Pesticide bioconcentration modelling for fruit trees

The model presented allows simulating the pesticide concentration evolution in fruit trees and estimating the pesticide bioconcentration factor in fruits. Pesticides are non-ionic organic compounds that are degraded in soils cropped with woody species, fruit trees and other perennials. The model allows estimating the pesticide uptake by plants through the water transpiration stream and also the time in which maximum pesticide concentration occur in the fruits. The equation proposed presents the relationships between bioconcentration factor (BCF) and the following variables: plant water transpiration volume (Q), pesticide transpiration stream concentration factor (TSCF), pesticide stem-water partition coefficient (K(Wood,W)), stem dry biomass (M) and pesticide dissipation rate in the soil-plant system (k(EGS)). The modeling started and was developed from a previous model "Fruit Tree Model" (FTM), reported by Trapp and collaborators in 2003, to which was added the hypothesis that the pesticide degradation in the soil follows a first order kinetic equation. The FTM model for pesticides (FTM-p) was applied to a hypothetic mango plant cropping (Mangifera indica) treated with paclobutrazol (growth regulator) added to the soil. The model fitness was evaluated through the sensitivity analysis of the pesticide BCF values in fruits with respect to the model entry data variability.     

Effects of dissolved oxygen and iron aging on the reduction of trichloronitromethane, trichloracetonitrile, and trichloropropanone

Iron metal (Fe(0)) is a potent reductant capable of reducing a wide variety of halogenated organic compounds including disinfection byproducts (DBPs). These reduction reactions may play a role in DBP fate in iron water mains and potentially could be exploited to remove DBPs from drinking water or wastewater in a packed-bed configuration. Oxidants (i.e., dissolved oxygen (DO) and chlorine) present in the water, however, may decrease the DBP degradation rate by competing for reactive sites and rapidly aging or corroding the iron surface. Thus, batch experiments were performed to investigate the effect of DO on the degradation rates of selected DBPs by Fe(0). Experiments were performed under anaerobic conditions, in initially oxygen saturated buffer without DO control, and under controlled DO (approximately 4.0 or 8.0 mg l⁻¹) conditions. The effect of short-term (25–105 min) iron aging in DO-containing buffer on DBP degradation rate also was investigated in separate experiments. For fresh Fe(0), the degradation rates of trichloronitromethane (TCNM) and trichloroacetonitrile (TCAN) in initially oxygen saturated buffer were similar to their respective rates under anaerobic conditions. The degradation rate of 1,1,1-trichloropropanone (1,1,1-TCP), however, decreased significantly in the presence of DO and the effect was proportional to DO concentration in the controlled DO experiments. For a DO concentration of 4 mg l⁻¹, the degradation rate of the three DBPs was greater for longer aging times as compared to their respective rates after 25 min, suggesting the formation of a mineral phase that increased reactivity. For a DO concentration of 8 mg l⁻¹, the effects of increasing aging time were mixed. TCNM degradation rates were stable for all aging times and comparable to that under anaerobic conditions. The TCAN and 1,1,1-TCP degradation rates, however, tended to decrease with increasing aging time. These results suggest that the reduction of highly reactive DBPs by Fe(0) will not be affected by the presence of DO but that the reaction rates will be slowed by DO for DBPs with slower degradation kinetics.     

Formation of disinfection by-products in chlorinated swimming pool water.

The formation of five volatile disinfection by-products (DBPs: chloroform, bromodichloromethane, chloral hydrate, dichloroacetonitrile, and 1,1,1-trichloropropanone) by the chlorination of the materials of human origin (MHOs: hair, lotion, saliva, skin, and urine) in a swimming pool model system was examined. Chlorination reactions took place with a sufficient supply of chlorine residuals (0.84 mg Cl2/l < total chlorine < 6.0 mg Cl2/l) in 300 ml glass bottles containing either ground water or surface water as a reaction medium at 30 degrees C and pH 7.0, for either 24 or 72 h. A longer reaction period of 72 h or a higher content of organic materials led to the increased formation of DBPs. Of the DBPs formed by the reaction, chloroform was a major compound found in both ground and surface waters. The formation of chloroform and bromodichloromethane per unit total organic carbon (TOC) concentration was suppressed when all types of MHOs were added to the surface water that already contained DBP precursors such as humic substances. However, the formation of dichloroacetonitrile was promoted, probably due to the increased degradation reactions of nitrogen-containing compounds such as urea and proteins of human origin. In conclusion, the materials of swimmers' origin including hair, lotion, saliva, skin, and urine add to the levels of DBPs in swimming pool water, and any mitigation measures such as periodic change of water are needed to protect swimmers from elevated exposures to these compounds.     

Reductive dechlorination of chlorinated methanes and ethanes by reduced iron (II) porphyrins

The reaction of a reduced iron (II) porphyrin with a series of chlorinated methanes and ethanes was examined under neutral conditions in buffered aqueous solutions containing an excess of the reducing agent. Carbon tetrachloride, chloroform and 1,1,1-trichloroethane were reduced to lower chlorinated homologs, while methylene chloride, 1,1,2-trichloroethane and 1,1-dichloroethane did not appear to be degraded in this system.     

The reductive degradation of 1,1,1-trichloroethane by Fe(0) in a soil slurry system

Most studies on the treatment of chlorinated contaminants by Fe(0) focus on aqueous system tests. However, few is known about the effectiveness of these tests for degrading chlorinated contaminants such as 1,1,1-trichloroethane (TCA) in soil. In this work, the reductive degradation performance of 1,1,1-TCA by Fe(0) was thoroughly investigated in a soil slurry system. The effects of various factors including acid-washed iron, the initial 1,1,1-TCA concentration, Fe(0) dosage, slurry pH, and common constituents in groundwater and soil such as Cl^?, HCO₃ ^?, SO₄ ^2?, and NO₃ ^? anions and humic acid (HA) were evaluated. The experimental results showed that 1,1,1-TCA could be effectively degraded in 12 h for an initial Fe(0) dosage of 10 g L^?1 and a soil/water mass ratio of 1:5. The soil slurry experiments showed two-stage degradation kinetics: a slow reaction in the first stage and a fast reductive degradation of 1,1,1-TCA in the second stage. The reductive degradation of 1,1,1-TCA was expedited as the mass concentration of Fe(0) increased. In addition, high pHs adversely affected the degradation of 1,1,1-TCA over a pH range of 5.4–8.0 and the reductive degradation efficiency decreased with increasing slurry pH. The initial 1,1,1-TCA concentration and the presence of Cl^? and SO₄ ^2? anions had negligible effects. HCO₃ ^? anions had a accelerative effect on 1,1,1-TCA removal, and both NO₃ ^? and HA had inhibitory effects. A Cl^? mass balance showed that the amount of Cl^? ions released into the soil slurry system during the 1,1,1-TCA degradation increased with increasing reaction time, suggesting that the main degradation mechanism of 1,1,1-TCA by Fe(0) in a soil slurry system was reductive dechlorination with 1,1-DCA as the main intermediate. In conclusion, this study provides a theoretical basis for the practical application of the remediation of contaminated sites containing chlorinated solvent.     

Biostimulation and bioaugmentation enhances aerobic biodegradation of dichloroethenes

The accumulation of dichloroethenes (DCEs) as dominant products of microbial reductive dechlorination activity in soil and water represent a significant obstacle to the application of bioremediation as a remedial option for chloroethenes in many contaminated systems. In this study, the effects of biostimulation and/or bioaugmentation on the biodegradation of cis- and trans-DCE in soil and water samples collected from contaminated sites in South Africa were evaluated in order to determine the possible bioremediation option for these compounds in the contaminated sites. Results from this study indicate that cis- and trans-DCE were readily degraded to varying degrees by natural microbial populations in all the soil and water samples tested, with up to 44% of cis-DCE and 41% of trans-DCE degraded in the untreated soil and water samples in two weeks. The degradation rate constants ranged significantly (P<0.05) between 0.0938 and 0.560 wk(-1) and 0.182 and 0.401 wk(-1), for cis- and trans-DCE, respectively, for the various treatments employed. A combination of biostimulation and bioaugmentation significantly increased the biodegradation of both compounds within two weeks; 14% for cis-DCE and 18% for trans-DCE degradation, above those observed in untreated soil and water samples. These findings support the use of a combination of biostimulation and bioaugmentation for the efficient biodegradation of these compounds in contaminated soil and water. In addition, the results clearly demonstrate that while naturally occurring microorganisms are capable of aerobic biodegradation of cis- and trans-DCE, biotransformation may be affected by several factors, including isomer structure, soil type, and the amount of nutrients available in the water and soil.     

The rate of degradation of 1,1,1-trichloroethane in water by hydrolysis and dehydrochlorination

Degradation of 1,1,1-trichloroethane in water by hydrolysis and dehydrochlorination may conceivably be a significant sink for this compound in the environment. The kinetics of these reactions have therefore been investigated over a wide range of temperature. The half-life at 20 °C is found to be 1.7 years.     

Influence of dispersants on bioconcentration factors of seven organic compounds with different lipophilicities and structures

Seven compounds with different lipophilicities and structures—1,3,5-trichlorobenzene, pentachlorobenzene, acenaphthylene, 1,4-dimethyl-2-(1-methylphenyl)benzene, 4-ethylbiphenyl, 4,4′-dibromobiphenyl, and 1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane—were subjected to bioconcentration tests in carp at concentrations below the water solubilities of the compounds in the presence or absence of a dispersant (either an organic solvent or a surfactant). The bioconcentration factors (BCFs) of the compounds were on the order of 10²–10⁴. The BCF values remained in the range of 15–49% for all the compounds, whether or not a dispersant was present, i.e., the BCF values in the presence of an organic solvent or a surfactant at a concentration below the critical micelle concentration were not significantly smaller than the BCF values in the absence of the solvent or surfactant. This result indicates that the dispersants had no influence on the evaluation of the bioconcentration potential of these test substances.     

Efficient removal of triphenylmethane dyes from aqueous medium by in situ electrogenerated Fenton's reagent at carbon-felt cathode

Fenton's reagent (Fe2+ +H2O2) has been electrogenerated in situ in an undivided electrolytic cell from the effective reduction of Fe3+ and O2 at carbon-felt cathode for the treatment of aqueous solutions of four triphenylmethane dyes (TPMs), namely malachite green (MG), crystal violet (CV), methyl green (MeG) and fast green FCF (FCF), at pH 3.0 and room temperature. MG has been used as a model among them to study the influence of some experimental parameters on the decay kinetics, COD removal and current efficiency. The results in such electro-Fenton system are explained in terms of the many parasitic reactions involving .OH. Higher efficiency values are obtained with rising organic content and decreasing applied current. The first stage of the mineralization process, involving aromatic by-products, leads to fast decoloration as well as quick initial COD removal that fit well to a pseudo-first-order kinetics. At prolonged electrolysis time, the mineralization rate and efficiency decrease due to the formation of hardly oxidizable compounds and the enhancement of wasting reactions. Solutions of all four TPMs are quickly degraded following a pseudo-first-order decay kinetics. The absolute rate constant (kTPM) for their reaction with .OH increases in the order MeG相似文献   

Correlations between experimental and predicted equilibrium distribution coefficient of chlorobenzene and chlorophenol compounds in soil-water systems using partial solubility parameters

Many pesticides are degraded to become chlorinated aromatic compounds in soils. Equilibrium distribution of chlorobenzene and chlorophenol compounds in soil-water systems of Yangmingshan loam, Pingcheng silty clay loam and Annei silty loam was studied with the integral distribution equilibrium equation involving the partial solubility parameters of the chemicals. If the adsorption of chemicals on soils is partitioning in soil organic matter surrounding the soil mineral particles, the absorption constant (Kd) of a chemical in soil-water system could be stated as the distribution coefficient (or partition constant, Koc) of the chemical in the two adjunct immiscible phases--water and soil organic matter. The distribution coefficient (Koc) of chemicals calculated from the integral distribution equilibrium equation agrees well with the experimental adsorption coefficient (Kd, or experimental Koc) of chemicals determined in this study, for all the three different types of soils in water according to multiple-regression analysis. Reference data of Karger or Tijssen are employed to estimate the Koc for both polar and non-polar chemicals. The integral distribution equilibrium equation can exactly describe the distribution behavior of nonionic compound of chlorobenzenes and chlorophenols in soil-water systems.     

Investigation of the behaviour of haloketones in water samples

The behaviour of the haloketones (HKs) 1,1-Dichloropropanone (1,1-DCP), 1,1,1-Trichloropropanone (1,1,1-TCP) and 1,3-Dichloropropanone (1,3-DCP) in ultrapure water solutions and in fortified drinking water samples was investigated. Their concentrations were determined at regular time intervals by the use of a gas chromatography-electron capture detector (GC-ECD) method. Two different temperatures were studied. The results have shown that HKs decompose both in ultrapure water solutions and in drinking water samples. The decomposition rates are higher in the drinking water samples, especially at higher temperature. 1,1,1-TCP is the compound which decomposes fastest followed by 1,3-DCP and 1,1-DCP. Chloroform was formed both in the ultrapure water solutions and in the drinking water samples, probably due to the decomposition of 1,1,1-TCP. In the drinking water samples, formation of chloral hydrate was also observed.     

Bio-beads with immobilized anaerobic bacteria,zero-valent iron,and active carbon for the removal of trichloroethane from groundwater

Chlorinated hydrocarbons are the most common organic pollutants in groundwater systems worldwide. In this study, we developed bio-beads with immobilized anaerobic bacteria, zero-valent iron (ZVI), and activated carbon (AC) powder and evaluated their efficacy in removing 1,1,1-trichloroethane (TCA) from groundwater. Bio-beads were produced by polyvinyl alcohol, alginate, and AC powder. We found that the concentration of AC powder used significantly affected the mechanical properties of immobilized bio-beads and that 1.0 % (w/v) was the optimal concentration. The bio-beads effectively degraded TCA (160 mg L^?1) in the anaerobic medium and could be reused up to six times. The TCA degradation rate of bio-beads was 1.5 and 2.3 times greater, respectively, than ZVI + AC treatment or microbes + AC treatment. Measuring FeS produced by microbial reactions indicated that TCA removal occurred via FeS-catalyzed dechlorination. Analysis of clonal libraries derived from bio-beads demonstrated that the dominant species in the community were Betaproteobacteria and Gammaproteobacteria, which may contribute to the long-term stability of ZVI reactivity during TCA dechlorination. This study shows that the combined use of immobilized anaerobic bacteria, ZVI, and AC in bio-beads is effective and practical for TCA dechlorination and suggests they may be applicable towards developing a groundwater treatment system for the removal of TCA.     

Biodegradation of phenol and phenol-related compounds by psychrophilic and cold-tolerant alpine yeasts

We characterized 32 cold-adapted, psychrophilic and cold-tolerant, yeast strains isolated from alpine habitats with regard to their taxonomy, growth temperature profile, and ability to degrade phenol and 18 phenol-related mono-aromatic compounds at 10 degrees C. Twenty of the strains were identified by sequencing of the ribosomal ITS region as seven species of the basidiomycota: Cryptococcus terreus (three strains), Cryptococcus terricola (one strain), Rhodosporidium lusitaniae (two strains), Rhodotorula creatinivora (10 strains), Rhodotorula ingeniosa (one strain), Mastigobasidium intermedium (one strain), and Sporobolomyces roseus (two strains). Twelve strains sharing closely related ITS sequences could not be identified to the species level; according to their ITS sequence they are included in the Microbotryomycetidae. These 12 strains were psychrophilic (no growth at temperatures above 20 degrees C); one-third of these strains did not grow above 15 degrees C. None of the 32 strains utilized any of the highly volatile mono-aromatic compounds (benzene, toluene, ethylbenzene, nitrobenzene, o-xylene, m-xylene, and p-xylene) as the sole carbon source. Non/low volatile aromatic compounds were degraded in the following order: phenol>hydroquinone>resorcinol>benzoate>catechol>salicylate>p-cresol>m-cresol. o-Cresol, guaiacol, p-nitrophenol, or p-nitrotoluene were not utilized for growth. R. creatinivora strains degraded up to seven compounds, whereas C. terricola and S. roseus strains degraded only two compounds. The toxicity of the compounds was determined via growth inhibition in the presence of toxicants and nutrients at 10 degrees C. R. creatinivora strains were characterized by higher IC50 values than other species, S. roseus was the most sensitive species. The most toxic compounds were the xylene isomers, ethylbenzene, p-nitrophenol, and m-cresol. There was a relation between the chemical structure of the compounds and their toxicity, whereas a relation between the toxicity of the compounds and the ability of the yeasts strains to utilize these compounds for growth was only detected in some cases.     

Toxicity to medaka of solutions of fenitrothion degraded by strong alkali

Various experiments were conducted to examine the effects of degradation products on organisms. Fenitrothion (MEP) emulsions adjusted to pH 10 or 14 were degraded by exposure to natural sunlight in winter with heat. Medaka eggs were exposed to various concentrations of the degraded solutions and an untreated MEP emulsion for 5 days starting 4-5 h following fertilisation. The eggs were then allowed to develop in dechlorinated tap water until the fish reached 3 months of age. The hatching rate and rate of survival in the degraded solutions tended to be lower than those in the untreated MEP emulsion, and the incidence of abnormal fry in the degraded solutions was higher than that of the untreated MEP emulsion. It thus appears that degradation products formed by MEP have toxic effects on medaka.     

Electrochemical oxidation of nitrogen-heterocyclic compounds at boron-doped diamond electrode

Nitrogen-heterocyclic compounds (NHCs) are toxic and bio-refractory contaminants widely spread in environment. This study investigated electrochemical degradation of NHCs at boron-doped diamond (BDD) anode with particular attention to the effect of different number and position of nitrogen atoms in molecular structure. Five classical NHCs with similar structures including indole (ID), quinoline (QL), isoquinoline (IQL), benzotriazole (BT) and benzimidazole (BM) were selected as the target compounds. Results of bulk electrolysis showed that degradation of all NHCs was fit to a pseudo first-order equation. The five compounds were degraded with the following sequence: ID > QL > IQL > BT > BM in terms of their rates of oxidation. Quantum chemical calculation was combined with experimental results to describe the degradation character of NHCs at BDD anode. A linear relationship between degradation rate and delocalization energy was observed, which demonstrated that electronic charge was redistributed through the conjugation system and accumulated at the active sites under the attack of hydroxyl radicals produced at BDD anode. Moreover, atom charge was calculated by semi empirical PM3 method and active sites of NHCs were identified respectively. Analysis of intermediates by GC-MS showed agreement with calculation results.     

The California TEAM study: Breath concentrations and personal exposures to 26 volatile compounds in air and drinking water of 188 residents of Los Angeles,Antioch, and Pittsburg,CA

The U.S. EPA carried out a study of personal exposures to 26 volatile organic chemicals in the air, drinking water, and exhaled breath of 188 California residents in 1984. Sixteen chemicals were often found above quantifiable limits in the personal air samples, but only the four trihalomethanes were often found in drinking water. The highest exposures were to 1,1,1-trichloroethane, para-dichlorobenzene, xylenes, benzene, and tetrachloroethylene. Indoor air concentrations generally exceeded outdoor air concentrations, particularly at the higher percentiles. Breath concentrations of eight chemicals showed significant correlations with preceding personal air concentrations in the two visits to Los Angeles. Smoking, employment, and automobile-related activities were identified as important sources of personal exposure to a number of target compounds.     

Enzymatic degradation of anthracene, dibenzothiophene and pyrene by manganese peroxidase in media containing acetone

The high hydrophobicity of polycyclic aromatic hydrocarbons (PAHs) greatly hamper their degradation in liquid media. The use of an organic solvent can assist the degradative action of ligninolytic enzymes from white rot fungi. The enzymatic action of the enzyme manganese peroxidase (MnP) in media containing a miscible organic solvent, acetone (36% v/v), was evaluated as a feasible system for the in vitro degradation of three PAHs: anthracene, dibenzothiophene and pyrene. These compounds were degraded to a large extent after a short period of time (7, 24 and 24h, respectively), at conditions maximizing the MnP-oxidative system. The initial amount of enzyme present in the reaction medium was determinant for the kinetics of the process. The order of degradability, in terms of degradation rates was as follows: anthracene>dibenzothiophene>pyrene. The intermediate compounds were determined using gas chromatography-mass spectrometry and the degradation mechanisms were proposed. Anthracene was degraded to phthalic acid. A ring cleavage product of the oxidation of dibenzothiophene, 4-methoxybenzoic acid, was also observed.     

Fe(3+)- and Cu(2+)-reduction by phenol derivatives associated with Azure B degradation in Fenton-like reactions

Several phenol derivatives were evaluated regarding their capacities for Fe(3+) and Cu(2+) reduction. Selected compounds were assayed in Fenton-like reactions to degrade Azure B. 3,4-Dihydroxyphenylacetic, 2,5-dihydroxyterephtalic, gallic, chromotropic and 3-hydroxyanthranilic acids were the most efficient reducers of both metallic ions. The reaction system composed of 3-hydroxyanthranilic acid/Fe(3+)/H(2)O(2) was able to degrade Azure B at higher levels than the conventional Fenton reaction (87% and 75% of decolorization after 20min reaction, respectively). Gallic and syringic acids, catechol and vanillin induced Azure B degradations at lower levels as compared with conventional Fenton reaction. Azure B was not degraded in the presence of 10% (v/v) methanol or ethanol, which are OH radical scavengers, confirming the participation of this radical in the degradation reactions. Iron-containing reactions consumed substantially more H(2)O(2) than reactions containing copper. In iron-containing reactions, even the systems that caused a limited degradation of the dye consumed high concentrations of H(2)O(2). On the other hand, the reactions containing Fe(3+), H(2)O(2) and 3-hydroxyanthranilic acid or 3,4-dihydroxyphenylacetic acid were the most efficient on degradation of Azure B and also presented the highest H(2)O(2) consumption. These results indicate that H(2)O(2) consumption occurs even when the dye is not extensively degraded, suggesting that part of the generated OH radicals reacts with the own phenol derivative instead of Azure B.     

Rapid anaerobic degradation of toxaphene in sewage sludge

We studied the degradation of technical toxaphene in anaerobic sewage sludge from a municipal waste water treatment plant. Chlorobornanes, chlorocamphenes and related compounds were rapidly degraded, with degradation rates in the order of decachloro>nonachloro>octochloro>heptachloro approximately = hexachloro compounds. The half-lives of individual congeners ranged from <1 day to several days. We also studied the degradation of technical toxaphene in previously sterilized sludge (control), and found it was slower than in the anaerobic sludge. The chlorobornanes that degraded most rapidly in the non-sterilized anaerobic sludge were those with gem chloro substitution on the 6-member carbon-ring, including the toxic congeners, Toxicant A and B. Non-gem chloro substituted congeners, like the biologically persistent P26 and P50, also degraded, but less rapidly. Toxaphene degradation in sewage sludge proceeded primarily via reductive dechlorination, leading to HxSed, HpSed, TC2 and other persistent metabolites. Enantioselective determinations indicated little, if any, enantioselectivity in the formation and/or degradation of these compounds. The isomer and enantiomer profiles of the hexa-, hepta-, and octachlorobornanes are similar to those observed in sediment from the Baltic Sea, suggesting that technical toxaphene is the source of these compounds and that its composition was changed via similar anaerobic degradation pathways.     

Sorption and Biodegradation of Vapor-Phase Organic Compounds with Wastewater Sludge and Food Waste Compost

ABSTRACT

To test the possible use of composted food waste and wastewater sludge as biofilters to treat gas-phase volatile organic compounds (VOCs), batch experiments were conducted with an isolated strain that could degrade aromatic compounds under aerobic conditions. A benzene and trichloroethylene (TCE) mixture was used as the gas-phase pollutant in experiments with composted food waste, sludge, and soil. Under aerobic conditions, benzene was degraded as a primary substrate and TCE was degraded cometabolically, with water contents varying from 6 to 60% (volume of water added/volume of solid). Optimal water content for VOC removal was 12% for the soil, 36% for the composted food waste, and 48% for the sludge.

The extent of VOC sorption and biodegradation at the optimal water content was different for each material. With the same initial VOC concentration, more VOCs were removed by sorption onto the composted food waste and the sludge, while less VOCs were biodegraded in comparison with the results using soil. The reason the biodegradation in the soil was greater may be partly attributed to the fact that, due to less sorption, the aqueous-phase concentration of VOCs, which microorganisms could utilize as a carbon source or cometabolize, was higher. We also speculate that the distribution of microorganisms in each medium affects the rate of biodegradation. A large number of microorganisms were attached to the composted food waste and sludge. Mass transfer of VOCs and oxygen to these microorganisms, which appear to have been heterogeneously distributed in clusters, may have been limited, resulting in hindered biodegradation.