The cationic degradable polymer poly(lactic acid) choline iodide ester methacrylate, poly(PLA₄ChMA), can be used to flocculate particles and dewater sediments from tailings ponds and wastewater. A suitable bioaccessibility method is required to characterize the interactions of this novel flocculant in the human gastrointestinal system. To this end, a physiologically based extraction test (PBET) was modified to evaluate the bioaccessibility of flocculants. Bioaccessibility (bioaccessible fraction) is a measure of the solubility of a contaminant in gastrointestinal fluids and that may be available for systemic absorption. The flocculants poly(PLA₄ChMA), SNF C3276, and FLOPAM A3338 were tested at a solid-to-liquid ratio of 1:200 in the absence and presence of kaolin clay, which is used as a model sediment compound. Bioaccessible fractions were characterized by proton nuclear magnetic resonance spectroscopy and estimated by gravimetry. The bioaccessibility of poly(PLA₄ChMA) in gastric and intestinal PBET solutions decreases from 78% and 100%, respectively, in the absence of kaolin to approximately 0% with kaolin, indicating that poly(PLA₄ChMA) remains adsorbed onto the clay surface throughout the PBET, a result confirmed by thermogravimetric analysis. The bioaccessibility of cationic SNF C3276 and anionic FLOPAM A3338 in gastric solution is approximately 76% and 26%, respectively, and is not affected by the presence of kaolin. However, in intestinal solutions, the bioaccessibility of SNF C3276 and FLOPAM A3338 (60–85% in the absence of kaolin) changes to 0% and 100%, respectively, in the presence of kaolin. These results, interpreted in terms of solution pH and surface charge, demonstrate that interactions with kaolin influence the solubility of flocculants and must be considered in the evaluation of bioaccessibility. In future works, such bioaccessibility methods can be applied to assess the human-health safety of using flocculants in wastewater treatments.

Assessment of microplastic impacts in biota is challenging due to the complex behavior of the test particles and their interactions with other particulates, including microorganisms, in the environment. To disentangle responses to microplastic exposure from those to other suspended solids, both microplastic and natural particles must be present in the test system. We evaluated how microplastic, non-plastic particles, and biofilms interacted in their effects on survivorship using acute toxicity assay with Daphnia magna. The animals were exposed to microplastic and kaolin at different concentrations of suspended solids (SS; 10, 100, and 1000 mg/L) with a varying microplastic contribution (%MP; 0–80%) and biofilm (presence/absence) associated with the solids. Also, we examined how these exposure parameters (SS, %MP, and Biofilm) affected aggregate formation that was analyzed using particle size distribution data. Under the exposure conditions, Daphnia mortality was primarily driven by SS concentration but ameliorated by both microplastic and biofilm. The ameliorating effects were related to increased particle aggregation in the presence of biofilm and high %MP. In addition, a weak yet significant positive effect of the biofilm on the survivorship was observed, presumably, due to microbial food supply to the daphniids in the exposure system; the bacteria were utilized at the absence of other food. Therefore, the effects of both natural and anthropogenic particulates depend on the particle behavior and aggregation in the water governed by microbial communities and physicochemical properties of the particles, which must be taken into account in the hazard assessment of plastic litter.

Several studies have investigated the effects of nano- and microplastics on daphnids as key freshwater species. However, while information is abundant on the acute toxicity of plastic beads, little is known regarding the multigenerational effects of irregular microplastics. In addition, a comparison of microplastics to naturally occurring particles is missing. Therefore, we investigated the effects of irregular, secondary polystyrene microplastics (<63 μm) and kaolin as natural reference particle on the survival, reproduction, and growth of Daphnia magna over four generations under food-limited conditions. Additionally, we tested the sensitivity of the neonates in each generation to a reference compound as a proxy for offspring fitness. Exposure to high concentrations of microplastics (10,000 and 2000 particles mL⁻¹) reduced daphnid survival, resulting in extinction within one and four generations, respectively. Microplastics also affected reproduction and growth. Importantly, an exposure to kaolin at similar concentrations did not induce negative effects. The sensitivity of neonates to potassium dichromate was not affected by maternal exposure to particles. Taken together, our study demonstrates that irregular PS particles are more toxic than natural kaolin in daphnids exposed over multiple generations under food limitation. Thus, our work builds towards more realistic exposure scenarios needed to better understand the impacts of microplastics on zooplankton.

Given the ubiquitous presence of microplastics in aquatic environments, an evaluation of their toxicity is essential. Microplastics are a heterogeneous set of materials that differ not only in particle properties, like size and shape, but also in chemical composition, including polymers, additives and side products. Thus far, it remains unknown whether the plastic chemicals or the particle itself are the driving factor for microplastic toxicity. To address this question, we exposed Daphnia magna for 21 days to irregular polyvinyl chloride (PVC), polyurethane (PUR) and polylactic acid (PLA) microplastics as well as to natural kaolin particles in high concentrations (10, 50, 100, 500 mg/L, ≤ 59 μm) and different exposure scenarios, including microplastics and microplastics without extractable chemicals as well as the extracted and migrating chemicals alone. All three microplastic types negatively affected the life-history of D. magna. However, this toxicity depended on the endpoint and the material. While PVC had the largest effect on reproduction, PLA reduced survival most effectively. The latter indicates that bio-based and biodegradable plastics can be as toxic as their conventional counterparts. The natural particle kaolin was less toxic than microplastics when comparing numerical concentrations. Importantly, the contribution of plastic chemicals to the toxicity was also plastic type-specific. While we can attribute effects of PVC to the chemicals used in the material, effects of PUR and PLA plastics were induced by the mere particle. Our study demonstrates that plastic chemicals can drive microplastic toxicity. This highlights the importance of considering the individual chemical composition of plastics when assessing their environmental risks. Our results suggest that less studied polymer types, like PVC and PUR, as well as bioplastics are of particular toxicological relevance and should get a higher priority in ecotoxicological studies.

Biochar sequesters cadmium (Cd) by immobilisation, but the process is often less effective in field trials than in the laboratory. Therefore, the involvement of soil components should be considered for predicting field conditions that could potentially improve this process. Here, we used biochar derived from Spartina alterniflora as the amendment for Cd-contaminated soil. In simulation trials, a mixture of kaolin, a representative soil model component, and S. alterniflora-derived biochar immobilised Cd by forming silicon-aluminium-Cd-containing complexes. Interestingly, the biochar recalcitrance index value increased from 48% to 53%–56% because of the formation of physical barriers consisting of kaolinite minerals and Cd complexes. Pot trials were performed using Brassica chinensis for evaluating the effect of S. alterniflora-derived biochar on plant growth in Cd-contaminated soil. The bio-concentration factor values in B. chinensis were 24%–31% after soil remediation with biochar than in control plants. In summary, these results indicated that soil minerals facilitated Cd sequestration by biochar, which reduced Cd bioavailability and improved the recalcitrance of this soil amendment. Thus, mechanisms for effective Cd remediation should include biochar-soil interactions.

Compacted clay is widely used as capillary barriers in landfill final cover system. Recently, biochar amended clay (BAC) has been proposed as a sustainable alternative cover material. However, the effects of biochar on saturated hydraulic conductivity (kₛₐₜ) of clay with high degree of compaction is not yet understood. The present study aims to investigate the effects of biochar on kₛₐₜ of compacted kaolin clay. Soil specimens were prepared by amending kaolin clay with biochar derived from peanut-shell at 0, 5 and 20% (w/w). The kₛₐₜ of soil specimens was measured using a flexible water permeameter. The effects of biochar on the microstructure of the compacted clay was also investigated using MIP. Adding 5% and 20% of biochar increased the kₛₐₜ of compacted kaolin clay from 1.2 × 10⁻⁹ to 2.1 × 10⁻⁹ and 1.3 × 10⁻⁸ ms⁻¹, respectively. The increase in kₛₐₜ of clay was due to the shift in pore size distribution of compacted biochar-amended clay (BAC). MIP results revealed that adding 20% of biochar shifted the dominant pore diameter of clay from 0.01–0.1 μm (meso– and macropores) to 0.1–4 μm (macropores). Results reported in this communication revealed that biochar application increased the kₛₐₜ of compacted clay, and the increment was positively correlated to the biochar percentage.

The effects of suspended and deposited sediments on the macroinvertebrates are well documented in upland streams but not in slower flowing lowland rivers. Using species found in lowland lotic environments, we experimentally evaluate mechanisms for sediments to affect macroinvertebrates, and in one experiment whether salinity alters the effect of suspended sediments. Suspended kaolin clay reduced feeding of Ischnura heterosticta (Odonata: Coenagrionidae) at high turbidity (1000–1500 NTU) but had no effects on feeding of Hemianax papuensis (Odonata: Aeshnidae) and Micronecta australiensis (Hemiptera: Corixidae). In freshwater (0.1 mS/cm), survival of Ischnura aurora was poor in clear water, but improved with suspended kaolin. Growth and feeding of I. aurora were unaffected by suspended sediments and salinity. Burial (1–5 mm) of eggs with kaolin or sand reduced hatching in Physa acuta (Gastropoda: Physidae), Gyraulus tasmanica (Gastropoda: Planorbidae) and Chironomus cloacalis (Diptera: Chironomidae). Settling sediments may pose greater risk to lowland lotic invertebrates than suspended sediments. Sediment deposition may be more directly detrimental to macroinvertebrates of lowland rivers than suspended sediments.

A bioflocculant-producing bacterial strain, designated MSI021, was isolated from the marine sponge Dendrilla nigra and demonstrated 94% flocculation activity in a kaolin clay suspension. MSI021 was identified as Bacillus cereus based on phylogenetic affiliation and biochemical characteristics. The purified extra-cellular bioflocculant was chemically elucidated as a polysaccharide molecule. The polysaccharide bioflocculant was stable under both acidic and alkaline conditions (pH 2.0–10.0) and temperatures up to 100 °C. The purified bioflocculant efficiently nucleated the formation of silver nanoparticles which showed broad spectrum antibacterial activity. The ability of the bioflocculant to remediate heavy metal toxicity was evaluated by measuring the inhibition of bioluminescence expression in Vibrio harveyi. Enrichment of heavy metals such as zinc, mercury and copper at concentrations of 1, 2 and 3 mM in culture media showed significant reduction of bioluminescence in Vibrio, whereas media enriched with heavy metals and bioflocculant showed dose dependent improvement in the expression of bioluminescence. The assay results demonstrated that the polysaccharide bioflocculant effectively mitigates heavy metal toxicity, thereby improving the expression of bioluminescence in Vibrio. This bioluminescence reporter assay can be developed into a high-throughput format to monitor and evaluate of heavy metal toxicity. The findings of this study revealed that a novel polysaccharide bioflocculant produced by a marine B. cereus demonstrated strong flocculating performance and was effective in nucleating the formation antibacterial silver nanoparticles and removing heavy metals. These results suggest that the MSI021 polysaccharide bioflocculant can be used to develop greener waste water treatment systems.

Riverine transport to the marine environment is an important pathway for microplastic. However, information on fate and transport of nano- and microplastic in freshwater systems is lacking. Here we present scenario studies on the fate and transport of nano-to millimetre sized spherical particles like microbeads (100 nm–10 mm) with a state of the art spatiotemporally resolved hydrological model. The model accounts for advective transport, homo- and heteroaggregation, sedimentation-resuspension, polymer degradation, presence of biofilm and burial. Literature data were used to parameterize the model and additionally the attachment efficiency for heteroaggregation was determined experimentally. The attachment efficiency ranged from 0.004 to 0.2 for 70 nm and 1050 nm polystyrene particles aggregating with kaolin or bentonite clays in natural freshwater. Modeled effects of polymer density (1–1.5 kg/L) and biofilm formation were not large, due to the fact that variations in polymer density are largely overwhelmed by excess mass of suspended solids that form heteroaggregates with microplastic. Particle size had a dramatic effect on the modeled fate and retention of microplastic and on the positioning of the accumulation hot spots in the sediment along the river. Remarkably, retention was lowest (18–25%) for intermediate sized particles of about 5 μm, which implies that the smaller submicron particles as well as larger micro- and millimetre sized plastic are preferentially retained. Our results suggest that river hydrodynamics affect microplastic size distributions with profound implications for emissions to marine systems.

Marine Oil Snow Sedimentation and Flocculent Accumulation (MOSSFA) can pose serious threats to the marine benthic ecosystem as it results in a deposition of oil contaminated marine snow on the sediment surface. In a microcosm experiment we investigated the effects of oil in combination with artificial marine snow or kaolin clay on two benthic invertebrate species and benthic meiofauna. The amphipod showed a dose-dependent decrease in survival for both oil-contaminated clay and oil-contaminated marine snow. The gastropod was only affected by the highest concentration of oil-contaminated marine snow and had internal concentrations of PAHs with a similar distribution as oil-contaminated marine snow. Benthic copepods showed higher survival in presence of marine snow. This study revealed that marine snow on the sediment after oil spills affects organisms in a trait-dependent way and that it can be a vector for introducing oil into the food web.