This article describes a stochastic method to calculate the annual pollutant loads and its application over several years at the outlet of three catchments drained by separate storm sewers. A stochastic methodology using Monte Carlo simulations is proposed for assessing annual pollutant load, as well as the associated uncertainties, from a few event sampling campaigns and/or continuous turbidity measurements (representative of the total suspended solids concentration (TSS)). Indeed, in the latter case, the proposed method takes into account the correlation between pollutants and TSS. The developed method was applied to data acquired within the French research project BINOGEV^ (innovations for a sustainable management of urban water) at the outlet of three urban catchments drained by separate storm sewers. Ten or so event sampling campaigns for a large range of pollutants (46 pollutants and 2 conventional water quality parameters: TSS and total organic carbon (TOC)) are combined with hundreds of rainfall events for which, at least one among three continuously monitored parameters (rainfall intensity, flow rate, and turbidity) is available. Results obtained for the three catchments show that the annual pollutant loads can be estimated with uncertainties ranging from 10 to 60%, and the added value of turbidity monitoring for lowering the uncertainty is demonstrated. A low inter-annual and inter-site variability of pollutant loads, for many of studied pollutants, is observed with respect to the estimated uncertainties, and can be explained mainly by annual precipitation.

International audience | Biocides are added to or applied on building materials to prevent microorganisms from growing on their surface or to treat them. They are leached into building runoff and contribute to diffuse contamination of receiving waters. This review aimed at summarizing the current state of knowledge concerning the impact of biocides from buildings on the aquatic environment. The objectives were (i) to assess the key parameters influencing the leaching of biocides and to quantify their emission from buildings; (ii) to determine the different pathways from urban sources into receiving waters; and (iii) to assess the associated environmental risk. Based on consumption data and leaching studies, a list of substances to monitor in receiving water was established. Literature review of their concentrations in the urban water cycle showed evidences of contamination and risk for aquatic life, which should put them into consideration for inclusion to European or international monitoring programs. However, some biocide concentration data in urban and receiving waters is still missing to fully assess their environmental risk, especially for isothiazolinones, iodopropynyl carbamate, zinc pyrithione and quaternary ammonium compounds, and little is known about their transformation products. Although some models supported by actual data were developed to extrapolate emissions on larger scales (watershed or city scales), they are not sufficient to prioritize the pathways of biocides from urban sources into receiving waters during both dry and wet weathers. Our review highlights the need to reduce emissions and limit their transfer into rivers, and reports several solutions to address these issues.

Legacy halogenated organic pollutants, including organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs), remain ubiquitous in the environment and continue to pose potential (eco-)toxicological threats because of their ongoing releases from land-based sources. This study investigated the spatial trends of freely dissolved PCBs and OCPs by polyethylene passive samplers, and provided evidence of their land-use-based sources and ecological risk in an urbanized estuary area of Narragansett Bay. Dissolved Σ₂₉PCB concentrations ranged from 0.01 to 1.37 ng L⁻¹, and exhibited higher concentrations in the upper, more urban/built-up watershed, and in north coastal areas. Major inputs of PCBs were urban stormwater or treated wastewater that might carry past releases of Aroclors, pigment manufacturing byproducts, and volatilization-associated PCBs from ageing buildings from the Narragansett watershed to the bay. The dioxin toxicity equivalent values of Σ₅PCBs were 8.6E-03 pg L⁻¹ in water. Dissolved OCP concentrations had similar spatial trends to PCBs and were dominated by DDTs (average 230 pg L⁻¹), followed by chlordanes (average 230 pg L⁻¹), and HCB (average 22 pg L⁻¹). Secondary sources of past usage and historic contamination were expected to re-enter the surface water via atmospheric transport and deposition. The risk quotients of DDE, DDD, DDT and α-Endosulfane showed medium to high ecological risks in the northern area, while chlordane, HCB, oxychlordane, and heptachlor epoxide showed low to negligible risks in all zones. This study presented new insights into the presence, sources and transport of legacy halogenated organic contaminants in an urban estuary's watershed by combining passive samplers and geographic information system (GIS) technology. The approach is promising and could be extended to get better understand of terrestrial pollutant mobilization into estuaries affected by anthropogenic activities.

Spatiotemporal variability complicates source apportionment of metals in urban lakes, especially when rainfall drives urban non-point source pollution. As, Cd, Cr, Pb, Hg, Ag, Co, Cu, Fe, Mn, Ni, Sb, Sr and Zn concentrations in 648 water samples collected before and after rain in 6 urban lakes of Beijing, China were determined during 2013–2015. The response of metals concentrations after rain to the interaction between rainfall and antecedent dry days was significant. Metals concentrations were normalized pursuant to the interaction effect as the input of positive matrix factorization (PMF) to develop the interaction normalized-PMF (IN-PMF). Four primary pollution sources were diagnosed. Sediment release was considered to be the main source of Fe, Co and Ni independent of rainfall. Hg, As and some Cr associated with pesticides and fertilizers were likely to come from soil erosion and runoff from green space. It is probable that road runoff was the dominant source for heavy metals related to traffic emissions, including Pb, Cd, Cu, Sb, Mn and Zn. Cr, Sr and some Cu and Zn as key elements of rooftops can be regarded as from roof runoff. The IN-PMF lowered roof and road runoff contributions and raised the contribution of soil erosion from green space, with Pb, Sb, Cu, Zn, Cd and Mn increasing by 15.9%, 10.7%, 13.1%, 12.2%, 13.3% and 16.8%. The results shed more light on the stormwater runoff pollution mitigation on impervious surfaces and metals enrichment problems in infiltration soil on green space in the low impact development (LID) setting. The Bayesian network revealed the spatial variability of transport and fate of metal elements from land surfaces to urban lakes, supplementing the secondary pollution sources from different land use. This study will provide new insights for source apportionment of non-point source pollution under the background of sponge city construction.

Microplastics (MPs) and microfibers (MFs) in stormwater have been poorly investigated. Data on their intra and inter rain events variability over time are still sparse. For the first time, the variability of microlitter concentrations in stormwater has been studied. MF and MP concentrations were investigated in stormwater runoff at the outlet of the suburban catchment at Sucy-en-Brie (a suburb of Paris, France), during four rain events. Median MF and MP concentrations were 1.9 and 29 items/L, with an interquartile range of 2.3 and 36 items/L, respectively (N = 18). A different pattern was observed between MFs and MPs. While no relationship or trends were observed for MFs, the highest MP concentrations were observed before the flow rate peak of the rain events. This could indicate a difference in the behaviour between MFs and MPs. We estimated the median MP mass concentration to be 56 μg/L with an interquartile range of 194 μg/L, whereas the mass concentration of macroplastics was estimated to be 31 μg/L with an interquartile range of 22 μg/L at the same sampling site, in a previous study. For this sampling site, MPs and macroplastics have the same order of magnitude. This study may have strong implications on microplastic assessment in urban waters.

Due to the complex sources and fate of perfluoroalkyl substance (PFAS), their source apportionment in the environment remains a challenge. A data set of 11 straight-chain PFAS in 139 samples of fish in the Great Lakes was analyzed using positive matrix factorization (PMF) to investigate their primary sources, whose spatial variations were examined against the surrounding environmental factors. PMF analysis produced five fingerprints. Factor 1 (72% of Σ₁₁PFAS, dominated by PFOS) probably represented emissions from primary sources (such as consumer products) and secondary sources (precursors), and increased in average abundance from west to east across the Great Lakes. Factor 2 (13% of Σ₁₁PFAS) and factor 3 (7% of Σ₁₁PFAS), highly loaded with long-chain PFAS and PFNA, respectively, were thought to represent PVDF manufacture or processing in metal plating. They showed higher contributions in sparsely populated Lakes Superior and Huron. Factor 4 (5% of Σ₁₁PFAS, highly loaded with PFOS and PFHxS) presented hot spots near current and former air force bases, suggesting it was related to aqueous film-forming foams (AFFFs). Factor 5 (4% of Σ₁₁PFAS) contained primarily PFOS and PFOSA, which may imply metabolism of precursors (PFOSA) to PFOS in vivo. Unexpectedly, the spatial trends of the five sources all showed abnormally low values near the more urbanized Chicago and Milwaukee in Lake Michigan, which may be due to their unique wastewater and stormwater infrastructure or may arise from atmospheric transport of precursors. Our study indicated that PMF was an effective tool to identify sources of PFAS in fish despite absorption, distribution, metabolism, and excretion (ADME) processes which might alter fingerprints in fish relative to their surrounding environment.

Passive samplers are useful tools for monitoring hydrophobic, persistent, and potentially bioaccumulative contaminants in the environment. In this study, low density polyethylene passive samplers were deployed in urban-influenced and background nearshore freshwaters of northwestern Lake Ontario and analyzed for a broad range of both legacy halogenated organic contaminants (HOCs) and halogenated flame retardants (HFRs). Non-targeted analysis was conducted for screening additional halogenated substances. For most compounds, concentrations were greatest in the industrialized Hamilton Harbour and more generally at sites that have stronger influences of wastewater effluent discharges and stormwater run-off through rivers and creeks. Polychlorinated biphenyls (PCBs) remain the dominant class of HOCs in water, with dissolved-phase concentrations ranging from 10 to 4100 pg/L (ΣPCBs), followed by polybrominated diphenylethers (ΣPBDEs; 14–960 pg/L) and the organochlorine pesticides (OCPs; 22–290 pg/L). Several non-PBDE brominated flame retardants (nBFRs) and chlorinated Dechlorane-related compounds were detected, with hexabromocyclododecanes (ΣHBCDD; sum of 3 diastereoisomers) the most abundant (1.0–21 pg/L). Non-targeted screening of samples by high resolution mass spectrometry using Kendrick mass defect plots for data analysis indicated that several other halogenated compounds were present in waters at relatively high abundances compared to the flame retardants, based on semi-quantitative estimates. These included methyl-triclosan, four halogenated anisoles (2,4,6-tribromoanisole, dimethyl-trichloroanisole, pentachloroanisole, and pentachlorothioanisole), and pentachloro-aniline. Dissolved-phase methyl-triclosan was estimated to contribute up to approximately 40% of the summed target HOC concentrations. Polyethylene passive samplers provided an excellent medium for both non-targeted screening of HOCs not currently included in monitoring programs and tracking brominated and chlorinated chemicals slated for reductions in uses and emissions through international (Stockholm Convention) and binational (Great Lakes) agreements.

Polycyclic aromatic hydrocarbons (PAHs) are prone to post-emission transformation and degradation to yield transformed PAH products (TPPs) that are potentially more hazardous than parent PAHs. This review provides a comprehensive evaluation of the potential environmental processes of PAHs such as sorption, volatilisation, photo- and bio-transformation and degradation on road surfaces, a significant accumulation point of PAHs. The review primarily evaluates key influential factors, toxicity implications, PAHs and TPPs fate and viable options for mitigating environmental and human health impacts. Photolysis was identified as the most significant transformation and degradation process due to the light absorption capacity of most PAHs. Climate conditions, physicochemical properties of road dust (sorbent), PAHs and TPPs and the existence of heavy metals such as Fe (III) are notable underlying factors for photolysis. Available data points to the predominance of carbonyl TPPs than other products such as nitro and hydroxyl TPPs with decreasing concentration trend of 9-fluorenone > 9,10-anthraquinone > benzo[a]fluorenone on road surfaces. The review recommends conducting future investigations targeting the influential factors pertaining to the fate of road deposited PAHs and TPPs. Furthermore, development of cost and time effective modern analytical methods is needed to quantify PAHs and TPPs present in minute quantities of samples. The review also identified that the unavailability of toxicity equivalency factors (TEF) for the most critical TPPs can be addressed using quantitative structure-activity relationship (QSAR) models and bioassays simultaneously. The content of this review is significant to the future work of researchers across various fields including analytical and environmental chemistry, stormwater pollution and toxicology.

A range of source tracking approaches have been developed to identify sources in the environmental pollution research field. A comparison of source tracking approaches is essential for a better understanding and practical applications of these approaches. This study compared the commonly used source tracking approaches, namely positive matrix factorization (PMF), Unmix, flag element ratio (FER), and chemical mass-balance based stochastic approach (SCMD). A case study was illustrated for tracing heavy metals (Pb, Zn, Cr, Cu, and Ni) attached to road deposited sediments, which can significantly influence urban road stormwater quality. The results indicated that the accuracy of PMF and Unmix are affected by the number of chemical species used and whether useful markers can be identified for particular sources. However, this does not have an essential influence on FER and SCMD. PMF and Unmix are easier on data preparation and calculation processes but more difficult for source identification process than FER and SCMD. This study also provided recommendations related to the selection of source tracking approach based on different study scenarios and result requirements. These study results are able to provide important guidance for undertaking effective source tracking and devising environmental pollution mitigations.

The quality of groundwater (GW) resources is decreasing partly due to chemical contaminations from a wide range of activities, such as industrial and agricultural enterprises and changes in land-use. In urban areas, one potential major pathway of GW contamination is associated with urban water management practices based on stormwater runoff infiltration systems (SIS). Data on the performance of the upper layer of soil and the unsaturated zone of infiltration basins to limit the contamination of GW by hydrophilic compounds are lacking. With this aim, the impact of infiltration practices on GW contamination was assessed for 12 pesticides and 4 pharmaceuticals selected according to their ecotoxicological relevance and their likelihood of being present in urban stormwater and GW. For this purpose, 3 campaigns were conducted at 4 SIS during storm events. For each campaign, passive samplers based on the use of Empore™ disk were deployed in GW wells upstream and downstream of SIS, as well as in the stormwater runoff entering the infiltration basins. Upstream and downstream GW contaminations were compared to evaluate the potential effect of SIS on GW contamination and possible relationships with stormwater runoff composition were examined. Our results showed two interesting opposite trends: (i) carbendazim, diuron, fluopyram, imidacloprid and lamotrigine had concentrations significantly increasing in GW impacted by infiltration, indicating a contribution of SIS to GW contamination, (ii) atrazine, simazine and 2 transformation products exhibited concentrations significantly decreasing with infiltration due to a probable dilution of historic GW contaminants with infiltrated stormwater runoff. The other 7 contaminants showed no general trend. This study demonstrates that passive samplers deployed in GW wells enabled the capture of emerging polar pollutants present at very low concentrations and allowed the assessment of infiltration practices on GW quality. New data on GW and urban stormwater are provided for poorly studied hazardous compounds.