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2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD) is the most toxic congener of dioxin and has serious long-term effects on the environment and human health. Pyruvate Kinase L/R (PKLR) gene expression levels and gene variants are associated with pyruvate kinase enzyme deficiency, which has been identified as the cause of several diseases linked to dioxin exposure. In this study, we estimated PKLR gene copy number and gene expression levels using real-time quantitative PCR (RT-qPCR) assays, genotyped PKLR SNP rs3020781 by Sanger sequencing, and quantified plasma pyruvate kinase enzyme activity in 100 individuals exposed to Agent Orange/Dioxin near Bien Hoa and Da Nang airfields in Vietnam and 100 healthy controls. The means of PKLR copy numbers and PKLR gene expression levels were significantly higher, while pyruvate kinase enzyme activity was significantly decreased in Agent Orange/Dioxin-exposed individuals compared to healthy controls (P < 0.0001). Positive correlations of PKLR gene copy number and gene expression with 2,3,7,8-TCDD concentrations were observed (r = 0.2, P = 0.045 and r = 0.54, P < 0.0001, respectively). In contrast, pyruvate kinase enzyme activity was inversely correlated with 2,3,7,8-TCDD concentrations (r = -0.52, P < 0.0001). PKLR gene copy number and gene expression levels were also inversely correlated with pyruvate kinase enzyme activity. Additionally, PKLR SNP rs3020781 was found to be associated with 2,3,7,8-TCDD concentrations and PKLR gene expression. In conclusion, PKLR copy number, gene expression levels, and pyruvate kinase enzyme activity are associated with 2,3,7,8-TCDD exposure in individuals living in Agent Orange/Dioxin-contaminated areas., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

This research aims to identifying the potential effect of using a hydrogen-producing reactor's effluent as an enrichment amendment for enhancing the degradation rates of 2,4-dichlorophenoxyacetic acid (2,4-D) during the bioremediation of contaminated paddy soils. The results showed that addition of the effluents to 2,4-D- degrading enrichment culture enhanced (up to 1.3-fold) the degradation rate constant of 2,4-D. The enhancement effect most probably resulted from the co-metabolic degradation of 2,4-D facilitated by volatile fatty acids (e.g., acetate, propionate, and butyrate) in the effluents which served as the beneficial substrates. Results from DNA sequencing analysis showed that the effluent additions shifted the bacterial community composition in the enrichment culture. Dechloromonas and Clostridium were two dominant bacterial genera involved in 2,4-D degradation. The findings will make a substantial contribution to remediation of soils contaminated with 2,4-D., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

The possible phytoremediation capacity of Plectranthus neochilus (boldo) exposed to the commercial pesticide (Aminol) in soil and water through consecutive extractions (days interval) was evaluated. After the exposure period, tea leaves from the plant were analyzed in terms of the presence of 2,4-D, total antioxidant capacity (DPPH), concentration of total polyphenols and flavonoids for plants exposed to soil and water. In water, 2,4-D remained up to 67% in the 60 days of experiment in the control group, which provided the use of two treatment groups with the plant (one group of plants for 30 days and another group in the remaining 30 days in the same system), thus, a decontamination up to 49% of the 2,4-D was obtained in this system with water. In both experiments (soil and water) the 2,4-D was not detected in tea leaves, the reduction of the antioxidant activity, polyphenols and flavonoids of plants exposed to the herbicide was also observed when compared to the non-exposed plants. In tea - plants in water - it was also possible to quantify the phenolic compounds and it was observed that in the group of plants of the first 30 days there was a decrease in caffeic acid and an increase in coumaric and ferulic acids, compared to the group of plants that were not exposed to 2,4-D. In the remaining 30 days with the new seedlings there was a decrease of the coumaric acid and an increase of the caffeic and ferulic acids., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

A multiple pin-plane corona discharge reactor was used to generate plasma for the degradation of 2,4 dichlorophenoxyacetic acid (2,4-D) from the aqueous solution. The 2,4-D of concentration 1 mg/L was completely removed within 6 min of plasma treatment. Almost complete mineralization was achieved after the treatment time of 14 min for a 2,4-D concentration of 10 mg/L. Effects of different water constituents such as carbonates, nitrate, sulphate, chloride ions, natural organic matter (humic acids) and pH on 2,4-D degradation was studied. A significant antagonistic effect of carbonate and humic acid was observed, whereas, the effects of other ions were insignificant. A higher first order rate constant of 1.73 min -1 was observed, which was significantly decreased in the presence of carbonate ions and humic acids. Also, a higher degradation of 2,4-D was observed in acidic pH conditions. Different 2,4-D intermediates were detected and the degradation pathway of 2,4-D in plasma treatment process was suggested. The toxicity of 10 mg/L 2,4-D was completely eradicated after 10 min of plasma treatment., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Vietnam has a double burden of dioxin from both industrial sources and historical sources. To evaluate the concentration of PCDD/Fs in ambient air in different areas of Vietnam and their possible sources, atmospheric samples were collected from three areas namely Son La (rural area) and Da Nang (harbor - Agent Orange hotspot area), and Ho Chi Minh City (metropolitan - industrial city). Vapor and solid phases of PCDD/Fs were collected and analyzed following the TO-9A sampling method. Principal Component Analysis and Positive Matrix Factorization model were applied to characterize the possible source. The average concentrations of PCDD/Fs were found to be 21.3 ± 13 fg I-TEQ/m 3 in Son La (n = 32), 65.2 ± 34 fg I-TEQ/m 3 in Da Nang (n = 16) and 139 ± 84 fg I-TEQ/m 3 in Ho Chi Minh City (n = 8). The findings of this study targeted open burning (42%) and biomass burning (51%) as the major emission sources of PCDD/Fs in ambient air of Son La, Vietnam. Major possible sources of PCDD/Fs in Da Nang could be transportation activities (64%), however, the other factor (36%) was suspected to be contaminated with 2,3,7,8-TeCDD from Agent Orange. Most of PCDD/Fs emitted in Ho Chi Minh City related to industrial activities (93%)., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

2,4-Dichlorophenoxyacetic acid (2,4-D) is one of the most applicable herbicides in the world. Therefore, its residue in aquatic environment threatens the human health and ecosystems. In this study, Fe 2 O 3 (hematite) nanoparticles (HNPs) were synthesized, and the characteristics of the obtained HNPs were determined using X-ray powder diffraction (XRD), field emission scanning electron microscopy (FESEM), Fourier transform infrared spectroscopy (FTIR), Brunauer-Emmett-Teller (BET) technique, and particle size analyzer (PSA). The catalytic activity of HNPs was evaluated for the activation of peroxymonosulfate (PMS) for the degradation of 2,4-D. The effects of the operating parameters were studied for the PMS/HNPs system. The results showed that the acidic condition provided higher efficiency, while overdosing of PMS had a scavenging effect. The PMS/HNPs showed high efficiency in comparison with the homogeneous forms of iron (Fe 2+ and Fe 3+ ). Reusability of HNPs was studied in five consequent usages. The presence of the anions (chloride, nitrate, and hydrogen phosphate) reduced the 2,4-D degradation. Moreover, the catalytic activity of HNPs was also investigated in the presence of other oxidants. UV irradiation increased the function of PMS/HNPs and its mechanism was described. The order of 2,4-D removal for the oxidants was PMS > persulfate > H 2 O 2  > percarbonate. A total of 29.7% of 2,4-D chlorine content was released during the destruction of 2,4-D. The quenching study showed that sulfate radical was the major agent in the degradation of 2,4-D., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Chicken and duck eggs collected from three different areas in Vietnam were examined for polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). These regions included a background area, an area sprayed with Agent Orange and the Bien Hoa airbase area where Agent Orange was handled by the US Army. The latter area now is inhabited and people keep their own laying hens. Egg samples were first screened with an in vitro reporter gene bioassay and a selection was analyzed by GC/HRMS. Samples from Bien Hoa airbase showed very high PCDD/F levels, up to 249 pg dioxin-equivalents (TEQ)/g fat, mainly due to 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD). In the sprayed areas, levels (3.2-8.2 pg TEQ g(-1)) were comparable to those observed in background areas (3.2-8.2 pg TEQ g(-1) fat). The estimated average consumption of 22 g d(-1) of the highly contaminated eggs will result in a 2-fold exceedance of the current exposure limits for adults and 5-fold for children, even without considering other contaminated food sources. This indicates a potential health risk from consumption of these highly contaminated eggs, which were not yet considered as a source for exposure to PCDD/Fs of people living in the highly contaminated areas., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

The graphitised carbon solid phase extraction (SPE) sorbent Envi-Carb has been used to fabricate glass fibre filter- Envi-Carb "sandwich" disks for use as a passive sampler for acid herbicides. Passive sampler uptake of a suite of herbicides, including the phenoxyacetic acid herbicides 4-chloro-o-tolyloxyacetic acid (MCPA), 2,4-dichlorophenoxyacetic acid (2,4-D) and 3,6-dichloro-2-methoxybenzoic acid (Dicamba), was achieved without pH adjustment, demonstrating for the first time a suitable binding phase for passive sampling of acid herbicides at neutral pH. Passive sampling experiments with Duck River (Tasmania, Australia) water spiked at 0.5 μg L(-1) herbicide concentration over a 7 d deployment period showed that sampling rates in Duck River water decreased for seven out of eight herbicides, and in the cases of 3,6-dichloro-2-pyridinecarboxylic acid (Clopyralid) and Dicamba no accumulation of the herbicides occurred in the Envi-Carb over the deployment period. Sampling rates for 4-amino-3,5,6-trichloro-2-pyridinecarboxylic acid (Picloram), 2,4-D and MCPA decreased to approximately 30% of the sampling rates in ultrapure water, whilst sampling rates for 2-(4,6-dimethylpyrimidin-2-ylcarbamoylsulfamoyl) benzoic acid, methyl ester (Sulfometuron-methyl) and 3,5,6-Trichloro-2-pyridinyloxyacetic acid (Triclopyr) were approximately 60% of the ultrapure water sampling rate. For methyl N-(2,6-dimethylphenyl)-N-(methoxyacetyl)-D-alaninate (Metalaxyl-M) there was little variation in sampling rate between passive sampling experiments in ultrapure water and Duck River water. SPE experiments undertaken with Envi-Carb disks using ultrapure water and filtered and unfiltered Duck River water showed that not only is adsorption onto particulate matter in Duck River water responsible for a reduction in herbicide sampling rate, but interactions of herbicides with dissolved or colloidal matter (matter able to pass through a 0.2 μm membrane filter) also reduces the herbicide sampling rate., (Crown Copyright © 2013. Published by Elsevier Ltd. All rights reserved.)

The levels of 14 micropollutants including nine pharmaceuticals, two pesticides, and three endocrine disruptors were measured in a water treatment plant (WTP) in Seoul, Korea. Among the measured micropollutants, 12 (excluding atrazine and triclocarban) were found in the influent and effluent from the WTP, at levels ranging from 2 to 482 ng L(-1). The removal efficiencies of the detected micropollutants in the WTP ranged from 6% to 100%. Among them diclofenac, acetaminophen, caffeine, carbamazepine, and 2,4-D were effectively removed (>80%). Metoprolol was unlikely to be removed (6%) in the WTP process. Concentrations of acetaminophen, metoprolol, ibuprofen, and naproxen were higher in winter, while levels of herbicides of 2,4-dichloro-phenoxyacetic acid (2,4-D) were higher in summer. Metoprolol was hardly removed in the water treatment process. Laboratory experiments showed that compounds with logKow>2.5 (especially bisphenol-A, 2,4-D, carbamazepine, triclocarban and 4-nonylphenol) were effectively removed by coagulation process, and adsorption effect increased in proportion with hydrophobicity of micropollutants and the turbidity of water. Sunlight photodegradation also effectively removed sulfamethoxazole, sulfamethazine, caffeine, diclofenac, ibuprofen, and acetaminophen, which are photosensitizes. Chlorination was relatively not effective for the removal of micropollutants due to the lower chlorine dosage (2 mg L(-1)), lower contact time (1h), and already lower levels of micropollutants at the chlorination stage at WTP. Our results imply that micropollutants during coagulation stage at WTP can be removed not only by coagulation itself, but also by adsorption to clay particle especially for high turbidity water, and by sunlight photodegradation in the areas open to the atmosphere., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

Clay minerals have obtained considerable attention for slow-release formulation of herbicides to increase weed control efficacy and reduce leaching potential and environmental pollution. This study deals with preparing, characterizing and examining the potentials of modified bentonite and zeoilite in adsorption and release of 2,4-dichlorophenoxyacetic acid (2,4-D) herbicide. 2,4-D sorption of the N-cetylpyridinium (NCP)-modified bentonites and zeolites were much higher than those of unmodified substrates. The 2,4-D adsorption capacity of the organo-minerals increased with increasing surfactant loading. Desorption isotherms of 2,4-D did not coincide their corresponding sorption isotherms showing hysteresis. The proportion of 2,4-D released from the organo-minerals after seven desorption cycles varied between 29% and 50% of the total retained herbicide. The sorbed 2,4-D on the adsorbents showed gradual release pattern with time. The release pattern of 2,4-D from NCP-modified bentonite and zeolite, make these synthetic organo-minerals suitable candidate for slow release formulation of 2,4-D., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

The Exposure Opportunity Index (EOI) is a proximity-based model developed to estimate relative exposure of ground troops in Vietnam to aerially applied herbicides. We conducted a detailed quantitative evaluation of the EOI model by using actual herbicide spray missions isolated in time and space. EOI scores were calculated for each of 36 hypothetical receptor location points associated with each spray mission for 30 herbicide missions for two time periods - day of herbicide application and day 2-3 post-application. Our analysis found an enormous range of EOI predictions with 500-1000-fold differences across missions directly under the flight path. This quantitative examination of the EOI suggests that extensive testing of the model's code is warranted. Researchers undertaking development of a proximity-based exposure model for epidemiologic studies of either Vietnam veterans or the Vietnamese population should conduct a thorough and realistic analysis of how precise and accurate the model results are likely to be and then assess whether the model results provide a useful basis for their planned epidemiologic studies.

The 2,4-dichlorophenoxyacetic acid (2,4-D) is a hormone-like herbicide widely used in agriculture. Although its half life in soil is approximately two weeks, the thousands of tons introduced in the environment every year represent a risk for human health and the environment. Considering the toxic properties of this compound and its degradation products, it is important to assess and monitor the 2,4-D residues in agricultural soils. Furthermore, experiments of phyto/bioremediation are carried out to find economic and environmental friendly tools to restore the polluted soils. Accordingly, it is essential to accurately measure the amount of 2,4-D and its metabolites in soils. There is evidence that 2,4-D extraction from soil samples seriously depends on the physical and chemical properties of the soil, especially in those soils with high content of humic acids. The aim of this work was to assess the variables that influence the recovery and subsequent analysis of 2,4-D and its main metabolite (2,4-dichlorophenol) from those soils samples. The results showed that the recovery efficiency depends on the solvent and method used for the extraction, the amount and kind of solvent used for dissolving the herbicide and the soil water content at the moment of spiking. An optimized protocol for the extraction and quantification of 2,4-D and its main metabolite from soil samples is presented.

Concentration of 2,4-dichlorophenoxyacetic acid (2,4-D) may affect its degradation kinetics in advanced oxidation systems, and combinations of two or more systems can be more effective for its mineralization at low concentration levels. Degradations and mineralizations of 0.045mM 2,4-D using O(3), O(3)/UV, UV/TiO(2) and O(3)/UV/TiO(2) systems were compared, and influence of reaction temperature on the mineralization in O(3)/UV/TiO(2) system was investigated. 2,4-D degradations by O(3), O(3)/UV and UV/TiO(2) systems were similar to the results of earlier investigations with higher 2,4-D concentrations. The degradations and total organic carbon (TOC) removals in the four systems were well described by the first-order reaction kinetics. The degradation and removal were greatly enhanced in O(3)/UV/TiO(2) system, and further enhancements were observed with larger O(3) supplies. The enhancements were attributed to hydroxyl radical (()OH) generation from more than one reaction pathway. The degradation and removal in O(3)/UV/TiO(2) system were very efficient with reaction temperature fixed at 20 degrees C. It was suspected that reaction temperature might have influenced ()OH generation in the system, which needs further attention.

Soil functional stability is the capacity of soil functions to resist and recover from an environmental perturbation and can be used to evaluate soil health. It can be influenced by the presence of xenobiotics such as herbicides. The impact of a fresh 2,4-D contamination (36 mg kg(-1) dry soil) on soil functional stability was evaluated by comparing the capacity of soil enzyme activities to resist and recover from a heat perturbation for both a clean and 2,4-D-contaminated soil. The functional stabilities of the soils (uniform sands, pH 6.9, 7% (w/w) organic matter) were calculated using the relative soil stability index (RSSI). The RSSI scores indicate the proportion of potential enzyme activity the soil retains after a perturbation compared to the potential activity of an unperturbed soil. Six extra-cellular enzyme activities (acid and alkaline phosphatases, arylsulfatase, urease, protease and beta-glucosidase) were monitored in soil microcosms during a 15-day period. During this period, a 60 degrees C heat perturbation was applied to the soil for 24 h. The activities of arylsulfatase and protease were found to be the most stable following heat perturbation obtaining the highest RSSI scores (87% and 77%, respectively). Urease activity showed the lowest RSSI score (38%). Although all enzyme activities were inhibited by the presence of 2,4-D, the RSSI results indicated that contamination lowered the stability of only three enzyme activities (arylsulfatase, beta-glucosidase and urease). The RSSI adequately described resistance, recovery and recovery rate parameters and enabled differentiation between functional stabilities of clean and contaminated soil and between different soil types.

Zeolites HY, Hbeta and HZSM-5 with different physico-chemical properties were chosen as support for TiO2 to illustrate their adsorption, dispersion and electronic structure in photocatalysis. The extent of TiO2 loading was monitored by XRD and BET surface area measurements. The adsorption capacity of HY zeolite was found to be high and hence chosen for further modification to continue the investigation. Photodegradation kinetics were carried out with 2,4-dichlorophenoxyacetic acid (2,4-D) in aqueous solution. The extent of 2,4-D degradation on TiO2/HY loading revealed the importance of adsorption in photocatalysis. Mineralisation studies on all three zeolites with 1 wt.% TiO2 loading demonstrated the good dispersion properties of TiO2/HY. Its photocatalytic activity was found to be excellent with formulated 2,4-D. Comparison of relative photonic efficiencies demonstrated that supported photocatalysts exhibited higher activity than some of the commercial photocatalysts. The high activity of supported TiO2 is due to synergistic effects of improved adsorption of 2,4-D and efficient delocalisation of photogenerated electrons by zeolite support.

Ninety strains of fungi from the collection of our mycology laboratory were tested in Galzy and Slonimski (GS) synthetic liquid medium for their ability to degrade the herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) and its by-product, 2,4-dichlorophenol (2,4-DCP) at 100 mg l(-1), each. Evolution of the amounts of each chemical in the culture media was monitored by HPLC. After 5 days of cultivation, the best results were obtained with Aspergillus penicilloides and Mortierella isabellina for 2,4-D and with Chrysosporium pannorum and Mucor genevensis for 2,4-DCP. The data collected seemed to prove, on one hand, that the strains responses varied with the taxonomic groups and the chemicals tested, and, on the other hand, that 2,4-D was less accessible to fungal degradation than 2,4-DCP. In each case, kinetics studies with the two most efficient strains revealed that there was a lag phase of 1 day before the onset of 2,4-D degradation, whereas there was none during 2,4-DCP degradation. Moreover, 2,4-DCP was detected transiently during 2,4-D degradation. Finally, M. isabellina improved its degradation potential in Tartaric Acid (TA) medium relative to GS and Malt Extract (ME) media.

Residues of five pesticides in surface water were surveyed during 2001 and 2003 in the Traiguen river basin in Southern Chile. Simazine, hexazinone, 2,4-D, picloram herbicides and carbendazim fungicide were selected through a pesticide risk classification index. Six sampling stations along the river were set up based on agricultural and forestry land use. The water sampling was carried out before and after the pesticide application periods and in correspondence to some rain events. Pesticides were analyzed by HPLC with DAD detection in a multiresidue analysis. During 2001, in the first sampling campaign (March), the highest concentrations of pesticides were 3.0 microg l(-1) for simazine and hexazinone and 1.8 microg l(-1) for carbendazim. In the second sampling (September), the highest concentration were 9.7 microg l(-1) for 2,4-D, 0.3 microg l(-1) for picloram and 0.4 microg l(-1) for carbendazim. In the last sampling period (December), samples indicated contamination with carbendazim fungicide at levels of up to 1.2 microg l(-1). In sampling carried out on May 2003, no pesticides were detected. In October 2003, the highest concentrations of pesticides were 4.5 microg l(-1) for carbendazim and 2.9 microg l(-1) for 2,4-D. Data are discussed in function of land use and application periods of the products, showing a clear seasonal pattern pollution in the Traiguen river. Risk assessment for these pesticides was calculated by using a risk quotient (RQ = PNEC/PEC). For picloram the calculated RQ < was 0, which indicates that no adverse effects may occur due to the exposure to this herbicide in the Traiguen river basin. For 2,4-D, simazine, hexazinone, carbendazim RQ > 1, meaning that adverse effects could occur and it is necessary to reduce pesticide exposure in surface waters. It is recommended to continue with a pesticide monitoring program and the implementation of ecotoxicological testing with local and standardized species in order to consider the probability of effects occurrence, with less uncertainty. Thus, it will be more feasible to make some recommendations to regulatory agencies regarding the pesticide use.

In the isolated Aluoi Valley of central Viet Nam, very high levels of 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) were measured in soil, fish fat, duck fat, pooled human blood and breast milk samples collected from A So village between 1996 and 1999. The village was situated on a former military base occupied by US Special Forces between 1963 and 1966. TCDD was a contaminant of the herbicide "Agent Orange", aerially sprayed in the valley between 1965 and 1970, and stored at the A So base. Measured levels were lower near the sites of two other former US bases in the valley which had been occupied for shorter periods of time. In areas where Agent Orange had been applied by low-flying aircraft, levels of TCDD in soil, food and human samples were elevated, but lower than those near the three former US bases. We confirm the apparent food chain transfer of TCDD from contaminated soil to cultured fish pond sediments to fish and duck tissues, then to humans as measured in whole blood and breast milk. We theorize that the Aluoi Valley is a microcosm of southern Viet Nam, where numerous reservoirs of TCDD exist in the soil of former military installations south of the former demilitarized zone. Large quantities of Agent Orange were stored at many sites, used in ground and aerial applications, and spilled. TCDD, through various forms of soil disturbance, can be mobilized from these reservoirs after decades below the surface, and subsequently, introduced into the human food chain.

This study reports on the effect of the presence of beta-cyclodextrin (beta-CD) on the adsorption and mobility of the pesticide 2,4-dichlorophenoxyacetic acid (2,4-D) through soil columns. The previous application of beta-CD to the soil produced a retarded leaching of 2,4-D through the soil column, due probably to herbicide adsorption on the soil through beta-CD adsorbed. However, the application of beta-CD solution to the soil column where 2,4-D had been previously adsorbed, led to the complete desorption of the herbicide, due to the formation of water-soluble 1:1 inclusion complexes between 2,4-D and beta-CD. Beta-CD can be viewed as a microscopic organic-phase extractant. It can be an advantage to remove from soil pesticides which are able to form inclusion complexes with cyclodextrins, making them possible candidates for use in in situ remediation efforts.

In mixed industrial effluent the presence of metal ions can retard the destruction of organic contaminants and the efficiency of recovery of the metal is reduced by the presence of the organic species. Results are presented for copper-2,4-dichlorophenoxyacetic acid (2,4-D) system in which both effects occur. An electrochemical cell alone can be used to recover copper in the pH range 1.5-4.5 but it is not capable of achieving complete disappearance of 2,4-D by anodic oxidation. A photolytic cell alone can achieve the destruction of 2,4-D at pH 3.5 but leaves copper in solution. A combined photolytic-electrochemical system using an activated carbon concentrator cathode achieves the rapid simultaneous destruction of 2,4-D and recovery of copper. Results are presented for the recovery of more than 90% copper from, and >99.9%, destruction of the organochlorine compound 2,4-D in, a solution containing 100 mg dm(-3) copper and 50 mg dm(-3) 2.4-D. The photolytic degradation of 2,4-D depends on the intensity of the UV-probe. Only 19% degradation is achieved after 8 h with the 150 W UV-probe but the corresponding value with the 400 W UV-probe is 100%. In the case of 150 W UV-probe the degradation of 2,4-D proceeds through the formation of 2,4-dichlorophenol and phenol. The concentration of these intermediates are very low in the case of 400 W UV-probe because the speed of the degradation of 2,4-D is very fast. The addition of TiO2 (1 g dm(-3)), as a semiconductor material, and H202 (1.5 g dm(-3)) as an oxidant, increases the photolytic degradation of 2,4-D.

The reproducibility of collection of atmospheric residues of the herbicides 2,4-D and triallate as bulk (wet plus dry) deposition samples by paired pan samplers and as particulate (filter) and vapour (PUF/XAD-2 resin cartridge) samples by paired high-volume air samplers was determined. Variability of herbicide concentrations in paired bulk deposition samples was within 25% for 65 and 80% of the samples for 2,4-D and triallate, respectively, with approximately 90% of the paired samples being within a factor of 2 for both herbicides. The vapour samples of 2,4-D and triallate showed similar reproducibilities. The highest reproducibility was observed for the filter samples with 92% of the paired data sets for 2,4-D being within 25% variability. No triallate was detected in the filter samples.