Wastewater and stormwater are both considered as critical pathways contributing microplastics (MPs) to the aquatic environment. However, there is little information in the literature about the potential influence of constructed wetlands (CWs), a commonly used wastewater and stormwater treatment system. This study was conducted to investigate the abundance and distribution of MPs in water and sediment at five CWs with different influent sources, namely stormwater and wastewater. The MP abundance in the water samples ranged between 0.4 ± 0.3 and 3.8 ± 2.3 MP/L at the inlet and from 0.1 ± 0.0 to 1.3 ± 1.0 MP/L at the outlet. In the sediment, abundance of MPs was generally higher at the inlet, ranging from 736 ± 335 to 3480 ± 4330 MP/kg dry sediment and decreased to between 19.0 ± 16.4 and 1060 ± 326 MP/kg dry sediment at the outlet. Although no significant differences were observed in sediment cores at different depth across the five CWs, more MPs were recorded in silt compared to sandy sediment which indicated sediment grain size could be an environmental factor contributing to the distribution of MPs. Polyethylene terephthalate (PET) fibres were the dominant polymer type found in the water samples while polyethylene (PE) and polypropylene (PP) fragments were predominantly recorded in the sediment. While the size of MPs in water varied across the studied CWs, between 51% and 64% of MPs in the sediment were smaller than 300 μm, which raises concerns about the bioavailability of MPs to a wider range of wetland biota and their potential ecotoxicological effects. This study shows that CWs can not only retain MPs in the treated water, but also become sinks accumulating MPs over time.

The inconsistency of available methods and the lack of harmonization in current microplastics (MPs) analysis in soils demand approaches for extraction and quantification which can be utilized across a wide variety of soil types. To enable robust and accurate assessment of extraction workflows, PET MPs with an inorganic tracer (Indium, 0.2% wt) were spiked into individual soil subgroups and standard soils with varying compositions. Due to the selectivity of the metal tracer, MPs recovery rates could be quickly and quantitatively assessed using ICP-MS. The evaluation of different methods specifically adapted to the soil properties were assessed by isolating MPs from complex soil matrices by systematically investigating specific subgroups (sand, silt, clay, non-lignified and lignified organic matter) before applying the workflow to standard soils. Removal of recalcitrant organic matter is one of the major hurdles in isolating MPs for further size and chemical characterization, requiring novel approaches to remove lignocellulosic structures. Therefore, a new biotechnological method (3-F-Ultra) was developed which mimics natural degradation processes occurring in aerobic (Fenton) and anaerobic fungi (CAZymes). Finally, a Nile Red staining protocol was developed to evaluate the suitability of the workflow for non-metal-doped MPs, which requires a filter with minimal background residues for further chemical identification, e.g. by μFTIR spectroscopy. Image analysis was performed using a Deep Learning tool, allowing for discrimination between the number of residues in bright-field and MPs counted in fluorescence mode to calculate a Filter Clearness Index (FCI). To validate the workflow, three well-characterized standard soils were analyzed applying the final method, with recoveries of 88% for MPs fragments and 74% for MPs fibers with an average FCI of 0.75. Collectively, this workflow improves our current understanding of how to adapt extraction protocols according to the target soil composition, allowing for improved MPs analysis in environmental sampling campaigns.

Plastic mulching and straw incorporation are common agricultural practices in China. Plastic mulching is suspected to be a significant source of microplastics in terrestrial environments. Straw incorporation has many effects on the storage of soil organic carbon (SOC) and greenhouse gas emissions, but these effects have not been studied in the presence of microplastic pollution. In this study, 365-day soil incubation experiments were conducted to assess the effects of maize straw and polyethylene microplastics on SOC fractions and carbon dioxide (CO₂) and nitrous oxide (N₂O) emissions in two different soils (fluvo-aquic and latosol). Against the background of straw incorporation, microplastics reduced the mineralization and decomposition of SOC, resulting in a microbially available SOC content decrease by 18.9%. In addition, microplastics were carbon-rich, but relatively stable and difficult to be used by microorganisms, thus increasing the mineral-associated SOC content by 52.5%. This indicated that microplastics had adverse effects on microbially available SOC and positive effects on mineral-associated SOC. Microplastics also decreased coarse particulate SOC (>250 μm), and increased non-aggregated silt and clay aggregated SOC (<53 μm). Furthermore, microplastics changed microbial community compositions, thereby reducing the CO₂ and N₂O emissions of straw incorporation by 26.5%–33.9% and 35.4%–39.7%, respectively. These results showed that microplastics partially offset the increase of CO₂ and N₂O emissions induced by straw incorporation. Additionally, the inhibitory effect of microplastics on CO₂ emissions in fluvo-aquic soil was lower than that in latosol soil, whereas the inhibitory effect on N₂O emissions had the opposite trend.

The performance of the radon (²²²Rn)-deficit technique has been evaluated at a site in which a complex DNAPL mixture (mostly hexachlorocyclohexanes and chlorobenzenes) has contaminated all four layers (from top to bottom: anthropic backfill, silt, gravel and marl) of the soil profile. Soil gas samples were collected at two depths (0.8 m and 1.7 m) in seven field campaigns and a total of 186 ²²²Rn measurements were performed with a pulse ionization detector. A statistical assessment of the influence of field parameters on the results revealed that sampling depth and atmospheric pressure did not significantly affect the measurements, while the location of the sampling point and ground-level atmospheric temperature did. In order to remove the bias introduced by varying field temperatures and hence to be able to jointly interpret ²²²Rn measurements from different campaigns, ²²²Rn concentrations were rescaled by dividing each individual datum by the mean ²²²Rn concentration of its corresponding field campaign. Rescaled ²²²Rn maps showed a high spatial correlation between ²²²Rn minima and maximum contaminant concentrations in the top two layers of the soil profile, successfully delineating the surface trace of DNAPL accumulation in the anthropic backfill and silt layers. However, no correlation could be established between ²²²Rn concentrations in superficial soil gas and contaminant concentration in the deeper two layers of the soil profile. These results indicate that the ²²²Rn-deficit technique is unable to describe the vertical variation of contamination processes with depth but can be an effective tool for the preliminary characterization of sites in which the distance between the inlet point of the sampling probe and the contaminant accumulation falls within the effective diffusion length of ²²²Rn in the affected soil profile.

Alprazolam, clonazepam and diazepam are drugs belonging to the benzodiazepine class. These drugs might be important environmental contaminants in aquatic media. A total understanding of behavior and fate of drugs in aquatic environment is not available for these and other drugs. Thus, in this work, a complete optimization of sample treatment and extraction of analytes from sediments and water was described, as well a study of sediment/water distribution comparing it with sample characteristics. Ultrasound for 10 min and 3 steps using 3 mL of extraction solvent were chosen as the stirring form for extraction. A methanol/water (1:1) solution pH 12 was the best extraction solvent. Aiming to eliminate interferences, an addition of 10 μL of NaCl 3.06 mol L⁻¹ was necessary after each step of extraction. Sediment and water samples were characterized, presenting different values on physical-chemical parameters. Six distinct sample sets of water and sediments were spiked with each benzodiazepine and analyzed. Kd values varied from 1.4 to 9.2 L kg⁻¹ for clonazepam, 1.8–11.5 L kg⁻¹ for alprazolam and 2.31–12 L kg⁻¹ for diazepam. A principal component analysis showed high dependence on Kd with sample characteristics mainly related to sediments. In the systems, whose sediments presented high levels of clay, silt and organic matter, the drugs presented a great interaction with the solid part of the system, increasing the Kd value. Koc values varied from 149.25 to 634.13 L kg⁻¹ for clonazepam, 186.57–852.48 L kg⁻¹ for alprazolam, and 194.68–1189.81 L kg⁻¹ for diazepam.

Packed column experiments were conducted to investigate the transport and blocking behavior of surfactant- and polymer-stabilized engineered silver nanoparticles (Ag-ENPs) in saturated natural aquifer media with varying content of material < 0.063 mm in diameter (silt and clay fraction), background solution chemistry, and flow velocity. Breakthrough curves for Ag-ENPs exhibited blocking behavior that frequently produced a delay in arrival time in comparison to a conservative tracer that was dependent on the physicochemical conditions, and then a rapid increase in the effluent concentration of Ag-ENPs. This breakthrough behavior was accurately described using one or two irreversible retention sites that accounted for Langmuirian blocking on one site. Simulated values for the total retention rate coefficient and the maximum solid phase concentration of Ag-ENPs increased with increasing solution ionic strength, cation valence, clay and silt content, decreasing flow velocity, and for polymer-instead of surfactant-stabilized Ag-ENPs. Increased Ag-ENP retention with ionic strength occurred because of compression of the double layer and lower magnitudes in the zeta potential, whereas lower velocities increased the residence time and decreased the hydrodynamics forces. Enhanced Ag-ENP interactions with cation valence and clay were attributed to the creation of cation bridging in the presence of Ca2+. The delay in breakthrough was always more pronounced for polymer-than surfactant-stabilized Ag-ENPs, because of differences in the properties of the stabilizing agents and the magnitude of their zeta-potential was lower. Our results clearly indicate that the long-term transport behavior of Ag-ENPs in natural, silicate dominated aquifer material will be strongly dependent on blocking behavior that changes with the physicochemical conditions and enhanced Ag-ENP transport may occur when retention sites are filled.

Sediment samples were collected to a depth of 60 cm along a 350-m sampling belt in a short-term-flooding riparian wetland in the Yellow River Delta of China in three sampling seasons. Contents of heavy metals were determined to investigate their spatial and temporal distributions, sources and ecotoxities. Our results showed that As contents in the top 20 cm sediments increased before decreasing along the sampling belt in summer, whereas they kept stable before increasing in fall and spring. Cd contents increased along the sampling belt in three sampling seasons, whereas Ni and Cr generally exhibited a decreasing tendency. Comparatively, Cu, Pb and Zn consistently increased at the first 50 m distance and then decreased before increasing from the distance of 150 m in summer and fall and increased to the maximum at the distance of 250 m and then showed a decrease in spring. Two “hotspots” of heavy metal accumulation in sediment cores along the belt were observed at the distance from 50 to 100 m in summer and at the distance from 200 to 300 m in spring. Most of sediment samples contained higher heavy metals in excess of threshold effect levels except for Zn and Pb in three sampling seasons and the values of toxic units in more than 30% of sediment samples exceeded 4 in summer. As, Ni and Cr had relatively higher contribution to the values of toxic units compared with other heavy metals in three sampling seasons. Multivariance analysis showed that As and Cd might originate from the same source and Cu, Zn, Cr, Pb and Ni might derive from another similar source. Cd was significantly correlated with salinity (p < 0.01) and pH (p < 0.05). Meanwhile, these heavy metals were also significantly correlated with other properties such as S, Al, TP, SOM and Silt + Clay.

Mining activities in the world's largest platinum mining area in South Africa have resulted in environmental contamination with Pt (e.g., the Hex River's vicinity). The present study compared a Pt mining area with a non-mining area along this river in terms of (1) metal concentrations in different grain size fractions from soils and aquatic sediments; (2) the toxicological potential of aquatic sediments based on the Consensus-Based Sediment Quality Guideline (CBSQG); and (3) the chronic toxicity of aqueous eluates from soils and sediments to Caenorhabditis elegans. Platinum concentrations were higher in the mining area than in the non-mining area. For most metals, the sediment silt and clay fraction contained the highest metal concentrations. Based on the CBSQG, most sampling sites exhibited a high toxicological potential, driven by Cr and Ni. Eluate toxicity testing revealed that C. elegans growth, fertility, and reproduction inhibition were not dependent on mining activities or the CBSQG predictions. Toxicity was instead likely due to Cd, Fe, Mn, Ni, Pt, and Pb. In conclusion, the investigated region is loaded with a high geogenic background resulting in high reproduction inhibition. The mining activities lead to additional environmental metal contamination (particularly Pt), contributing to environmental soil and sediment toxicity.

Hard coal is the predominant energy source in Poland. The unavoidable consequence of coal combustion is the production of huge amounts of ash which can be concentrated in radionuclides. The ashes from coal combustion are utilized or stored and may affect the quality of the environment. Therefore, the estimation of radionuclides in hard coal and by-products is of crucial importance. The analyzed samples included ashes produced in ash furnaces, power plants and individual home furnaces operating in the Upper Silesian Industrial Region, Southern Poland, during the hard coal burning. This paper presents radioactivity concentrations of ²²⁸Ra, ²²⁶Ra and ⁴⁰K in hard coal, bottom and fly ash samples from Polish coal-fired power plants obtained during various technological coal combustion processes and generated in individual domestic furnaces, determined using the HPGe gamma spectrometry technique. The measurements of ²³⁴,²³⁸U concentrations were performed after sample preparation using alpha-particle spectrometer. The concentrations of the obtained radionuclides differ greatly in the fly and bottom ash samples. The lowest concentrations of ²²⁶Ra, ²²⁸Ra, ²³⁴U, ²³⁸U were observed in bottom ashes from the co-firing of hard coal and biomass in a fluidized-bed furnace, whereas the highest concentrations of ²²⁶Ra (163 ± 6 Bq/kg), ²²⁸Ra (100 ± 2 Bq/kg) isotopes were found in the ashes from individual household furnaces. This means that both the feed coal type and combustion techniques have a direct impact on the concentration of radionuclides in ash. Hard coal silt samples may be enriched in radionuclides and the radioactive equilibrium between ²²⁶Ra and ²³⁸U even in the case of coal is not always achieved. The concentrations of the analyzed isotopes in ashes are 5-7-fold higher than in feed coal. Given that combustion by-products are utilized as construction products, it should be noted that for some ash samples, the radiological hazard indices approach or exceed the maximum permitted levels.

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.