Dissolved organic matter influences the indigenous bacterial community and polycyclic aromatic hydrocarbons biodegradation in soils.

In polycyclic aromatic hydrocarbon (PAH) contaminated soils, bioremediation is superior to other strategies owing to its low cost and environmental friendliness. However, dissolved organic matter (DOM) and indigenous bacterial communities can affect the efficiency of PAH-degrading bacteria (PDB). This study found that exogenous PDB (C1) including the genera Acinetobacter, Stenotrophomonas, and Comamonas, decreased the bacterial diversity of Alfisol, Ultisol, Inceptisol, and Mollisol, and DOM enhanced the diffusion of PDB and the bioavailability of PAH. In addition, bacteria preferred to ingest low molecular weight DOM fractions, and the abundances of lipid-like and protein-like substances decreased by 0.12-3.03 % and 1.73-4.60 %. The DOM fractions had a more marked influence on the indigenous bacteria than the exogenous PDB, and PDB dominated the PAH biodegradation process in the soils. More COO functional groups promoted the utilization of higher molecular weight-related homologue fractions by bacteria, and lower molecular weight fractions carrying more CH2 functional groups declined during biodegradation. This study investigated the variations in bacterial communities during biodegradation and revealed the effects of DOM fractions on biodegradation in PAH-contaminated soils at the molecular level. These results will promote the development of bioremediation strategies for organics-contaminated soil and provide guidance for prediction models of soil biodegradation kinetics.

Exchangeable versus residual metals in naturally aged plastic litter.

Metals may be associated with plastics as additives arising from manufacture or through acquisition from the environment, but these associations are often poorly defined or referred to synonymously when considering metal availability. In this study, samples of plastic litter (n = 22) have been collected from various environmental and industrial compartments of Lublin Province, Poland, and fractionated according to polymer type (polyethylene, polyethylene terephthalate, nylon, expanded polystyrene, polypropylene, and "mixed") before being micronised to < 2 mm. Composites (n = 89) were subjected to two phases of a standardised and widely employed sequential extraction protocol (Bureau Communautaire de Reference; BCR) in order to define available (acid-soluble and exchangeable) and residual (soluble in boiling aqua regia) concentrations of Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, and Zn. For a given metal, total content, calculated by summing available and residual components, was highly variable, both between locations and amongst polymer categories, reflecting the heterogeneous distribution of a multitude of different additives. Overall, however, concentrations were greatest for Fe, with medians of several hundred to several thousand mg kg-1 amongst the different polymers, and lowest for Cd, Co, and Ni, where nearly all concentrations were below 10 mg kg-1. Median percentage metal availabilities were greatest for expanded polystyrene and were above 25% for Mn and Zn and below 10% for Cr and Fe in all polymer types. These observations are largely, but not entirely, attributed to the relative contributions of metals acquired from the environment and metals present as additives and residues. Significantly, the approach employed allows direct comparisons of metal availability in plastics with metal availability in environmental solids in order to evaluate the overall impacts of plastics in metal risk assessments.

Formation and biotoxicity of environmentally persistent free radicals in steelworks soil under thermal treatment.

Thermal treatment are commonly used to address organic contaminated soils. In particular, the pyrolysis of organic substances can result in the creation of environmentally persistent free radicals (EPFRs). We investigated a steelworks site in Chongqing (China) to observe changes in EPFRs before and after thermal treatment. Our findings revealed that the EPFRs were carbon-centered radicals with a g-factor < 2.0030 and a spin density ranging from n.d.-5.23 × 1015 spins/mg. The formation of EPFRs was driving by polycyclic aromatic hydrocarbons (PAHs), Mn, Cu, and total organic carbon (TOC). Following the thermal treatment, the spin densities of EPFRs increased by a factor of 0.25 to 1.81, with maximum levels reached at 300 °C. High molecular weight PAHs exhibited high heat capacity, enabling the generation of more EPFRs. The thermal decay of EPFRs occurred in two stages, with the shortest 1/e lifetime lasting up to 16.8 h. Raising the temperature or prolonging time can significantly reduce EPFRs levels. Thermal treatment increased the generation of EPFRs, hydroxyl radicals (•OH) and superoxide radical (•O2-), leading to a decrease in bacterial luminescence. Specifically, •OH contributed to approximately 73% of the B. brilliantus inhibition. Our results highlight that the thermal treatment significantly enhance EPFRs concentrations, and the treated soil remained ecologically risky. The knowledge of the formation of EPFRs and their biotoxicity is shedding new light on the thermal treatment risk management.

The high dose of biochar reduces polycyclic aromatic hydrocarbons losses during co-composting of sewage sludge and wheat straw.

The aim of the study was to investigate the effect of the biochar (BC) dose on solvent extractable (Ctot) and freely dissolved (Cfree) polycyclic aromatic hydrocarbons (PAHs) content during co-composting. A significantly better reduction of Σ16 Ctot PAHs after 98 days occurred during composting with BC (for 1% of BC - 44% and for 5% of BC - 23%) than in the control (15%). Despite the relatively high reduction of Ctot PAHs in the experiment with 5% BC rate, the content of the PAHs was still the highest compared to other variants. Regarding Cfree PAHs, 5% rate of BC resulted in the best reduction of PAHs, while the 1% BC dose resulted in a lower reduction of Cfree than the control. For 1% BC, PAHs losses was more effective, and sequestration processes played a less significant role than in the experiment with 5% dose of BC. The total and dissolved organic carbon, and ash were predominantly responsible for Ctot and Cfree losses, and additionally pH for Cfree. The results of the experiment indicate that BC performs a crucial role in composting, affecting the Ctot and Cfree PAHs in the compost but the final effect strictly depends on the BC dose.

Increased concentration of PAH derivatives in biochar-amended soil observed in a long-term experiment.

During biochar preparation or application some toxic substances may be formed. The established limitations of the content of polycyclic aromatic hydrocarbons (PAHs) aim to monitor the fate of PAHs in the life cycle of biochar. The latest studies have revealed that besides PAHs, some of their derivatives with confirmed toxicity are formed. There has been no policy regards PAH derivatives in biochar yet. The aim of the presented studies was the estimation the changes in the content of PAHs and their derivatives during the agricultural application of biochar. A pot experiment with grass revealed that in a short time, both the content of PAHs and their derivatives was reduced. Similarly, when biochar was added to soil in a long-term experiment, the content of determined derivatives was below the limit of detection, whereas interestingly, the content of pristine PAHs increased with time. Co-addition of biochar and sewage sludge increased the content of PAHs and their derivatives indicating potential environmental hazard due to their presence. However, the key point is the estimation of the bioavailability of PAHs and their derivatives as only the bioavailable fraction is revealing the environmental hazard.

Effect of chemical aging on phosphate adsorption and ecotoxicological properties of magnesium-modified biochar.

Using magnesium-biochar composites (Mg-BC) in adsorption allows for the efficient and economically relevant removal of phosphate (PO43-) from water and wastewater. Applying Mg-BC for pollutant removal requires evaluating the adsorption capacity of composites and their ecotoxicological properties. Investigating the composite aging during the application of these composites into the soil is also essential. In the present study, nonaged and aged (at 60 or 90 °C) Mg-BC composites were investigated in the context of pyrolysis temperature (500 or 700 °C). All analyzed biochars were examined by Fourier transform infrared spectroscopy, X-ray powder diffraction, X-ray photoelectron spectroscopy, Raman spectroscopy and surface area. The content of polycyclic aromatic hydrocarbons (PAHs) (bioavailable Cfree and organic solvent-extractable Ctot), heavy metals (HMs), and environmentally persistent free radicals (EPFRs) were determined. Ecotoxicity was evaluated using tests with Folsomia candida and Allivibrio fischeri. The dependence of adsorption on pyrolysis temperature and composite aging time was observed. Changes in physicochemical properties occurring as a result of aging reduced the adsorption of PO43- on Mg-BC composites. It was found that nonaged Mg-BC700 was more effective (9.55 mg g -1) in the adsorption of PO43- than Mg-BC500 (5.75 mg g-1). The adsorption capacities of aged composites were from 21 to 61% lower than those of the nonaged composites. Due to aging, the content of Cfree PAHs increased by 3-5 times depending on the pyrolysis temperature. However, aging reduced the Ctot PAHs in all composites from 24 to 35% depending on the pyrolysis temperature. Ecotoxicological evaluation of Mg-BC composites showed increased toxicity after aging to both organisms. The use of aged BC potentially increases the contaminant content and toxicity of Mg-BC composites.

Effect of zinc-biochar composite aging on its physicochemical and ecotoxicological properties.

The stability of Zn-biochar composites is determined by environmental factors, including the aging processes. This paper focused on the ecotoxicological evaluation of Zn-biochar (Zn-BC) composites subjected to chemical aging. Pristine biochars and composites produced at 500 or 700 °C were incubated at 60 and 90 °C for six months. All biochars were characterized in terms of their physicochemical (elemental composition, Fourier transform infrared spectroscopy (FTIR), X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy and porous structure), ecotoxicological properties (tested with Folsomia candida and Aliivibrio fischeri) and contaminant content (polycyclic aromatic hydrocarbons (PAH), heavy metals (HM) and environmentally persistent free radicals (EPFR)). An increase in the number of surface oxygen functional groups and increased hydrophilicity and polarity of all Zn-BC composites were observed due to oxidation during aging. It was also found that Zn-BC aging at 90 °C resulted in a 28-30% decrease in solvent-extractable PAHs (Æ©16 Ctot PAHs) compared to nonaged composites. The aging process at both temperatures also caused a 104 fold reduction in EPFRs in Zn-BC composites produced at 500 °C. The changes in the physicochemical properties of Zn-BC composites after chemical aging at 90 °C (such as pH and HM content) caused an increase in the toxicity of the composites to Folsomia candida (reproduction inhibition from 19 to 24%) and Aliivibrio fischeri (luminescence inhibition from 96 to 99%). The aging of composites for a long time may increase the adverse environmental impact of BC-Zn composites due to changes in physicochemical properties (itself and its interactions with pollutants) and the release of Zn from the composite.

Fast and reliable determination of phthalic acid esters in soil and lettuce samples based on QuEChERS GC-MS/MS.

Phthalates are commonly used as plasticizers, and solvents in industry and households. We propose an application of the QuEChERS method for the determination of six PAEs in the soil and lettuce (roots and leaves) by GC-MS/MS. The QuEChERS method validation procedure was performed and good linearity (>0.997), recovery (97.2-99.1 %), very low detection limits (0.09-0.43 ng/g), and satisfactory inter- and intraday precision (∼4%) were obtained confirming that QuEChERS GC-MS/MS applied for PAEs determination in the environmental samples is a cheap and environmentally friendly method. In general, the higher the number of carbon atoms in PAEs, the higher the percentage noted in the lettuce roots. At higher PAEs concentration (60 ng/g) the main bis(2-ethylhexyl) phthalate (DEHP) sink were roots whereas at lower concentrations (30 ng/g) most of DEHP was noted in lettuce leaves implying that the fate of PAEs was governed not by the chemical structure of PAEs but rather partitioning (logKow).

Extractability and phytotoxicity of heavy metals and essential elements from plastics in soil solutions and root exudates.

Plastic waste is increasing and is a serious environmental problem. Among the threats associated with plastics is the release of contaminants into the environment. This study aimed to evaluate the efficiency of metals release from plastics (low-density polyethylene (LDPE), polyethylene terephthalate (PET), and polypropylene (PP)) as affected by different soil solution types, artificial root exudates, and distilled water. The extent of metal release varied depending on the type of solution and plastic used. Metals were leached most effectively from plastics in soil solutions, followed by root exudates, and least effectively by distilled water. LDPE released the highest concentrations of Cu and Na into solution, PP released the greatest amount of Fe, and PET released the most Cr. The efficiencies of Mg and Zn release from the plastics (PP and PET) varied by solution type. Among the plastics studied, LDPE exhibited the strongest ability to adsorb metals, such as Fe, Cr, Mg, and Zn from soil solutions. The amount of metal released from the plastics was also dependent on pH, dissolved organic carbon (DOC) concentrations, and the electrical conductivity (EC) of the solutions. Moreover, plastic extracts were found to have negative effects on germination and growth in Lepidium sativum.

The promoted degradation of biochar-adsorbed 2,4-dichlorophenol in the presence of Fe(III).

Organic pollutant degradation by biochar could be promoted by Fe because of the Fenton-like reaction. However, studies have also confirmed that reactive oxygen species (ROS) play only a limited role in organic pollutant degradation by biochar. Herein, we quantitatively identified 2,4-dichlorophenol (2,4-DCP) adsorption and degradation in Fe-biochar systems and obtained degradation (k1) and adsorption rate constants (k2) by two-compartment first-order kinetics modeling. The k1 was approximately 7-10 times lower than the corresponding k2 and the positive correlation between k1 and k2 illustrated that adsorption and degradation were kinetically associated. ROS quenching only slightly inhibited 2,4-DCP degradation. Chemicals with similar structures to ROS quenchers (without quenching ability) also inhibited 2,4-DCP degradation, probably because of the competition of the active degradation sites on biochars. Electrochemical analysis and pH-impact experiments further elucidated that 2,4-DCP underwent oxidation-dominated degradation in the adsorbed phase via direct electron transfer. Fe(III) obviously increased 2,4-DCP adsorption through cation bridging and enhanced electron density by Fe-O conjugations on the biochar surface, which facilitated subsequent degradation. This study emphasized the importance of degradation on the biochar solid phase and that a breakthrough of the mass transfer bottleneck of adsorption will greatly promote degradation.

Transcriptional response of Cu-deficient barley (Hordeum vulgare L.) to foliar-applied nano-Cu: Molecular crosstalk between Cu loading into plants and changes in Cu homeostasis genes.

For safe and effective nutrient management, the cutting-edge approaches to plant fertilization are continuously developed. The aim of the study was to analyze the transcriptional response of barley suffering from Cu deficiency to foliar application of nanoparticulate Cu (nano-Cu) and its ionic form (CuSO4) at 100 and 1000 mg L-1 for the examination of their supplementing effect. The initial interactions of Cu-compounds with barley leaves were analyzed with spectroscopic (ICP-OES) and microscopic (SEM-EDS) methods. To determine Cu cellular status, the impact of Cu-compounds on the expression of genes involved in regulating Cu homeostasis (PAA1, PAA2, RAN1, COPT5), aquaporins (NIP2.1, PIP1.1, TIP1.1, TIP1.2) and antioxidant defense response (SOD CuZn, SOD Fe, SOD Mn, CAT) after 1 and 7 days of exposure was analyzed. Although Cu accumulation in plant leaves was detected overtime, the Cu content in leaves exposed to nano-Cu for 7 days was 44.5% lower than in CuSO4 at 100 mg L-1. However, nano-Cu aggregates remaining on the leaf surface indicated a potential difference between measured Cu content and the real Cu pool present in the plant. Our study revealed significant changes in the pattern of gene expression overtime depending on Cu-compound type and dose. Despite the initial puzzling patterns of gene expression, after 7 days all Cu transporters showed significant down-regulation under Cu-compounds exposure to prevent Cu excess in plant cells. Conversely, aquaporin gene expression was induced after 7 days, especially by nano-Cu and CuSO4 at 100 mg L-1 due to the stimulatory effect of low Cu doses. Our study revealed that the gradual release of Cu ions from nano-Cu at a lower rate provided a milder molecular response than CuSO4. It might indicate that nano-Cu maintained better metal balance in plants than the conventional compounds, thus may be considered as a long-term supplier of Cu.

Estrogens and xenoestrogen residues in manure-based fertilizers and their potential ecological risks.

Optimal manure treatment aimed at usage as agricultural soil fertilizers is a prerequisite ecological pollution control strategy. In this work, livestock manure-based fertilizers were collected from 71 animal farms across 14 provinces in China. The contamination levels and potential ecotoxicological risks of residual steroid estrogens (SEs): estrone (E1), estriol (E3), 17α-estradiol (17α-E2), 17ß-estradiol (17ß-E2) and xenoestrogen (XE) bisphenol A (BPA), were investigated. The results showed that the occurrence frequencies for SEs and XE ranged from 66.67% to 100%, and the mean concentration varied considerably across the study locations. The total content of SEs and XE in Hebei province was the highest, and swine manure-based fertilizers concentrations were higher than the levels reported in other animal fertilizers. Compared with farm level manure, manure-based fertilizers are processed by composting, and the micropollutants quantities are significantly reduced (mean: 87.65 - 534.02 µg/kg). The total estradiol equivalent quantity (EEQ) that might migrate to the soil was estimated to be 1.23 µg/kg. Based on the estimated application rate of manure, 38% of the fertilizers risk quotients exceeded 0.1, indicating medium to high risks pressure on terrestrial organisms. Nonetheless, the estrogenic risk was lower in manure-based fertilizers than in manure. This study highlights the significance of proper treatment of livestock manure and designing an optimal manure fertilization strategy to mitigate the risks posed by SEs and XEs to the agroecosystems.

The effect of biotransformation of sewage sludge- and willow-derived biochars by horseradish peroxidase on total and freely dissolved polycyclic aromatic hydrocarbon content.

This study analyzed the effect of enzymatic aging (horseradish peroxidase) of biochars on their content of solvent extractable (Ctot) and freely dissolved (Cfree) polycyclic aromatic hydrocarbons (PAHs). Physicochemical properties and phytotoxicity of pristine and aged biochars were also compared. The study used biochars obtained at 500 or 700 °C from sewage sludges (SSLs) or willow. Compared to SSL-derived biochars, willow-derived biochars were more susceptible to enzymatic oxidation. Aging increased the specific surface area and pore volume of most SSL-derived biochars. An opposite direction, however, was found in the willow-derived biochars. Low-temperature biochars, regardless of their feedstock, underwent physical changes, such as removal of labile ash components or degradation of aromatic structures. The enzyme caused an increase in the content of Ctot light PAHs in biochars (by 34-3402 %) and heavy PAHs (≥4 rings) in the low-temperature SSL-derived biochars (by 46-713 %). In turn, the content of Cfree PAHs decreased in aged SSL-derived biochars (by 32-100 %). In the willow-derived biochars the bioavailability of acenaphthene increased (by 337-669 %), while the immobilization degree of some PAHs was lower (25-70 %) compared to the SSL-derived biochars (32-83 %). Nevertheless, aging positively affected the ecotoxicological properties of all biochars by increasing their stimulation effects or removing their phytotoxic effects on both Lepidium sativum seed germination and root growth. Significant relationships between the changes in Cfree PAH content, pH and salinity of SSL-derived biochars and seed germination/root growth inhibition were found. The study demonstrates that the risk associated with application of SSL-derived biochars, regardless of the type of SSL and pyrolysis temperature, can be lower in terms of Cfree PAHs than in the case of willow-derived biochars. Regarding to Ctot PAHs, high-temperature SSL-derived biochars are safer than low-temperature ones. In the case of application of high-temperature SSL-derived biochars, these with moderate alkalinity and salinity will not bring risks for plants.

A novel type of biochar from chitinous Hermetia illucens waste with a built-in stimulating effect on plants and soil arthropods.

The breeding of insects generates waste in the form of insect excrement and feed residues. In addition, a specific chitinous waste in the form of insect larvae and pupae exuvia is also left. Recent research tries to manage it, e.g., by producing chitin and chitosan, which are value-added products. The circular economy approach requires testing new, non-standard management methods that can develop products with unique properties. To date, the possibility of biochar production from chitinous waste derived from insects has not been evaluated. Here we show that the puparia of Hermetia illucens are suitable for biochar production, which in turn exhibits original characteristics. We found that the biochars have a high nitrogen level, which is rarely achievable in materials of natural origin without artificial doping. This study presents a detailed chemical and physical characterization of the biochars. Moreover, ecotoxicological analysis has revealed the biochars' stimulation effect on plant root growth and the reproduction of the soil invertebrate Folsomia candida, as well as the lack of a toxic effect on its mortality. This predisposes these novel materials with already built-in stimulating properties to be used in agronomy, for example as a carriers for fertilizers or beneficial bacteria.

Microplastics identification in water by TGA-DSC Method: Maharloo Lake, Iran.

Nowadays, one of the biggest challenges is the lack of coordination between the microplastic identification methods used by researchers. To advance our global understanding of microplastic contamination and address the knowledge gaps, we require acceptable or similar identification methods or instruments designed to support the quantitative characterization of the microplastics data. In the current study, we focused on the thermogravimetric analysis (TGA) with differential scanning calorimetry (DSC) method which is usually used experimentally by other researchers, while we tried to look at this method in a real aquatic environment, Maharloo Lake and its Rivers. A number of 22 sites were chosen for sampling microplastics from water. The mean and median of total organic matter percentage for rivers samples (mean = 88%;median = 88%) was similar to the Maharloo lake (mean = 88.33%; median = 89%), suggesting the existence of a robust potential sink. The differentiation of the organic matter part into labile (e.g., carbon aliphatic and polysaccharides), recalcitrant (e.g., aromatic compounds and most plastics), and refractory fractions was implemented and the results indicated that labile organic matter was dominant in both the lake and the rivers, while recalcitrant and refractory fractions were lower. The river's average labile and refractory fractions were similar to the lake. Although the overall results of the study show combining TGA techniques with other analytical procedures can improve the technical quality of polymers, interpreting the complex information of those measurements requires a high level of expertise and the technology is still maturing.

The impact of cyclic freezing and thawing (physical aging) on properties and polycyclic aromatic hydrocarbon content in biochars.

In this study, we investigated the effect of freeze-thaw cycles of sewage sludge (SSL)- and willow-derived biochars obtained at different temperatures on their physicochemical properties and total (Ctot) and freely dissolved (Cfree) polycyclic aromatic hydrocarbon (PAH) content. In our research, we showed that the fate of Ctot PAHs depended on the type of SSL and may differ, which is determined mainly by the properties of the feedstock. The properties affect low-temperature SSL-derived biochars (500 °C) especially, in which the interactions based on π-π bonds between the PAHs and matrix during aging were weakened by newly created functional groups on the biochar surface. Additionally, the removal of ash or biochar particle fragmentation during aging increased the availability of solvent non-extractable PAHs, which resulted in an increase in the content of high molecular weight Ctot PAHs after aging. In turn, the Σ16 Cfree PAHs in biochars gradually decreased with their progressive surface functionalization, increase in specific surface area and pore volume and generally were independed on properties of feedstock and biochar. The obtained results evidence that the environmental risk associated with the use of SSL as a feedstock for biochar production is similar to or even lower than in the case when willow is used and depending on SSL type, the potential risk may be reduced or increased for low-temperature biochars.

Highly efficient capture of mercury from complex water matrices by AlZn alloy reduction-amalgamation and in situ layered double hydroxide.

Mercury pollution is a critical, worldwide problem and the efficient, cost-effective removal of mercury from complex, contaminated water matrices in a wide pH range from strongly acidic to alkaline has been a challenge. Here, AlZn and AlFe alloys are investigated and a new process of synergistic reduction-amalgamation and in situ layered double hydroxide (SRA-iLDH) for highly efficient capture of aqueous Hg(II) is developed using AlZn alloys. The parameters include the pH values of 1-12, the Hg(II) concentrations of 10-1000 mg L-1, and the alloy's Zn concentrations of 20%, 50% and 70% and Fe concentrations of 10%, 20% and 50%. The initial rate of Hg(II) uptake by AlZn alloys decreases with increasing Zn concentration while the overall rate is not affected. Specifically, AlZn50 alloy removes >99.5% Hg(II) from 10 mg L-1 solutions at pH 1-12 in 5 min at a rate constant of 0.055 g mg-1 min-1 and achieves a capacity of 5000 mg g-1, being the highest value reported so far. The super-performance of AlZn alloy is attributed to multiple functions of chemical reduction, dual amalgamation, in situ LDH's surface complexation and adsorption, isomorphous substitution and intercalation. This study provides a simple and highly efficient approach for removing Hg(II) from complex water matrices.

Entrainment and horizontal atmospheric transport of microplastics from soil.

Soils are an important source of microplastics (MPs) to the atmosphere but the fluxes and mechanisms involved in MPs entrainment are not well understood. In the present study, a series of horizontally aligned sediment traps have been deployed at different heights within 1 m above the ground for a two-month period at various locations in an arid region (Sarakhs, Iran). MPs were isolated from sediments and were quantified and characterised according to size, colour, shape and polymer composition by established techniques. Most MPs were <250 µm in length, fibres were the most important shape, black and blue-green were the dominant colours, and polymer abundance decreased in the order polyethylene > nylon > polypropylene > polystyrene > polyethylene terephthalate. The distributions of sediment mass (range <0.01-9 g) and number of MPs (range = 0 to 21) were heterogeneous, both between sites and at the different heights sampled, and yielded median, vertically-averaged horizontal fluxes for the region of about 450 g m-2 d-1 and 2600 MP m-2 d-1, respectively. However, when data were pooled, the number of MPs normalised to sediment mass exhibited a significant inverse relationship with sediment mass, an effect attributed to the presence of ambient suspended MPs and sediment that are diluted by the suspension of soil and deposited MPs at higher wind speeds. The mechanisms of MP saltation and entrainment were not ascertained but a theoretical framework for threshold shear velocity based on regularly-shaped particles and density considerations is presented. Further experimental work is required to verify this framework, and in particular for fibrous MPs with different aerodynamic properties to soil particles.

Ecotoxicological characteristics and properties of zinc-modified biochar produced by different methods.

Despite the dynamic progress of BC engineering, there is a lack of knowledge on the toxicity and environmental impact of modified BC. The aim of this study was the ecotoxicological evaluation of BC modified with zinc (Zn) using different methods: impregnation of feedstock with Zn before pyrolysis (PR), impregnation with Zn after pyrolysis (PS) and impregnation with Zn after pyrolysis with an additional calcination step (PST). The ecotoxicological assessment was based on tests with invertebrates (Folsomia candida, Daphnia magna) and bacteria (Aliivibrio fischeri). The post-treated and calcined composites had a higher content of total (Ctot) PAHs (144-276 µg kg-1) than pre-treated BC-Zn (68-157 µg kg-1). All BC-Zn treatments stimulated the reproduction of F. candida at the lowest BC dose (0.5%) by 4-24%. Increasing the biochar dose to 1% and 3% retained the stimulating effect of the pre-modified biochars (from 19 to 41%). Pre-modified BC-Zn reduced the luminescence of A. fischeri from 40% to 80%. Post-treated BCs reduced bacterial luminescence by 99%, but the calcination step limited the toxic effects to the level observed for the control. Post-treated BCs had a toxic effect on D. magna, with EC50 values ranging from 433 to 783 mg L-1. The ecotoxicity of composites depends on modification methods, BC dose and pyrolysis temperature. The application of limiting conditions for HM leaching (i.e., pre-modification, calcination) increased the safety of using Zn-biochar composites.

Ecotoxicological characterization of engineered biochars produced from different feedstock and temperatures.

Biochar (BC) engineering, which has recently gained a lot of interest, allows designing the functional materials. BC modification improves the properties of pristine biochar, especially in terms of adsorption parameters. An interesting type of modification is the introduction of metals into the BC's structure. There is a knowledge gap regarding the effects of modified BC (e.g., BC-Mg, BC-Zn) on organisms. The aim of this study was the ecotoxicological evaluation of BC-Mg and BC-Zn composites, received under diverse conditions from willow or sewage sludge at 500 or 700 °C. The ecotoxicological tests with bacteria Vibrio fischeri (V. fischeri) and invertebrates Folsomia candida (F. candida) were applied to determine the toxicity of BC. The content of toxic substances (e.g., polycyclic aromatic hydrocarbons (PAHs), heavy metals (HMs), environmentally persistent free radicals (EPFRs)) in BC were also determined and compared with ecotoxicological parameters. The ecotoxicity of studied BCs depends on many variables: feedstock type, pyrolysis temperature and the modification type. The Zn and Mg modification reduced (from 28 to 63 %) the total Æ©16 PAHs content in willow-derived BCs while in SL-derived BCs the total Æ©16 PAHs content was even 1.5-3 times higher compared to pristine BCs. The Zn modified willow-derived BCs affected positively on F. candida reproduction but showed inhibition of luminescence V. fischeri. BC-Mg exhibited harmful effect to F. candida. The ecotoxicological assessment carried out sheds light on the potential toxicity of BC-Zn and BC-Mg composites, which are widely used in the removal of heavy metals, pharmaceuticals, dyes from waters and soils.