Arsenic (As) contamination and bioaccumulation are a serious threat to agricultural plants. To address this issue, we checked the efficacy of As tolerant plant growth promoting bacteria (PGPB), zinc oxide nanoparticles (ZnO NPs) and oxalic acid (OA) in Luffa acutangula grown on As rich soil. The selected most As tolerant PGPB i.e Providencia vermicola exhibited plant growth promoting features i.e solubilzation of phosphate, potassium and siderophores production. Innovatively, we observed the synergistic effects of P. vermicola, ZnO NPs (10 ppm) and OA (100 ppm) in L. acutangula grown on As enriched soil (150 ppm). Our treatments both as alone and in combination alleviated As toxicity exhibited by better plant growth and metabolism. Results revealed significantly enhanced photosynthetic pigments, proline, relative water content, total sugars, proteins and indole acetic acid along with As amelioration in L. acutangula. Furthermore, upregulated plant resistance was manifested with marked reduction in the lipid peroxidation and electrolyte leakage and pronounced antagonism of As and zinc content in leaves under toxic conditions. These treatments also improved level of nutrients, abscisic acid and antioxidants to mitigate As toxicity. This marked improvement in plants’ defense mechanism of treated plants under As stress is confirmed by less damaged leaves cell structures observed through the scanning electron micrographs. We also found substantial decrease in the As bioaccumulation in the L. acutangula shoots and roots by 40 and 58% respectively under the co-application of P. vermicola, ZnO NPs and OA in comparison with control. Moreover, the better activity of soil phosphatase and invertase was assessed under the effect of our application. These results cast a new light on the application of P. vermicola, ZnO NPs and OA in both separate and combined form as a feasible and ecofriendly tool to alleviate As stress in L. acutangula.

Bio-stimulation of the indigenous microbial community is considered as an effective strategy for the bioremediation of polluted environments. This examination explored the near effects of various bio-stimulants on pyrene degradation, prokaryotic community compositions, and functions using 16S rRNA amplicon sequencing and qPCR. At first, the results displayed significant differences (p < 0.05) between the prokaryotic community structures of the control group, PYR (contains pyrene only), and bio-stimulants amended groups. Among the bio-stimulants, biochar, oxalic acid, salicylate, NPK, and ammonium sulfate augmented the pyrene degradation potential of microbial communities. Moreover, the higher abundance of genera, such as Flavobacterium, Hydrogenophaga, Mycobacterium, Rhodococcus, Flavihumibacter, Pseudomonas, Novosphingobium, etc., across the treatments indicated that these genera play a vital role in pyrene metabolism. Based on the higher abundance of GP-RHD and nidA genes, we speculated that Gram-positive prokaryotic communities are more competent in pyrene dissipation than Gram-negative. Furthermore, the marked abundance of nifH, and pqqC genes in the NPK and SA treatments, respectively, suggested that different bio-stimulants might enrich certain bacterial assemblages. Besides, the significant distinctions (p < 0.05) between the bacterial consortia of HA (humic acid) and SA (sodium acetate) groups from NPK, OX (oxalic acid), UR (urea), NH4, and SC (salicylate) groups also suggested that different bio-stimulants might induce distinct ecological impacts influencing the succession of prokaryotic communities in distinct directions. This work provides new insight into the bacterial degradation of pyrene using the bio-stimulation technique. It suggests that it is equally important to investigate the community structure and functions along with studying their impacts on degradation when devising a bio-stimulation technology.

Based on the goal of green and effective removal of chromium (Cr(VI)) pollution in water and the idea of treating waste with waste, rice straw (RS) was firstly and successfully used in enhancing the photoreduction of highly toxic Cr(VI) to less toxic Cr(III) by oxalic acid (Ox). Batch experiments (the effect of Ox concentration, initial Cr(VI) concentration, RS dosage and coexisting ions) in Ox + RS + UV photoreduction system were designed to investigate the reaction process. Through studying the effect of initial pH in the solution, the change of pH during the photoreduction process and the free radical scavenging test, the Cr(VI) photoreduction mechanism in Ox + RS + UV system was revealed. The role of RS in Ox + RS + UV system was also deduced by the analysis of FT-IR, XRD, Mott-Schottky and the verification test of the role of –OH and SiO₂ on RS. The results showed that RS could significantly synergize Ox to reduce Cr(VI) under UV, 1 mM Cr(VI) in aqueous solution was completely removed in 60 min by Ox + RS + UV system. The Cr(VI) photoreduction mechanism in Ox + RS + UV system consisted of multiple parts: the chemical reduction by Ox(few part), the photoreduction by Ox(some part), and the synergistic photoreduction by RS with Ox(large part). The synergism of RS in Ox + RS + UV system was mainly attributed to its components of SiO₂ and –OH of cellulose.

Arsenic (As) is a highly toxic metalloid adversely affecting the environment, human health, and crop productivity. The present study assessed the synergistic effects of salinity and As on photosynthetic attributes, stomatal regulations, and metabolomics responses of the xero-halophyte Salvadora persica to decipher the As-salinity cross-tolerance mechanisms and to identify the potential metabolites/metabolic pathways involved in cross-tolerance of As with salinity. Salinity and As stress-induced significant stomatal closure in S. persica suggests an adaptive response to decrease water loss through transpiration. NaCl supplementation improved the net photosynthetic rate (by +39%), stomatal conductance (by +190%), water use efficiency (by +55%), photochemical quenching (by +37%), and electron transfer rate (54%) under As stress as compared to solitary As treatment. Our results imply that both stomatal and non-stomatal factors account for a reduction in photosynthesis under high salinity and As stress conditions. A total of 64 metabolites were identified in S. persica under salinity and/or As stress, and up-regulation of various metabolites support early As-salinity stress tolerance in S. persica by improving antioxidative defense and ROS detoxification. The primary metabolites such as polyphenols (caffeic acid, catechin, gallic acid, coumaric acid, rosmarinic acid, and cinnamic acid), amino acids (glutamic acid, cysteine, glycine, lysine, phenylalanine, and tyrosine), citrate cycle intermediates (malic acid, oxalic acid, and α-ketoglutaric acid), and most of the phytohormones accumulated at higher levels under combined treatment of As + NaCl compared to solitary treatment of As. Moreover, exogenous salinity increased glutamate, glycine, and cysteine, which may induce higher synthesis of GSH-PCs in S. persica. The metabolic pathways that were significantly affected in response to salinity and/or As include inositol phosphate metabolism, citrate cycle, glyoxylate and dicarboxylate metabolism, amino acid metabolism, and glutathione metabolism. Our findings indicate that inflections of various metabolites and metabolic pathways facilitate S. persica to withstand and grow optimally even under high salinity and As conditions. Moreover, the addition of salt enhanced the arsenic tolerance proficiency of this halophyte.

Polyethylene (PE) and polypropylene (PP) microplastics (MPs), as carriers, can bind with pesticides, which propose harmful impacts to aqueous ecosystems. Meanwhile, carbofuran and carbendazim (CBD), two widely used carbamate pesticides, are toxic to humans because of the inhibition of acetylcholinesterase activity. The interaction between two MPs and two pesticides could start in farmland and be maintained during transportation to the ocean. Herein, the adsorption behavior and mechanism of carbofuran and carbendazim (CBD) by PE and PP MPs were investigated via characterization and density functional theory (DFT) simulation. The adsorption kinetic and thermodynamic data were best described by pseudo-second-order kinetics and the Freundlich models. The adsorption behaviors of individual carbofuran/CBD on both MPs were very similar. The CBD adsorption rate and capacity of PE and PP MPs were higher than those of carbofuran. This phenomenon explained the lower negative effects of DOM (oxalic acid, glycine (Gly)) on CBD adsorption relative to those of carbofuran. The presence of oxalic acid and Gly decreased the PE adsorption by 20.40–48.02% and the PP adsorption by 19.27–42.11%, respectively. It indicated the significance of DOM in carbofuran cycling. The adsorption capacities were negatively correlated with MPs size, indicating the importance of specific surficial area. Fourier transformation infrared spectroscopy before and after adsorption suggested that the adsorption process did not produce any new covalent bond. Instead, intermolecular van der Waals forces were one of the primary adsorption mechanisms of carbofuran and CBD by MPs, as evidenced by DFT calculations. Based on the zeta potential, the electrostatic interaction explained the higher adsorption CBD by MPs than carbofuran.

To explore whether lead (Pb)-induced defense responses are responsible for the low root-to-shoot Pb translocation, we exposed saplings of the two contrasting poplar species, Populus × canescens with relatively high root-to-shoot Pb translocation and P. nigra with low Pb translocation, to 0 or 8 mM PbCl₂. Pb translocation from the roots to aboveground tissues was lower by 57% in P. nigra than that in P. × canescens. Lower Pb concentrations in the roots and aerial tissues, greater root biomass, and lower ROS overproduction in the roots were found in P. nigra than those in P. × canescens treated with Pb. P. nigra roots had higher proportions of cell walls (CWs)-bound Pb and water insoluble Pb compounds, and higher transcript levels of some pivotal genes related to Pb vacuolar sequestration, such as phytochelatin synthetase 1.1 (PCS1.1), ATP-binding cassette transporter C1.1 (ABCC1.1) and ABCC3.1 than P. × canescens roots. Pb exposure induced defense responses including increases in the contents of pectin and hemicellulose, and elevated oxalic acid accumulation, and the transcriptional upregulation of PCS1.1, ABCC1.1 and ABCC3.1 in the roots of P. nigra and P. × canescens. These results suggest that the stronger defense barriers in P. nigra roots are probably associated with the lower Pb translocation from the roots to aerial tissues, and that Pb exposure-induced defense responses can enhance the barriers against Pb translocation in poplar roots.

Selenium (Se) and arsenic (As) are toxic contaminants in surface water and drinking water. The human body needs little quantity of Se, but too high dose is not allowed. Metal oxides such as iron oxides were used for adsorption or co-precipitation removal of As from water. However, the regeneration and stability problems of metals oxides sorbents are unsatisfactory , and there is not enough adsorbent for Se removal from water also. We developed the acrylic amine fiber (AAF) for adsorption reomval of Se and As from water and systematically studied the influenced factors. Batch experiments were conducted for investigating the adsorption edges, while column filtration tests were employed for dynamic application edges. At neutral pH, the Langmuir isotherm fittings gave the maximum adsorption capacities of As(V), As(III), Se(VI) and Se(IV) are 270.3, 40.5, 256.4, and 158.7 mg/g, respectively. Effects of co-existing inorganic anions on As(V) and Se(VI) adsorption using AAF gave the order of PO₄³⁻ > SO₄²⁻ > NO₃⁻ > SiO₃²⁻, while different organic acids obey the order of citric acid > oxalic acid > formic acid. Fourier transform infrared analysis showed the PO₄³⁻ and SO₄²⁻ competition mechanisms are electrostatic repulsions, while the competition of organic acids derived from acid-base reaction between the carboxyl group and the amino group. Column filtration and regeneration results showed that the spent AAF can be regenerated using 0.5 mol/L HCl solution and reused with no much decrease of adsorption capacity.

Identifying effective and low-cost agents for the remediation of Pb-contaminated soil is of great importance for field-scale applications. In this study, the feasibility of reusing incinerated sewage sludge ash (ISSA), a waste rich in phosphorus, under activation by oxalic acid (OA) for the remediation of high-Pb contaminated soil was investigated. ISSA and OA were mixed at different proportions for the treatment of the high-Pb contaminated soil (5000 mg/kg). The Pb immobilization efficacy was further examined by both the standard deionized water leaching test and the toxicity characteristic leaching procedure (TCLP). The overall results showed that the use of the ISSA alone and an appropriate mixture of the ISSA and OA could effectively reduce the leachability of Pb from soil. 20% ISSA together with 30% OA (0.2 mol/L) reduced leached Pb concentration by 99%. The main stabilization mechanisms were then explored by different microstructural and spectroscopic analytical techniques including SEM, XRD and FTIR. Apparently, OA released phosphate from the ISSA and Pb from soil via acid attack, which combined and precipitated as stable lead phosphate minerals. However, excessive OA could cause high leaching of phosphate and zinc from the ISSA. Overall, this study indicates that ISSA could be used together with OA to remediate high-Pb contaminated soil, but careful design of mix proportions is necessary before practical application to avoid excessive leaching of phosphate and zinc from the ISSA.

Adding exogenous low-molecular weight organic acids is an effective technique to improve phytoremediation of Cd-contaminated soil and has been well documented, but how acid application rate affects remediation efficiency and its underlying limiting factors remains elusive. We investigated this using pot experiments with rapeseed (Brassica napus L.) as the model plant. Plastic pots packed with a sandy loam contaminated by Cd at 4.838 mg/kg were amended with acetic acid, oxalic acid, citric acid, malic acid and tartaric acid, respectively, at an application rate gradient varying from 0.0 to 12.0 mmol/kg. Plants in each pot were harvested after growing for five months, and we then measured the exchangeable, carbonate, Fe–Mn oxide, organic and residual Cd in the rhizosphere, as well as Cd in both roots and shoots. The results showed that all organic acids improved plant uptake of Cd and, compared with the control without acid addition, they could improve Cd uptake by more than 100%. The enhanced Cd extraction was due to the increase in exchangeable Cd in the rhizosphere. Plant Cd was weakly correlated to the amount of Cd lost from a unit volume of the rhizosphere due to root extraction (R² = 0.06), but a good negative correlation was found between them after normalizing the lost Cd by root biomass (R² = 0.36). Mass balance analysis revealed that the average Cd content in soil (rhizosphere and bulk soils combined) was much higher than the Cd content in the rhizosphere, and the improved Cd mobility after acid addition was thus due to the increased chelation. As diffusion of ligands in water is one order in magnitude smaller than diffusion of Cd ions, our results suggested that Cd migration from the bulk soil into the rhizosphere was a major factor limiting Cd phytoextraction by rapeseed after adding the exogenous organic acids.

Soil chemistry of toxic metalloids and metals differs, making their simultaneous removal difficult. Soil contaminated with As, Pb, Zn and Cd was washed with oxalic acid, Na-dithionite and EDTA solution. Toxic elements were removed from the washing solution by alkalinisation with CaO to a pH 12.5: As was co-precipitated with Fe from Fe-EDTA chelate formed after the soil washing. The toxic metals precipitated after substitution of their EDTA chelates with Ca. The novel method was scaled up on the ReSoil® platform. On average, 60, 76, 29, and 53% of As, Pb, Zn, and Cd were removed, no wastewater was generated and EDTA was recycled. Addition of zero-valent iron reduced the toxic elements’ leachability. Remediation was most effective for As: phytoaccessibility (CaCl₂ extraction), mobility (NH₄NO₃), and accessibility from human gastric and gastrointestinal phases were reduced 22, 104, 6, and 51 times, respectively. Remediation increased pH but had no effect on soil functioning assessed by fluorescein diacetate hydrolysis, dehydrogenase, β-glucosidase, urease, acid and alkaline phosphatase activities. Brassica napus produced 1.9 times more biomass on remediated soil, accumulated no As and 5.0, 2.6, and 9.0 times less Pb, Zn and Cd, respectively. We demonstrated the novel remediation technology as cost-efficient (material cost = 41.86 € t⁻¹) and sustainable.