International audience | Due to the dramatic quantity of plastic debris released into our environment, one of the biggest challenges of the next decades is to trace and quantify microplastics (MPs) in our environments, especially to better evaluate their capacity to transport other contaminants such as trace metals. In this study, trace elements (Fe, Cu, Zn, As, Cd, Sn, Sb, Pb, and U) were analyzed in the microplastic subsurface (200 μm) using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Microplastics subjected to the marine environment were collected on beaches (Guadeloupe) exposed to the north Atlantic gyre. We established a strategy to discriminate sorbed contaminants from additives based on the metal concentration profiles in MP subsurface using qualitative and quantitative approaches. A spatiotemporal correlation of the sorption pattern was proposed to compare MPs in terms of relative exposure time and time-weighted average concentrations in the exposure media.

Microplastics have attracted much attention in recent years because they are able to interact with other pollutants including pesticides, with implications for the potential risks to biota. However, the sorption behavior of pesticides on microplastics, especially on biodegradable microplastics which are promising alternatives to conventional polymers, has been insufficiently studied. In this study, triadimefon and difenoconazole were selected as model triazole fungicides, and their sorption behavior on a typical biodegradable microplastics (PBS: polybutylene succinate) and two conventional polyethylene (PE) and polyvinyl chloride (PVC) microplastics was investigated with batch experiments in an aqueous solution. PBS presented the highest sorption capacity for triadimefon (104.2 ± 4.8 μg g⁻¹) and difenoconazole (192.8 ± 2.3 μg g⁻¹), which was 1.8- and 1.3-fold that on PE and 4.4- and 7.4-fold that of PVC, respectively. The results of sorption kinetic and isotherm modeling were better fit by a pseudo-second order model and linear model, respectively. More importantly, the effects of environmental factors (pH, salinity and dissolved organic matter) on the sorption behavior were investigated. Fungicide sorption on PBS was generally not affected by salinity, pH or dissolved organic matter. However, in contrast, salinity and dissolved organic matter both significantly decreased sorption on PE and PVC. The results showed that not only the sorption capacities of biodegradable microplastics but also their responses to environmental factors are quite different from those of conventional microplastics. This finding highlights the importance of the role played by biodegradable microplastics in the accumulation and transportation of organic pollutants.

Polybrominated diphenyl ethers (PBDEs) serve as flame retardants in many household materials such as electrical and electronic devices, furniture, textiles, plastics, and baby products. Though the use of PBDEs like penta-, octa- and deca-BDE greatly reduces the fire damage, indoor pollution by these toxic emissions is ever-growing. In fact, a boom in the global market projections of PBDEs threatens human health security. Therefore, efforts are made to minimize PBDEs pollution in USA and Europe by encouraging voluntary phasing out of the production or imposing compelled regulations through Stockholm Convention, but >500 kilotons of PBDEs still exist globally. Both ‘environmental persistence’ and ‘bioaccumulation tendencies’ are the hallmarks of PBDE toxicities; however, both these issues concerning household emissions of PBDEs have been least addressed theoretically or practically. Critical physiological functions, lipophilicity and toxicity, trophic transfer and tissue specificities are of utmost importance in the benefit/risk assessments of PBDEs. Since indoor debromination of deca-BDE often yields many products, a better understanding on their sorption propensity, environmental fate and human toxicities is critical in taking rigorous measures on the ever-growing global deca-BDE market. The data available in the literature on human toxicities of PBDEs have been validated following meta-analysis. In this direction, the intent of the present review was to provide a critical evaluation of the key aspects like compositional patterns/isomer ratios of PBDEs implicated in bioaccumulation, indoor PBDE emissions versus human exposure, secured technologies to deal with the toxic emissions, and human toxicity of PBDEs in relation to the number of bromine atoms. Finally, an emphasis has been made on the knowledge gaps and future research directions related to endurable flame retardants which could fit well into the benefit/risk strategy.

The sorption behaviour of three perfluoroalkyl substances (PFASs), namely perfluorooctane sulfonic acid (PFOS), perfluorooctanoic acid (PFOA) and perfluorohexane sulfonic acid (PFHxS), was determined on 28 tropical soils. Tropical soils are often highly weathered, richer in sesquioxides than temperate soils and may contain variable charge minerals. There are little data on sorption of PFASs in tropical soils. The highest Kd values were found for PFOS with mean values ranging from 0 to 31.6 L/kg. The Kd values for PFOA and PFHxS ranged from 0 to 4.9 L/kg and from 0 to 5.6 L/kg, respectively. While these values are in the range of literature sorption data, the average Kd values for PFOS and PFOA from the literature were 3.7 times and 3.6 times higher, respectively, than those measured in this study. Stepwise regression analysis did explain some of the variance, but with different explanatory variables for the different PFASs. The main soil properties explaining sorption for PFOS and PFOA were oxalate-extractable Al and pH, and for PFHxS was pH.

The application of surfactants is an effective way to inhibit the migration of organic contaminants (OCs) from soil to plants, and thus would be a great candidate method for producing safe agricultural products in organic-contaminated farmland. In this study, it was found that cetyltrimethyl ammonium bromide (CTMAB) reduced the OCs in cabbage by 22.0–64.1%, and those in lettuce by 18.8–36.5%. We developed a mathematical model to predict the accumulation of OCs in plants in the presence of surfactants. The successive partitioning of OCs among three phases, namely, soil, soil water and plant roots, was considered. The equilibrium of OC between the soil and soil water was scaled using the sorption coefficient of OCs on soils normalized by the soil organic carbon (Kₒc) and carbon-normalized OCs sorption coefficient with the sorbed surfactants (Kₛₛ). To precisely calculate the Kₒc and Kₛₛ, the bioavailable and bound OCs were measured using a sequential extraction method. Linear positive correlations between the logarithm of Kₒc (or Kₛₛ) and the logarithm of the octanol-water partition coefficient (log Kₒw) of OCs were established for laterite soils, paddy soils and black soils. In the presence of CTMAB, the equilibrium of OCs between the soil water and plant roots was scaled using the carbon-normalized OC sorption coefficient with the sorbed surfactants (Kₛf), whose logarithmic value was linearly correlated with the log Kₒw of the OCs. A three-phase-successive partition-limited model was developed based on these relationships, demonstrating an average prediction accuracy of 76.6 ± 36.8%. Our results indicated that the decrease in bioavailable OCs in soils and the increase in sorption of OCs on roots should be taken into consideration when predicting plant uptake. This research provides a validated mathematical model for predicting the concentration of OCs in plants in the presence of surfactants.

Microplastics have attracted much attention in recent years as they can interact with pollutants in water environment. However, nanoplastics (NPs) with or without the surface functionalization modification have not been thoroughly explored. Here, the sorption behaviors of two fluoroquinolones (FQs), including norfloxacin (NOR) and levofloxacin (LEV) on polystyrene NPs (nano-PS) and carboxyl-functionalized polystyrene NPs (nano-PS-COOH) were investigated. The results showed that sorption isotherms were nonlinear and well fitted by Langmuir model. The sorption capacities of NOR and LEV on nano-PS-COOH were higher than those on nano-PS, and their physical interactions, including polar interaction, electrostatic interaction and hydrogen bonding may be the dominant mechanisms. Moreover, the increase of pH firstly increased the sorption of two FQs on NPs and then decreased because NOR and LEV had a reverse charge at different pH values. Salinity and dissolved organic matter both inhibited the sorption process. These findings show that NPs with or without the surface functionalization modification have different sorption behaviors for environmental pollutants, which deserve our further concern.

The purpose of this long-term experiment was on gaining more insights into the environmental behaviour of veterinary antibiotics in the subsurface after application with manure. Therefore, manure spiked with a bromide tracer and eight antibiotics (enrofloxacin, lincomycin, sulfadiazine, sulfamethazine, tetracycline, tiamulin, tilmicosin and tylosin) in concentrations of milligrams per litre were applied at an experimental field site. Their pathway was tracked by continuous extraction of soil pore water at different depths and systematic sampling of groundwater for a period of two years. Seven target compounds were detected in soil pore water of which four leached into groundwater. Concentrations of the detected target compounds were, with few exceptions, in the range of nanograms per litre. It was concluded that a large fraction of the investigated antibiotics sorbed or degraded already within the first meter of the soil. Further, it was inferred from the data that long and warm dry periods cause attenuation of the target compounds through increased degradation or sorption occurring in the soil. In addition, the comprehensive data-set allowed to estimate a retardation factor between 1.1 and 2.0 for sulfamethazine in a Plaggic Anthrosol soil, and to classify the individual compounds by environmental relevance based on transport behaviour and persistence. According to the distribution of resistant genes in the environment, sulfamethazine was found to be the most mobile and persistent substance.

Total concentrations of hydrophobic organic contaminants (HOCs) in sediment present a poor quality assessment parameter for aquatic organism exposure and environmental risk because they do not reflect contaminant bioavailability. The bioavailability issue of HOCs in sediments can be addressed by application of multi-ratio equilibrium passive sampling (EPS). In this study, riverbed sediment samples were collected during the Joint Danube Survey at 9 locations along the Danube River in 2013. Samples were ex-situ equilibrated with silicone passive samplers. Desorption isotherms were constructed, yielding two endpoints: pore water (CW:₀) and accessible (CAS:₀) concentration of polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), polycyclic aromatic hydrocarbons (PAHs) and polybrominated diphenyl ethers in sediment. CW:₀ concentrations of DDT and its breakdown products exhibited elevated levels in the low Danube, with the maximum in the river delta. Other investigated HOCs did not show any clear spatial trends along the river, and only a moderate CW:₀ variability. CAS:₀ in sediment ranged from 10 to 90% of the total concentration in sediment. CW:₀ was compared with freely dissolved concentration in the overlaying surface water, measured likewise by passive sampling. The comparison indicated potential compound release from sediment to the water phase for PAHs with less than four aromatic rings, and for remaining HOCs either equilibrium between sediment and water, or potential compound deposition in sediment. Sorption partition coefficients of HOC to organic carbon correlated well with octanol-water partition coefficients (KOW), showing stronger sorption of PAHs to sediment than that of PCBs and OCPs having equal logKOW. Comparison of CW:₀ values with European environmental quality standards indicated potential exceedance for hexachlorobenzene, fluoranthene and benzo[a]pyrene at several sites. The study demonstrates the utility of passive sampling as an innovative approach for risk-oriented monitoring of HOCs in river catchments.

Soil organic matter (SOM) affects arsenic (As) and antimony (Sb) mobility in soils under waterlogged conditions by acting as an electron donor, by catalyzing redox–cycling through electron shuttling and by acting as a competing ligand. This study was set up to disentangle these different effects of SOM towards As and Sb sorption in anaerobic soils. Nine samples were taken at different depths in an agricultural soil profile to collect samples with a natural SOM gradient (<1–40 g soil organic carbon kg⁻¹). The samples were incubated either or not under waterlogged conditions in an anaerobic chamber for 63–70 days, and glucose (5 g C kg⁻¹) was either or not added to the anaerobic incubated samples as an electron donor that neither acts as an electron shuttle nor as a competing ligand. The solid-liquid distribution coefficients (KD) of As and Sb were measured at trace levels. The KD values of As decreased ∼2 orders of magnitude upon waterlogging the SOM rich topsoil, while no additional changes were observed when glucose was added. In contrast, smaller changes in the As KD values were found in the low SOM containing subsoil samples, unless glucose was added that mobilised As. The Sb KD values increased upon reducing conditions up to factor 20, but again only in the high SOM topsoil samples. Surprisingly, the Sb immobilisation during waterlogging only occurred in Sb amended soils whereas the geogenic Sb was mobilised upon reducing conditions, although total dissolved Sb concentrations remained low (<10 nM). The change in As and Sb sorption upon waterlogging was similar in the SOM rich topsoil as in the low SOM subsoil amended with glucose. This suggests that the SOM dependent changes in As and Sb mobility in response to soil waterlogging are primarily determined by the role of SOM as electron donor.

The identification and quantification of pharmaceutical and personal care products (PPCPs) in aquatic ecosystems is critical to further studies and elucidation of their fate as well as the potential threats to aquatic ecology and human health. This study used mass balances to analyse the sources, transformation, and transport of PPCPs in rivers based on the population and consumption habits of residents, the removal level of sewage treatment, the persistence and partitioning mechanisms of PPCPs, hydrological conditions, and other natural factors. Our results suggested that in an urbanized river of Guangzhou City, China, the daily consumption of PPCPs was the main reason for the variety of species and concentrations of PPCPs. Through the determination of PPCPs in the river water samples and a central composite design (CCD) methodology, the dominant elimination mechanisms of caffeine and carbamazepine from river water were photolysis and biodegradation, but that of triclosan was sorption rather than biodegradation. The mass data of 3 PPCPs were estimated and corroborated using the measured data to evaluate the accuracy of the mass balance. Finally, caffeine, carbamazepine and triclosan discharged from the Shijing River into the Pearl River accounted for 97.81%, 99.52%, and 28.00%, respectively, of the total mass of these three compounds in the surface water of Shijing River. The results suggest that photolysis are the main process of natural attenuation for selected PPCPs in surface waters of river systems, and the transfer processes of PPCPs is mainly attributed to riverine advection. In addition, the low concentration of dissolved oxygen inhibited the degradation of PPCPs in the surface water of Shijing River.