The wide utilization of plastic related products leads to the ubiquitous presence of plastic particles in natural environments. Plastic particles could interact with kaolinite (one type of typical clay particles abundant in environments) and form plastic-kaolinite heteroaggregates. The fate and transport of both plastic particles and kaolinite particles thus might be altered. The cotransport and deposition behaviors of micron-sized plastic particles (MPs) with different surface charge (both negative and positive surface charge) with kaolinite in porous media in both 5 and 25 mM NaCl solutions were investigated in present study. Both types of MPs (negatively charged carboxylate-modified MPs (CMPs) and positively charged amine-modified MPs (AMPs)) formed heteroaggregates with kaolinite particles under both solution conditions examined, however, CMPs and AMPs exhibited different cotransport behaviors with kaolinite. Specifically, the transport of both CMPs and kaolinite was increased under both ionic strength conditions when kaolinite and CMPs were copresent in suspensions. While, when kaolinite and positively charged AMPs were copresent in suspensions, negligible transport of both kaolinite and AMPs were observed under examined salt solution conditions. The competition deposition sites by kaolinite (the portion suspending in solution) with CMPs-kaolinite heteroaggregates led to the increased transport both CMPs and kaolinite when both types of colloids were copresent. In contrast, the formation of larger sized AMPs-kaolinite heteroaggregates with surface charge heterogeneity led to the negligible transport of both kaolinite and AMPs when they were copresent in suspensions. The results of this study show that when plastic particles and kaolinite particles are copresent in natural environments, their interaction with each other will affect their transport behaviors in porous media. The alteration in the transport of MPs or kaolinite (either increased or decreased transport) is highly correlated with the surface charge of MPs.

Tetracyclines (TCs) are frequently detected in agricultural soils worldwide, causing a potential threat to crops and human health. In this study, diffusive gradients in thin films technique (DGT) was used to measure the distribution and exchange rates of three TCs (tetracycline (TC), oxytetracycline (OTC) and chlortetracycline (CTC)) between the solid phase and solution in five farmland soils. The relationship between the accumulated masses with time suggested that TCs consumption in soil solution by DGT would induce the supply from the soil solid phase. The distribution coefficient for the labile antibiotics (Kdl), response time (Tc) and desorption/adsorption rates (kb and kf) between dissolved and sorbed TCs were derived from the dynamic model of DIFS (DGT induced fluxes in soils). The Kdl showed similar sizes of labile solid phase pools for TC and OTC while larger pool sizes were observed for CTC in the soils. Although the concentrations of CTC were lowest in soil solution, the potential hazard caused by continuous release from soil particles could not be ignored. The long response time (>30 min in most cases) suggested that the resupply of TCs from soil solids was limited by their desorption rates (1.26-121 × 10−6 s−1). The soils in finer texture, with higher clay and silt contents (<50 μm) showed a greater potential for TCs release.

Condensed organic matters (COM) with black carbon-like structures are considered as long-term carbon sinks because of their high stability. It is difficult to distinguish COM from general organic matter by conventional chemical analysis, thus the contribution by and interaction mechanisms of organo-mineral complexes in COM stabilization are unclear and generally neglected. Molecular markers related to black carbon-like structures, such as benzene polycarboxylic acids (BPCAs), are promising tools for the qualitative and quantitative analysis of COM. In this study, one natural soil and two cultivated soils with 25 y- or 55 y-tillage activities were collected and the distribution characteristics of BPCAs were detected. All the investigated soils showed similar BPCA distribution pattern, and over 60% of BPCAs were detected in clay fraction. The extractable BPCA contents were substantially increased after mineral removal. The ratios of BPCA contents before and after mineral removal indicate the extent of COM-mineral particle interactions, and our results suggested that up to 73% COM were protected by mineral particles, and more stronger interactions were noted on clay than on silt. The initial cultivation dramatically decreased COM-clay interactions, and this interaction was recovered only slowly after 55-y cultivation. Kaolinite and muscovite are important for COM protection. But a possible negative correlation between BPCAs and reactive iron oxides of the cultivated soils suggested that iron may promote COM degradation when disturbed by tillage activities. This study provided a new angle to study the stabilization of COM and emphasized the importance of organo-mineral complexes for COM stabilization.

Multi-layered engineered landfill consists of the bottom liner layer (mainly bentonite clay (B)) upon which the hazardous wastes are dumped. In current practice, sand (S) is mixed with bentonite to mitigate the adverse effects of using bentonite alone in the liner layer. Incorporation of waste and unutilized fly ash (FA) as an amendment material to B has been explored in terms of its hydro-mechanical properties, but not gauged its adsorption potential. Indian subcontinent primarily relies on the thermal power source, and FA dumps have already reached its full capacity. The objective of this study is to explore the adsorption characteristics of four B-FA composite mixes sourced within India, considering Pb²⁺ as a model contaminant. The effect of fly ash type, fly ash amendment rate and adsorbate concentration was explored in the current study and juxtaposed with B-S mixes, based on 960 batch adsorption tests. Both B-FA and B-S mixes reached equilibrium adsorption capacity within 65 min. At higher adsorbate concentrations (commonly observed in the liner), B-FA mixes exhibited superior adsorption capacity, mainly one mixed with Neyvelli fly ash (NFA). The effect of higher amendment rate had little impact on the adsorption capacity at different concentration, but gradually decreased the percentage removal of Pb²⁺. The B-S mix showed a drastic decrease in percentage removal at higher adsorbate concentration among all tested mixes. Systematic characterization including geotechnical properties, microstructure and chemical analysis was also done to interpret the obtained results. Both Freundlich and Langmuir models fitted the isotherm data well for all B-FA mixes. The maximum adsorption capacity from the isotherm was correlated to easily measurable Atterberg limits by two empirical relationships.

In agriculture, wastewater is used as an alternative source to meet the water and nutritional requirements of plants. However, long-term application of wastewater may degrade soil attributes. This study aimed to evaluate the soil physical quality of Oxisol fertigated with treated sewage effluent (TSE). The experiment was conducted in an area under TSE application for 4 years in Oxisol (625 g kg⁻¹ clay) cultivated with Urochloa brizantha. The treatments consisted of six levels of TSE in irrigation depth, 0%, 11%, 31%, 60%, 87%, and 100%, with four repetitions. Undisturbed and disturbed soils samples were collected in three layers (0.00–0.10 m; 0.10–0.20 m, and 0.20–0.30 m). Aggregation, porosity and water infiltration attributes were evaluated. This work concludes a long-term study on the effects of TSE application on soil properties and on the Urochloa brizantha crop. In other works, carried out in the experimental area of the present study, it was found that TSE fertigation increases the yield and quality of Urochloa brizantha, increases soil fertility and does not lead to soil heavy metal contamination. We note the TSE fertigation does not change the aggregation, porosity, water infiltration rate and organic carbon content in the soil. Irrigation with TSE is recommended in areas with clayey soil and those cultivated with perennial grasses as it does not cause any damage to the physical quality of the soil. Thus, the TSE fertigation can be used on many crops as a source of water and nutrients, reducing the environmental contamination potential.

Polychlorinated biphenyls (PCBs) have been detected as prevalent environmental contaminants in water, food and biota. Previous studies in vitro have shown that a variety of sorbent materials, including carbon, can sorb PCBs; however, PCB sorbents that can be added to food or drinking water to decrease toxin bioavailability in humans and animals have not been reported. To address this problem, we have developed a broad-acting and highly effective sorbent for PCBs using montmorillonite clays reported to be safe for consumption in animals and humans. In this study, calcium montmorillonite clays were acid processed (APMs) and the interactions of six PCB congeners (PCB 77, 126, 153, 157, 154 and 155) on the surfaces of APMs were characterized. Computational models and isothermal analyses were used to derive surface capacities and affinities, delineate mechanisms and predict the thermodynamics of sorption. To confirm the safety and predict the efficacy of APMs against individual PCBs and common mixtures (Aroclors 1254 and 1260), we have also used a living organism (Hydra vulgaris) that is sensitive to toxins. APMs significantly protected hydra against the toxicity of PCBs and Aroclors. This finding was supported by studies showing tight binding; high capacity, affinity, and enthalpy; and a low therapeutic dose.

Mangroves act as sinks for terrigenous pollutants to alleviate their influence on offshore marine ecosystem. The nationwide study of PBDEs contamination in mangrove wetlands of China has not been explored, and their risk for human health lack quantitative analysis. In this study, sediment samples were collected in six mangrove wetlands along coastal area of South China to evaluate the levels, congener distributions and ecological risks of eight PBDEs, including BDE-28, -47, −99, −100, −153, −154, −183, and −209. Levels of ∑PBDEs (the sum of seven PBDEs except BDE-209) and BDE-209 were 0.13–2.18 ng g−1 and 1.44–120.28 ng g−1, respectively. In particular, mean level of BDE-209 was highest in Futian, followed by Yunxiao, Fangchenggang, Zhanjiang, Dongzhaigang, and Dongfang. As dominant PBDE congener, BDE-209 accounted for 63.6%–99.1% of the total PBDEs, suggesting the major sources of commercial deca-BDE mixtures. Among seven PBDE congeners except BDE-209, slightly different percentages of PBDE congeners were detected, with BDE-154, -47, and −100 being predominant congeners. Positive relationship was observed for total organic matter (TOM) with BDE-209, with no such relationships found for particle size compositions (clay, silt and sand). As for sediment-dwelling organism, the ecological risks from tri-, tera-, and hexa-BDE congeners could be negligible, and those from penta- and deca-BDE congeners were low or moderate, indicating major ecological risk drivers of penta- and deca-BDE congeners in mangrove wetlands in China. The ecological risk of PBDEs in mangrove sediments for human health was thought to be consumption of fish which would bioaccumulate PBDEs from the contaminated sediment. As for human health, the levels of non-cancer risks of PBDEs were all lower than 1, and the cancer risk was far less than the threshold level (10−6), demonstrating low risk for human health.

Antibiotics resistance genes (ARGs) are considered as an emerging pollutant among various environments. As a sink of ARGs, a comprehensive study on the spatial and temporal distribution of ARGs in the estuarine sediments is needed. In the present study, six ARGs were determined in sediments taken along the Yangtze Estuary temporally and spatially. The sulfonamides, tetracyclines and fluoroquinolones resistance genes including sul1, sul2, tetA, tetW, aac(6’)-Ib, and qnrS, were ubiquitous, and the average abundances of most ARGs showed significant seasonal differences, with relative low abundances in winter and high abundances in summer. Moreover, the relative high abundances of ARGs were found at Shidongkou (SDK) and Wusongkou (WSK), which indicated that the effluents from the wastewater treatment plant upstream and inland river discharge could influence the abundance of ARGs in sediments. The positive correlation between intI1 and sul1 implied intI1 may be related to the occurrence and propagation of sulfonamides resistance genes. Correlation analysis and redundancy discriminant analysis showed that antibiotic concentrations had no significant correlation to their corresponding ARGs, while the total extractable metal, especially the bioavailable metals, as well as other environmental factors including temperature, clay, total organic carbon and total nitrogen, could regulate the occurrence and distribution of ARGs temporally and spatially. Our findings suggested the comprehensive effects of multiple pressures on the distribution of ARGs in the sediments, providing new insight into the distribution and dissemination of ARGs in estuarine sediments, spatially and temporally.

Microplastics (plastic particles, 0.1 μm–5 mm in size) are widespread marine pollutants, accumulating in benthic sediments and shorelines the world over. To gain a clearer understanding of microplastic availability to marine life, and the risks they pose to the health of benthic communities, ecological processes and food security, it is important to obtain accurate measures of microplastic abundance in marine sediments. To date, methods for extracting microplastics from marine sediments have been disadvantaged by complexity, expense, low extraction efficiencies and incompatibility with very fine sediments.Here we present a new, portable method to separate microplastics from sediments of differing types, using the principle of density floatation. The Sediment-Microplastic Isolation (SMI) unit is a custom-built apparatus which consistently extracted microplastics from sediments in a single step, with a mean efficiency of 95.8% (±SE 1.6%; min 70%, max 100%). Zinc chloride, at a density of 1.5 g cm−3, was deemed an effective and relatively inexpensive floatation media, allowing fine sediment to settle whilst simultaneously enabling floatation of dense polymers. The method was validated by artificially spiking sediment with low and high density microplastics, and its environmental relevance was further tested by extracting plastics present in natural sediment samples from sites ranging in sediment type; fine silt/clay (mean size 10.25 ± SD 3.02 μm) to coarse sand (mean size 149.3 ± SD 49.9 μm). The method presented here is cheap, reproducible and is easily portable, lending itself for use in the laboratory and in the field, eg. on board research vessels. By employing this method, accurate estimates of microplastic type, distribution and abundance in natural sediments can be achieved, with the potential to further our understanding of the availability of microplastics to benthic organisms.

Chlorotriazine herbicides (CTs) are widely used pest control chemicals. In contrast to groundwater contamination, little attention has been given to the circumstances of residue formation of parent compounds and transformation products in soils.Seventy-five cultivated floodplain topsoils in the Czech Republic were sampled in early spring of 2015, corresponding to a minimum of six months (current-use terbuthylazine, TBA) and a up to a decade (banned atrazine, AT and simazine, SIM) after the last herbicide application. Soil residues of parent compounds and nine transformation products were quantified via multiple residue analysis using liquid chromatography - tandem mass spectrometry of acetonitrile partitioning extracts (QuEChERS). Using principal component analysis (PCA), their relation to soil chemistry, crops and environmental parameters was determined.Of the parent compounds, only TBA was present in more than one sample. In contrast, at least one CT transformation product, particularly hydroxylated CTs, was detected in 89% of the sites, or 54% for banned triazines. Deethylated and bi-dealkylated SIM or AT residues were not detectable. PCA suggests the formation and/or retention of CT hydroxy-metabolite residues to be related to low soil pH, and a direct relation between TBA and soil organic carbon, and between deethyl-TBA and clay or Ca contents, respectively, the latter pointing towards distinct sorption mechanisms. The low historic application of simazine contrasted by the high abundance of its residues, and the co-occurrence with AT residues suggests the post-ban application of AT and SIM banned triazines as a permitted impurity of TBA formulations as a recent, secondary source.The present data indicate that topsoils do not contain abundant extractable residues of banned parent chlorotriazines, and are thus likely not the current source for related ground- and surface water contamination. In contrast, topsoils might pose a long-term source of TBA and CT transformation products for ground and surface water contamination.