Stability of Activated Persulfate in the Presence of Aquifer Solids

Bench-scale experiments were performed to investigate the persistence of activated persulfate using citric acid (CA) chelated ferrous (Fe(II)), peroxide (H₂O₂), or hydroxide (OH^?) activation in the presence of well-characterized aquifer solids. Chelation by citric acid was ineffective in controlling the interaction between persulfate and Fe(II), and oxidation of Fe(II) was observed, causing a rapid initial decrease in persulfate concentration. Subsequent to this loss, first-order persulfate degradation rate coefficients (k_obs) were estimated, which were up to four times higher than the unactivated case due to the interaction with Fe(III), Fe(II), or CA. Total oxidation strength (TOS) was measured for peroxide activation experiments and was observed to decrease rapidly early due to peroxide degradation. This was followed by slow degradation kinetics similar to that of unactivated persulfate, implying that the initial TOS degradation was peroxide-dominated and the long-term kinetics were dominated by persulfate degradation. The k_obs later used to capture TOS degradation were ～1 to 100 times higher than k_obs for unactivated persulfate. For alkaline activation, k_obs were only one to four times higher than unactivated persulfate, and therefore alkaline conditions demonstrated the least overall impact on persulfate stability among the various activation strategies explored.     

Remediation of Nitrobenzene Contaminated Soil by Combining Surfactant Enhanced Soil Washing and Effluent Oxidation with Persulfate

The combination of surfactant enhanced soil washing and degradation of nitrobenzene (NB) in effluent with persulfate was investigated to remediate NB contaminated soil. Aqueous solution of sodium dodecylbenzenesulfonate (SDBS, 24.0 mmol L^-1) was used at a given mass ratio of solution to soil (20:1) to extract NB contaminated soil (47.3 mg kg^-1), resulting in NB desorption removal efficient of 76.8%. The washing effluent was treated in Fe²⁺/persulfate and Fe²⁺/H₂O₂ systems successively. The degradation removal of NB was 97.9%, being much higher than that of SDBS (51.6%) with addition of 40.0 mmol L^-1 Fe²⁺ and 40.0 mmol L^-1 persulfate after 15 min reaction. The preferential degradation was related to the lone pair electron of generated SO₄•⁻, which preferably removes electrons from aromatic parts of NB over long alkyl chains of SDBS through hydrogen abstraction reactions. No preferential degradation was observed in •OH based oxidation because of its hydrogen abstraction or addition mechanism. The sustained SDBS could be reused for washing the contaminated soil. The combination of the effective surfactant-enhanced washing and the preferential degradation of NB with Fe²⁺/persulfate provide a useful option to remediate NB contaminated soil.     

Treatment of Diesel-Contaminated Soil by Fenton and Persulfate Oxidation with Zero-Valent Iron

The objective of this research is to investigate Fenton and persulfate oxidation with zero-valent iron [Fe(0)] as a batch type ex-situ remediation technology for the treatment of diesel-contaminated soil. Results from batch experiments indicate that Fe(0) is a better catalyst for H₂O₂ and persulfate than Fe²⁺ for the enhancement of Fenton and persulfate oxidation in a batch system. Maximum removal was obtained after 12 h when 1 and 2 g of Fe(0) were added to hydrogen peroxide (250 mg/L) and persulfate (250 mg/L), respectively, in a soil-water system. As the amounts of Fe(0) and persulfate were increased three times at the optimal ratio, the removal of total petroleum hydrocarbon (TPH) was enhanced accordingly. More than 90% of the TPH was removed in 3 h, and the treated soil met the Korean regulation level (500 mg/kg) for TPH. Increased amounts of Fe(0) and hydrogen peroxide (up to 10 g and 1250 mg/L, respectively) also significantly enhanced degradation under the optimal conditions. The results of our study suggest that Fe(0)-assisted Fenton and persulfate oxidation in a batch reactor may be an alternative option to treat diesel-contaminated soil.     

Defluorination of Aqueous Perfluorooctanesulfonate by Activated Persulfate Oxidation

Activated persulfate oxidation technologies based on sulfate radicals were first evaluated for defluorination of aqueous perfluorooctanesulfonate (PFOS). The influences of catalytic method, time, pH and K₂S₂O₈ amounts on PFOS defluorination were investigated. The intermediate products during PFOS defluorination were detected by using LC/MS/MS. The results showed that the S₂O₈ ²⁻ had weak effect on the defluorination of PFOS, while the PFOS was oxidatively defluorinated by sulfate radicals in water. The defluorination efficiency of PFOS under various treatment was followed the order: HT (hydrothermal)/K₂S₂O₈ > UV (ultraviolet)/K₂S₂O₈ > Fe²⁺/K₂S₂O₈ > US (ultrasound)/K₂S₂O₈. Low pH was favorable for the PFOS defluorination with sulfate radicals. Increase in the amount of S₂O₈ ²⁻ had positive effect on PFOS defluorination. However, further increase in amounts of S₂O₈ ²⁻ caused insignificant improvement in PFOS defluorination due to elimination of sulfate radicals under high concentration of S₂O₈ ²⁻. CF₃(CF₂)_nCOOH (n = 0–6) were detected as intermediates during PFOS defluorination. Sulfate radicals oxidation and hydrolysis were the main mechanisms involved in defluorination process of PFOS.     

Treatment of Groundwater Contaminated with PAHs, Gasoline Hydrocarbons, and Methyl tert-butyl Ether in a Laboratory Biomass-Retaining Bioreactor

In this study, we investigated the treatability of co-mingled groundwater contaminated with polycyclic aromatic hydrocarbons (PAHs), gasoline hydrocarbons, and methyl tert-butyl ether (MtBE) using an ex-situ aerobic biotreatment system. The PAHs of interest were naphthalene, methyl-naphthalene, acenaphthene, acenaphthylene, and carbazole. The gasoline hydrocarbons included benzene, toluene, ethyl benzene, and p-xylene (BTEX). Two porous pot reactors were operated for a period of 10 months under the same influent contaminant concentrations. The contaminated groundwater was introduced into the reactors at a flow rate of 4 and 9 l/day, resulting in a hydraulic retention time (HRT) of 32 and 15 h, respectively. In both reactors, high removal efficiencies were achieved for the PAHs (>99%), BTEX and MtBE (>99.7%). All the PAHs of interest and the four BTEX compounds were detected at concentrations less than 1 μg/l throughout the study duration. Effluent MtBE from both reactors was observed at higher levels; nevertheless, its concentration was lower than the 5 μg/l Drinking Water Advisory for MtBE implemented in California.     

Evaluation of the Soil Contamination of Tangier (Morocco) by the Determination of BTEX,PCBs, and PAHs

Benzene, toluene, ethylbenzene, and xylenes (BTEX), twelve polycyclic aromatic hydrocarbons (PAHs) and seven polychlorinated biphenyls (PCBs), were selected as pollutants to evaluate the contamination of soils in the urban and industrial areas of Tangier (Morocco). PAHs and PCBs were determined by gas chromatography-mass spectrometry (GC-MS) after a microwave-assisted extraction (MAE) and gel permeation chromatography (GPC) clean-up. BTEX were directly determined by head-space GC-MS. Results obtained in this study show the presence of high levels of BTEX and PAHs in the soil near the urban waste deposit. However, the analysis of pollutants in the other sampling sites provided comprehensive evidence that soils of Tangier city are not contaminated.     

Washing of Cadmium(II) from a Contaminated Soil Column

The washing of cadmium (from CdO_(s)) from a soil column employing either an acid solution or EDTA (a strong metal chelator) was examined. For Cd(II) levels of 50 to 1000 mg/kg, the fraction removed was essentially independent of the initial Cd(II) concentration. The most efficient washing of cadmium was achieved using an acid wash solution at pH 2.5. Lower Cd(II) removals were found at lower pH, apparently due to inhibition of CdO_(s) dissolution by constituents released from the soil under highly acidic conditions. EDTA wash solutions were employed at EDTA:cadmium molar ratios ranging from 1:1 to 10:1. Up to 90% removal of total Cd(II) was achieved at the 10:1 ratio after the passage of the first 50?PV of wash solution. Although higher chelate levels enhanced Cd(II) removal, the utilization efficiency of EDTA for cadmium decreased.     

Iron (II) Ions Induced Oxidation of Ascorbic Acid and Glucose

Lipid peroxidation (LPO) of polyunsaturated fatty acids (PUFAs) is suspected to be involved in the generation of chronic diseases. A model reaction for LPO is the air oxidation of PUFAs initiated by Fe²⁺ and ascorbic acid. In the course of such model reactions glycolaldehyde (GLA) was detected as main aldehydic product. Since it is difficult to explain the generation of GLA by oxidation of PUFAs, it was suspected that GLA might be derived by oxidation of ascorbic acid. This assumption was verified by treatment of ascorbic acid with Fe²⁺.

Produced aldehydic compounds were trapped by addition of pentafluorobenzylhydroxylamine hydrochloride (PFBHA-HCl), trimethylsilylated and finally identified by gas chromatography/mass spectrometry (GC/MS). Oxidation of ascorbic acid with O₂ in presence of iron ions produced not only glycolaldehyde (GLA), but also glyceraldehyde (GA), dihydroxyacetone (DA) and formaldehyde. Glyoxal (GO) and malondialdehyde (MDA) were detected as trace compounds.

The yield of the aldehydic compounds was increased by addition of lipid hydroperoxides (LOOH) or H₂O₂. The buffer influenced the reaction considerably: Iron ions react with Tris buffer by producing dihydroxyace-tone (DA). Since ascorbic acid is present in biological systems and Fe²⁺ ions are obviously generated by cell damaging processes, the production of GLA and other aldehydic components might add to the damaging effects of LPO.

Glucose suffers also oxidation to short-chain aldehydic compounds in aqueous solution, but this reaction requires addition of equimolar amounts of Fe²⁺ together with equimolar amounts of H₂O₂ or 13-hydroperoxy-9-cis-11-trans-octadecadienoic acid (13-HPODE). Therefore this reaction, also influenced by the buffer system, seems to be not of biological relevance.     

Alkyl Polyglucoside (APG) Amendment for Improving the Phytoremediation of Pb-PAH Contaminated Soil by the AquaticPlant Scirpus triqueter

This study assessed the potential abilities of Scirpus triqueter for phytoremediation of soils contaminated with Pb-PAHs, amended with environment-friendly surfactant alkyl polyglucoside (APG). The effects of APG on the removal of PAHs from soil and the plant uptake and translocation of Pb were tested with plant growth and soil enzymatic activities. Experiments demonstrated that APG has an ability to facilitate PAH degradation and Pb uptake in the plant body at appropriate concentrations (20–40mg L^?1). The highest PAH removal rate was observed in 30 mg L^?1 APG treatment, and the highest accumulation of Pb was detected as 40 mg L^?1 APG. Experiments documented the effects of APG on plant growth, soil enzymatic activity, bioaccumulation and translocation of Pb in Scirpus triqueter. Results indicated that the addition of appropriate APG enhanced PAH removal rate and increased plant uptake and translocation of Pb.     

Experimental Evaluation of Catalyzed Hydrogen Peroxide and Sodium Persulfate for Destruction of BTEX Contaminants

Due to the toxicity and prevalence of BTEX contaminants (benzene, toluene, ethylbenzene, and xylenes) at hazardous waste sites, approaches for their remediation are of interest, especially those that particularly address benzene, which is often the limiting factor for achieving regulatory cleanup at these contaminated sites. In situ chemical oxidation (ISCO) is a viable technology for BTEX destruction, and hydrogen peroxide and sodium persulfate are two oxidants of interest for BTEX treatment.

Laboratory studies were conducted to compare BTEX contaminant destruction and oxidant persistence for these two oxidants and for varied methods of oxidant activation/propagation. Additionally, studies were performed to compare contaminant destruction and oxidant persistence in laboratory contaminant spike systems vs. field site contaminant systems. Finally, contaminant destruction and oxidant persistence in field porous media with varied characteristics were evaluated. Contaminant and oxidant concentrations were measured at multiple time points over a three-week reaction period in each oxidant and oxidant activation/propagation system.

Under the comparable conditions evaluated here, sodium persulfate systems demonstrated greater BTEX contaminant destruction and greater oxidant persistence than hydrogen peroxide systems. FeSO₄ and citric acid activation of sodium persulfate resulted in greater BTEX destruction and greater oxidant persistence than pH adjustment or hydrogen peroxide activation in both laboratory contaminant spike systems and field gas condensate systems. Additionally, results indicate that the response of the contaminant(s) and oxidant (extent and rate of depletion) are both contaminant-and porous media type-dependent.     

Nitrate-Dependent Ferrous Iron Oxidation by Anaerobic Ammonium Oxidation (Anammox) Bacteria

We examined nitrate-dependent Fe²⁺ oxidation mediated by anaerobic ammonium oxidation (anammox) bacteria. Enrichment cultures of “Candidatus Brocadia sinica” anaerobically oxidized Fe²⁺ and reduced NO₃⁻ to nitrogen gas at rates of 3.7 ± 0.2 and 1.3 ± 0.1 (mean ± standard deviation [SD]) nmol mg protein⁻¹ min⁻¹, respectively (37°C and pH 7.3). This nitrate reduction rate is an order of magnitude lower than the anammox activity of “Ca. Brocadia sinica” (10 to 75 nmol NH₄⁺ mg protein⁻¹ min⁻¹). A ¹⁵N tracer experiment demonstrated that coupling of nitrate-dependent Fe²⁺ oxidation and the anammox reaction was responsible for producing nitrogen gas from NO₃⁻ by “Ca. Brocadia sinica.” The activities of nitrate-dependent Fe²⁺ oxidation were dependent on temperature and pH, and the highest activities were seen at temperatures of 30 to 45°C and pHs ranging from 5.9 to 9.8. The mean half-saturation constant for NO₃⁻ ± SD of “Ca. Brocadia sinica” was determined to be 51 ± 21 μM. Nitrate-dependent Fe²⁺ oxidation was further demonstrated by another anammox bacterium, “Candidatus Scalindua sp.,” whose rates of Fe²⁺ oxidation and NO₃⁻ reduction were 4.7 ± 0.59 and 1.45 ± 0.05 nmol mg protein⁻¹ min⁻¹, respectively (20°C and pH 7.3). Co-occurrence of nitrate-dependent Fe²⁺ oxidation and the anammox reaction decreased the molar ratios of consumed NO₂⁻ to consumed NH₄⁺ (ΔNO₂⁻/ΔNH₄⁺) and produced NO₃⁻ to consumed NH₄⁺ (ΔNO₃⁻/ΔNH₄⁺). These reactions are preferable to the application of anammox processes for wastewater treatment.     

In-Situ Bioremediation of DDTs and PAH Contaminated Aging Farmland Soil Using Blood Meal

The use of blood meal was studied for in-site bioremediation of contaminated farmland soil. The combination of blood meal and indigenous microorganisms helped to in-site remediate the combined contaminated aging farmland soil of DDTs and PAH in Shenyang, China. The concentration of DDTs and PAHs was 47.94 ± 0.63 μg/kg and 690.10 ± 5.16 μg/kg, respectively. Biostimulation using blood meal or glucose promoted the bioremediation rate of DDTs and PAHs. Compared to glucose, blood meal was a longer term repair additive of DDTs and PAHs, and the remediation result was more efficient and durable. In the blood meal treatment, plowing the soil once every 7 days could increase the soil enzyme activities and bacterial populations, and it could significantly promote the remediation rates of DDTs (P < 0.05) and more evidently promote the remediation rates of PAHs. The DDTs and PAHs remediation rates increased from 32.18% and 20.17% to 43.41% and 26.09%, respectively, in soil treated with blood meal and plowed weekly after the five month remediation. This study provides an highly efficient in-site farmland soil bioremediation technology that could have practical utility.     

Fluorene and Phenanthrene Uptake and Accumulation by Wheat,Alfalfa and Sunflower from the Contaminated Soil

Polycyclic Aromatic Hydrocarbons (PAHs) are diverse organic contaminants released into the environment by both natural and anthropogenic activities. These compounds have negative impacts on plants growth and development. Although there are many reports on their existence in different parts of plant, their uptake and translocation pathways and mechanisms are not well understood yet. This paper highlights the uptake, translocation and accumulation of PAHs by wheat, sunflower and alfalfa through an experimental study under controlled conditions. Seeds were cultivated in a soil containing 50 mg/kg of phenanthrene and fluorene and their concentrations in plants roots and shoots were determined using a gas chromatograph after 7 and 14 days. The results showed that phenanthrene and fluorene concentrations in the treated plants were increased over the time. PAHs bioavailability was time and species dependent and generally, phenanthrene uptake and translocation was faster than that of fluorene, probably due to their higher K_ow. Fluorene tended to accumulate in roots, but phenanthrene was transported to aerial parts of plants.     

稳定同位素探针技术在有机污染物生物降解中的应用

稳定同位素探针技术(Stable isotope probing,SIP)是稳定同位素标记技术和各种分子生物学手段相结合的一系列技术总称。将其应用于探查污染物降解的功能微生物,实现了不经过分离培养直接把微生物的代谢功能、微生物间相互作用与微生物种群结合起来,从而克服了传统分离培养的缺陷,扩大了微生物资源的利用空间,具有广阔的发展前景。本文介绍了稳定同位素探针技术的基本原理和技术路线,对常规PLFA-SIP、DNA-SIP、RNA-SIP的特点进行了阐述和对比;综述了SIP在有机污染物——苯系物、多环芳烃、多氯联苯生物降解方面的研究进展,提出SIP应用于根际研究是今后该技术在生物降解研究中的一个发展方向。     

Chromium(III) Oxidation Coupled with Microbially Mediated Mn(II) Oxidation

Abstract

Reductive immobilization of Cr(VI) has been widely explored as a cost-effective approach for Cr-contaminated site remediation. In soils containing manganese oxides, however, the immobilized form of chromium, i.e., Cr(III), could potentially be reoxidized. In this study, batch experiments were conducted to assess whether there were any microbial processes that could accelerate Cr(III) oxidation in aerobic, manganese-containing systems. The results showed that in the presence of at least one species of manganese oxidizers, Pseudomonas putida, Cr(III) oxidation took place at low concentrations of Cr(III). About 30–50% of added Cr(III) (10–200 μ M) was oxidized to Cr(VI) within five days in the systems with P. putida and biogenic Mn oxides. The rate of Cr(III) oxidation was approximately proportional to the initial concentration of Cr(III) up to 100 μ M, but the growth of P. putida was partially inhibited by Cr(III) at 200 μ M and totally stopped when it reached 500 μ M. Cr(III) oxidation was dependent upon the biogenic formation of Mn oxides, though the oxidation rate was not directly proportional to the amount of Mn oxides formed. Chromium(III) oxidation took place through a catalytic pathway, in which the microbes mediated Mn(II) oxidation to form Mn-oxides, and Cr(III) was subsequently oxidized by the biogenic Mn-oxides.     

Anaerobic Nitrate-Dependent Iron (II) Oxidation by a Novel Autotrophic Bacterium,Citrobacter freundii Strain PXL1

Anaerobic Fe(II) Oxidizing Denitrifiers (AFODN), a type of newly found Fe(II)-oxidizing bacteria, play an important role in iron and nitrogen cycling. In the present study, a novel AFODN strain PXL1 was isolated from anaerobic activated sludge. Phylogenetic analysis of 16S rRNA gene sequence revealed similarity between this strain and Citrobactor freundii. The strain reduced 30% of nitrate and oxidized 85% of Fe(II) over 72 h with an initial Fe(II) concentration of 3.4 mM and nitrate concentration of 9.5 mM. Oxidation of iron was dependent on the reduction of nitrate to nitrite in the absence of other electron donors or acceptors. Nitrate reduction and Fe(II) oxidation followed first-order reaction kinetics. Iron oxides accumulated in the culture were analyzed by Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD) spectroscopy and scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDS). The strain recovered deposited oxidized Fe in the form of amorphous Fe oxides.     

Oxidation of malononitrile complex of pentaammineruthenium(II)

The oxidation of Ru(NH₃)₅NCCH₂CN²⁺ complex by the peroxydisulfate ion in the aqueous solution yields two products, Ru(NH₃)₅NHCOCH₂CN²⁺ with λ_max = 373 nm and withλ_max = 863 nm. The distribution of the products and the amount of oxidant required for the maximum yield of the binuclear complex depend on the acidity of the solution. The production of the binuclear complex was favored at lower acid concentrations. The formation of CC bond in the binuclear complex was characterized by both the spectral and the electrochemical results. A mechanism for the oxidation has been proposed by the kinetic studies in the region of 0.001-0.10 M acid concentrations.