Plastics are produced and used in large quantities worldwide (e.g. as food packaging). In line with this, plastic particles are found throughout the ecosphere and in various foods. As a result, plastics are also present in energy-rich waste biomass derived from the food industry, supermarkets, restaurants, etc. These waste streams are a valuable source for biogas production but can also be used to feed insects that in turn upcycle it into new high-value biomass. In both applications, the remaining residue can be used as fertilizer. Due to the present plastic particles, these applications could pose a continued threat to the environment, and both human and animal health. Therefore, the need of determining the (micro)plastic content to assess the potential danger is rising. In this research, a closed-vessel microwave-assisted acid digestion method was developed to accurately determine meso- and microplastic contents in food (waste) matrices by solubilising this food matrix. Polyvinyl chloride (PVC) food packaging foil was used to develop the method, using a full factorial design with three parameters (nitric acid concentration (c(HNO₃)), temperature (T), and time (t)). According to this model, the best practical conditions were c(HNO₃) = 0.50 mol/L, T = 170 °C, and t = 5.00 min. Subsequently, the method was tested on five other plastics, namely high- and low-density polyethylene (HDPE and LDPE), polypropylene (PP), polystyrene (PS), and polyethylene terephthalate (PET), mixed with a food matrix, resulting in a mean plastic recovery of 102.2 ± 4.1%. Additionally, the polymers were not oxidised during the microwave digestion. For PVC and PS hardly any degradation was found, while HDPE, LDPE, and PP showed slight chain degradation, although without recovery loss. In conclusion, the method is an accurate approach to quantify the total meso- and microplastic content in food (waste) matrices with minimal change in their intrinsic characteristics.

The rapid determination of the bioaccessibility of polycyclic aromatic hydrocarbons (PAHs) in soils is challenging due to their slow desorption rates and the insufficient extraction efficiency of the available methods. Herein, magnetic poly(β-cyclodextrin) microparticles (Fe₃O₄@PCD) were combined with hydroxypropyl-β-cyclodextrin (HPCD) or methanol (MeOH) as solubilizing agents to develop a rapid and effective method for the bioaccessibility measurement of PAHs. Fe₃O₄@PCD was first validated for the rapid and quantitative adsorption of PAHs from MeOH and HPCD solutions. The solubilizing agents were then coupled with Fe₃O₄@PCD to extract PAHs from soil-water slurries, affording higher extractable fractions than the corresponding solution extraction and comparable to or higher than single Fe₃O₄@PCD or Tenax extraction. The desorption rates of labile PAHs could be markedly accelerated in this process, which were 1.3–12.0 times faster than those of single Fe₃O₄@PCD extraction. Moreover, a low HPCD concentration was sufficient to achieve a strong acceleration of the desorption rate without excessive extraction of the slow desorption fraction. Finally, a comparison with a bioaccumulation assay revealed that the combination of Fe₃O₄@PCD with HPCD could accurately predict the PAH concentration accumulated in earthworms in three field soil samples, indicating that the method is a time-saving and efficient procedure to measure the bioaccessibility of PAHs.

Marine deposit feeders are of ecological significance in transferring sedimentary Cd along aquatic food chains. A key process for this transfer is these organisms’ dietary uptake of Cd via solubilization of Cd present in ingested contaminated sediment. To better understand the bioavailability of sedimentary Cd to deposit feeders, the present study used in vitro extraction experiments to explore the contribution of different digestive agents (proteins, amino acids and surfactants) to the solubilization of Cd from sediment collected in a highly-contaminated Chinese bay. This was done for various commercially-available mimetic digestive agents (the protein BSA, a mixture of amino acids, and the surfactants rhamnolipid and SDS), and for proteins and surfactants collected from the gut juice of a sipunculan worm. The Cd mobilization capacity of BSA was significantly higher than that of the amino acids and the commercial surfactants. In the presence of BSA, > 70% of the released Cd became associated with this protein. In contrast, the digestive proteins from the sipunculan had a lower Cd mobilization capacity than was the case for the other digestive agents and the majority of the released Cd (∼80%) was associated with small molecular weight fractions. The differences in Cd mobilization between the BSA and the digestive proteins were attributed to differences in their sediment-adsorption tendencies and their Cd-complexing capacities. While the digestive surfactants had minor effects on the release of sedimentary Cd, they significantly enhanced Cd mobilization by the digestive proteins when both were present simultaneously. Our results suggest that the characteristics of proteins should be considered when using commercially-available mimetic digestive agents to explore Cd bioavailability in sediments. Furthermore, digestive surfactants seem to have important effects on the solubilization of Cd during gut passage by reducing the adsorption of the digestive proteins to the sediments.

Marine oil spill often causes contamination of drinking water sources in coastal areas. As the use of oil dispersants has become one of the main practices in remediation of oil spill, the effect of oil dispersants on the treatment effectiveness remains unexplored. Specifically, little is known on the removal of dispersed oil from contaminated water using conventional adsorbents. This study investigated sorption behavior of three prototype activated charcoals (ACs) of different particle sizes (4–12, 12–20 and 100 mesh) for removal of dispersed oil hydrocarbons, and effects of two model oil dispersants (Corexit EC9500A and Corexit EC9527A). The oil content was measured as n-alkanes, polycyclic aromatic hydrocarbons (PAHs), and total petroleum hydrocarbons (TPHs). Characterization results showed that the smallest AC (PAC100) offered the highest BET surface area of 889 m2/g and pore volume of 0.95 cm3/g (pHPZC = 6.1). Sorption kinetic data revealed that all three ACs can efficiently adsorb Corexit EC9500A and oil dispersed by the two dispersants (DWAO-I and DWAO-II), and the adsorption capacity followed the trend: PAC100 > GAC12 × 20 > GAC4 × 12. Sorption isotherms confirmed PAC100 showed the highest adsorption capacity for dispersed oil in DWAO-I with a Freundlich KF value of 10.90 mg/g∙(L/mg)1/n (n = 1.38). Furthermore, the presence of Corexit EC9500A showed two contrasting effects on the oil sorption, i.e., adsolubilization and solubilization depending on the dispersant concentration. Increasing solution pH from 6.0 to 9.0 and salinity from 2 to 8 wt% showed only modest effect on the sorption. The results are useful for effective treatment of dispersed oil in contaminated water and for understanding roles of oil dispersants.

The distribution pattern of root-associated bacteria in native plant growth in tailing dumps with extreme conditions remains poorly understood and largely unexplored. Herein we chose a native plant, Bidens bipinnata, growing on both an Sb tailing dump (WKA) and adjacent normal soils (WKC) to in-depth understand the distribution pattern of root-associated bacteria and their responses on environmental factors. We found that the rhizosphere microbial diversity indices in the tailing dump were significantly different from that in the adjacent soil, and that such variation was significantly related with soil nutrients (TC, TOC, TN) and metal(loid) concentrations (Sb and As). Some dominant genera were significant enriched in WKA, suggesting their adaption to harsh environments. Notably, these genera are proposed to be involved in nutrient and metal(liod) cycling, such as nitrogen fixing (Devosia, Cellvibrio, Lysobacter, and Cohnella), P solubilizing (Flavobacterium), and Sb and As oxidation (Paenibacillus, Bacillus, Pseudomonas, and Thiobacillus). Our results suggest that certain root-associated bacteria in tailing dump were governed by soil edaphic factors and play important ecological roles in nutrient amendments and metal cycling for the successful colonization of Bidens bipinnata in this tailing dump.

Water availability is paramount in the response of soil invertebrates towards stress situations. This study aimed to evaluate the effects of forecasted soil moisture scenarios on the avoidance behavior of two invertebrate species (the arthropod Folsomia candida and the soft-bodied oligochaete Enchytraeus crypticus) in soils degraded by different types of anthropogenic metal(loid) contamination (mining soil and agricultural soil affected by industrial chemical wastes). Different soil moisture contents (expressed as % of the soil water holding capacity, WHC) were evaluated: 50% (standard soil moisture conditions for soil invertebrates' tests); 75% (to simulate increasing soil water availability after intense rainfalls and/or floods); 40%, 30%, 25% and 20% (to simulate decreasing soil water availability during droughts). Invertebrates’ avoidance behavior and changes in soil porewater major ions and metal(loid)s were assessed after 48 h exposure. Soil incubations induced a general solubilization/mobilization of porewater major ions, while higher soil acidity favored the solubilization/mobilization of porewater metal(loid)s, especially at 75% WHC. Folsomia candida preferred soils moistened at 50% WHC, regardless the soils were contaminated or not and the changing soil porewater characteristics. Enchytraeus crypticus avoided metal(loid) contamination, but this depended on the soil moisture conditions and the corresponding changes in porewater characteristics: enchytraeids lost their capacity to avoid contaminated soils under water stress situations (75% and 20–25% WHC), but also when contaminated soils had greater water availability than control soils. Therefore, forecasted soil moisture scenarios induced by global warming changed soil porewater composition and invertebrates capacity to avoid metal(loid)-contaminated soils.

Hexabromocyclododecanes (HBCDDs) are common chemical additives in expanded polystyrene foam (EPS). To evaluate the bioaccumulation potential of endogenous HBCDDs in EPS microparticles by earthworms, two ecologically different species of earthworms (Eisenia fetida and Metaphire guillelmi) were exposed to soil added with EPS microparticles of different particle sizes (EPS2000, 830–2000 μm and EPS830, <830 μm). To clarify the accumulation mechanisms, leaching experiments using EPS microparticles in different solutions were conducted. After exposure to EPS microparticles-amended soils (S-EPS) for 28 d, the total concentrations of HBCDDs reached 307–371 ng g−1 dw in E. fetida and 90–133 ng g−1 dw in M. guillelmi, which were higher than those in earthworms exposed to the soil that was artificially contaminated with a similar level of HBCDDs directly (ACS). The accumulation of HBCDDs in earthworms was significantly influenced by EPS microparticles' size and earthworms' species. The total concentrations of HBCDDs in earthworms' cast were significantly higher than the theoretical concentration of HBCDDs in S-EPS, which suggested that EPS microparticles can be ingested by earthworms. The release rate of HBCDDs from EPS5000 (2000–5000 μm) into water-based solutions (<1%) after a 3.5-h incubation was far lower than that into earthworm digestive fluid (7%). These results illustrated that the ingestion of EPS microparticles and consequent solubilization of HBCDDs by digestive fluid play an important role in the accumulation of HBCDDs contained in EPS microparticles in earthworms. After a 28-d incubation with the soil solution, 4.9% of the HBCDDs was accumulatively leached from the EPS5000, which indicated that HBCDDs can be released from EPS microparticles to soil environment, and then accumulated by earthworms. Moreover, similar to those exposed to ACS, the diastereoisomer- and enantiomer-specific accumulation of HBCDDs in earthworms occurred when exposed to S-EPS. This study provides more evidence for the risk of microplastics to the soil ecosystem.

Mining activities have contaminated many riverine floodplains with arsenic (As). When floodplain soils become anoxic under water-saturated conditions, As can be released from the solid phase. Several microbially-driven As solubilization processes and numerous influential factors were recognized in the past. However, the interplay and relative importance of soil properties and the influence of environmental factors such as temperature remain poorly understood, especially considering the (co)variation of soil properties in a floodplain. We conducted anoxic microcosm experiments at 10, 17.5, and 25 °C using 65 representative soils from the mining-impacted Ogosta River floodplain in Bulgaria. To investigate the processes of As solubilization and its quantitative variation we followed the As and Fe redox dynamics in the solid and the dissolved phase and monitored a range of other solution parameters including pH, Eh, dissolved organic C, and dissolved Mn. We related soil properties to dissolved As observed after 20 days of microcosm incubation to identify key soil properties for As solubilization. Our results evidenced reductive dissolution of As-bearing Fe(III)-oxyhydroxides as the main cause for high solubilization. The availability of nutrients, most likely organic C as the source of energy for microorganisms, was found to limit this process. Following the vertical nutrient gradient common in vegetated soil, we observed several hundred μM dissolved As after 1–2 weeks for some topsoils (0–20 cm), while for subsoils (20–40 cm) with comparable total As levels only minor solubilization was observed. While high Mn contents were found to inhibit As solubilization, the opposite applied for higher temperature (Q10 2.3–6.1 for range 10–25 °C). Our results suggest that flooding of nutrient-rich surface layers might be more problematic than water-saturation of nutrient-poor subsoil layers, especially in summer floodings when soil temperature is higher than in winter or spring.

Microplastic particles are increasingly being discovered in diverse habitats and a host of species are found to ingest them. Since plastics are known to sorb hydrophobic organic contaminants (HOCs) there is a question of what risk of chemical exposure is posed to aquatic biota from microplastic-associated contaminants. We investigate bioavailability of polychlorinated biphenyls (PCBs) from polypropylene microplastic by measuring solid-water distribution coefficients, gut fluid solubilization, and bioaccumulation using sediment invertebrate worms as a test system. Microplastic-associated PCBs are placed in a differential bioavailability framework by comparing the results to several other natural and anthrogenic particles, including wood, coal, and biochar. PCB distribution coefficients for polypropylene were higher than natural organic materials like wood, but in the range of lipids and sediment organic carbon, and smaller than black carbons like coal and biochars. Gut fluid solubilization potential increased in the order: coal < polypropylene < biochar < wood. Interestingly, lower gut fluid solubilization for polypropylene than biochar infers that gut fluid micelles may have solubilized part of the biochar matrix while bioaccessibility from plastic can be limited by the solubilizing potential of gut fluids dependent on the solid to liquid ratio or renewal of fluids in the gut. Biouptake in worms was lower by 76% when PCBs were associated with polypropylene compared to sediment. The presence of microplastics in sediments had an overall impact of reducing bioavailability and transfer of HOCs to sediment-ingesting organisms. Since the vast majority of sediment and suspended particles in the environment are natural organic and inorganic materials, pollutant transfer through particle ingestion will be dominated by these particles and not microplastics. Therefore, these results support the conclusion that in most cases the transfer of organic pollutants to aquatic organisms from microplastic in the diet is likely a small contribution compared to other natural pathways of exposure.

To determine if trinitrotoluene (TNT) forms nonextractable residues in mussels (Mytilus galloprovincialis) and fish (Cyprinodon variegatus) and to measure the relative degree of accumulation as compared to extractable TNT and its major metabolites, organisms were exposed to water fortified with 14C-TNT. After 24 h, nonextractable residues made up 75% (mussel) and 83% (fish) while TNT accounted for 2% of total radioactivity. Depuration half-lives for extractable TNT, aminodinitrotoluenes (ADNTs) and diaminonitrotoluenes (DANTs) were fast initially (<0.5 h), but slower for nonextractable residues. Nonextractable residues from organisms were identified as ADNTs and DANTs using 0.1 M HCL for solubilization followed by liquid chromatography-tandem mass spectrometry. Recovered metabolites only accounted for a small fraction of the bound residue quantified using a radiotracer likely because of low extraction or hydrolysis efficiency or alternative pathways of incorporation of radiolabel into tissue.