evaluation of the Stockholm Convention in the case of POPs. This simple approach using open source data has a broad potential for application for other classes of air pollutants

Impacts of Proximity to Primary Source Areas on Concentrations of POPs at Global Sampling Stations Estimated from Land Cover Information

Given the considerable financial and logistical resources supporting long-term monitoring for air pollutants, and the use of these data for performance evaluation of mitigation measures, it is important to account for contributions from primary versus secondary sources. We demonstrate a simple approach for using open source Global land cover raster data from the National Mapping Organization from the Geospatial Information Authority of Japan to assess local source inputs for air measurements of legacy persistent organic pollutants (POPs)polychlorinated biphenyls (PCBs) and organochlorine pesticidesreported under the Global atmospheric passive sampling (GAPS) Network at 119 locations for the time period 2005–2014. The land cover composition within a 10 km radius around the GAPS sites was identified to create source impact indicator (SII) vectors to quantify and rank the remoteness of the sites from human infrastructure. Using principal component analysis, three SII vectors were established to rank sites by impact of (i) general infrastructure/remoteness, (ii) urban infrastructure, and (iii) agricultural infrastructure. General infrastructure describes the combined effects of settlements and agricultural infrastructure. We found significant correlations (p < 0.05) between POP concentrations in air and specific SIIs. PCB levels in air had a statistically significant correlation to the SII ranking urban impacts around the sampling sites, while Endosulfan I, Endosulfan II, and Endosulfan sulfate had a statistically significant correlation with SII ranking agricultural impacts. The complete GAPS data set from 2004–2014 (1040 samples at 119 locations) was standardized based on the SII rankings to assess the global temporal trends of legacy POPs. SIIs were incorporated in the multiple regression analysis to determine global halving times. This includes short-term monitoring data from 79 locations that were previously excluded. Furthermore, the SII approach allows the integration of global monitoring data from different studies for broader global temporal trend analysis. This ability to link the results of independent and small-scale studies can enhance temporal trend analysis in support of the larger scale initiatives, such as inter alia, the Global Monitoring Plan and Effectiveness Evaluation of the Stockholm Convention in the case of POPs. This simple approach using open source data has a broad potential for application for other classes of air pollutants

Global Atmospheric Concentrations of Brominated and Chlorinated Flame Retardants and Organophosphate Esters

Polyurethane foam (PUF) disk passive air samples, deployed during 2014 in the Global Atmospheric Passive Sampling (GAPS) Network, were analyzed for a range of flame retardants (FRs) including polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCD), brominated and chlorinated novel FRs, and organophosphate esters (OPEs). Mean concentrations of PBDEs and novel FRs at the 48 sites monitored ranged from 0.097 to 93 pg/m³ for Σ₁₄PBDEs and from below detection limits to 126 pg/m³ for Σ₁₅novel FRs. For PBDEs, the detected concentrations were similar to those previously reported from samples collected in 2005 at GAPS sites, suggesting global background atmospheric concentrations of PBDEs have not declined since regulatory measures were implemented. OPEs were detected at every GAPS site, with Σ₁₈OPEs ranging from 69 to 7770 pg/m³. OPE concentrations were at least an order of magnitude higher than the PBDEs. This study presents the first data on global distributions of OPEs in the atmosphere, obtained from a single passive sampling monitoring network. Challenges that can arise in passive air sampling campaigns are also highlighted and addressed with suggested recommendations for future campaigns

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

High-Resolution Mass Spectrometric Profiling of Stormwater in an Australian Creek

Urban stormwater runoff is a major source of pollutants into receiving water bodies. The pollutant profile of stormwater samples collected from an Australian creek during a major storm event in 2020 was investigated using high-resolution mass spectrometry and chemometric tools. The samples were solid phase-extracted and analyzed by liquid chromatography coupled to a quadrupole time-of-flight mass spectrometer (LC-QToF-MS/MS). The detected features were prioritized using two independent but complementary workflows to identify the highly abundant stormwater-related compounds. A total of 174 features were detected at elevated levels during the storm. Four compounds were identified to a confidence level of 1 and 11 at level 2, including nonpolymeric surfactants, plastic additives, rubber and resin-related products, and natural products. Forty two percent were characterized as oligomers such as poly­(ethylene glycol) (PEG)-related compounds and octylphenol ethoxylates. Due to a lack of database experimental data, many compounds remained unidentified. Compounds belonging to the same class were clustered using Global Natural Product Social (GNPS) Molecular Networking analysis, highlighting the benefit of this platform in environmental analysis. The prioritization workflow used here is characterized as an effective tool for assessing key stormwater-related compounds and identifying which should receive attention in assessing the environmental effects of stormwater-related chemicals

Concentrations of Tire Additive Chemicals and Tire Road Wear Particles in an Australian Urban Tributary

Tire road wear particles (TRWPs) are one of the largest sources of microplastics to the urban environment with recent concerns as they also provide a pathway for additive chemicals to leach into the environment. Stormwater is a major source of TRWPs and associated additives to urban surface water, with additives including the antioxidant derivative N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine-quinone (6PPD-quinone) demonstrating links to aquatic toxicity at environmentally relevant concentrations. The present study used complementary analysis methods to quantify both TRWPs and a suite of known tire additive chemicals (including 6PPD-quinone) to an urban tributary in Australia during severe storm events. Concentrations of additives increased more than 40 times during storms, with a maximum concentration of 2760 ng/L for ∑15additives, 88 ng/L for 6PPD-quinone, and a similar profile observed in each storm. TRWPs were detected during storm peaks with a maximum concentration between 6.4 and 18 mg/L, and concentrations of TRWPs and all additives were highly correlated. Contaminant mass loads to this catchment were estimated as up to 100 g/storm for ∑15additives, 3 g/storm for 6PPD-quinone, and between 252 and 730 kg of TRWPs/storm. While 6PPD-quinone concentrations in this catchment were lower than previous studies, elevated concentrations post storm suggest prolonged aquatic exposure

Atmospheric Concentrations of New Persistent Organic Pollutants and Emerging Chemicals of Concern in the Group of Latin America and Caribbean (GRULAC) Region

A special initiative was run by the Global Atmospheric Passive Sampling (GAPS) Network to provide atmospheric data on a range of emerging chemicals of concern and candidate and new persistent organic pollutants in the Group of Latin America and Caribbean (GRULAC) region. Regional-scale data for a range of flame retardants (FRs) including polybrominated diphenyl ethers (PBDEs), organophosphate esters (OPEs), and a range of alternative FRs (novel FRs) are reported over 2 years of sampling with low detection frequencies of the novel FRs. Atmospheric concentrations of the OPEs were an order of magnitude higher than all other FRs, with similar profiles at all sites. Regional-scale background concentrations of the poly- and perfluoroalkyl substances (PFAS), including the neutral PFAS (n-PFAS) and perfluoroalkyl acids (PFAAs), and the volatile methyl siloxanes (VMS) are also reported. Ethyl perfluorooctane sulfonamide (EtFOSA) was detected at highly elevated concentrations in Brazil and Colombia, in line with the use of the pesticide sulfluramid in this region. Similar concentrations of the perfluoroalkyl sulfonates (PFAS) were detected throughout the GRULAC region regardless of location type, and the VMS concentrations in air increased with the population density of sampling locations. This is the first report of atmospheric concentrations of the PFAAs and VMS from this region