Insights into the release of triclosan from microplastics in aquatic environment assessed with diffusive gradient in thin-films.

Organic chemicals associated with microplastics (MPs) can be released and thus pose potential risks during weathering processes. However, the thermodynamics and kinetics of their release processes still need to be better understood. Herein, the adsorption and desorption kinetics of triclosan on polystyrene (PS) and polyvinyl chloride (PVC) were investigated by using both batch experiments and diffusive gradients in thin-films (DGT) technique. The pseudo-second-order model fitted the data best, implying that both intraparticle diffusion and external liquid film diffusion influence the adsorption and desorption processes. DGT continuously accumulated triclosan from MP suspensions but slower than theoretical values, indicating some restrictions to desorption. The DGT-induced fluxes in Soils/Sediment (DIFS) model, employed to interpret DGT data, gave distribution coefficients for labile species (Kdl) of 5000 mL g-1 (PS) and 1000 mL g-1 (PVC) and the corresponding response times (Tc) were 10 s and 1000 s, respectively. Higher Kdl but smaller Tc for PS than PVC showed that more triclosan adsorbed on PS could be rapidly released, while there were some kinetic limitations for triclosan on PVC. A novel finding was that pH and ionic strength individually and interactively affected the supply of triclosan to DGT. This is the first study to quantify interactions of organics with MPs by using DGT, aiding our understanding of MPs' adsorption/desorption behavior in the aquatic environment.

In situ measurement of an emerging persistent, mobile and toxic (PMT) substance - Melamine and related triazines in waters by diffusive gradient in thin-films.

Melamine has received increasing public attention as a persistent, mobile and toxic (PMT) substance. To better assess environmental exposure and risks of melamine and related triazines (cyromazine, ammeline, and atrazine), a new passive sampling method based on the diffusive gradients in thin films (DGT) technique has been developed and validated in this study. The studied triazines were adsorbed quickly and strongly by the selected mixed cation exchange (MCX) binding gels. This MCX-DGT can linearly accumulate these chemicals over at least 5 days, with neither significant individual influence from pH (6-8), ionic strength (0.01-0.5 M) or dissolved organic matter (0-10 M), or interaction effects. Field applications in Southern China showed that DGT performed well in both sewage treatment plant (STP) and river samples. Melamine was found to be the dominant triazine with the concentrations at µg·L-1 in the STP and receiving river. Surprisingly, much higher concentration of melanine was found in the STP effluent than influent, and appeared to be some of the highest concentrations reported in STPs worldwide to date. Comparable melamine and atrazine concentraions in the STP effluent and receiving river suggested other sources to the river. The MCX-DGT sampler developed here was demonstrated to be reliable and robust for measuring the triazines in waters, and is promising as an in situ tool in understanding the occurrence, sources, and fate of the emerging PMT substances in aquatic environment.

A first European scale multimedia fate modelling of BDE-209 from 1970 to 2020.

The European Variant Berkeley Trent (EVn-BETR) multimedia fugacity model is used to test the validity of previously derived emission estimates and predict environmental concentrations of the main decabromodiphenyl ether congener, BDE-209. The results are presented here and compared with measured environmental data from the literature. Future multimedia concentration trends are predicted using three emission scenarios (Low, Realistic and High) in the dynamic unsteady state mode covering the period 1970-2020. The spatial and temporal distributions of emissions are evaluated. It is predicted that BDE-209 atmospheric concentrations peaked in 2004 and will decline to negligible levels by 2025. Freshwater concentrations should have peaked in 2011, one year after the emissions peak with sediment concentrations peaking in 2013. Predicted atmospheric concentrations are in good agreement with measured data for the Realistic (best estimate of emissions) and High (worst case scenario) emission scenarios. The Low emission scenario consistently underestimates measured data. The German unilateral ban on the use of DecaBDE in the textile industry is simulated in an additional scenario, the effects of which are mainly observed within Germany with only a small effect on the surrounding areas. Overall, the EVn-BTER model predicts atmospheric concentrations reasonably well, within a factor of 5 and 1.2 for the Realistic and High emission scenarios respectively, providing partial validation for the original emission estimate. Total mean MEC:PEC shows the High emission scenario predicts the best fit between air, freshwater and sediment data. An alternative spatial distribution of emissions is tested, based on higher consumption in EBFRIP member states, resulting in improved agreement between MECs and PECs in comparison with the Uniform spatial distribution based on population density. Despite good agreement between modelled and measured point data, more long-term monitoring datasets are needed to compare predicted trends in concentration to determine the rate of change of POPs within the environment.

A new multimedia contaminant fate model for China: how important are environmental parameters in influencing chemical persistence and long-range transport potential?

We present a new multimedia chemical fate model (SESAMe) which was developed to assess chemical fate and behaviour across China. We apply the model to quantify the influence of environmental parameters on chemical overall persistence (POV) and long-range transport potential (LRTP) in China, which has extreme diversity in environmental conditions. Sobol sensitivity analysis was used to identify the relative importance of input parameters. Physicochemical properties were identified as more influential than environmental parameters on model output. Interactive effects of environmental parameters on POV and LRTP occur mainly in combination with chemical properties. Hypothetical chemicals and emission data were used to model POV and LRTP for neutral and acidic chemicals with different KOW/DOW, vapour pressure and pKa under different precipitation, wind speed, temperature and soil organic carbon contents (fOC). Generally for POV, precipitation was more influential than the other environmental parameters, whilst temperature and wind speed did not contribute significantly to POV variation; for LRTP, wind speed was more influential than the other environmental parameters, whilst the effects of other environmental parameters relied on specific chemical properties. fOC had a slight effect on POV and LRTP, and higher fOC always increased POV and decreased LRTP. Example case studies were performed on real test chemicals using SESAMe to explore the spatial variability of model output and how environmental properties affect POV and LRTP. Dibenzofuran released to multiple media had higher POV in northwest of Xinjiang, part of Gansu, northeast of Inner Mongolia, Heilongjiang and Jilin. Benzo[a]pyrene released to the air had higher LRTP in south Xinjiang and west Inner Mongolia, whilst acenaphthene had higher LRTP in Tibet and west Inner Mongolia. TCS released into water had higher LRTP in Yellow River and Yangtze River catchments. The initial case studies demonstrated that SESAMe performed well on comparing POV and LRTP of chemicals in different regions across China in order to potentially identify the most sensitive regions. This model should not only be used to estimate POV and LRTP for screening and risk assessments of chemicals, but could potentially be used to help design chemical monitoring programmes across China in the future.

Challenges in assessing release, exposure and fate of silver nanoparticles within the UK environment.

There are significant challenges in assessing the fate and exposure of nanoparticles (NPs) in the environment owing to the lack of information on their use, potential pathways and sinks in the environment. In order to better understand the environmental exposure of silver nanoparticles (AgNPs), we reviewed the uses and potential exposure sources of both Ag and AgNPs. The approach taken was to identify the range of products that utilise its properties, identify potential environmental release pathways and subsequent fate once released into the environment. We then compared measured environmental concentrations with modelled concentrations from our work and others. We estimate that within the United Kingdom (UK) a total quantity of 8.8 tonnes per year of AgNPs is released from products containing AgNPs and enters UK waste water systems. Sewage sludge was identified as an important receiving compartment. Agricultural land with sludge applied was estimated to have a yearly increase in AgNP concentration of 36 µg per kg per year. Available ecotoxicity data for soil and the predicted environmental concentrations are used to perform a risk characterisation. This work highlights the on-going challenges faced when undertaking a risk assessment of AgNPs in the environment.

Estimating European historical production, consumption and atmospheric emissions of decabromodiphenyl ether.

A European scale production, consumption and environmental emissions inventory is produced for decabromodiphenyl ether (DecaBDE) for the period 1970-2020. A dynamic substance flow analysis model of DecaBDE is developed and emission of the main congener, BDE-209, to environmental compartments is estimated. From 1970 to 2010, it is estimated that a total of 185,000-250,000 tonnes of DecaBDE was consumed in Europe. Consumption peaked in the late 1990s at approximately 9,000 tonnes/year and has declined by ~30% in 2010. Predicted BDE-209 atmospheric emissions peak in 2004 at 10 tonnes/year. The waste management phase of the BDE-209 life cycle is responsible for the majority of atmospheric emissions via volatilisation and particle bound emissions from landfills, whilst leakage from Sewerage systems is the major source of emissions to the hydrosphere. Use of sewage sludge from wastewater treatment works as an agricultural fertiliser is the most important pathway of BDE-209 to soil. Although DecaBDE consumption has declined in recent years, the stock in use for 2010 remains considerable (60,000 tonnes) and is likely to act as a source of atmospheric emissions for several decades. Uncertainties exist in these estimations and more field or experimental data is needed to clarify the significance of certain emission pathways, in particular, emissions from landfill sites.

Can car air filters be useful as a sampling medium for air pollution monitoring purposes?

Urban air quality and real human exposure to chemical environmental stressors is an issue of high scientific and political interest. In an effort to find innovative and inexpensive means for air quality monitoring, the ability of car engine air filters (CAFs) to act as efficient samplers collecting street level air, to which people are exposed to, was tested. In particular, in the case of taxis, air filters are replaced after regular distances, the itineraries are almost exclusively urban, cruising mode is similar and, thus, knowledge of the air flow can provide with an integrated city air sample. The present pilot study focused on polycyclic aromatic hydrocarbons (PAHs), the most important category of organic pollutants associated with traffic emissions. Concentrations of ΣPAHs in CAFs ranged between 650 and 2900 µg CAF(-1), with benzo[b]fluoranthene, benzo[k]fluoranthene and indeno[123-cd]pyrene being the most abundant PAHs. Benzo[a]pyrene (BaP) ranged between 110 and 250 µg CAF(-1), accounting regularly for 5-15% of the total carcinogenic PAHs. The CAF PAH loads were used to derive road-level atmospheric PAH concentrations from a standard formula relating to the CAF air flow. Important parameters/assumptions for these estimates are the cruising speed and the exposure duration of each CAF. Based on information obtained from the garage experts, an average 'sampled air volume' of 48,750 m(3) per CAF was estimated, with uncertainty in this calculation estimated to be about a factor of 4 between the two extreme scenarios. Based on this air volume, ΣPAHs ranged between 13 and 56 ng m(-3) and BaP between 2.1 and 5.0 ng m(-3), suggesting that in-traffic BaP concentrations can be many times higher than the limit values set by the UK (0.25 ng m(-3)) and the European Union (1.0 ng m(-3)), or from active sampling stations normally cited on building roof tops or far from city centres. Notwithstanding the limitations of this approach, the very low cost, the continuous availability of very high amounts of "sample", and the "retroactivity" render it very useful and complementary to existing passive sampling techniques. This approach yields estimated air concentrations that reflect the pollutant concentrations to which taxi drivers, pedestrians, cyclists and road-related professionals are exposed.

Coupling passive air sampling with emission estimates and chemical fate modeling for persistent organic pollutants (POPs): a feasibility study for Northern Europe.

Passive air samplers (polyurethane foam disks) were deployed at 23 background locations along a broadly west-east transect in 8 northern European countries and analyzed for PCBs, PBDEs, PAHs, and a range of organochlorine pesticides (HCB, DDTs, and DDEs). PCBs and PAHs were highest at the center of the transect (Denmark) and lowest in northern Norway. HCB was relatively uniformly distributed, reflecting its persistence and high degree of mixing in air. Higher DDE and DDT levels occurred in Eastern Europe and at several sites in Central Europe. PBDE levels were generally similar at all sites, but lower for some locations in Eastern Europe and Ireland. Emissions information for PCBs, HCB, and PBDEs was used as input for a multi-media chemical fate model, to generate predicted air concentrations and compare with these measured values. Different scenarios were highlighted by this exercise: (i) country and compound combinations where the national inventory gave predicted air concentrations in close agreement with those measured (e.g., PCBs in the UK); (ii) country and compound combinations where predicted concentrations were well below those measured, but where advection of emissions from elsewhere is likely to be important (e.g., PCBs in Norway); (iii) consistent underestimation of compound concentrations by the emissions modeling (i.e., HCB); and (iv) general overestimation of ambient concentrations (i.e., PBDEs). Air mass trajectory analysis showed the likely role of long-range atmospheric transport (LRAT) on national levels. In general, advection from the south and west of Europe appeared to contribute to ambient POPs levels for countries in the center and northeast of the transect. Guidelines are presented as to how countries that want to assess their POPs source inventories can do so with this relatively cheap initial screening approach.

Spatial and temporal variability in air concentrations of short-chain (C10-C13) and medium-chain (C14-C17) chlorinated n-alkanes measured in the U.K. atmosphere.

Two studies were carried out on short-chain (C10-C13) and medium-chain (C14-C17) polychlorinated n-alkanes (sPCAs and mPCAs) in U.K. air samples. The first study entailed taking 20 24-h air samples with a pair of Hi-Vol air samplers at the Hazelrigg field station, near Lancaster University. These samples were carefully selected to coincide with times when air masses were predicted to have a fairly constant back trajectory for 24 h and to give a broad spectrum of different origins. The second study was a spatial survey of PCAs in the air at 20 outdoor sites in northern England and four indoor locations in Lancaster, using polyurethane foam (PUF) disk passive air samplers. Levels of the sPCAs in the Hi-Vol samples ranged from <185 to 3430 pg m(-3) (average 1130 pg m(-3)) and were higher than those previously measured at this site in 1997. Levels of the mPCAs ranged from <811 to 14500 pg m(-3) (average 3040 pg m(-3)); that is, they were higher than sPCAs. Both sPCA and mPCA air concentrations are of the same order of magnitude as PAH at this site. Back trajectory analysis showed that the history of the air mass in the 48 h prior to sampling had an important effect on the concentrations observed, with overland samples having higher levels than oceanic, implying that the U.K. is probably responsible for most of the PCAs measured in the U.K. atmosphere. Amounts of both sPCAs and mPCAs in the passive air samples followed a rural-urban gradient. PCAs appear to be released from multiple sources around the country, as a result of the diffusive, open industrial and construction use of the technical mixtures.

An input-output balance study for PCBs in humans.

Polychlorinated biphenyl (PCB) input-output balance studies were performed on five male volunteers, aged between 24 and 30, for periods of 8-14 days in 1998. Dietary exposure was quantified by the duplicate meals method and varied between 220 and 460 ng of sigmaPCB (sum of 20 congeners) per day for each of the five individuals over the study period. Dietary intake was dominated by congeners 118, 138, 153 and 180. Average faecal outputs for the five volunteers were 50-290 ng of sigmaPCB (sum of 20 congeners) per day for each of the five individuals over the same period and was dominated by the same four congeners. Whilst the total PCB fluxes were therefore into the body (i.e., accumulation), important differences were noted for different individual congeners. PCBs 44, 47, 49, 52, 60, 66, 101, 105, 110, 118, 149, 151 and 183 all showed net absorption for all five volunteers. Some congeners showed a net absorption in some of the individuals but net excretion in others, as seen by other workers. These congeners (PCBs 138, 153, 180, 187 and 194) are all higher chlorinated congeners and lack meta-para-vicinal hydrogen atoms. There were differences in the net absorption/excretion between individuals, which appeared to be a function of body fat index (BFI). The volunteers with the lowest BFIs showed net excretion for the greatest number of congeners, whilst the individual with the highest BFI was a net absorber of all the congeners studied. The problems in determining and interpreting absorption efficiency values for use in quantitative exposure assessments are discussed. Various factors that influence net absorption of PCBs and other persistent organic pollutants are identified. These include compound properties (including susceptibility to metabolism), the individual's fat status and balance, exposure history and diet.

Using PCDD/F congener patterns to determine the source of elevated TEQ concentrations in cows milk: a case study.

PCDD/F congener profiles have been used to determine the source of elevated TEQ concentrations in cows' milk collected in the vicinity of several industrial sites. Principal components analysis and modelling of the air-to-milk transfer of individual PCDD/F congeners have shown that the milk fingerprint was related to that of sediment taken from the River Rother adjacent to the farm where the cows had grazed. It is suggested that sediment from the river had been washed onto the grazing land during periods of flooding, and this had been ingested by the grazing cows. This pathway could represent an important route of contaminant intake for livestock grazing on the regularly inundated floodplains of rivers containing contaminated sediments.