Intensive ammonium fertilizer addition activates iron and carbon conversion coupled cadmium redistribution in a paddy soil under gradient redox conditions.

While over-fertilization and nitrogen deposition can lead to the enrichment of nitrogen in soil, its effects on heavy metal fractions under gradient moisture conditions remains unclear. Here, the effect of intensive ammonium (NH4+) addition on the conversion and interaction of cadmium (Cd), iron (Fe) and carbon (C) was studied. At relatively low (30-80 %) water hold capacity (WHC) NH4+ application increased the carbonate bound Cd fraction (F2Cd), while at relatively high (80-100 %) WHC NH4+ application increased the organic matter bound Cd fraction (F4Cd). Iron­manganese oxide bound Cd fractions (F3Cd) and oxalate-Fe decreased, but DCB-Fe increased in NH4+ treatments, indicating that amorphous Fe was the main carrier of F3Cd. The variations in F1Cd and F4Cd observed under the 100-30-100 % WHC treatment were similar to those observed under low moisture conditions (30-60 % WHC). The C=O/C-H ratio of organic matter in soil decreased under the 30-60 % WHC treatment, but increased under the 80-100 % WHC treatment, which was the dominant factor influencing F4Cd changes. The conversion of NH4+ declined with increasing soil moisture content, and the impact on oxalate-Fe was greater at 30-60 % WHC than at 80-100 % WHC. Correspondingly, genetic analysis showed the effect of NH4+ on Fe and C metabolism at 30-60 % WHC was greater than at 80-100 % WHC. Specifically, NH4+ treatment enhanced the expression of genes encoding extracellular Fe complexation (siderophore) at 30-80 % WHC, while inhibiting genes encoding Fe transmembrane transport at 30-60 % WHC, indicating that siderophores simultaneously facilitated Cd detoxification and Fe complexation. Furthermore, biosynthesis of sesquiterpenoid, steroid, butirosin and neomycin was significantly correlated with F4Cd, while glycosaminoglycan degradation metabolism and assimilatory nitrate reduction was significantly correlated with F2Cd. Overall, this study gives a more comprehensive insight into the effect of NH4+ on activated Fe and C conversion on soil Cd redistribution under gradient moisture conditions.

Deciphering silver nanoparticles perturbation effects and risks for soil enzymes worldwide: Insights from machine learning and soil property integration.

Globally extensive research into how silver nanoparticles (AgNPs) affect enzyme activity in soils with differing properties has been limited by cost-prohibitive sampling. In this study, customized machine learning (ML) was used to extract data patterns from complex research, with a hit rate of Random Forest > Multiple Imputation by Chained Equations > Decision Tree > K-Nearest Neighbors. Results showed that soil properties played a pivotal role in determining AgNPs' effect on soil enzymes, with the order being pH > organic matter (OM) > soil texture ≈ cation exchange capacity (CEC). Notably, soil enzyme activity was more sensitive to AgNPs in acidic soil (pH < 5.5), while elevated OM content (>1.9 %) attenuated AgNPs toxicity. Compared to soil acidification, reducing soil OM content is more detrimental in exacerbating AgNPs' toxicity and it emerged that clay particles were deemed effective in curbing their toxicity. Meanwhile sand particles played a very different role, and a sandy soil sample at > 40 % of the water holding capacity (WHC), amplified the toxicity of AgNPs. Perturbation mapping of how soil texture alters enzyme activity under AgNPs exposure was generated, where soils with sand (45-65 %), silt (< 22 %), and clay (35-55 %) exhibited even higher probability of positive effects of AgNPs. The average calculation results indicate the sandy clay loam (75.6 %), clay (74.8 %), silt clay (65.8 %), and sandy clay (55.9 %) texture soil demonstrate less AgNPs inhibition effect. The results herein advance the prediction of the effect of AgNPs on soil enzymes globally and determine the soil types that are more sensitive to AgNPs worldwide.

Predicting the effect of silver nanoparticles on soil enzyme activity using the machine learning method: type, size, dose and exposure time.

In this study, machine learning models predicted the impact of silver nanoparticles (AgNPs) on soil enzymes. Artificial neural network (ANN) optimized with genetic algorithm (GA) (MAE = 0.1174) was more suitable for simulating overall trends, while the gradient boosting machine (GBM) and random forest (RF) were ideal for small-scale analysis. According to partial dependency profile (PDP) analysis, polyvinylpyrrolidone coated AgNPs (PVP-AgNPs) had the most inhibitory effect (average of 49.5%) on soil enzyme activity among the three types of AgNPs at the same dose (0.02-50 mg/kg). The ANN model predicted that enzyme activity first declined and then rose when AgNPs increased in size. Based on predictions from the ANN and RF models, when exposed to uncoated AgNPs, soil enzyme activities continued to decrease before 30 d, but gradually rose from 30 to 90 d, and fell slightly after 90 d. The ANN model indicated the importance order of four factors: dose > type > size > exposure time. The RF model suggested the enzyme was more sensitive when experiments were conducted at doses, sizes, and exposure times of 0.01-1 mg/kg, 50-100 nm, and 30-90 d, respectively. This study presents new insights on the regularity of soil enzyme responses to AgNPs.

Arsenic speciation, oxidation and immobilization in an unsaturated soil in the presence of green synthesized iron oxide nanoparticles and humic acid.

While the availability of arsenic (As) in soil is well known to be highly correlated with the presence of iron (Fe) oxides and humic acid (HA) in the soil, the relationship between Fe oxides and HA and As species in the soil is less well understood. In this study, As speciation in an unsaturated soil in the presence of external HA and green synthesized Fe oxide nanoparticles (FeNPs) showed that As(V) was mainly distributed to the specifically-bound (F2), amorphous and poorly-crystalline hydrous oxides of Fe, Al (F3) and the well-crystallized hydrous oxides of Fe and Al (F4). While As(III). This was the major component in unsaturated soil, and was mainly distributed to F4 and the residual fraction (F5). As bound to F3 and F5 was most sensitive to the addition of HA and FeNPs, while HA/FeNPs treatment increased the F3-bound As(V); however, it decreased the F5-bound As(III). Nonetheless the effect of HA on As is completely different to the HA/FeNPs treatment. The increase of As(V) in F3 resulted from F5-bound As(III) oxidation when treated by HA/FeNPs. Cyclic voltammetry confirmed that HA and Fe3+/Fe2+ redox enhanced As(III) oxidation, while FTIR revealed that HA-bound As(III) was the least available fraction in the soil. Finally, a mechanism involving a combination of HA and FeNPs was proposed for explaining the redistribution of As species in the soil.

Enhanced oxidation and stabilization of arsenic in a soil-rice system by phytosynthesized iron oxide nanomaterials: Mechanistic differences under flooding and draining conditions.

Despite arsenic (As) bioavailability being highly correlated with water status and the presence of iron (Fe) minerals, limited information is currently available on how externally applied Fe nanomaterials in soil-rice systems affect As oxidation and stabilization during flooding and draining events. Herein, the stabilization of As in a paddy soil by a phytosynthesized iron oxide nanomaterials (PION) and the related mechanism was investigated using a combination of chemical extraction and functional microbe analysis in soil at both flooding (60 d) and draining (120 d) stages. The application of PION decreased both specifically bound and non-specifically bound As. The As content in rice root, stem, husk and grain was reduced by 78.5, 17.3, 8.4 and 34.4%, respectively, whereas As(III) and As(V) in root declined by 96.9 and 33.3% for the 1% PION treatment after 120 d. Furthermore, the 1% PION treatment decreased the ratio of As(III)/As(V) in the rhizosphere soil, root and stem. Although PION had no significant effect on the overall Shannon index, the distribution of some specific functional microbes changed dramatically. While no As(III) oxidation bacteria were found at 60 d in any treatments, PION treatment increased As(III) oxidation bacteria by 3-9 fold after 120 d cultivation. Structural equation model analysis revealed that the ratio of Fe(III)/Fe(II) affected As stabilization directly at the flooding stage, whereas nitrate reduction and As(III) oxidation microbial groups played a significant role in the stabilization of As at the draining stage. These results highlight that PION exhibits a robust ability to reduce As availability to rice, with chemical oxidation, reduction inhibition and adsorption dominating at the flooding stage, while microbial oxidation, adsorption and coprecipitation dominant during draining.

Effects of green synthesized and commercial nZVI on crystal violet degradation by Burkholderia vietnamiensis C09V: Dose-dependent toxicity and biocompatibility.

The increasingly common remedial application of nanoscale zero-valent iron (nZVI) to alleviate specific contaminant issues may inadvertently lead to nZVI accumulation in wastewater. This is a potential concern, because the effect of nZVI on the common microbes essential for wastewater biotreatment is not known. This is further complicated when there are many ways available to synthesize nZVI, which may interreact with bacteria differently. Thus, in this study, the different effects of nZVI synthesized by Eucalyptus leaves (EL-nZVI) and a commercially synthesized nZVI on the biodegradation of crystal violet by Burkholderia vietnamiensis C09V (B.V. C09V) was studied. At high dose (1000 mg/L), EL-nZVI and commercial nZVI both significantly inhibited the removal of crystal violet by B.V. C09V, decreasing removal rates by 10.5 and 13.1% respectively. Optical density (OD600) and soluble protein assays indicated that the growth of B.V. C09V improved under low doses (100 mg/L), but remained inhibited under high doses (500 and 1000 mg/L) of both commercial and EL-nZVI. Enzymes were also sensitive to nZVI, where the commercial variant exerted a greater effect on both the activity of lactate dehydrogenase (LDH) and superoxide dismutase (SOD) than EL-nZVI, indicating that EL-nZVI was less toxic than commercial nZVI. LIVE/DEAD staining also showed that the number of apoptotic cells was significantly higher when exposed to commercial nZVI rather than EL-nZVI. Furthermore, scanning electron microscopy (SEM) confirmed that direct contact between nZVI and cells at 1000 mg/L nZVI caused cell membrane disruption. Whereas, at 100 mg/L EL-nZVI, B.V. C09V grew better due to the formation of dense biofilms around the suspended EL-nZVI at a. Fourier transform infrared spectra (FTIR), confirmed an abundance of oxygen-containing functional groups on the surface of EL-nZVI which provided better biocompatibility than commercial nZVI. Overall, while dose was the most significant factor influencing nZVI toxicity, surface composition and morphology was also important. These new findings suggest chemical synthesis of metal nanoparticles should be replaced by biosynthetic routes to maintain viable microbial pollution during wastewater treatment.

How do phytogenic iron oxide nanoparticles drive redox reactions to reduce cadmium availability in a flooded paddy soil?

While soil redox reactions are known to determine heavy metal soil availability, specific information on how iron (Fe) nanomaterials reduce heavy metal availability in bulk soil and in the rice rhizosphere is limited. Here a pot experiment was performed to examine the effect of phytogenic iron oxide nanoparticles (PION) on the availability of cadmium (Cd) in flooded soil. PION significantly reduced soil Cd availability, with Cd in rice shoot being 2.72, 1.21 and 0.40 mg kg-1 for the control, 1 and 5% PION treatments, respectively. In addition, following PION application, Illumina MiSeq sequencing indicated that the abundance of Lentimicrobium and Anaeromyxobacter increased, while the abundance of Geobacter and Thiobacillus decreased. Structural equation model analysis revealed that redox reactions, driven by carbon, nitrogen, iron and sulfur cycling related functional groups, played an important role in the immobilization of Cd in flooded soil. Co-occurrence network analysis showed that the rhizosphere soil was far more complex than the bulk soil. Overall, PION addition enhanced the inherent soil microbe's activity and the involved in reducing Cd availability to rice by converting mobile Cd into stabler forms. This initial result paves the way for establishing a practical low-cost remediation strategy for Cd contaminated paddy soils.

Impact of green reduced graphene oxide on sewage sludge bioleaching with Acidithiobacillus ferrooxidanse.

Worldwide graphene use is rapidly increasing in a variety of industrial applications to such an extent that efflux into the environment seems inevitable where the likely final reservoirs of graphene wastes is likely to be wastewater treatment plants are. Despite this an understanding of how graphene products impact the bioleaching of metals from sludge is still limited. In this study, the effect of reduced graphene oxide synthesized from eucalyptus leaf extracts (EL-rGO) on Zn2+ and Cu2+ bioleaching from sludge was investigated. The major new findings were that EL-rGO had a negative effect on Acidithiobacillus ferrooxidans (A. ferrooxidans) growth; since optical density decreased by 0.059 as EL-rGO dose increased from 1 to 50 mg/L, and the bioleaching of Cu2+ and Zn2+ decreased by 27.7 and 20.2%, respectively. While at a EL-rGO dose of 1 mg/L A. ferrooxidans grew better, scanning electron microscopy (SEM) confirmed that exposure to EL-rGO caused cell membrane disruption at 50 mg/L. Cytotoxicity tests showed that this was related to an increase in lactate dehydrogenase (LDH) release rate and a decrease in superoxide dismutase (SOD) activity. These new findings provide evidence that green synthesized rGO is toxic to microorganisms and that toxicity increased with rGO dose.

Impact of green synthesized iron oxide nanoparticles on the distribution and transformation of As species in contaminated soil.

Iron nanoparticles (Fe NPs) have often been used for in situ remediation of both groundwater and soil. However, the impact of Fe NPs on the distribution and transformation of As species in contaminated soil is still largely unknown. In this study, green iron oxide nanoparticles synthesized using a euphorbia cochinchinensis leaf extract (GION) were used to stabilize As in a contaminated soil. GION exhibited excellent As stabilization effects, where As in non-specifically-bound and specifically-bound fractions decreased by 27.1% and 67.3% after 120 days incubation. While both arsenate (As (V)) and arsenite (As (III)) decreased after GION application, As (V) remained the dominant species in soil. X-ray photoelectron spectroscopy (XPS) confirmed that As (V) was the dominant species in specifically-bound fractions, while As (III) was the dominant species in amorphous and poorly-crystalline hydrous oxides of Fe and Al. Correlation analysis showed that while highly available As fractions were negatively correlated to oxalate and DCB extractable Fe, they were positively correlated to Fe2+ content, which indicated that Fe cycling was the main process influencing changes in As availability. X-ray fluorescence (XRF) spectroscopy also showed that the Fe2O3 content increased by 47.9% following GION soil treatments. Overall, this work indicated that As would be transformed to more stable fractions during the cycling of Fe following GION application and that the application of GION, even in small doses, provides a low-cost and ecofriendly method for the stabilization of As in soil.

The stabilizing mechanism of cadmium in contaminated soil using green synthesized iron oxide nanoparticles under long-term incubation.

Despite numerous studies having been conducted on the stabilization of heavy metal contaminated soil, our understanding of the mechanisms involved remains limited. Here green synthesized iron oxide nanoparticles (GION) were applied to stabilize cadmium (Cd) in a contaminated soil. GION not only stabilized soil Cd, but also improved soil properties within one year of incubation. After GION application both the exchangeable and carbonate bound Cd fractions decreased by 14.2-83.5% and 18.3-85.8% respectively, and most of the Cd was translocated to the residual Cd fraction. The application of GION also strongly altered soil bacterial communities. In GION treatments, the abundance of Gemmatimonadetes, Proteobacteria, and Saccharibacteria increased which led to a shift in the dominant bacterial genera from Bacillus to Candidatus koribacter. The variation in bacteria confirmed the restoration of the contaminated soil. The most abundant bacterial genus and species found in GION treatments were related to (i) plant derived biomass decomposition; (ii) ammoxidation and denitrification; and (iii) Fe oxidation. GION application may enhance the formation of larger soil aggregates with anaerobic centers and coprecipitation coupled Fe (II) oxidization, ammoxidation and nitrite reduction followed by Fe mineral ripening may be involved in Cd stabilization. The predominant stabilization mechanism was thus coprecipitation-ripening-stabilization.

Immobilization of cadmium in polluted soils by phytogenic iron oxide nanoparticles.

While phytogenic nanomaterials have been successfully used to remove heavy metals in wastewater, the potential to successfully use such materials to immobilize heavy metals in soils is still unclear. In this study, phytogenic iron oxide nanoparticles (PION) were used to immobilize cadmium (Cd) in six soils. Amendment with PION effectively immobilized Cd, with a concomitant increase in the concentrations of iron oxides, soil pH and dissolved organic carbon (DOC) under both oxic and anoxic conditions. However, observed changes in soil properties and Cd fractions were different under oxic and anoxic conditions. After PION application, the exchangeable Cd fraction decreased by up to 91 and 69%, while the carbonate bound Cd fraction decreased by up to 61 and 75%, under oxic and anoxic conditions, respectively. Pearson correlation analysis revealed that under both oxic and anoxic conditions, Cd fractions were significantly and positively correlated with free iron oxide content and pH, where free iron oxide content was positively correlated with amorphous iron oxide, DOC and pH. The Cd immobilization mechanisms potentially involved either (1) formation of insoluble hydroxides at elevated pH; (2) participation of biomolecules released from PION in ligand complexation with Cd and (3) co-precipitated of Cd during the formation of iron oxides. This study provided new insights into the potential effects of PION applications for practical Cd immobilization in contaminated soils.

Aerobic denitrification by Paracoccus sp. YF1 in the presence of Cu(II).

This study of Cu(II)'s impact on aerobic denitrification of Paracoccus sp. YF1 revealed that the denitrification rate decreased markedly from 99.8%, 98.0%, 68.7% to 16.3% when the concentrations of Cu(II) rose from 0, 0.01 mM, 0.05 mM to 0.1 mM, respectively. This outcome was confirmed by the successful test of OD600, total protein and enzyme activities. As the concentration of Cu(II) increased from 0 to 0.1 mM, the total protein contents declined over a period of 48 h, and the activities of nitrate reductase (NR) and nitrite reductase (NIR) decreased remarkably during the first 24 h in a NO3- sufficient state. Meanwhile, the reduction of NO3- and NO2- was positively correlated with the expression level of NR and NIR. The removal rate of nitrate in the control treatment and different concentration of Cu(II) treatment fitted approximately to the zero-order model. Scanning electron microscopy (SEM) confirmed that the cell surfaces of Paracoccus sp. YF1 were disrupted when exposed to 0.1 mM Cu(II). The adsorption of Cu(II) onto the cells' surface was confirmed by Energy dispersive spectrometer (EDS), Fourier transform infrared spectra (FTIR), and X-ray photoelectron spectroscopy analysis (XPS). The insights obtained here regarding the influence of Cu(II) on aerobic denitrification will be of great significance for the treatment of heavy metals and nitrite co-existing sewage.

A process-based model for pentachlorophenol dissipation in a flooded paddy soil.

Process-based models have been widely used for predicting environmental fate of contaminants. Nevertheless, accurate modeling of pentachlorophenol (PCP) dissipation in soils at the millimeter-scale remains a challenge due to the scarcity of observation data and uncertainty associated with model assumptions and estimation of the model parameters. To provide quantitative analysis of PCP-dissipation at the anaerobic/aerobic interface of a rhizobox experiment, this study implemented Bayesian parameter estimation for a process-based reactive chemical transport model. The model considered the main transport and transformation processes of chemicals including diffusion, sorption and degradation. The contributions of the processes to PCP dissipation were apportioned both in space and time. Using the maximum-a-posteriori (MAP) estimation of parameters, our model fitted the experimental data better compared with the previous work. Our results indicated that the most reactive zone for PCP dissipation occurred in the layer of 0-2.4 mm where degradation in solid phase dominated the PCP dissipation, while upward diffusion was the main mechanism for the reduction of PCP concentration in deeper layer (2.4-4.8 mm). By considering the coupled reactive transport of PCP and Cl-, the average degrees of PCP dechlorination in each layer were estimated from corresponding total concentrations of PCP and Cl-. The degrees of PCP dechlorination in the ponding water and the top layer of soil profile were highest, while 2,3,4,5- TeCP and 3,4,5- TCP were identified as the main dechlorination products in the soil. This study demonstrated that combining Bayesian estimation with process-based reactive chemical transport model can provide more insights of PCP dissipation at the millimeter-scale. This approach can help to understand complex dissipation mechanisms for other contaminants.

Biosynthesized iron oxide nanoparticles used for optimized removal of cadmium with response surface methodology.

To effectively reuse adsorbent in removal of Cd (II), magnetic modification was considered as an alternative. In this study, iron oxide nanoparticles (IONPs) synthesized from the extract of Excoecaria cochinchinensis Lour leaves were modified by low-temperature calcination, and used to remove Cd (II). Transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and magnetic properties analysis confirmed the successful synthesis of nanoscale magnetic FeOC composite. Response surface methodology (RSM) served to optimize the adsorption of Cd (II) by IONPs based on Box-Behnken design (BBD). According to the quadratic model, the effect of each factor on the removal of Cd (II) by IONPs was: pH > dosage > ionic strength > temperature. In percentage terms, 98.50% of Cd (II) (10 mg L-1) was removed when the pH, absorbent dosage, temperature and ionic strength conditions were 8.07, 2.5 g L-1, 45 °C, and 0.07 mol L-1, respectively. The adsorption of Cd (II) by IONPs is consistent with pseudo-second order kinetics and Langmuir adsorption isotherm models, indicating that the process of adsorption of Cd (II) by IONPs belongs to monolayer chemical adsorption. The -COOH, -COH, Cπ electron and ≡FeOH may be the binding sites for Cd (II) on the surface of IONPs. Overall, IONPs can be used to remove Cd (II) effectively from aqueous solution in a wide range of conditions.

The effects of different types of crop straw on the transformation of pentachlorophenol in flooded paddy soil.

The incorporation of various types of crop straw to agricultural soils has long been practiced to improve soil fertility. However, the effects of crop straw on the fate of organo-chlorine pesticides in flooded paddy soils are not well understood. The dechlorination of pentachlorophenol (PCP) in four vertical profiles (0-10, 10-20, 20-30, 30-50 mm depth) of two flooded paddy soils, a Plinthudult (Soil 1) and a Tropudult (Soil 2) was investigated following the application of four crop straws (rice, wheat, rape and Chinese milk vetch) to them. In all treatments, PCP dechlorination decreased with increasing soil depth. In the crop straw treatments, PCP was almost completely dechlorinated within 60 days, and rapidly transformed to 2,3,4,5-tetrachlorophenol, and further to 3,4,5-trichlorophenol. Further dechlorination of 3,4,5-trichlorophenol also occurred in all treatments except for the rape straw. It is possible that the NH4+ and NO3- derived from the straw are responsible for the inhibition of the 3,4,5-trichlorophenol dechlorination. The reduction of Fe (III) and SO42- increased following application of the crop straws. The RDA analysis indicated that the Fe (III) reducing bacteria might be involved in the ortho-dechlorination, while SO42- reducing bacteria were involved in para- and meta-dechlorination of PCP. The complete detoxification of PCP depended upon both the crop straw type and soil properties.

The toxicity of graphene and its impacting on bioleaching of metal ions from sewages sludge by Acidithiobacillus sp.

The increasing production of graphene raised concerns about their releasing into sewage sludge, however, there is little information about graphene impacting on the growth of bacteria and hence their bioleaching of metal ions from sewages sludge. In this study, we reported that Acidithiobacillus sp., isolated from sewages, were used to bioleach Cu2+ and Zn2+ from sewages sludge in the presence of graphene. The negative effect on the growth of Acidithiobacillus sp. and dose-dependent were observed in presence of graphene, where the optical density (OD420) of the culture decreased from 0.163 to 0.045, while the bioleaching efficiency of Cu2+ (70%-16%) and Zn2+ (80%-48%) were also reduced when the graphene dose decreased from 50 mg L-1 to 1 mg L-1. Furthermore, scanning electron microscopy (SEM) and atomic force microscopy (AFM) confirmed that the direct contacts between graphene and cell at 1 mg L-1 graphene caused cell membrane disruption, while Acidithiobacillus sp. grew better by forming dense biofilms around the suspended graphene at a 50 mg L-1. LIVE/DEAD staining further demonstrated that almost no live cells were detected at 1 mg L-1 graphene. The toxicity of graphene could generally be explained by depending on the concentration of graphene. The new findings provide an insight into dose dependence, which impacted on the growth of Acidithiobacillus sp. and their bioleaching of metal ion from sludge.

Functional kaolin supported nanoscale zero-valent iron as a Fenton-like catalyst for the degradation of Direct Black G.

Kaolin supported nanoscale zero-valent iron (K-nZVI) is synthesized and applied as the Fenton-like oxidation catalyst to degrade a model azo dye, Direct Black G (DBG). The characterization of K-nZVI by the high resolution transmission electronmicroscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), Energy Diffraction Spectrum (EDS) and X-ray diffraction (XRD) show that kaolin as a support material not only reduces the aggregation of zero-valent iron (nZVI) but also facilitates the Fenton-like oxidation by increasing the local concentration of DBG in the vicinity of nZVI. Pseudo first-order and pseudo second-order kinetic models are employed to reveal the adsorption and degradation of the DBG using K-nZVI as the catalyst. A better fit with pseudo second-order model for the adsorption process and equal excellent fits with pseudo first-order and pseudo second-order models for the degradation process are observed; the adsorption process is found to be the rate limiting step for overall reactions. The adsorption, evaluated by isotherms and thermodynamic parameters is a spontaneous and endothermic process. High-performance liquid chromatography-mass spectrometry (LC-MS) analysis was used to test degraded products in the degradation of DGB by K-nZVI. A removal mechanism based on the adsorption and degradation is proposed, including (i) prompt adsorption of DBG onto the K-nZVI surface, and (ii) oxidation of DBG by hydroxyl radicals at the K-nZVI surface. The application of K-nZVI to treat real wastewater containing azo dyes shows excellent degradation efficiency.

Remediation of water contaminated with diesel oil using a coupled process: Biological degradation followed by heterogeneous Fenton-like oxidation.

The treatment of a synthetically prepared wastewater containing diesel oil has been investigated using combined treatment schemes based on the biological treatment followed by an advanced oxidation process. 78% of diesel oil was degraded by Acinetobacter venetianus in 96 h, while the removal efficiency of chemical oxygen demand (COD) in the aqueous phase was only 56.8%, indicating that degraded metabolites existed in solution. To solve this problem, a Fenton-like system consisting of nanoscale zero-valent iron (nZVI) and hydrogen peroxide was used for further oxidation of the metabolites after biodegradation. Results showed that the total COD removal increased from 56.8% to 89% under the optimal condition. In addition, effects of initial pH (2.0-9.0), ZVI dosage (0-2.0 g L-1), hydrogen peroxide (H2O2) dosage concentration (0-15 mmol L-1) and temperature (298-308 K) on the treatment efficiency of the combined process were studied. Scanning electron microscopy (SEM) demonstrated that changes to the surface of nZVI occurred. GC-MS revealed that the degraded metabolites were mineralized practically by nZVI/H2O2 system. The results points towards the potential of Fenton-like oxidation as a short post-treatment after a biological process for the treatment of organic pollutants in wastewater.

Dissipation of phenanthrene and pyrene at the aerobic-anaerobic soil interface: differentiation induced by the rhizosphere of PAH-tolerant and PAH-sensitive rice (Oryza sativa L.) cultivars.

A pot experiment was conducted to reveal the removal of two polycyclic aromatic hydrocarbons (PAHs) (phenanthrene, PHE, and pyrene, PYR) during rice cultivation in a paddy field. The rhizosphere effect on facilitating dissipation of PAHs varied simultaneously as a function of soil properties, PAH types, cultivation time, and genotypes within rice cultivars, with differences performed for PYR but not PHE. Changes in soil PLFA profiles evidenced that the growth of rice roots modified the dominant species within rhizosphere microbial communities and induced a selective enrichment of Gram-negative aerobic bacteria capable of degrading, thereby resulting in the differentiated dissipation of PYR. While the insignificant differences in PHE dissipation might be attributed to its higher solubility and availability under flooded condition that concealed the differences in improvement of bioavailability for microorganisms between rhizosphere and non-rhizosphere, and between both soils and both rice cultivars. Our findings illustrate that the removal of PAHs in paddy soils was more complex relative to those in dryland soils. This was possibly due to the specialty of rice roots for oxygen secretion that provides development of redox heterogeneous microbial habitats at root-soil interface under flooded condition.