Stable isotope fractionation of toluene under dynamic phase exchange was studied aiming at ascertaining the effects of gas-liquid partitioning and biodegradation of toluene stable isotope composition in liquid-air phase exchange reactors (Laper). The liquid phase consisted of a mixture of aqueous minimal media, a known amount of a mixture of deuterated (toluene-d) and non-deuterated toluene (toluene-h), and bacteria of toluene degrading strain Pseudomonas putida KT2442. During biodegradation experiments, the liquid and air-phase concentrations of both toluene isotopologues were monitored to determine the observable stable isotope fractionation in each phase. The results show a strong fractionation in both phases with apparent enrichment factors beyond −800‰. An offset was observed between enrichment factors in the liquid and the gas phase with gas-phase values showing a stronger fractionation in the gas than in the liquid phase. Numerical simulation and parameter fitting routine was used to challenge hypotheses to explain the unexpected experimental data. The numerical results showed that either a very strong, yet unlikely, fractionation of the phase exchange process or a – so far unreported – direct consumption of gas phase compounds by aqueous phase microorganisms could explain the observed fractionation effects. The observed effect can be of relevance for the analysis of volatile contaminant biodegradation using stable isotope analysis in unsaturated subsurface compartments or other environmental compartment containing a gas and a liquid phase.

To provide insight into how climate-driven diet shifts may impact contaminant exposures of Arctic species, we compared feeding ecology and contaminant concentrations in ringed seals (Pusa hispida) from two Canadian sub-Arctic (Nain at 56.5°N, Arviat at 61.1°N) and two Arctic sites (Sachs Harbour at 72.0 °N, Resolute Bay at 74.7 °N). In the sub-Arctic, empirical evidence of changing prey fish communities has been documented, while less community change has been reported in the Arctic to date, suggesting current sub-Arctic conditions may be a harbinger of future Arctic conditions. Here, Indigenous partners collected tissues from subsistence-harvested ringed seals in 2018. Blubber fatty acids (FAs) and muscle stable isotopes (δ¹⁵N, δ¹³C) indicated dietary patterns, while measured contaminants included heavy metals (e.g., total mercury (THg)), legacy persistent organic pollutants (e.g., dichlorodiphenyltrichloroethanes (DDTs)), polybrominated diphenyl ethers (PBDEs), and per-/polyfluoroalkyl substances (PFASs). FA signatures are distinct between sub-Arctic and Resolute Bay seals, likely related to higher consumption of southern prey species including capelin (Mallotus villosus) in the sub-Arctic but on-going feeding on Arctic species in Resolute Bay. Sachs Harbour ringed seals show FA overlap with all locations, possibly consuming both southern and endemic Arctic species. Negative δ¹³C estimates for PFAS models suggest that more pelagic, sub-Arctic type prey (e.g., capelin) increases PFAS concentrations, whereas the reverse occurs for, e.g., THg, ΣPBDE, and ΣDDT. Inconsistent directionality of δ¹⁵N estimates in the models likely reflects baseline isotopic variation not trophic position differences. Adjusting for the influence of diet suggests that if Arctic ringed seal diets become more like sub-Arctic seals due to climate change, diet-driven increases may occur for newer contaminants like PFASs, but not for more legacy contaminants. Nonetheless, temporal trends studies are still needed, as are investigations into the potential confounding influence of baseline isotope variation in spatial studies of contaminants in Arctic biota.

In acidic medium, hazardous heavy metals of lead-zinc tailing (LZT) are easily leachable and mobilizable. Thus, the hazard, amount, form, and complexity of the leached heavy metals under acidic precipitation become a major environmental concern. This work investigates the gangue minerals, toxicity, speciation, leaching characteristics of heavy metals in LZT under simulated acid rain, as well as immobilization effects and mechanisms using a sustainable binder. In LZT, dolomite, quartz, calcite, and muscovite are the main gangue minerals, tiny hazardous metallic minerals were absorbed in the surface. The results revealed that Pb, Zn, Cr, and Cd were the predominant harmful elements, particularly Pb and Zn. Zn is leached completely and is the concerned hazardous element under simulated acid rain. In the acid rain neutralization ability test, the amount of leachable Pb, Cr, Ca, and Si maintained in equilibrium, leached Zn, Cd, Al, and Mg depended on the addition of acid. Pb and Ca were sedimented in residues. Immobilization of Pb, Zn, Cr, and Cd depended on the stability of Ca(OH)₂/C–S–H of hydrates, and 70% LZTHP after curing 7 days can be used for some practical engineering projects. This work opens up deeply understandings for the leached heavy metals under acidic precipitation and improves the sustainable and safe in the field of immobilization of heavy metals.

Increased organized monitoring is key to improving our understanding of marine debris on shorelines. Shorelines are demonstrated sinks for marine debris but efforts to quantify debris often fail to capture and report core variables and survey design techniques necessary to ensure study repeatability, comparability and to provide meaningful results. Here, we systematically review the available literature regarding marine debris distribution and abundance on shorelines of countries bordering the North Pacific Ocean (NPO), which are demonstrated to have unusually high marine debris abundance and diversity both at the ocean surface and stranded on shorelines. The majority of the 81 papers documenting shoreline debris in the NPO were studies that took place for less than one year (76.5%). Additionally, most sampling sites were visited only once (57.3%). Precise site locations (GPS coordinates) were provided in only 44.4% of the evaluated studies. Debris quantities were reported using nine different measurement units, with item counts per area and item counts per mass being most commonly reported for macro- and microplastics, respectively. Taken together, most of the reviewed studies could not be repeated by others given the information provided. We propose a series of guidelines with regard to marine debris shoreline sampling metrics, indicators, methods, and target goals in the NPO in order to improve comparability and repeatability. These follow the basic tenets of environmental survey design, which when not accounted for, can limit the applicability and value of large-scale shoreline monitoring efforts.

The settling of microplastics (MPs) is crucial for their removal from municipal wastewater treatment plants (WWTPs) and sedimentation in static waterbodies, where they can accumulate in bottom sediments. Biofilm formation on MPs enhances their aggregation with other particles, thereby changing their density and size and altering their settling rates. However, only a few studies have investigated the settling of MPs of different sizes and materials. Specifically, the settling of small-sized MPs (<150 μm) has been poorly documented. In this study, cylindrical and fragmented particles of four polymer types (high-density polyethylene (HDPE), polypropylene (PP), polystyrene (PS), and poly(ethylene terephthalate) (PET)) were used to investigate the settling or floating of reference MPs (20–130 μm) in a custom-made column that simulated a primary sedimentation tank in a typical WWTP before and after incubation in wastewater influent. The settling velocity of the reference MP particles was strongly influenced by the particle size and density. The settled fractions of all the cylindrical reference MPs increased significantly (up to 5 times) due to biofilm formation at overflow velocities of 0.15, 0.26, and 0.40 mm s⁻¹. This was observed even for HDPE and PP (density <1 g cm⁻³) after biofilm formation. The fragmented reference MPs showed complex and rather unpredictable behavior, possibly due to their irregular shape. Generally, the settling of pristine PS and PET in the laboratory tests was consistent with the theoretical predictions obtained using Stokes’ law. The experimental findings of this study can be used to develop models that predict the removal efficiencies of MPs in WWTPs and to estimate the sinking of MPs to bottom sediments of static waterbodies.

The composition of root exudates is modulated by several environmental factors, and it remains unclear how that affects beneficial rhizosphere or inoculated microorganisms under heavy metal (HM) contamination. Therefore, we evaluated the transcriptional response of Pseudomonas putida E36 (a Miscanthus x giganteus isolate with plant growth promotion-related properties) to Cd, Pb and Zn in an in vitro study implementing root exudates from M. x giganteus. To collect root exudates and analyse their composition plants were grown in a pot experiment under HM and control conditions. Our results indicated higher exudation rate for plants challenged with HM. Further, out of 29 organic acids identified and quantified in the root exudates, 8 of them were significantly influenced by HM (e.g., salicylic and terephthalic acid). The transcriptional response of P. putida E36 was significantly affected by the HM addition to the growth medium, increasing the expression of several efflux pumps and stress response-related functional units. The additional supplementation of the growth medium with root exudates from HM-challenged plants resulted in a downregulation of 29% of the functional units upregulated in P. putida E36 as a result of HM addition to the growth medium. Surprisingly, root exudates + HM downregulated the expression of P. putida E36 functional units related to plant colonization (e.g., chemotaxis, motility, biofilm formation) but upregulated its antibiotic and biocide resistance compared to the control treatment without HM. Our findings suggest that HM-induced changes in root exudation pattern may attract beneficial bacteria that are in turn awarded with organic nutrients, helping them cope with HM stress. However, it might affect the ability of these bacteria to colonize plants growing in HM polluted areas. Those findings may offer an insight for future in vivo studies contributing to improvements in phytoremediation measures.

Nitric oxide (NO) is an important phytohormone for plant adaptation to mercury (Hg) stress. The effect of Hg on lignin synthesis, NO production in leaf, sheath and root and their relationship were investigated in two members of the grass family - wheat and maize. Hg stress decreased growth and lignin contents, significantly affected phenylpropanoid and monolignol pathways (PAL, phenylalanine ammonia-lyase; 4-coumarate: CoA ligase, 4CL; cinnamyl alcohol dehydrogenase, CAD), with maize identified to be more sensitive to Hg stress than wheat. Among the tissue types, sheath encountered severe damage compared to leaves and roots. Hg translocation in maize was about twice that in wheat. Interestingly, total NO produced under Hg stress was significantly decreased compared to control, with maximum reduction of 43.4% and 42.9% in wheat and maize sheath, respectively. Regression analysis between lignin and NO contents or the activities of three enzymes including CAD, 4CL and PAL displayed the importance of NO contents, CAD, 4CL and PAL for lignin synthesis. Further, the gene expression profiles encoding CAD, 4CL and PAL provided support for the damaging effect of Hg on wheat sheath, and maize shoot. To validate NO potential to mitigate Hg toxicity in maize and wheat, NO donor and NO synthase inhibitor were supplemented along with Hg. The resulting phenotype, histochemical analysis and lignin contents showed that NO mitigated Hg toxicity by improving growth and lignin synthesis and accumulation. In summary, Hg sensitivity was higher in maize seedlings compared to wheat, which was associated with the lower lignin contents and reduced NO contents. External supplementation of NO is proposed as a sustainable approach to mitigate Hg toxicity in maize and wheat.

Despite several studies having addressed the bioaccumulation of Dechlorane Plus (DP) flame retardant in wildlife, there is still a dearth of information for reptiles in general and for snakes in particular. Here, we report the residue levels and trophic transfer of syn-, anti-, and anti-Cl₁₁-DP in a frog-eating snake—namely, the striped keelback snake Amphiesma stolata—from a DP hotspot in South China. The concentrations of syn-, anti-, and anti-Cl₁₁-DP in A. stolata ranged from 1.06–21.2, 2.13–21.5, and 0.16–10.6 ng/g lipid weight, respectively, with significantly higher levels in males compared with females. Statistical analysis showed that the concentrations of these chemicals were negatively correlated with body sizes (length and mass) of the snake. The fractional abundance of anti-DP (fₐₙₜᵢ) did not significantly differ either between the sexes or between A. stolata and its diet (i.e., frogs). However, fₐₙₜᵢ showed positive correlations with the snake's body size and negative correlations with ∑DP concentrations (summed concentrations of syn- and anti-DP), indicating that body size and DP residue levels are important factors influencing DP isomeric profiles in these snakes. Biomagnification factors estimated based on the relationship between A. stolata and frogs were 0.49 ± 0.01 (mean ± SE), 0.44 ± 0.09, and 1.79 ± 0.54 for syn-, anti-, and anti-Cl₁₁-DP, respectively, suggesting trophic dilution of syn- and anti-DP and a mild biomagnification of anti-Cl₁₁-DP from frogs to snakes.

Breast milk samples were collected from 51 mothers in a seaside city Dalian, where the residents usually have higher dietary exposure to polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and polychlorinated biphenyls (PCBs) due to the larger consumption of seafood. The lipid-basis concentrations of ∑Cl₂–₈DD/Fs, ∑Cl₂–₁₀Bs, and total toxicity equivalent (WHO-TEQ) were measured to be in the ranges of 35.7–2727.8 pg/g, 4.91–52.64 ng/g, and 2.27–36.30 pg/g, respectively. The average proportion of ∑Cl₂–₃DD/Fs was higher than that of ∑Cl₄–₇DD/Fs in the collected human breast milk samples, suggesting that the health risk of Cl₂–₃DD/Fs should be especially concerned. The concentration data of PCDD/Fs and PCBs in human breast milk essentially followed a positive skew probability distribution. Women in high-level exposure scenarios exhibited a higher potential to accumulate homologues Cl₄DFs, Cl₇DFs, Cl₈DF, and Cl₆Bs in breast milk. Three PCDD/F congeners (1,2,3,6,7,8-Cl₆DF, 1,2,3,4,7,8-Cl₆DF, and 1,2,3,4,6,7,8-Cl₇DD) and three PCB congeners (PCB 126, PCB 138, and PCB 169) were identified as good indicators for the accumulation of PCDD/Fs and PCBs in human breast milk, respectively. The food-to-milk accumulation factors (FMAF) were calculated to evaluate the accumulation potentials of different PCDD/F and PCB congeners in human breast milk via dietary exposure. The calculated FMAF value presented a non-monotonic variation with the logarithm of n-octanol–water partition coefficient (log KOW) with a peak at a log KOW value of about 7.3 and a valley at a log KOW value of about 8. The mean value of the estimated daily intake (EDI) of total WHO-TEQ for breast-fed infants in Dalian, predicted by Monte Carlo simulation, was 10 folds higher than the upper range of the tolerable daily intake (TDI) value (4 pg WHO-TEQ/kg bw/d), suggesting continued and enhanced efforts should be made to reduce the exposure risk of infants to PCDD/Fs and PCBs.

Herbicide pollution is persistent, which not only has a negative impact on individual organisms, but also may endanger the interspecific relationship between predators and prey. Cladocerans, i.e. zooplankton that plays an important role in the energy flow and material circulation in freshwater ecosystem, usually develop induced defense in response to predation risk. We used atrazine, one of the most used herbicides in the world, and Daphnia pulex, a representative cladocerans, to test the possible interference effect of herbicides on the induced defensive traits of cladocerans in response to predator fish (Rhodeus ocellatus) kairomone, including morphological defense, life history strategies, and the expression of defense-related genes. Atrazine reduced the body size, spine size, growth rate, total offspring, and the relative reproductive output of D. pulex, which further affected the response strength of the morphological and life history defenses, i.e., atrazine significantly reduced the spine size, relative spine size, and fecundity of D. pulex in response to R. ocellatus kairomone. Exposure to atrazine affected the expression of defense-related genes, and we speculated that atrazine affected the signaling process in the induced anti-predation defense of cladocerans. Specially, fish kairomone attenuated the negative effects of high concentrations of atrazine on the life history traits of D. pulex. Our results will help to accurately assess the potential risk of artificial compounds in freshwater ecosystems from the perspective of interspecific relationships, and help to understand the impact of environmental changes on the inducible anti-predator defense of prey in aquatic ecosystems.