Emerging investigator series: sunlight photolysis of 2,4-D herbicides in systems simulating leaf surfaces.

Pesticides are commonly applied on foliage, forming dry deposits on the leaf cuticular wax. However, their photochemical transformation in this lipophilic environment is much less understood compared with that in surface water. In this work, sunlight photolysis of six chlorinated phenoxyacetic acid herbicides (i.e., 2,4-D and structural analogues) was evaluated in four organic solvents, on quartz, and on paraffin wax. In solvents of low polarity (i.e., n-heptane and 2-propanol), direct photolysis of 2,4-D herbicides was enhanced due to the relatively high quantum yields in these solvents. Photolysis on paraffin wax was slower than photolysis on quartz by a factor of 3-9, but was comparable with that in solvents of low polarity. With environmentally relevant irradiation and surface loading, the half-lives of 2,4-D herbicides on paraffin wax were 27-159 h, which are within the same range reported for biodegradation, the dominant dissipation pathway in the current 2,4-D fate model. Product analyses showed that photoreductive dechlorination is the dominant pathway in organic solvents, accounting for 68-100% of parent compound decay. On quartz and paraffin wax surfaces, however, photoreductive dechlorination products accounted for <60% of parent compound decay. Combining kinetic modeling and product analyses, it was shown that neither could the two additional putative pathways (photosubstitution of chlorine by hydroxyl group and cleavage of the ether bond) fully account for the total phototransformation on surfaces. These results suggest that rapid photolysis on surfaces can be attributed to unique pathways that are absent in the organic solvent phase.

Catalytic degradation of 2,4-dichlorophenoxyacetic acid (2,4-D) by nano-Fe2O3 activated peroxymonosulfate: Influential factors and mechanism determination.

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, Fe2O3 (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 (Fe2+ and Fe3+). 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 > H2O2 > 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.

Fabrication of In2S3 nanoparticle decorated TiO2 nanotube arrays by successive ionic layer adsorption and reaction technique and their photocatalytic application.

In2S3 nanoparticle (NP) decorated self-organized TiO2 nanotube array (In2S3/TiO2 NT) hybrids were fabricated via simple successive ionic layer adsorption and reaction (SILAR) technique. The In2S3 NPs in a size of about 15 nm were found to deposit on the top surface of the highly oriented TiO2 NT while without clogging the tube entrances. The loading amount of In2S3 NPs on the TiO2 NT was controlled by the cycle number of SILAR deposition. Compared with the bare TiO2 NT, the In2S3/TiO2 NT hybrids showed stronger absorption in the visible light region and significantly enhanced photocurrent density. The photocatalytic activity of the In2S3/TiO2 NT photocatalyst far exceeds that of bare TiO2 NT in the degradation of typical herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) under simulated solar light. After 160-min irradiation, almost 100% 2,4-D removal is obtained on the 7-In2S3/TiO2 NT prepared through seven SILAR deposition cycles, much higher than 26% on the bare TiO2 NT. After 10 successive cycles of photocatalytic process with total 1,600 min of irradiation, In2S3/TiO2 NT maintained as high 2,4-D removal efficiency as 95.1% with good stability and easy recovery, which justifies the potential of the photocatalytic system in application for the photocatalytic removal of organic pollutants such as herbicides or pesticides from water.

Photo-Fenton degradation of phenol, 2,4-dichlorophenoxyacetic acid and 2,4-dichlorophenol mixture in saline solution using a falling-film solar reactor.

In this work, a saline aqueous solution of phenol, 2,4-dichlorophenoxyacetic acid (2,4-D) and 2,4-dichlorophenol (2,4-DCP) was treated by the photo-Fenton process in a falling-film solar reactor. The influence of the parameters such as initial pH (5-7), initial concentration of Fe2+ (1-2.5mM) and rate of H202 addition (1.87-3.74mmol min-1) was investigated. The efficiency of photodegradation was determined from the removal of dissolved organic carbon (DOC), described by the species degradation of phenol, 2,4-D and 2,4-DCP. Response surface methodology was employed to assess the effects of the variables investigated, i.e. [Fe2+], [H202] and pH, in the photo-Fenton process with solar irradiation. The results reveal that the variables' initial concentration of Fe2+ and H202 presents predominant effect on pollutants' degradation in terms of DOC removal, while pH showed no influence. Under the most adequate experimental conditions, about 85% DOC removal was obtained in 180 min by using a reaction system employed here, and total removal of phenol, 2,4- and 2,4-DCP mixture in about 30min.

Efficient removal of herbicide 2,4-dichlorophenoxyacetic acid from water using Ag/reduced graphene oxide co-decorated TiO2 nanotube arrays.

A new photocatalyst, Ag nanoparticles (NPs) and reduced graphene oxide (RGO) co-decorated TiO(2) nanotube arrays (NTs) (Ag/RGO-TiO(2) NTs), was designed and facilely produced by combining electrodeposition and photoreduction processes. The structures and properties of the photocatalysts were characterized. The ternary catalyst exhibited almost 100% photocatalytic removal efficiency of typical herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) from water under simulated solar light irradiation. The photodegradation rate toward 2,4-D over Ag/RGO-TiO(2) NTs is 11.3 times that over bare TiO(2) NTs. After 10 successive cycles with 1600 min of irradiation, Ag/RGO-TiO(2) NTs maintained as high 2,4-D removal efficiency as 97.3% with excellent stability and easy recovery, which justifies the photocatalytic system a promising application for herbicide removal from water.

Experimental study of the degradation of 2,4-D induced by vacuum-UV radiation.

Vacuum-UV (VUV) photoinduced degradation of the herbicide 2,4-D was studied. A flow-through VUV photoreactor was used (i) in batch mode to study the kinetics of degradation and (ii) in continuous mode under steady state to analyze the potential utilization of this process in commercial applications. In both cases, the reactants were recycled to minimize diffusive resistances. Experimental results from the batch studies showed that the initial degradation rate of 2,4-D in ultrapure water was independent of the initial concentration of the herbicide. However, a reduction in the reaction rate was obtained over the course of the treatment, largely due to the formation of 2,4-D partial oxidation by-products which compete with 2,4-D molecules for HO (scavenging effect). Increases in water alkalinity reduced 2,4-D degradation rate as a consequence of the scavenging of HO by carbonates and bicarbonates. The degradation of 2,4-D in raw surface waters was also investigated. A noticeable reduction in the degradation rate was observed because of the presence of NOM and alkalinity, both being known HO scavengers. Additionally, the presence of inorganic species/ions that absorb VUV may also have contributed to the reduction of the overall degradation rate. High conversions were obtained in the continuous system. At a residence time of 25 seconds, conversions of 97% and 65% were achieved for inlet herbicide concentrations of 1 and 10 mg L(-1), respectively. Under these conditions, the received dose of 185 nm radiation was 44.8 mJ cm(-2).

[Effects of Has-Fe(III) complex on the photodegradation of 2, 4-D in aqueous environment].

To elucidate the roles of humic acids (HAs) and iron on the environmental fate and transport of organic pollutants in natural water, the interactions of HAs with Fe(III) were characterized by Fourier transform infrared spectroscopy (FTIR) spectra, Ultraviolet-visible (UV-vis) spectra and fluorescence spectra, indicating the formation of HAs-Fe(III) complex. Electron paramagnetic resonance (EPR) spectra show *OH radicals are generated and can participate in the photoreaction in solutions containing HAs, Fe(III) and HAs-Fe(III) complex. Under Xe lamp irradiation (lamda >290 nm), the photodegradation of 2,4-dichlorophenoxyacetic acid (2,4-D), as a kind of herbicide, followed the pseudo-first-order reaction kinetics. The pseudo-first-order rate constant of 2,4-D photodegradation with the presence of only 2,4-D (2 mg x L(-1)) was 0.007 h(-1). In the presence of HAs (5 mg x L(-1)), Fe(III) (0.2 mmol x L(-1)) and HAs-Fe(III) complex, the rate constants of 2,4-D degradation were 0.004, 0.034 and 0.046 h(-1), respectively. It was interesting to note that in the existence of HAs, 2,4-D photodegradation was inhibited. While in the presence of Fe(III), 2,4-D photodegradation was enhanced. Furthermore, in the coexistence of HAs and Fe(III), HAs-Fe(III) complex showed better increased effect on the photodegradation of 2,4-D than Fe(III) alone.

Mineralisation of 2,4-dichlorophenoxyacetic acid by acoustic or hydrodynamic cavitation in conjunction with the advanced Fenton process.

The mineralisation of 2,4-dichlorophenoxyacetic acid (2,4-D) in the presence of zero-valent iron and hydrogen peroxide (the advanced Fenton process--AFP) whilst being subjected to acoustic or hydrodynamic cavitation is reported. If the reaction is merely stirred then there is 57% removal of TOC whilst on irradiation the figure is 64% although the latter reaction is more rapid. Use of ultrasound alone results in only 11% TOC removal in 60 min of treatment time. Addition of iron powder marginally enhances the extent of degradation but an appreciable increase is observed in the presence of hydrogen peroxide which acts as a source for hydroxyl radicals by Fenton chemistry as well as by dissociation in the presence of ultrasound. The use of hydrodynamic cavitation in conjunction with the advanced Fenton process has also been found to be a useful tool for continuous remediation of water contaminated with 2,4-D. After 20 min of treatment the residual TOC is reduced to 30% and this probably represents the remaining highly recalcitrant small organic molecules.

The role of organic ligands in ferrous-induced photochemical degradation of 2,4-dichlorophenoxyacetic acid.

Recent studies have shown that hydrogen peroxide is generated in a ferrioxalate-induced photoreductive reaction, but information about the effect of organic ligands on the photochemical behaviour of ferrous species is limited. The degradation of the herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) by a ferrous-catalyzed oxidation in the presence of various ligands such as formate, citrate, malelate, oxalate, and ethylenediaminetetra-acetic acid (EDTA) was studied. The experiments were conducted under either dark or irradiated (350n m) conditions. Forty-two percent and 34% of 2,4-D were removed by the Fe(2+)/oxalate/UV and Fe(2+)/citrate/UV processes, respectively, after 30 min of reaction and oxidative intermediates were obtained in both cases. The presence of hydroxylated intermediates suggests that 2,4-D may be attacked by hydroxyl radicals, which are the products of the photo-Fenton-like reaction. As such, hydrogen peroxide was produced by the photolysis of ferrous oxalate or ferrous citrate, referred to hereafter as photogenerated H(2)O(2). As expected, the total removal percentage of 2,4-D jumped to 97% when 1mM of hydrogen peroxide (so-called spiked H(2)O(2)) was externally added to the reaction vessel to initiate the Fe(2+)/oxalate/UV process. Therefore, the treatment of 2,4-D by the Fe(2+)/oxalate/H(2)O(2)/UV system can be operated in two steps: the photolysis of ferrous oxalate first, followed by adding the spiked H(2)O(2) sometime after the commencement of the reaction. A two-phase model has been developed to describe this tandem ferrous-catalyzed photooxidation, which would help to achieve the mineralization of 2,4-D.

Pilot scale mineralization of organic acids by electro-Fenton process plus sunlight exposure.

The viability of the electro-Fenton degradation of aqueous solutions of benzoic acid, 2,4-dichlorophenoxyacetic acid and oxalic acid has been studied at 20 A using a pilot flow reactor containing an anode and an oxygen diffusion cathode, both of 100 cm(2) section. Pollutants were preferentially oxidized by hydroxyl radicals formed in solution from reaction of Fe(2+) with electrogenerated H(2)O(2), allowing mineralization of benzoic acid and 2,4-D. For oxalic acid no electrochemical mineralization was observed. After electrolysis, samples of the different effluents were exposed to sunlight (Helielectro-Fenton process) and almost complete mineralization was reached after ca. 30-50 min without additional cost. Effects of parameters such as electrolysis time, pH and solar irradiation time on the process efficiencies were studied.

Fine route for an efficient removal of 2,4-dichlorophenoxyacetic acid (2,4-D) by zeolite-supported TiO2.

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.

pH effect on OH radical production in photo/ferrioxalate system.

In wastewater treatment using the Fenton and photofenton processes, pH is one of the critical operating parameters, due to the fact that the Fenton reaction can work only under acidic pH conditions. It is hoped that Ferric iron complexed with oxalate (Fe(III)-oxalate; ferrioxalate) will provide an alternative to the traditional Fenton process with its limited range of pH conditions, since its high solubility in aqueous media can broaden the available pH range of the Fenton reaction up to the near neutral pH regime. In this study, we investigated the pH dependency of OH production in the photo/ferrioxalate system, in the presence and absence of externally supplied H(2)O(2), where 2,4--D was used as the probe compound for OH production at a wide range of pH values (1.2--7.4). In the absence of externally supplied H(2)O(2), the 2,4--D degradation was considerably enhanced with increasing pH, whereas it was reduced with increasing pH in the presence of an excess amount of H(2)O(2). These variations in the degradation of 2,4--D were thus found to be precisely related to the formation of H(2)O(2), a factor to which little attention was paid in previous studies. In the absence of H(2)O(2) addition, the in situ formation of H(2)O(2) is facilitated with increasing pH by the reaction of Fe(II) with O(2)(-), which increases with pH, augmenting the production of OH and thereby leading to the faster degradation of 2,4--D. This same reaction can also provide an explanation for the opposite pH dependence of 2,4--D degradation in the presence of H(2)O(2).

Monitoring of toxicity during degradation of selected pesticides using ionizing radiation.

The optimization of experimental conditions for radiolytic removal of organic pollutants from water and waste with the use of ionizing radiation via controlling the concentration of target compound(s) requires also monitoring the toxicity changes during the process. Commonly used herbicides 2,4-D and dicamba were shown to increase toxicity measured with the Microtox test at low irradiation doses resulting from formation of more toxic transient products, which can be decomposed at larger doses. The changes of toxicity were examined with respect to dose magnitude and the presence of commonly occurring scavengers of radiation.

Vapor and liquid phase photolysis of the n-butyl ester of 2,4-dichlorophenoxyacetic acid.

The n-butyl ester of 2,4-dichlorophenoxyacetic acid in the liquid and vapor phase was irradiated in a pyrex reactor for 188 hr by ultraviolet light of 300 nm using an intensity similar to that around 300 nm in the solar spectrum. In both phases, the ester was dechlorinated at the ortho position together with simultaneous reduction and Photo-Fries rearrangement to produce volatile photoproducts. Ether bond cleavage to produce chlorophenols, and a Norrish Type II photoprocess, also occurred. A 79% mass balance was accounted for by volatile chlorinated organic residues. HCL gas was also evolved. The production of Cl was also demonstrated in both vapor and liquid phases. The half time of decomposition was around 13 days. The possible effects of the volatile photoproducts on off-target plants were also noted.