Several laccases from different sources have been used in dye decolourization processes. However, only in a reduced number of studies have efforts been done to identify the metabolites produced by the enzymatic treatment as well as to evaluate the toxicity of degradation products. Taking these gaps into account, the objective of this work was to use a laccase from Ganoderma lucidum in the decolourization of the synthetic dye Congo red (C.I. No. 22120, Direct Red 28), largely used in the textile industry. After 6 h of treatment at pH 4.0 and 40 °C, the enzyme was able to decolourize 80 % of Congo red. Fourier transform infrared spectroscopy (FTIR), photoacoustic spectroscopy (PAS) and mass spectrometry allow concluding that laccase effectively changed the structure of Congo red, reducing the colour by modifying the chromophore groups and other parts of the molecule. Several degradation products with m/z ⁺ ranging from 298 to 745 were identified. It is proposed that the first degradation step could be an asymmetric cleavage of the azo bond present in the Congo red structure forming the intermediate with m/z ⁺ 298. The results also suggest a reduction in the toxicity of Congo red after laccase treatment, as indicated by the lettuce seed germination model. In conclusion, G. lucidum laccase could be used in a novel azo dye bioremediation strategy.

Here, we report on the ability of two different water treatment residues, a Fe-based (Fe-WTR) and an Al-based (Al-WTR) ones, to accumulate Cd(II) and Zn(II) from aqueous solutions at different pH values (pH 4.5, 5.5, and 7.0). Fe-WTR showed a greater Zn(II) and Cd(II) sorption capacity than Al-WTR at all the pH values investigated, in particular at pH 7.0 (e.g., ∼0.200 and ∼0.100 mmol g⁻¹ of Me(II) sorbed by Fe- and Al-WTR at pH 7.0, respectively). The greater capacity of the Fe-WTR to accumulate Me(II) seems to be linked to its higher content of iron and manganese ions and to its higher CEC value compared to Al-WTR. The role of the inorganic and organic fractions of WTRs in metal sorption was also assessed. A higher affinity of Cd(II) with respect to Zn(II) toward functional groups of the organic matter of both WTRs was observed, while Zn(II) showed a stronger association with the inorganic phases. The sorption of both metal ions appeared mainly governed by the formation of inner-sphere surface complexes with the inorganic and organic phases of WTRs, as suggested by the sequential extraction data.

Pig farms have achieved importance in the last few decades from the perspective of environment protection as a consequence of the intensive rearing systems in livestock production. Ammonia (NH₃) and greenhouse gases (GHG), such as methane (CH₄), carbon dioxide (CO₂), and nitrous oxide (N₂O), are emitted from slurry storage at farm prior to land application, but little is known about these losses under on-farm conditions in Spain. This study assessed the influence of management and environmental parameters on NH₃ and GHG emissions from slurry storage in spring and autumn. Gas emissions were measured in a commercial pig-fattening farm from two lagoons (1000 and 768 m³ capacity, respectively) during 30 days by the floating dynamic chamber system in spring and autumn 2011 (average temperature 19 and 9 °C, respectively). Low NH₃ and CH₄ emissions were registered in spring (range 10–406 and 3–17 mg m⁻² min⁻¹, respectively) probably as a result of low pH values of stored slurry (6.5 to 7.0) and rainfall. High variability on NH₃, CH₄, and CO₂ emissions was observed as a result of differences in temperature and rainfall. No NH₃ emission and low CH₄ and CO₂ emissions were observed in autumn (average 1.2 ± 0.9 and 27 ± 22 mg m⁻² min⁻¹, respectively). Slurry loading operations increased NH₃ losses from storage.

Microbial Cr(VI) reduction is a significant process in detoxification of Cr(VI) pollution. In this study, a new Cr(VI)-reducing bacterial strain, Cr-4, was isolated from soil around the chromium-containing slag. The analysis of the 16S ribosomal RNA (rRNA) gene sequence revealed that the newly isolated strain was closely related to Bacillus anthracis. The response to Cr(VI) stress and reduction capacity of the isolate were investigated. Cell growth decreased with the increase of Cr(VI) concentration. Cell morphology varied and cell growth was inhibited remarkably in the presence of 125 mg/L Cr(VI). The strain grew well and removed Cr(VI) effectively at a Cr(VI) concentration lower than 50 mg/L. Cr(VI)-reducing activity was inhibited by Zn²⁺, while significantly stimulated by Cu²⁺. The activity of Cr(VI) reduction by cell-free extract was demonstrated. Total chromium analysis and the energy-dispersive X-ray analysis (EDAX) spectrum revealed that Cr(VI) removal was caused mainly by microbial reduction rather than by biosorption and the main part of the reduced Cr(III) existed as soluble form in solutions.

This study proposes an improved activation for hydrogen peroxide and persulfate using Fe-modified diatomite (MD) to favorably lead the reaction to generate hydroxyl and sulfate radicals to degrade the contaminants phenanthrene and anthracene. Diatomite was modified by impregnating it with a mixture of ferrous (Fe²⁺) and ferric (Fe³⁺) ions in the form of precipitated iron oxides and hydroxides. The raw and synthesized materials were characterized by powder X-ray diffraction (XRD), X-ray fluorescence (XRF), particle size by laser diffraction, chemical microanalysis of the elements by energy-dispersive X-ray, and scanning electron microscopy (SEM). Batch experiments were performed to compare the new activator material (modified diatomite) with traditional methods of activation for these oxidants and to statistically study the optimum ratio between the amount of this material and the concentration of one oxidant to the degradation of the contaminants phenanthrene and anthracene. The characterization results showed that the materials are amorphous and that the Fe ion concentration was 4.78 and 17.65 % for the raw and modified diatomites, respectively. This result shows a significant increase in the amount of iron ions after synthesis. Comparing the traditional activation method with the modified diatomite, the results of batch experiments showed that the synthesized material presents significant catalytic activity for the oxidation of these contaminants, using sodium persulfate and hydrogen peroxide as oxidants. The analysis of the variables results showed that the concentration of the oxidant has higher significance than the amount of the catalyst.

The objectives of the survey were to analyse the structure of the mollusc communities in the mining subsidence reservoirs that were created as a result of land subsidence over exploited hard coal seams and to determine the most predictive environmental factors that influence the distribution of mollusc species. The reservoirs are located in urbanised and industrialised areas along the Trans-Regional Highway, which has a high volume of vehicular traffic. They all have the same sources of supply but differ in the physical and chemical parameters of the water. In total, 15 mollusc species were recorded including four bivalve species. Among them Anodonta cygnea is classified as Endangered according to the Polish Red Data Book of Animals and also as Near Threatened according to the European Red List of Non-marine Molluscs. Eleven of the 15 mollusc species are included on the European Red List of Non-marine Molluscs as Least Concern. Conductivity, pH and the concentration of calcium were the parameters most associated with the distribution of mollusc species. Canonical correspondence analysis showed that Potamopyrgus antipodarum, Radix balthica, Physella acuta, Gyraulus crista and Pisidium casertanum were associated with higher conductivity and lower pH values. A. cygnea, Anodonta anatina and Ferrissia fragilis were negatively influenced by these parameters of the water. The results of this survey showed that the mining subsidence reservoirs located in urbanised and industrialised areas provide refuges for rare and legally protected species and that they play an essential role in the dispersal of alien species as well.

A kind of volcanic tephra (VT) as abundant natural mineral in China was studied for phosphate (P) removal from rural micro-polluted wastewater. Physical and chemical properties of VT were investigated by scanning electron microscopy (SEM), energy dispersive X-ray spectrometer (EDX), X-ray diffraction (XRD), UV-visible diffuse reflectance spectrometry, and Fourier transform infrared spectroscopy (FT-IR). The uptake of P decreased with the increase of the initial solution pH, and the optimum solution pH required for maximum P removal rate was 2.0. Zeta potential analyses were carried out to vividly describe the surface charges at different solution pH. The equilibrium data were both fitted well for Langmuir and Freundlich isotherm models. Thermodynamic parameters including changes in standard enthalpy (ΔH⁰), standard entropy (ΔS⁰), and standard Gibbs free energy (ΔG⁰) were calculated. The removal of P was predominantly based on ion-exchange process when the initial solution pH in the range of 2.0–6.0. A given dose of VT can be recycled for eight times. VT minerals were attempted for P removal from rural micro-polluted wastewater collected in Shanghai, China containing 50 mg L⁻¹P, and the removal rate was determined to be nearly 100 % with the capacity of 0.5 mg P/g VT minerals. All our results indicated that VT could be a promising choice for P removal from micro-polluted wastewater in rural area with the distinct advantages of being low cost and environmentally benign.

The large spatial heterogeneity in soil physico-chemical and microbial parameters challenges our ability to predict and model pesticide leaching from agricultural land. Microbial mineralization of pesticides is an important process with respect to pesticide leaching since mineralization is the major process for the complete degradation of pesticides without generation of metabolites. The aim of our study was to determine field-scale variation in the potential for mineralization of the herbicides glyphosate, bromoxyniloctanoate, diflufenican, and bentazone and to investigate whether this variation can be predicted by variations in basic soil parameters. Sixty-five soil samples were sampled from an agricultural, loamy field in Silstrup, Denmark, from a 60 × 165 m rectangular grid. The mineralization potential of the four pesticides was determined using a 96-well microplate ¹⁴C-radiorespirometric method. Initial mineralization rates were determined using first-order kinetics for glyphosate and bromoxyniloctanoate and zero-order kinetics for diflufenican and bentazone. The mineralization rates of the four pesticides varied between the different pesticides and the different soil samples, but we could not establish correlations between the pesticide mineralization rates and the measured soil parameters. Only the glyphosate mineralization rates showed slightly increasing mineralization potentials towards the northern area of the field, with increasing clay and decreasing OC contents. The mineralization potentials for glyphosate and bentazone were compared with 9-years leaching data from two horizontal wells 3.5 m below the field. The field-scale leaching patterns, however, could not be explained by the pesticide mineralization data. Instead, field-scale pesticide leaching may have been governed by soil structure and preferential flow events.

Carbamazepine (CBZ) is a representative of a group of compounds found in our rivers that have been classified as upcoming contaminants. Its pharmacological activity to treat mood and neurological disorders is based on its effects on ion channels, but effects on aquatic organisms have not yet been thoroughly investigated.In our initial analysis, we compared CBZ effects on two microalgae species differing in CBZ sensitivity: Parachlorella kessleri and Neochloris pseudoalveolaris. While we observed a stimulation in the growth rate in cultures of P. kessleri in the presence of 10 μg L⁻¹ CBZ, no effect on growth rates of N. pseudoalveolaris cultures could be documented at this concentration. Any higher tested CBZ concentration led to growth inhibition.To gain insight into these effects, biochemical and physiological parameters of these two microalgae species were measured in the presence of CBZ in a concentration-dependent manner.As the severe inhibition of growth rate correlated with a significant inhibition of most tested parameters in cultures of N. pseudoalveolaris, the primary reason for the adverse effect of CBZ on cultures of this microalgae species could not be identified. In cultures of N. pseudoalveolaris, experimental data indicate that inhibition of growth rate occurs when the microalgae are no longer able to compensate for adverse CBZ-induced ROS effects.Analysis of the CBZ response of cultures of P. kessleri showed a reduction of growth stimulatory effect if the CBZ concentration exceeds a threshold value. In general, cultures of P. kessleri show a great potential to withstand CBZ as an environmental pollutant.

The processing, storage, and flux of inorganic carbon in rivers and streams play an influential role in the lateral transfer of atmospheric and terrestrial carbon to the marine environment. Quantifying and understanding this transfer requires a rapid and accurate means of measuring representative concentrations of dissolved inorganic carbon (DIC) and CO₂in field settings. This paper describes a field method for the determination of DIC based on the direct measurement of dissolved CO₂using a commercial carbonation meter. A 100-mL water sample is combined with 10 mL of a high ionic strength, low-pH, citrate buffer, mixed well, and the dissolved CO₂concentration is measured directly. The DIC is then calculated based on the dissolved CO₂concentration, buffer-controlled ionic strength, pH, and temperature of the mixture. The method was accurate, precise, and comparable to standard laboratory analytical methods when tested using prepared sodium bicarbonate solutions up to 40 mM DIC, North Atlantic seawater, commercial bottled waters, and carbonate spring waters. Coal mine drainage waters were also tested and often contained higher DIC concentrations in the field than in subsequent laboratory measurements; the greatest discrepancy was for the high-CO₂samples, suggesting that degassing occurred after sample collection. For chemically unstable waters and low-pH waters, such as those from high-CO₂mine waters, the proposed field DIC method may enable the collection of DIC data that are more representative of natural settings.