A critical appraisal of single-step extraction procedures of chromium species from soil was done in terms of their selectivity towards Cr(III) and Cr(VI) species. Samples of natural mineral and organic soil and samples of soil enriched with different chromium compounds of various solubility (in liquid or solid form) were used to simulate contamination of soil by liquid and solid wastes. The efficiency of extraction of Cr(III) and Cr(VI) species with various reagents, e.g. acetic acid, chelating agents (EDTA, DTPA) or inorganic salts (phosphates and carbonates), was evaluated on the basis of recovery results obtained for enriched samples. None of used reagents allow for quantitative extraction of added Cr(III) form. Procedures based on extraction of soil with Na₂CO₃ at room and elevated temperature (90–95 °C) were suitable for extraction of Cr(VI) species from mineral soil, whereas for organic soil, the procedure based on extraction with Na₂CO₃ at room temperature was recommended. The developed extraction procedures were validated using certified reference material (CRM 041 soil) and applied for analysis of contaminated soil samples. The studies showed that the physical state of waste, initial form and oxidation state of chromium and soil properties influenced the final chromium species and their mobility in soil, which have an impact on contamination of environment. The analysis of contaminated soil samples from a tannery area showed that the share of Cr(VI) was very low (only 0.8–4.5%) despite the high total content of chromium, which confirmed that chromium was present in immobile forms.

In this study, the photocatalytic degradation of toxic pollutant (2-chlorophenol) in the presence of ZnO nanoparticles (ZnO NPs) was investigated under solar radiation. The three main factors, namely pH of solution, solar intensity and calcination temperature, were selected in order to examine their effects on the efficiency of the degradation process. The response surface methodology (RSM) technique based on D-optimal design was applied to optimise the process. ANOVA analysis showed that solar intensity and calcination temperature were the two significant factors for degradation efficiency. The optimum conditions in the model were solar intensity at 19.8 W/m², calcination temperature at 404 °C and pH of 6.0. The maximum degradation efficiency was predicted to be 90.5% which was in good agreement with the actual experimental value of 93.5%. The fit of the D-optimal design correlated very well with the experimental results with higher values of R ² and R ² ₐdⱼ correlation coefficients of 0.9847 and 0.9676, respectively. The intermediate mechanism behaviour of the 2-chlorophenol degradation process was determined by gas chromatography-mass spectrometry (GC-MS). The results confirmed that 2-chlorophenol was converted to acetic acid, a non-toxic compound.

The utilization of propionic, n-butyric, and isobutyric acids in microbial electrolysis cells (MECs) was examined by monitoring individual short-chain fatty acid concentration and using electrochemical techniques, such as linear sweep voltammetry (LSV) and electrochemical impedance spectroscopy (EIS). When n-butyric or isobutyric acid was provided as a single substrate, acetic acid was consistently observed in experiments, indicating that acetic acid was produced as a byproduct and utilized by exoelectrogenic bacteria as an additional substrate in MECs. When isobutyric acid was given as a sole substrate, the applied potential governed the electric current (i.e., rate of substrate utilization). In addition, the coulombic efficiency was substantially high (90%), indicating direct utilization of isobutyric acid by exoelectrogenic bacteria. However, the coulombic efficiency was relatively low (30–60%) when n-butyric acid was provided as a sole substrate. In another experiment, the magnitude of electric current was more dependent on the concentration of acetic acid than that of other short-chain fatty acids. In the EIS analysis, the exchange current was found to be a more reliable indicator of substrate favorability than the charge transfer resistance.

Applications of cadmium (Cd) and salinity-containing manures contribute to Cd pollution and salinization in greenhouse soils. In this study, chicken manure polluted with Cd (5.6 mg/kg) was mildly electrokinetically treated (0.25 V/cm) for 48 h with intermittent replacement of catholyte with 20 mM acetic acid solution to remove Cd and salinity for application without need of post-treatment in greenhouse soil. The electrokinetic treatment created pH conditions mainly ranging from 5.0 to 8.0 within the manure for minimizing re-precipitation of desorbed Cd and evaporative loss of ammonium. However, without manure pre-acidification, electrokinetic treatment resulted in negligible removal of total Cd but 61.7% of increase in the small fraction of exchangeable Cd, due to poor desorption but enhanced formation of exchangeable Cd. In contrast, manure pre-acidification with 20 mM acetic acid favored Cd desorption, leading to electrokinetic removal of exchangeable, carbonate-bound, and total Cd by 32.2%, 34.5%, and 14.5%, respectively. Mild electrokinetic treatment of manure with and without pre-acidification resulted in similar removal of salinity (72.3% and 68.0%), similar pH condition (7.2 and 7.4), and basically same evaporative loss of ammonium (14.6% and 14.2%). Overall, the mild electrokinetic treatment considerably lowered the risk of Cd and the salinity from the pre-acidified manure for improved applicability in greenhouse soil, and more studies are needed to enhance the performance of electrokinetic Cd removal from manure.

Photocatalytic degradation of 4-chloro-2-methylphenoxyacetic acid (MCPA) in aqueous solution using Cr(III)-doped TiO₂ under UV and visible light was investigated. The semiconductor material was synthesized by a microwave-assisted sol–gel method with Cr(III) doping contents of 0.02, 0.04, and 0.06 wt%. The catalyst was characterized using X-ray powder diffraction (XRD), scanning electron microscopy (SEM), nitrogen physisorption, UV–Vis diffuse reflectance spectroscopy (DRS), and atomic absorption spectroscopy (AAS). The photocatalytic activity for the photodegradation of MCPA was followed by reversed-phase high-performance liquid chromatography (HPLC) and total organic carbon (TOC) analysis. The intermediates formed during degradation were identified using gas chromatography–mass spectrometry (GC–MS). Chloride ion evolution was measured by ion chromatography. Characterization results showed that Cr(III)-doped TiO₂ materials possessed a small crystalline size, high surface area, and mesoporous structure. UV–Vis DRS showed enhanced absorption in the visible region as a function of the Cr(III) concentration. The Cr(III)-doped TiO₂ catalyst with 0.04 wt% of Cr(III) was more active than bare TiO₂ for the degradation of MCPA under both UV and visible light. The intermediates identified during MCPA degradation were 4-chloro-2-methylphenol (CMP), 2-(4-hydroxy-2-methylphenoxy) acetic acid (HMPA), and 2-hydroxybuta-1,3-diene-1,4-diyl-bis (oxy)dimethanol (HBDM); the formation of these intermediates depended on the radiation source.

Silver nanoparticles synthesized using the leaf extract of Albizia saman (Jacq.) Merr. were tested for induction of cytogenetic abnormality in root tip cells of Drimia indica (Roxb.) Jessop (family Asperagaceae). The leaves are known to be rich in various phytochemicals like flavonoids, glycosides, saponins, steroids, tannins, and terpenoids, which may be responsible for bioreduction, biocapping, and stabilization of nanoparticles. The various instruments used for characterization include UV-VIS spectrophotometer, fourier transform infrared spectroscopy (FTIR), atomic force microscopy (AFM), X-Ray diffractometer (XRD), and high resolution transmission electron microscope (HR-TEM). The present study aims to evaluate the cytotoxic effect of biogenic silver nanoparticles on mitotic chromosomes by using root tip cells of D. indica. The root tips of D. indica was treated with suspensions of silver nanoparticles mixed in distilled water at different concentrations viz., 25, 50, 75, and 100% (w/v) for 6, 12, 18, and 24 h and then fixed in 1:3 ethanol: acetic acid following pre-treatment with 0.05% colchicine for cytological analysis. Silver nanoparticles induced a dose dependent decrease of mitotic index in root meristems. Furthermore, the treated meristem cells showed various types of chromosomal and mitotic aberrations such as anaphase bridge, sticky metaphase, lagging, or forward chromosome indicating genotoxic damage.

In the present study, the effects of low-molecular-weight organic acids (OAs) on the toxicity of copper (Cu) to the earthworm Eisenia fetida (E. fetida) were investigated in a simulated soil solution. We exposed E. fetida to soil solution containing Cu and a variety of OAs (acetic acid, oxalic acid, citric acid, and EDTA). We found that the addition of OAs reduced the toxicity of Cu to E. fetida, where the reduction was strongest in EDTA and weakest in acetic acid. These compounds decreased the mortality rate of E. fetida that were exposed to Cu and reduced levels of antioxidant enzymes and malondialdehyde to unexposed control levels. E. fetida were exposed to Cu with OAs had reduced Cu²⁺, which were likely caused by Cu forming complexes with the OAs, reducing the availability of Cu. The presence of OAs also reduced Cu-induced damage on earthworm cellular ultrastructures and changed the subcellular distribution of Cu. These results demonstrated that OAs could reduce the toxicity, as well as the bioavailability, of heavy metals in soil solutions where both OAs and heavy metals often coexist.

Organic amendments have been widely proposed as a remediation technology for metal-contaminated soils, but there exist controversial results on their effectiveness. In this study, the effect of pig manure addition on cadmium (Cd) bioavailability in Cd-contaminated soils was systematically evaluated by one dynamic, in situ technique of diffusive gradients in thin films (DGT) and four traditional methods based on the equilibrium theory (soil solution concentration and the three commonly used extractants, i.e., acetic acid (HAc), ethylenediamine tetraacetic acid (EDTA), and calcium chloride (CaCl2). Wheat and maize were selected for measurement of plant Cd uptake. The results showed that pig manure addition could promote the growth of two plants, accompanied by increasing biomasses of shoots and roots with increasing doses of pig manure addition. Correspondingly, increasing additions of pig manure reduced plant Cd uptake and accumulation, as indicated by the decreases of Cd concentrations in shoots and roots. The bioavailable concentrations of Cd in Cd-contaminated soils reflected by the DGT technique obviously decreased with increasing doses of pig manure addition, following the same changing trend as plant Cd uptake. Changes in soil solution Cd concentration and extractable Cd by HAc, EDTA, and CaCl2 in soils were similar to DGT measurement. Meanwhile, the capability of Cd resupply from solid phase to soil solution decreased with increasing additions of pig manure, as reflected by the decreases in the ratio (R) value of CDGT to Csol. Positive correlations were observed between various bioavailable indicators of Cd in soils and Cd concentrations in the tissues of the two plants. These findings provide stronger evidence that pig manure amendment is effective in reducing Cd mobility and bioavailability in soils and it is an ideal organic material for remediation of Cdcontaminated soils.

Adsorption is an important mechanism to immobilize cadmium (Cd) in soil, for which humic substances have a potential. However, commercial humic substances are either very acidic (pH = 2) or alkaline/Na⁺-enriched, making them less suitable for use in acid and saline soils. Here, we used leonardite to produce humic adsorbents HA (pH = 4.02), Ca-HA (pH = 10.9), and Ca-CPAM-HA (pH = 9.62) by using HCl, CaCl₂, or CaCl₂-polyacrylamide as a flocculant. Their elemental compositions, acidity, and spectroscopic properties were determined, and their Cd adsorption characteristics were assessed by batch kinetic and thermodynamic experiments at environmentally relevant concentrations. Further, HA was mixed with Cd-contaminated soils and incubated for a month to assess its effect on Cd immobilization. Good fitting of kinetic adsorption data into pseudo-second-order model, together with FTIR spectroscopic data, suggested the chemisorption mechanism by forming Cd(II)-carboxyl complexes. The maximum adsorption capacity derived from the Langmuir equation was 129, 114, and 110 mg Cd(II)/g for HA, Ca-HA, and Ca-CPAM-HA, respectively. These values are almost the same on carbon-normalized basis. HA reduced acetic acid extractable Cd by 31% or more. Besides their high propensity for Cd adsorption, humic adsorbents are inexpensive, safe, and beneficial to soil quality.

Eragrostis plana Nees (EPN) was used as new and eco-friendly adsorbent for the removal of crystal violet dye (CV) from aqueous solution. Specific surface area (BET), scanning electron microscopy (SEM), infrared spectroscopy (ATR–FTIR), point of zero charge (pHPZC), and modified Boehm titration method were used to characterize the EPN material. The effects of initial pH of solution, adsorbent mass, contact time and initial dye concentration, and temperature were studied in batch adsorption mode. Kinetic data were evaluated by pseudo-first-order and pseudo-second-order models. The result exhibited that pseudo-second-order model well described the adsorption kinetics of CV onto EPN. Langmuir, Freundlich, and Sips isotherm models were used for analysis of the isothermal data. The equilibrium data of adsorption of CV onto EPN was better fitted with the Sips isotherm. Based on the Sips isotherm model, the maximum adsorption capacity was 76.20 ± 1.20 mg g⁻¹ at 333 K. A high desorption of CV from EPN was obtained using 1.00 mol L⁻¹ of CH₃COOH as eluent. The thermodynamic data indicated that the adsorption was spontaneous, endothermic, and physical process. EPN can be used as alternative adsorbent to remove CV from aqueous solution.