Although microplastics (MPs) are ubiquitous in agricultural soil, little is known about the effects of MPs combined with pesticides on soil organisms and their biogenic transport through the soil profile. In this study, we conducted mesocosm experiments to observe the effects of microplastics (polyethylene (LDPE-MPs) and biodegradable microplastics (Bio-MPs)) and chlorpyrifos (CPF) on earthworm (Lumbricus terrestris) mortality, growth and reproduction, as well as the biogenic transport of these contaminants through earthworm burrows. The results showed that earthworm reproduction was not affected by any treatment, but earthworm weight was reduced by 17.6% and the mortality increased by 62.5% in treatments with 28% Bio-MPs. Treatments with 28% LDPE-MPs and 7% Bio-MPs combined with CPF showed greater toxicity while the treatment with 28% Bio-MPs combined with CPF showed less toxicity on earthworm growth as compared to treatments with only MPs. The treatments with 1250 g ha−1 CPF and 28% Bio-MPs significantly decreased the bioaccumulation of CPF in earthworm bodies (1.1 ± 0.2%, w w−1), compared to the treatment with CPF alone (1.7 ± 0.4%). With CPF addition, more LDPE-MPs (8%) were transported into earthworm burrows and the distribution rate of LDPE-MPs in deeper soil was increased. No effect was observed on the transport of Bio-MPs. More CPF was transported into soil in the treatments with LDPE-MPs and Bio-MPs, 5% and 10% of added CPF, respectively. In addition, a lower level of the CPF metabolite 3,5,6-trichloropyridinol was detected in soil samples from the treatments with MPs additions than without MP additions, indicating that the presence of MPs inhibited CPF degradation. In conclusion, Bio-MPs caused significant toxicity effects on earthworms and the different types of MPs combined with CPF affected earthworms differently, and their transport along the soil profile. Thus, further research is urgently needed to understand the environmental risks of MPs and MP-associated compounds in the soil ecosystem.

Adsorption and transport of levofloxacin (LEV) and ofloxacin (OFL) enantiomers in a matrix containing goethite and natural organic matter (NOM) were investigated using batch and column experiments. In batch studies, competition and enantioselectivity were observed in the adsorption of LEV and OFL. Enantioselectivity upon adsorption was investigated by comparing changes in the enantiomer fraction (EF) (the ratio of LEV to the sum of LEV and OFL remaining in the solution) after and before adsorption. At pH < 7, there was hardly any selectivity in adsorption of OFL and LEV to goethite. At pH > 7, OFL showed a stronger adsorption than LEV to goethite, and this preference remained when NOM samples of Leonardite humic acid (LHA) and Elliott Soil fulvic acid (ESFA) were added. However, when Suwannee River NOM (SRNOM) was added, the preference was reversed, and LEV was adsorbed more strongly. In single systems, the presence of different types of NOM increased adsorption of LEV and OFL, especially LEV. In column studies, preloaded NOM decreased the transport of LEV and OFL through goethite-coated sand. The EF values in the effluent increased with retention time and reached the largest values (0.59–0.72) at around 1.5 pore volume (PV), and then decreased again, reaching a stable value at 5.0–30.0 PV. Both batch and column experiments showed that, fractionation of LEV and OFL occurred during adsorption and transport in the presence of NOM-goethite complexes, which would eventually affect their environmental fate

Microplastics (MPs) in soil undergo different aging processes such as photoaging, mechanical abrasion and biodegradation, leading to alterations in the surface properties of MPs. In this study, we investigated the adsorption-desorption of chlorpyrifos (CPF) on pristine and UV light-aged low-density polyethylene (LDPE) and biodegradable (Bio) MPs that were derived from plastic mulch films. We also tested the bioconcentration of pristine and aged MPs (LDPE- and Bio-MPs aged under UV light and LDPE-MPs aged in three different soils) associated with CPF by earthworms (Lumbricus terrestris). The results showed that UV-aged MPs showed higher CPF adsorption capacities than pristine MPs, with the adsorption capacities at 184.9 ± 5.3, 200.5 ± 1.8, 193.0 ± 8.7, and 215.9 ± 1.1 μg g−1 for pristine LDPE-, UV-aged LDPE-, pristine Bio- and UV-aged Bio-MPs, respectively. The desorption rate of CPF from UV-aged LDPE-MPs within 48 h was lower than the desorption from pristine ones (28.8 ± 7.7% vs. 40.0 ± 3.9%), while both pristine and UV-aged Bio-MPs showed very low CPF desorption rates. A 4-day Petri dish experiment showed that UV-aged MPs were significantly less concentrated in earthworm casts than pristine counterparts (52% and 36% lower for UV-aged LDPE- and Bio-MPs), while UV-aged MPs with adsorbed CPF were concentrated significantly more than UV-aged MPs without CPF. Interestingly, LDPE-MPs aged in soil with a high carbon, nitrogen, and carbon-to-nitrogen ratio were significantly more concentrated in earthworm casts than pristine LDPE-MPs. In conclusion, UV-aged MPs acted as stronger vectors for CPF than pristine MPs. The bioconcentration of MPs differed significantly due to microplastic aging, as well as the combined effect with CPF. Moreover, LDPE-MPs aged in soil with enriched carbon and nitrogen were significantly concentrated in earthworm casts. Further studies on the environmental behaviours of aged MPs associated with other pollutants in soil, especially soils high in carbon and nitrogen, are needed.

Remediation of residually contaminated soils remains a widespread problem. Biochar can immobilize polycyclic aromatic hydrocarbons (PAH). However, studies on its ability to immobilize PAH and N, S, and O substituted PAH (hetero-PAH) in real soils, and benchmarking with commercial activated carbon are missing. Here, we compared the ability of pristine biochar (BC), steam-activated biochar (SABC), and commercial activated carbon (AC) to immobilize PAH and hetero-PAH. The three carbons were tested on soils from four different contaminated sites in Austria. Different amendment rates (w/w) of the carbons were investigated (BC: 1.0, 2.5, and 5%; SABC: 0.5, 1.0, and 2.0%; AC: 1%) in batch experiments to cover meaningful ranges in relation to their performance. SABC performed better than AC, removing at least 80% PAH with the lowest application rate of 0.5%, and achieving a complete removal at an application rate of 1.0%. BC performed slightly worse but still acceptable in residually contaminated soils (40 and 100% removal at 1 and 5% amendment, respectively). The ability of BC and SABC to immobilize PAH decreased as the PAH-molar volume increased. PAH with three or more rings were preferentially removed by AC compared to SABC or BC. This can be explained by the difference in pore size distribution of the carbons which could limit the accessibility of PAH and hetero-PAH to reach sorption sites for π- π electron donor-acceptor interactions, which drive PAH and hetero-PAH sorption to carbons. Column percolation tests confirmed the results obtained in batch tests, indicating, that decisions for soil remediation can be derived from simpler batch experiments. In soil samples with 1% BC, a reduction of over 90% in the total concentration of PAH in the leached water was observed. Overall, BC and SABC were demonstrated to be valid substitutes for AC for stabilizing residually contaminated soils.

The increasing occurrence of micropollutants in natural water bodies has medium to long-term effects on both aquatic life and human health. The aim of this study is to optimize the degradation of two pharmaceutical pollutants of emerging concern: amoxicillin and acetaminophen in aqueous solution at laboratory and pilot scale, by solar photo-Fenton process carried out at neutral pH using ethylenediamine-N,N′-disuccinic acid (EDDS) as a complexing agent to maintain iron in solution. The initial concentration of each compound was set at 1 mg/L dissolved in a simulated effluent from a municipal wastewater treatment plant (MWTP). A factorial experimental design and its surface response analysis were used to optimize the operating parameters to achieve the highest initial degradation rate of each target. The evolution of the degradation process was measured by ultra-performance liquid chromatography (UPLC/UV), obtaining elimination rates above 90% for both contaminants. Statistical study showed the optimum concentrations of Fe(III) at 3 mg/L at an Fe-EDDS ratio of 1:2 and 2.75 mg/L H2O2 for the almost complete removal of the target compounds by solar photo-Fenton process. Validation of the experimental design was successfully carried out with actual MWTP effluent spiked with 100 μg/L of amoxicillin and acetaminophen, each at pilot plant scale.

Antifouling paints (APs) are one of the important sources of Cu and Zn contamination in coastal environments. This study applied for the first-time a multi-isotope (Cu, Zn, and Pb) and multi-elemental characterization of different AP brands to improve their tracking in marine environments. The Cu and Zn contents of APs were shown to be remarkably high ∼35% and ∼8%, respectively. The δ65CuAE647, δ66ZnIRMM3702, and 206Pb/207Pb of the APs differed depending on the manufacturers and color (−0.16 to +0.36‰, −0.34 to +0.03‰, and 1.1158 to 1.2140, respectively). A PCA analysis indicates that APs, tires, and brake pads have also distinct elemental fingerprints. Combining isotopic and elemental ratios (e.g., Zn/Cu) allows to distinguish the environmental samples. Nevertheless, a first attempt to apply this approach in highly urbanized harbor areas demonstrates difficulties in source apportionments, because the sediment was chemically and isotopically homogeneous. The similarity of isotope ranges between the harbor and non-exhaust traffic emission sources suggests that most metals are highly affected by urban runoff, and that APs are not the main contributors of these metals. It is suspected that AP-borne contamination should be punctual rather than dispersed, because of APs low solubility properties. Nevertheless, this study shows that the common coastal anthropogenic sources display different elemental and isotopic fingerprints, hence the potential for isotope source tracking applications in marine environments. Further study cases, combined with laboratory experiments to investigate isotope fractionation during releasing the metal sources are necessary to improve non-traditional isotope applications in environmental forensics.

Plastic waste and its fragments (microplastics; <5 mm) have been observed in almost all types of environments. However, the mechanisms underlying the flow and transport processes of plastics are unknown. This is particularly valid for river sediments, where complex interactions occur between particles and influence their vertical and horizontal distribution patterns. In this study, we investigated the vertical redistribution of 14 pristine microplastics (MPs) with different densities, sizes, and shapes within disturbed sediment without lateral transport (i.e., low-velocity flow). MPs were spiked into sediments (height: 8 cm) in a column with a height of 1 m (diameter: 6 cm) filled to the top with water. The sediment was perturbed by turning the column upside-down to simulate remobilization and the subsequent deposition of sediment. After the complete sedimentation of the particles, the water column was filtered and the sediment was cut into vertical sections. MPs were then extracted from the sediment using sieves and a density separation method, and were counted under a stereomicroscope. Low-density polymers were mainly recovered in the water column and at the surface of the sediment, whereas high-density polymers were found within all sediment sections. The vertical distribution of high-density polymers changes primarily with the sediment grain size. The distribution of each polymer type changes depending on the size and/or shape of the particles with complex interactions. The observed distributions were compared with the expected distributions based only on the vertical velocity formulas. Overall, the formulas used did not explain the sedimentation of a portion of low-density polymers and predicted a lower distribution in the sediment than those observed in the experiment. In conclusion, this study highlights the importance of considering MPs as multi-dimensional particles and provides clues to understand their fate in low-velocity flow systems, considering that they undergo scavenging in sediments.

In aquatic ecosystems, microalgae are exposed to light fluctuations at different frequencies due to daily and seasonal changes. Although concentrations of herbicides are lower in Arctic than in temperate regions, atrazine and simazine, are increasingly found in northern aquatic systems because of long-distance aerial dispersal of widespread applications in the south and antifouling biocides used on ships. The toxic effects of atrazine on temperate microalgae are well documented, but very little is known about their effects on Arctic marine microalgae in relation to their temperate counterparts after light adaptation to variable light intensities. We therefore investigated the impacts of atrazine and simazine on photosynthetic activity, PSII energy fluxes, pigment content, photoprotective ability (NPQ), and reactive oxygen species (ROS) content under three light intensities. The goal was to better understand differences in physiological responses to light fluctuations between Arctic and temperate microalgae and to determine how these different characteristics affect their responses to herbicides. The Arctic diatom Chaetoceros showed stronger light adaptation capacity than the Arctic green algae Micromonas. Atrazine and simazine inhibited the growth and photosynthetic electron transport, affected the pigment content, and disturbed the energy balance between light absorption and utilization. As a result, during high light adaptation and in the presence of herbicides, photoprotective pigments were synthesized and NPQ was highly activated. Nevertheless, these protective responses were insufficient to prevent oxidative damage caused by herbicides in both species from both regions, but at different extent depending on the species. Our study demonstrates that light is important in regulating herbicide toxicity in both Arctic and temperate microalgal strains. Moreover, eco-physiological differences in light responses are likely to support changes in the algal community, especially as the Arctic ocean becomes more polluted and bright with continued human impacts.

Many animals migrate after reproduction to respond to seasonal environmental changes. Environmental conditions experienced on non-breeding sites can have carryover effects on fitness. Exposure to harmful chemicals can vary widely between breeding and non-breeding grounds, but its carryover effects are poorly studied. Mercury (Hg) contamination is a major concern in the Arctic. Here we quantified winter Hg contamination and its carryover effects in the most abundant Arctic seabird, the little auk Alle. Winter Hg contamination of birds from an East Greenland population was inferred from head feather concentrations. Birds tracked with Global Location Sensors (GLS, N = 28 of the total 92) spent the winter in western and central North Atlantic waters and had increasing head feather Hg concentrations with increasing longitude (i.e., eastward). This spatial pattern was not predicted by environmental variables such as bathymetry, sea-surface temperature or productivity, and needs further investigation. Hg concentrations in head feathers and blood were strongly correlated, suggesting a carryover effect of adult winter contamination on the consequent summer concentrations. Head feather Hg concentrations had no clear association with telomere length, a robust fitness indicator. In contrast, carryover negative effects were detected on chick health, as parental Hg contamination in winter was associated with decreasing growth rate of chicks in summer. Head feather Hg concentrations of females were not associated with egg membrane Hg concentrations, or with egg volume. In addition, parental winter Hg contamination was not related to Hg burdens in chicks’ body feathers. Therefore, we hypothesise that the association between parental winter Hg exposure and the growth of their chick results from an Hg-related decrease in parental care, and needs further empirical evidence. Our results stress the need of considering parental contamination on non-breeding sites to understand Hg trans-generational effects in migrating seabirds, even at low concentrations.

Monitoring the abundance and characteristics of microplastics in estuarine waters is crucial for understanding the fate of microplastics at the land-sea continuum, and for developing policies and legislation to mitigate associated risks. However, if protocols to monitor microplastic pollution in ocean waters or beach sediments are well established, they may not be adequate for estuarine environments, due to the complex 3D hydrodynamics. In this note, we review and discuss sampling methods and strategies in relation to the main environmental forcing, estuarine hydrodynamics, and their spatio-temporal scales of variability. We propose recommendations about when, where and how to sample microplastics to capture the most representative picture of microplastic pollution. This note opens discussions on the urgent need for standardized methods and protocols to routinely monitor microplastics in estuaries which should, at the same time, be easily adaptable to the different systems to ensure consistency and comparability of data across different studies.