Oxidation of carbaryl in aqueous solution by membrane anodic fenton treatment

Carbaryl, a commonly used insecticide, was used in this study as a probe to investigate a new Fenton treatment technology, ion exchange membrane anodic Fenton treatment (membrane AFT). It was found that the degradation kinetics of carbaryl by membrane AFT obeys a previously published AFT model quite well. The NaCl (electrolyte) concentration in two half-cells was optimized for two kinds of membrane. Effects of the H(2)O(2)/Fe(2+) ratio and the Fenton reagent delivery rate were also investigated. The treatment efficiency for anion membrane AFT is higher than for salt-bridge AFT under the same operating conditions. Decreasing the delivery rate of Fenton reagents and increasing the treatment temperature also increase the treatment efficiency. The activation energy for carbaryl degradation by anion membrane AFT was estimated to be 14.7 kJ x mol(-1). 1-Naphthol, 1,4-naphthoquinone, and (phthalic acid-O-)yl N-methylcarbamate were detected by GC-MS as the degradation products of carbaryl by Fenton treatment. No decrease in carbaryl degradation rate was found during repeated use (100 times) of the anion exchange membrane. High and stable treatment efficiency can be achieved using an anion exchange membrane rather than a salt-bridge in the AFT system. Because of its effectiveness and convenience, the use of an ion exchange membrane as a substitute for the salt-bridge used in the previous AFT system has brought the AFT technology a major step closer to practical application.     

Competitive degradation and detoxification of carbamate insecticides by membrane anodic Fenton treatment

The competitive degradation of six carbamate insecticides by membrane anodic Fenton treatment (AFT), a new Fenton treatment technology, was carried out in this study. The carbamates studied were dioxacarb, carbaryl, fenobucarb, promecarb, bendiocarb, and carbofuran. The results indicate that AFT can effectively degrade these insecticides in both single component and multicomponent systems. The carbamates compete for hydroxyl radicals, and their kinetics obey the previously developed AFT kinetic model quite well. Hydroxyl radical reaction rate constants were obtained, and they decrease in the following order: dioxacarb approximately carbaryl > fenobucarb > promecarb > bendiocarb > carbofuran. The AFT is shown to have higher treatment efficiency at higher temperature. Degradation products of the carbamates were determined by gas chromatography/mass spectrometry, and it appears that degradation can be initiated by hydroxyl radical attack at different sites in the molecule, depending on the individual structure of the compound. Substituted phenols are the commonly seen degradation products. The AFT treatment can efficiently remove the chemical oxygen demand of the carbamate mixture, significantly increasing the biodegradability. Earthworm studies show that the AFT is also an effective detoxification process.     

Modeling evaluation of carbaryl degradation in a continuously stirred tank reactor by anodic fenton treatment

Anodic Fenton treatment (AFT) has been shown to be effective in removing pesticides from aqueous solution in batch reactors with the formation of less toxic and more biodegradable products. To facilitate practical application of AFT, carbaryl degradation in a continuously stirred tank reactor (CSTR) by AFT was investigated under different experimental conditions, such as carbaryl inlet concentration, Fenton reagent concentration/ratio, and carbaryl feeding flow rate. A higher Fe2+ delivery rate and H2O2 to Fe2+ ratio (H2O2:Fe2+) were found to favor the carbaryl degradation process, whereas flow rate was shown to be a much less significant factor to influence the degradation rate under the evaluated experimental conditions. A kinetic-based semiempirical model was developed to simulate the experimental data, and a very good fit between the model and the raw data was found (R2 > 0.99). A dimensionless parameter (k/q2) was found to be a good indicator of the degradation rate; that is, the higher the k/q2value is, the faster the degradation process is. The rate parameter (k) can be used to evaluate the degradation rate when the flow rate is invariant for a given pesticide. The shape parameter (beta) is most likely related to the availability and reactivity of Fenton reagents and hydroxyl radicals. To compare the degradation rate of different pesticides, more information other than k/q2, k, and beta values, such as the instantaneous degradation rate vs time relationship, needs to be considered.     

Kinetic modeling of 2,4-dichlorophenoxyacetic acid (2,4-D) degradation in soil slurry by anodic fenton treatment

Anodic Fenton treatment (AFT) has been shown to be a promising technology in pesticide wastewater treatment. However, no research has been conducted on the AFT application to contaminated soils. In this study, the 2,4-D degradation kinetics of AFT in a silt loam soil slurry were investigated for the first time, and the effects of various experimental conditions including initial 2,4-D concentration, Fenton reagent delivery rate, amount of humic acid (HA) addition, and pH were examined. The 2,4-D degradation in soil slurry by AFT was found to follow a two-stage kinetic model. During the early stage of AFT (the first 4-5 min), the 2,4-D concentration profile followed a pseudo-first-order kinetic model. In the later stage (typically after 5 or 6 min), the AFT kinetic model provided a better fit. This result is most likely due to the existence of (*)OH scavengers and 2,4-D sorption on soil. The Fe(2+) delivery rate was shown to be a more significant factor in degradation rate than the H(2)O(2) delivery rate when the Fe(2+)/H(2)O(2) ratios were in the range of 1:2 to 1:10. The presence of HA in soil lowered the AFT rate, most probably due to the competition with 2,4-D for consumption of (*)OH and increased sorption of 2,4-D on soil. The optimal pH for 2,4-D degradation in soil slurry by AFT was observed to be in the range of pH 2-3.     

Degradation of ethylene thiourea (ETU) with three fenton treatment processes

Anodic Fenton treatment (AFT), an electrochemical, hydroxyl radical oxidation treatment system, was developed for the degradation of aqueous pesticides and other aqueous organic wastes. AFT of ethylene thiourea (ETU) was optimized and compared with electrochemical Fenton treatment (EFT) and classic Fenton treatment (CFT). ETU is a known carcinogen and is an impurity and degradation product of the widely used ethylenebisdithiocarbamate (EBDC) fungicide group. ETU was degraded effectively in all treatment methods, with CFT being the most rapid; however, significant differences in degradation product profiles were noted over the course of treatments. AFT displayed the most efficient degradation of primary degradation products of ETU.     

Adsorption of pesticides from water by functionalized organobentonites

Replacement of natural inorganic cations of clay minerals with organic cations has been proposed as a strategy to improve the adsorptive capacity of clay minerals for organic compounds, including pesticides. The organic cations most commonly used for this purpose have been quaternary ammonium ions containing alkyl or aryl chains without specific functional groups. In this work, we evaluated the ability of two bentonites (SWy-2 and SAz-1) exchanged with four natural organic cations containing diverse functional groups (L-carnitine, L-cysteine ethyl ester, L-cystine dimethyl ester, and thiamine) as adsorbents of pesticides varying in their chemical structures (simazine, hexazinone, triadimefon, alachlor, carbaryl, and imazethapyr). For comparison purposes, the adsorptive properties of two "classical" organobentonites, hexadecyltrimethylammonium- and phenyltrimethylammonium-exchanged bentonites, were also determined. Most organobentonites displayed higher affinity for the pesticides than the untreated bentonites, but the improvement in adsorption capacity varied depending on the characteristics of the pesticide and the interlayer organic cation. Triadimefon, carbaryl, and imazethapyr displayed the highest affinity for carnitine (K(f) = 229-2377)-, thiamine (K(f) = 83-354)-, and cystine (K(f) = 96-100)-treated bentonites, respectively, whereas alachlor was adsorbed similarly by all organobentonites. In general, pesticide adsorption-desorption hysteresis was greater for adsorbents with the highest adsorption capacities. The results demonstrate that selective modification of smectitic clay minerals with natural organic cations containing appropriate functional groups can be a useful strategy to improve their performance for the removal of specific pesticides from the environment.     

Degradation of chloroacetanilide herbicides by anodic fenton treatment

Anodic Fenton treatment (AFT) is an electrochemical treatment employing the Fenton reaction for the generation of hydroxyl radicals, strong oxidants that can degrade organic compounds via hydrogen abstraction. AFT has potential use for the remediation of aqueous pesticide waste. The degradation rates of chloroacetanilides by AFT were investigated in this work, which demonstrates that AFT can be used to rapidly and completely remove chloroacetanilide herbicides from aqueous solutions. Acetochlor, alachlor, butachlor, metolachlor, and propachlor were treated by AFT, and parent compound concentrations were analyzed over the course of the treatment time. Degradation curves were plotted and fitted by the AFT kinetic model for each herbicide, and AFT model kinetic parameters were used to calculate degradation rate constants. The reactivity order of these five active ingredients toward hydroxyl radical was acetochlor approximately metolachlor > butachlor approximately alachlor > propachlor. Treatment of the chloroacetanilides by AFT removed the parent compounds but did not completely mineralize them. However, AFT did result in an increase in the biodegradability of chloroacetanilide aqueous solutions, as evidenced by an increase in the 5-day biochemical oxygen demand to chemical oxygen demand ratio (BOD5/COD) to >0.3, indicating completely biodegradable solutions. Several degradation products were formed and subsequently degraded, although not always completely. Some of these were identified by mass spectral analyses. Among the products, isomers of phenolic and carbonyl derivatives of parent compounds were common to each of the herbicides analyzed. More extensively oxidized products were not detected. Degradation pathways are proposed for each of the parent compounds and identified products.     

Synthesis of highly intercalated urea-clay nanocomposite via domestic montmorillonite as eco-friendly slow-release fertilizer

The present study describes the preparation and characterization of montmorillonite-urea nanocomposites (Mt-Ur) using aqueous suspension technique at various stirring times and different ratio of montmorillonite to urea (Mt/Ur) via an impure and domestic montmorillonite (Mt), without the application of any chemical reagents and high-energy-demand process (environmentally friendly). The intercalation of urea into Mt interlayer was clearly demonstrated by a significant expansion of d₀₀₁ spacing (interlayer space of Mt) from 1.23 to 1.71 nm which has not yet been reported by aqueous suspension technique. Analyses performed by Fourier transform-infrared spectroscopy (FT-IR), Thermogravimetric analysis (TGA) and X-ray diffraction (XRD) also confirmed the effectiveness of this simple process to intercalate the urea into clay lamella. The release pattern demonstrated that the nanocomposite had a slow-release behaviour for urea dissolution. The results also suggested that the Mt type applied in the current study, in a 1:20 Mt/Ur ratio and stirred for 1 h, possessed desirable ecological and economic efficiency in the production of slow-release urea fertilizer due to the application of the impure and domestic clay which is of very low-cost and eco-friendly. Nevertheless, urea was fully intercalated into the interlayer of clay by a simple technique and with a good slow-release behaviour.     

Aspects of the adsorption of pirimicarb by smectites and soils

A study was conducted to examine the adsorption and interaction mechanism of pirimicarb with smectites and soils. Studies were carried out in pesticide-smectite or soil-water systems and in pesticide-smectite-organic solvent systems, using homoionic samples of montmorillonite, smectites of different layer charge and soils with smectite in their clay fraction. The adsorption isotherms obtained at 30° and 45°C follow the empirical equation of Freundlich. In the adsorption of the pesticide by soils a highly significant correlation was seen between adsorption (distribution coefficient) and the content of smectite in them. In the studies in organic medium the formation of a smectite-pirimicarb bilayer complex with a basal d₀₀₁ spacing of 18.55 Å was observed; the formation of this is also related to the nature of the interlayer cation and the layer charge of the smectite. According to the I.R. results, the interlayer cations of the silicate and the oxygen atom of the C–O group of the pesticide molecule are involved in the interaction mechanism.     

THE INTERACTION OF PARAQUAT (1: 1'-DIMETHYL 4:4'-DIPYRIDYLIUM DICHLORIDE) WITH MINERAL SOILS

Investigation of the adsorption of 1:1′-dimethyl 4:4′-dipyridylium (paraquat) dichloride by a range of soils, using a solution-equilibration technique, has shown that the adsorption is characterized by three factors: 1. Up to a limiting value, defined as the Strong Adsorption Capacity (SAC), the solution concentration of paraquat is reduced below the level of chemical detection by suspended soil: this strongly adsorbed paraquat is preferentially held against 0.1 to 2.0N solutions of ammonium ion. A range of strengths of adsorption probably exists within the strong adsorption range, but the greater part of the strongly adsorbed material is de-activated herbicidally; this accounts for the herbicidal de-activation of paraquat in soils. 2. Removal of soil organic matter by treatment with hydrogen peroxide usually does not greatly change the SAC. Strong adsorption of paraquat is primarily a property of clay minerals, and the presence of expanding lattice minerals is of particular importance. 3. For fortifications above the strong adsorption region, there is a region of weaker adsorption but the total adsorption capacities of soils at saturation are less than their cation exchange capacities for inorganic cations. Taken with the difficulty of displacement, this indicates that the adsorption of paraquat is strongly influenced by factors other than simple electrostatic interaction.     

Potential contributions of smectite clays and organic matter to pesticide retention in soils.

Soil organic matter (SOM) is often considered the dominant sorptive phase for organic contaminants and pesticides in soil-water systems. This is evidenced by the widespread use of organic-matter-normalized sorption coefficients (K(OM)) to predict soil-water distribution of pesticides, an approach that ignores the potential contribution of soil minerals to sorption. To gain additional perspective on the potential contributions of clays and SOM to pesticide retention in soils, we measured sorption of seven pesticides by a K-saturated reference smectite clay (SWy-2) and SOM (represented by a muck soil). In addition, we measured the adsorption of atrazine by five different K-saturated smectites and Ca-saturated SWy-2. On a unit mass basis, the K-SWy-2 clay was a more effective sorbent than SOM for 4,6-dinitro-o-cresol (DNOC), dichlobenil, and carbaryl of the seven pesticides evaluated, of which, DNOC was sorbed to the greatest extent. Atrazine was sorbed to a similar extent by K-SWy-2 and SOM. Parathion, diuron, and biphenyl were sorbed to a greater extent by SOM than by K-SWy-2. Atrazine was adsorbed by Ca-SWy-2 to a much lesser extent than by K-SWy-2. This appears to be related to the larger hydration sphere of Ca(2+) (compared to that of K(+)) which shrinks the effective size of the adsorption domains between exchangeable cations, and which expands the clay layers beyond the apparently optimal spacing of approximately 12.2 A for sorption of aromatic pesticide structures. Although a simple relation between atrazine adsorption by different K-smectites and charge properties of clay was not observed, the highest charge clay was the least effective sorbent; a higher charge density would result in a loss of adsorption domains. These results indicate that for certain pesticides, expandable soil clays have the potential to be an equal or dominant sorptive phase when compared to SOM for pesticide retention in soil.     

Thermospectroscopic study of the adsorption mechanism of the hydroxamic siderophore ferrioxamine B by calcium montmorillonite

The behavior of iron-chelating agents in soils is highly affected by interactions with the solid phase. Still this aspect is frequently ignored. In this research the adsorption of the siderophore ferrioxamine B by Ca-montmorillonite, as a free ligand (desferrioxamine B, DFOB) and as a complex with Fe3+ (ferrioxamine B, FOB), was studied, using thermo X-ray diffraction (thermo-XRD) in the temperature range 25-360 degrees C and thermo-FTIR spectroscopy in the temperature range 25-170 degrees C. The effect of pH (4-7.5) on the adsorption was examined. Extensive use of curve-fitting analysis was required due to significant overlapping of the characteristic absorption bands of the various functional groups. Thermo-XRD analysis showed that both DFOB and FOB penetrated into the interlayer space of Ca-montmorillonite. FTIR results indicated strong interactions of DFOB within the interlayer, which involved all functional groups (NH3+, secondary amide groups, and hydroxamate groups). In contrast, the folded Fe complex of FOB retained its molecular configuration upon adsorption, and the basal spacing of the clay increased correspondingly. FOB interacted in the interlayer space of the clay, mainly through the NH of the secondary amide groups and NH3+, while the functional groups bound to the central Fe cation remained unchanged. The suspension pH had no significant effect on both DFOB and FOB adsorption at the examined range. Adsorption protected the adsorbates from thermal degradation compared to the nonadsorbed samples up to 105 degrees C. At 170 degrees C both DFOB and FOB were already partially degraded, but to a lesser extent than the nonadsorbed samples. Degradation of the molecules occurred mainly through the hydroxamic groups, which constitute the Fe-chelating center in the hydroxamic siderophore.     

INTERACTION OF BTPYRIDYLIUM HERBICIDES WITH ORGANO-CLAY COMPLEX

The adsorption of diquat (1,1′-ethylene-2,2′-bipyridylium dibromide) and paraquat (1, 1′-dimethyl-4,4′-dipyridylium dichloride) by an organo-clay complex has been investigated. Paraquat was adsorbed by the organo-clay complex in greater amounts than was diquat. Infrared studies suggest the formation of charge-transfer complexes between diquat or paraquat and the organo-clay complex. Organic matter upon interaction with clay may facilitate the adsorption of diquat and paraquat on clay minerals in soil.     

A method for preventing the rehydration of heated smectites during X‐ray diffraction analysis

Abstract

Heating samples of clays to various temperatures is a common pretreatment for identification of clay minerals by X‐ray diffraction (XRD). The exchangeable cations in the interlayer region of smectitic clays can rehydrate when the sample is cooled after the heat treatments. Because the basal spacings (d(001)) of smectites are a function of the hydration state of the interlayer cations, they can be easily misinterpreted if the hydration state is not controlled during the XRD analysis. In this report a method for preventing the rehydration of interlayer cations during XRD analysis is described, and its effectiveness is demonstrated on selected samples of clays.     

Effect of forage crop establishment on dissolved organic carbon dynamics and leaching in a hill country soil

Intensive agricultural activities could affect the dynamics and leaching of dissolved organic carbon (DOC) and nitrate from agricultural soils to receiving waters. This study investigated soil DOC dynamics immediately (0–12 days) after spraying a hill country perennial pasture with agrochemicals to establish a winter forage crop for supplementary feed production. Two treatments were examined—perennial pasture (without agrochemicals) and swede (Brassica napobrassica Mill.) cropping (after spraying with agrochemicals), both growing on a Typic Eutrudept. Soil samples were collected from various depths down to 1 m, before the application of agrochemicals (day 0) and 1, 6 and 12 days thereafter. Dissolved organic carbon concentration below the surface soil (<5 cm) was generally not altered by the agrochemicals. This was further proved by the isotopic monitoring of DOC leaching on this soil. Conversely, the agrochemicals significantly (p = 0.03) increased DOC concentration within the 0–5‐cm soil depth on day 1, due to the direct contribution of organic molecules and/or displacement of organic compounds at adsorption sites by the agrochemicals; and on day 6, due to root necromass decomposition. The increase of nitrate in soil solution at this depth (0–5 cm) on days 6 and 12 suggests that the agrochemicals may have also enhanced nitrogen (N) mineralization in the surface soil. However, the significantly (p = 0.04) higher DOC/nitrate (molar ratio) of the agrochemical treatment suggests that the agrochemicals used for clearing out pasture before forage crop establishment could lead to a short‐term increase in surface soil denitrification.     

有机酸对高岭石, 针铁矿和水铝英石吸附镉的影响

Effects of organic acids （oxalic, acetic, and citric） on adsorption characteristics of Cadmium （Cd） on soil clay minerals （kaolinite, goethite, and bayerite） were studied under different concentrations and different pH values. Although the types of organic acids and minerals were different, the effects of the organic acids on the adsorption of Cd on the minerals were similar, i.e., the amount of adsorbed Cd with an initial solution pH of 5.0 and initial Cd concentration of 35 mg L^-1 increased with increasing concentration of the organic acid in solution at lower concentrations, and decreased at higher concentrations. The percentage of Cd adsorbed on the minerals in the presence of the organic acids increased considerably with increasing pH of the solution. Meanwhile, different Cd adsorption in the presence of the organic acids, due to different properties on both organic acids and clay minerals, on kaolinite, goethite, or bayerite for different pHs or organic acid concentrations was found.     

虱螨脲在土壤中的降解、吸附和移动特性

采用室内模拟试验方法,研究了虱螨脲在3种土壤中的降解、吸附和移动特性。结果表明：25℃下,虱螨脲在江西红壤中的降解半衰期为101d,属于中等降解农药;在太湖水稻土和东北黑土中的降解半衰期分别为74.5d和55.5d,属于较易降解农药。土壤有机质含量是影响虱螨脲降解速率的主要因素;3种土壤对虱螨脲具有较强的吸附性,且土壤有机质含量越高,对虱螨脲的吸附性越强;3种土壤对虱螨脲的吸附自由能变化均小于40kJ·mol^-1,属于物理吸附;虱螨脲在土壤中不易移动,正常条件下不会造成地下水的污染。     

Mutual influence of copper and paraquat on their adsorption in soil

Paraquat and copper (Cu) are commonly used and detected in soil.Therefore,it is important to understand their mobility in the environment.In this study,the competitive effects of paraquat and Cu on their adsorption in five representative Chinese soils were investigated using batch adsorption equilibrium experiments and spectroscopic analysis.The results showed that the adsorption of paraquat in soil varied with soil type and was positively correlated with both soil cation exchange capacity and o...     

Towards Establishing the Age,Location, and Identity of the Inert Soil Organic Matter of a Spodosol

An interlayer clay-organic complex has been isolated from a near-surface horizon of a recent Spodosol from New Zealand. Treatment with hydrogen peroxide selectively removed the organic material attached to external clay surfaces. The radiocarbon age of the treated complex, determined by accelerator mass spectrometry, was 6716 ± 524 years B.P. Since this value refers to the interlayer organic species which has been completely protected against microbial attack, and contamination by “young” carbon, it may be regarded as the “true” age of the soil, that is, the starting point of humus formation and pedogenesis. The interlayer organic carbon comprised approximately 13 percent of the total carbon in the soil horizon. We propose that a biologically inert organic matter (IOM) fraction may be isolated from most soils as this fraction is commonly associated with clay-size particles. Evidence is also accumulating to indicate that IOM is dominantly composed of polymethylenic structures, probably derived from natural waxes, and aliphatic biopolymers present in protective layers of vascular plants.     

Isotopic evidence and quantification assessment of in situ RDX biodegradation in the deep unsaturated zone

Hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) is an explosive compound whose extensive use has resulted in significant contamination of soils and groundwater worldwide. We studied its in situ biodegradation along the unsaturated zone beneath an explosives wastewater lagoon using compound-specific isotope analysis (CSIA) of RDX in the unsaturated zone, together with biodegradation slurry experiments under anaerobic conditions. We found the highest degradation potential of RDX and its nitroso derivatives in the upper part of the soil profile while in the lower parts, RDX-degradation potential was lower and the nitroso derivatives tended to persist. This was also observed in the field, as reflected by the isotopic composition of RDX along the profile. We also found a correlation between biodegradation potential and clay content: biodegradation was further enhanced in layers characterized by high-clay content or in those influenced by the high-clay layers. In addition, in the presence of high organic matter content, further enhancement of biodegradation was observed. We obtained different isotopic enrichment factors (?) for RDX biodegradation in different sections of the unsaturated profile and suggest that different degradation pathways exist simultaneously in situ, in variable proportions. Using the range of enrichment factors, we were able to assess the biodegradation extent of RDX at different sampling points along the profile, which ranged between 30 and 99.4%. The novel application of CSIA together with slurry experiments provides better insight into degradation processes that are otherwise difficult to detect and assess.