The objective of present study was to obtain the fixation of nano zero valent iron (nZVI) particles on a permeable matrix and evaluate the performance of this composite material for the removal of Cr(VI) from contaminated waters. The experiments were carried out using the cationic resin Dowex 50WX2 as porous support of the iron nanoparticles. The work was carried out in two phases. The first phase involved the fixation of nZVI on the resin matrix. The resin granules were initially mixed with a FeCl3 solution to obtain the adsorption of Fe(III). Then the Fe(III) loaded resin (RFe) was treated with polyphenol solutions to obtain the reduction of Fe(III) to the elemental state. Two polyphenol solutions were tested as reductants, i.e. green tea extract and gallic acid. Green tea was found to be inefficient, probably due to the relatively big size of the contained polyphenol molecules, but gallic acid molecules were able to reach adsorbed Fe(III) and reduce the cations to the elemental state. The second phase was focused on the investigation of Cr(VI) reduction kinetics using the nanoiron loaded resins (R-nFe). It was found that the reduction follows a kinetic law of first order with respect to Cr(VI) and to the embedded nanoiron. Compared to other similar products, this composite material was found to have comparable performance regarding reaction rates and higher degree of iron utilization. Namely the rate constant for the reduction of Cr(VI), in the presence of 1 mM nZVI, was equivalent to 1.4 h of half-life time at pH 3.2 and increased to 24 h at pH 8.5. The degree of iron utilization was as high as 0.8 mol of reduced Cr(VI) per mole of iron. It was also found that this composite material can be easily regenerated and reused for Cr(VI) reduction without significant loss of efficiency.

Estuarine Microplastics (MPs) are limited to know globally. By filtering subsurface water through 330 μm nets, MPs in Jiaojiang, Oujiang Estuaries were quantified, as well as that in Minjiang Estuary responding to Typhoon Soulik. Polymer matrix was analyzed by Raman spectroscopy. MP (<5 mm) comprised more than 90% of total number plastics. The highest MPs density was found in Minjiang, following Jiaojiang and Oujiang. Fibers and granules were the primary shapes, with no pellets found. Colored MPs were the majority. The concentrations of suspended microplastics determine their bioavailability to low trophic organisms, and then possibly promoting the transfer of microplastic to higher trophic levels. Polypropylene and polyethylene were the prevalent types of MPs analyzed. Economic structures in urban estuaries influenced on MPs contamination levels. Typhoon didn't influence the suspended MP densities significantly. Our results provide basic information for better understanding suspended microplastics within urban estuaries and for managerial actions.

Microplastics (MPs, plastics < 5 mm) are a growing concern in ecosystems, being found in the soil and water environment. One of the primary sources of MPs has been suspected to be road dust in urban areas as it can flow into waters with runoff. To understand the occurrence of MPs (100 μm–5 mm) in surface road dust of three cities (Kusatsu, Shiga, Japan; Da Nang, Vietnam; and Kathmandu, Nepal), we collected surface road dust samples. The samples were pretreated (organic matter decomposition and gravity separation), and all MP candidates were individually observed by microscope for color, shape, and size; and analyzed their polymer types using fourier transform infrared spectrometry. The abundances of MPs 100 μm to 5 mm in size were 2.0 ± 1.6 pieces/m2 (13 polymer types) in Kusatsu, 19.7 ± 13.7 pieces/m2 in Da Nang (14 types), and 12.5 ± 10.1 pieces/m2 in Kathmandu (15 types). We classified the MPs into two groups; containers/packaging-MPs and rubber-MPs. Among all MPs, the containers/packaging-MPs accounted for 55 ± 5% of the polymer types composition. In contrast, the rubber-MPs accounted for 16 ± 6% of all MPs which were higher than those previously published for environmental water and sediment samples. The containers/packaging-MPs were fragments of various colors while most of the rubber-MPs were fragments or granules in black. The number–size distributions of MPs showed that the mode of formation explains the differences between their polymer types (tearing for containers/packaging-MPs and abrasion for rubber-MPs). In Da Nang and Kathmandu, the abundance of containers/packaging-MPs and rubber-MPs were correlated so that those MPs might be micronized from the originated materials in the sources with the similar composition (e.g. dump points). It was indicated that the characteristics of MPs pollution in surface road dust might be different depending on waste management practices.

The present study deals with the cyto-genotoxicological impact of ionic liquids, 1-butyl-3-methylimidazolium bromide, trihexyl tetradecylphosphonium dicyanamide, 1-decyl-3-methylimidazolium tetrafluoroborate, benzyldimethyltetradecylammonium chloride, and 1-butyl-4-methylpyridinium chloride, on animal cells and their biodegradation. The long alkyl chain containing ionic liquids were found to be more toxic whereas benzene functional group in benzyldimethyltetradecylammonium chloride enhances its toxicity. Aerobic bacterial granules, a bacterial consortium, were developed that have promising ability to break down these organic pollutants. These aerobic bacterial granules have been applied for the biodegradation of ionic liquids. The biological oxygen demand (5 days) and chemical oxygen demand parameters confirmed that the biodegradation was solely due to aerobic bacterial granules which further decreased the time period needed for regular biodegradation by biological oxygen demand (28 days). The high resolution mass spectrometry analysis further approved that the degradation of ionic liquids was mainly via removal of the methyl group. Elevated N-demethylase enzyme activity supports the ionic liquids degradation which may be occurring through demethylation mechanism. The amplicon sequencing of aerobic bacterial granules gives insight into the involvement of the bacterial community in the biodegradation process.

Bacillus subtilis YB1 is a strain that can efficiently transform nicosulfuron. In order to study its remediation ability and effects on other microorganisms in the soil, indoor biological remediation experiments and rhizosphere microbial diversity analysis were performed. B. subtilis YB1 granules were prepared and applied to the nicosulfuron contaminated soil. The concentration of nicosulfuron was detected by ultra-performance liquid chromatography-mass spectrometry (UPLC-MS) and changes in the physiological indicators of wheat were measured. At the same time, the changes in the rhizosphere soil microbial diversity were determined by 16S RNA sequencing. Results showed that the YB1 granules made a contribution to the transformation of nicosulfuron (0.05 mg kg⁻¹) in the soil within 55 days. The physiological indicators of wheat also showed consistent result about nicosulfuron transformation. Rhizosphere soil microbial diversity results indicated the relative abundance of Firmicutes decreased (3.0%–0.35%) and Acidobacteria first decreased (25.82%–22.38%) and then increased (22.3%–26.1%) with nicosulfuron added (N group). The relative abundance of Acidobacteria first decreased (25.8%–15.3%) and then increased (15.3%–21.7%) while Proteobacteria increased (26.5%–38.08%). At the same time, Firmicutes first increased (2.6%–12.3%) and then decreased to original level (12.3%–0.7%) in the N group with YB1 granules (NYB1 group). Members of the genus Bacillus initially increased and then decreased to the original level as the Control group, therefore, they did not become dominant in the rhizosphere soil. Alpha diversity analyses showed no obvious differences in species diversity among the N, NYB1 and Control groups. So YB1 did not have obvious influence on the rhizosphere microbial community structure during nicosulfuron transformation, which only had some effect on species abundance. This study revealed the successful indoor bioremediation of nicosulfuron in the soil, providing a potential strategy for solving the problem of nicosulfuron contamination.

The metalloid arsenic is one of the most conspicuous groundwater contaminants in the Indian subcontinent and its removal from aqueous medium is the main focus of this study. The study aims at functionalising melanin using iron and copper for the efficient removal of arsenic and rendering water fit for consumption. Melanin obtained from the marine bacteria Pseudomonas stutzeri was functionalised by iron impregnation (Fe-melanin) and copper impregnation (Cu-melanin). Morphological studies using FESEM portrayed the impregnated iron and copper granules on the surface of melanin, while XRD analysis confirmed the presence of Fe₂O₃ and CuO on melanin. Adsorption studies on As (V) and As (III) were conducted using Fe-melanin and Cu-melanin for different operating variables like pH, temperature and contact time. More than 99% per cent of As (III) and As (V) from water was removed at a pH range between 4 and 6 within 50 min in the case of Fe-melanin and 80 min for Cu-melanin. Adsorption equilibrium studies showed better fit with Langmuir adsorption isotherm and had good agreement with Redlich-Peterson’s three-parameter model. The maximum adsorption capacities of Fe-melanin and Cu-melanin obtained from Langmuir adsorption model are 50.12 and 20.39 mg/g, respectively, for As (V) and similarly 39.98 and 19.52 mg/g, respectively, for As (III). Arsenic-binding to the functionalised melanin was confirmed using FT-IR and the XPS analysis. Reuse of the adsorbent was effectively done by desorbing the iron and copper together with the bound As (III) and As (V) and further re-impregnation of iron and copper in melanin. Re-functionalised melanin showed 99% adsorption efficiency up to four cycles of adsorption/desorption.

The presence of microplastics in the environment is currently receiving a lot of attention. Rubber particles from tire wear have been estimated in several mass emission inventories to be a major contributor to the total microplastic release. This work used dynamic probabilistic material flow analysis to quantify the flows of rubber particles from tires to roads and further onto soils and surface waters of Switzerland. The model considered the whole life-cycle of tires from import over the use phase to the end-of-life and the re-use of scrap tires. Uncertainties of model parameters and data variability were considered by using a probabilistic approach. Mass flows onto soils and through road drainage by both uncontrolled dispersal and engineered systems are considered. In addition, the release of rubber from artificial turfs was included. The accumulation of rubber particles in the environment was quantified over the time frame from 1988 to 2018. The results show that in 2018, 1.29 ± 0.45 kg/capita of rubber was emitted from tire wear (97%) and rubber granules (3%). Street cleaning and waste water treatment removed around 26% of this rubber mass before finally reaching the receiving environmental compartment, resulting in an effective input of 0.96 ± 0.35 kg/capita of rubber in 2018 into the natural environment. Most of this mass (74%) was deposited on roadside soils (up to 5 m distance from road), 22% flowed into surface waters and the remaining part (4%) was emitted to soils. The dynamic modeling showed an increase of the input into the environment by about 10% from 1990 to 2018. The ban of sewage sludge application on soils resulted in a marked decrease in the amount transferred to soils after the year 2000. In total, 219 ± 22 ktonnes of rubber particles have accumulated in the environment since 1988 in Switzerland.

Zebra mussels (Dreissena polymorpha) were exposed to polyvinylpyrrolidone (PVP)-coated silver nanoparticles (AgNP; hydrodynamic diameter 80 nm; solid diameter 50 nm) to investigate the behavior of Ag in the tank water with respect to its uptake, bioaccumulation, elimination and subcellular distribution in the mussel soft tissue. Parallel experiments were performed with ionic Ag (AgNO3) to unravel possible differences between the metal forms. The recovery of the applied Ag concentration (500 μg/L) in the tank water was clearly affected by the metal source (AgNP < AgNO3) and water type (reconstituted water < tap water). Filtration (<0.45 μm) of water samples showed different effects on the quantified metal concentration depending on the water type and Ag form. Ag accumulation in the mussel soft tissue was neither influenced by the metal source nor by the water type. Ag concentrations in the mussel soft tissue did not decrease during 14 days of depuration. For both metal forms the Ag distribution within different subcellular fractions, i.e. metal-rich granules (MRG), cellular debris, organelles, heat-sensitive proteins (HSP) and metallothionein-like proteins (MTLP), revealed time-dependent changes which can be referred to intracellular Ag translocation processes. The results provide clear evidence for the uptake of Ag by the mussel soft tissue in nanoparticulate as well as in ionic form. Thus, zebra mussels could be used as effective accumulation indicators for environmental monitoring of both Ag forms.

Partitioning tissue metal concentration into subcellular compartments reflecting toxicologically available pools may provide good descriptors of the toxicological effects of metals on organisms. Here we investigated the relationships between internal compartmentalization of Cd, Pb and Zn and biomarker responses in a model soil organism: the earthworm. The aim of this study was to identify metal fractions reflecting the toxic pressure in an endogeic, naturally occurring earthworm species (Aporrectodea caliginosa) exposed to realistic field-contaminated soils.After a 21 days exposure experiment to 31 field-contaminated soils, Cd, Pb and Zn concentrations in earthworms and in three subcellular fractions (cytosol, debris and granules) were quantified. Different biomarkers were measured: the expression of a metallothionein gene (mt), the activity of catalase (CAT) and of glutathione-s-transferase (GST), and the protein, lipid and glycogen reserves. Biomarkers were further combined into an integrated biomarker index (IBR).The subcellular fractionation provided better predictors of biomarkers than the total internal contents hence supporting its use when assessing toxicological bioavailability of metals to earthworms. The most soluble internal pools of metals were not always the best predictors of biomarker responses. metallothionein expression responded to increasing concentrations of Cd in the insoluble fraction (debris + granules). Protein and glycogen contents were also mainly related to Cd and Pb in the insoluble fraction. On the other hand, GST activity was better explained by Pb in the cytosolic fraction. CAT activity and lipid contents variations were not related to metal subcellular distribution. The IBR was best explained by both soluble and insoluble fractions of Pb and Cd.This study further extends the scope of mt expression as a robust and specific biomarker in an ecologically representative earthworm species exposed to field-contaminated soils. The genetic lineage of the individuals, assessed by DNA barcoding with cytochrome c oxidase subunit I, did not influence mt expression.

The sediment-dwelling ragworm, Nereis diversicolor was exposed to sediment spiked with aqueous Cu (CuAq, CuCl2), CuO nanoparticles (CuONP) or CuO microparticles (CuOMicro) at 150 μg Cu g−1 dw sediment for 10d. Exposures to CuAq and CuOMicro caused mortality (62.5 and 37.5%, respectively), whereas mean burrowing time increased during exposure to CuAq and CuONP from 0.12 h (controls) to 19.3 and 12.2 h, respectively. All Cu treatments bioaccumulated, especially CuAq (up to 4 times more than the other treatments). Cu was roughly equally distributed among the five subcellular fractions in controls and worms exposed to CuONP or CuOMicro. In contrast, ≈50% of accumulated Cu in CuAq exposed worms was found in metal rich granules and significantly more Cu was present in heat-denatured proteins and organelles than in worms exposed to CuOMicro or in controls. Our results suggest that Cu form affects its bioaccumulation and subsequent toxicity and detoxification in a polychaete like N. diversicolor.