Analysing the fate of nanopesticides in soil and the applicability of regulatory protocols using a polymer-based nanoformulation of atrazine

For the first time, regulatory protocols defined in the OECD guidelines were applied to determine the fate properties of a nanopesticide in two agricultural soils with contrasting characteristics. The nanoformulation studied had no effect on the degradation kinetics of atrazine indicating that (1) the release of atrazine from the polymer nanocarriers occurred rapidly relative to the degradation kinetics (half-lives 36–53 days) and/or that (2) atrazine associated with the nanocarriers was subject to biotic or abiotic degradation. Sorption coefficients, derived from a batch and a centrifugation technique at a realistic soil-to-solution ratio, were higher for the nanoformulated atrazine than for the pure active ingredient. Results indicate that the nanoformulation had an effect on the fate of atrazine. However, since the protocols applied were designed to assess solutes, conclusions about the transport of atrazine loaded onto the nanocarriers should be made extremely cautiously. The centrifugation method applied over time (here over 7 days) appears to be a useful tool to indirectly assess the durability of nanopesticides under realistic soil-to-solution ratios and estimate the period of time during which an influence on the fate of the active ingredient may be expected. More detailed investigations into the bioavailability and durability of nanopesticides are necessary and will require the development of novel methods suitable to address both the “nano” and “organic” characteristics of polymer-based nanopesticides.     

Application of the method of temporal moments to interpret solute transport with sorption and degradation

In this note, we applied the temporal moment solutions of [Das and Kluitenberg, 1996. Soil Sci. Am. J. 60, 1724] for one-dimensional advective-dispersive solute transport with linear equilibrium sorption and first-order degradation for time pulse sources to analyse soil column experimental data. Unlike most other moment solutions, these solutions consider the interplay of degradation and sorption. This permits estimation of a first-order degradation rate constant using the zeroth moment of column breakthrough data, as well as estimation of the retardation factor or sorption distribution coefficient of a degrading solute using the first moment. The method of temporal moment (MOM) formulae was applied to analyse breakthrough data from a laboratory column study of atrazine, hexazinone and rhodamine WT transport in volcanic pumice sand, as well as experimental data from the literature. Transport and degradation parameters obtained using the MOM were compared to parameters obtained by fitting breakthrough data from an advective-dispersive transport model with equilibrium sorption and first-order degradation, using the nonlinear least-square curve-fitting program CXTFIT. The results derived from using the literature data were also compared with estimates reported in the literature using different equilibrium models. The good agreement suggests that the MOM could provide an additional useful means of parameter estimation for transport involving equilibrium sorption and first-order degradation. We found that the MOM fitted breakthrough curves with tailing better than curve fitting. However, the MOM analysis requires complete breakthrough curves and relatively frequent data collection to ensure the accuracy of the moments obtained from the breakthrough data.     

Biodegradation of petroleum hydrocarbon vapors: laboratory studies on rates and kinetics in unsaturated alluvial sand

Predictions of natural attenuation of volatile organic compounds (VOCs) in the unsaturated zone rely critically on information about microbial biodegradation kinetics. This study aims at determining kinetic rate laws for the aerobic biodegradation of a mixture of 12 volatile petroleum hydrocarbons and methyl tert-butyl ether (MTBE) in unsaturated alluvial sand. Laboratory column and batch experiments were performed at room temperature under aerobic conditions, and a reactive transport model for VOC vapors in soil gas coupled to Monod-type degradation kinetics was used for data interpretation. In the column experiment, an acclimatization of 23 days took place before steady-state diffusive vapor transport through the horizontal column was achieved. Monod kinetic parameters Ks and vmax could be derived from the concentration profiles of toluene, m-xylene, n-octane, and n-hexane, because substrate saturation was approached with these compounds under the experimental conditions. The removal of cyclic alkanes, isooctane, and 1,2,4-trimethylbenzene followed first-order kinetics over the whole concentration range applied. MTBE, n-pentane, and chlorofluorocarbons (CFCs) were not visibly degraded. Batch experiments suggested first-order disappearance rate laws for all VOCs except n-octane, which decreased following zero-order kinetics in live batch experiments. For many compounds including MTBE, disappearance rates in abiotic batch experiments were as high as in live batches indicating sorption. It was concluded that the column approach is preferable for determining biodegradation rate parameters to be used in risk assessment models.     

Study of atrazine degradation in subsurface flow constructed wetland under different salinity

To evaluate the treatment capability of subsurface flow constructed wetland (SFCW) and the effect of salinity on the degradation of atrazine, the degradation of atrazine in SFCW was studied. Under the static condition, the degradation of atrazine in SFCW followed first-order kinetics: c=0.09679 exp(-0.0396t) (c, residue concentration, mg l(-1); t, retention time, d), with a half-life of approximately 17.5 days. The atrazine degradation kinetic functions were established for salinities of 1.5, 3.0, 5.0, 10.0 and 15.0 g l(-1), respectively, which appeared to approach first-order kinetics. The effect of salinity on the atrazine treatment efficiency showed an exponential inhibition: lnk=3.204+0.04991 C (k, degradation constant; C, NaCl concentration, mg l(-1)). The attenuation of atrazine in SFCW cannot be a result of hydrolysis or sorption process. It was considered that some bacteria in the wetland system degraded atrazine into deethylatrazine (DEA) and deisopropylatrazine (DIA) and sequentially into CO(2) and H(2)O. Salinity impacted on the growth of bacteria resulting in a switch of the microbial community. With the increase of salinity, Shannon-Wiener Diversity Index in the SFCW system declined. The relationship between atrazine degradation constant (k) and Shannon Index was established as shown in linear phase, y=-0.07286+0.0363x. The positive correlation between them indicated that microbial community played an important role in the atrazine degradation process.     

Alginate immobilized enrichment culture for atrazine degradation in soil and water system

An atrazine degrading enrichment culture, a consortium of bacteria of genus Bacillus along with Pseudomonas and Burkholderia, was immobilized in sodium alginate and was used to study atrazine degradation in mineral salts medium (MSM), soil and wastewater effluent. Sodium alginate immobilized consortium, when stored at room temperature (24 ± 5°C), was effective in degrading atrazine in MSM up to 90 days of storage. The survival of bacteria in alginate beads, based on colony formation unit (CFU) counts, suggested survival up to 90 days and population counts decreased to 1/5^th on 120 days. Comparison of atrazine degrading ability of the freely suspended enrichment culture and immobilized culture suggested that the immobilized culture took longer time for complete degradation of atrazine as a lag phase of 2 days was observed in the MSM inoculated with alginate immobilized culture. The free cells resulted in complete degradation of atrazine within 6 days, while immobilized cells took 10 days for 100% atrazine degradation. Further, immobilized cultures were able to degrade atrazine in soil and wastewater effluent. Alginate beads were stable and effective in degrading atrazine till 3rd transfer and disintegrated thereafter. The study suggested that immobilized enrichment culture, due to its better storage and application, can be used to degrade atrazine in soil water system.     

Mathematical prediction of imidacloprid persistence in two Croatian soils with different texture,organic matter content and acidity under laboratory conditions

In the present laboratory study, persistence of imidacloprid (IMI) as a function of initial insecticide concentration and soil properties in two Croatian soils (Krk sandy clay and Istria clay soils) was studied and described mathematically. Upon fitting the obtained experimental data for the higher concentration level (5 mg/kg) to mathematical models, statistical parameters (R ², scaled root mean squared error and χ ² error) indicated that the single first-order kinetics model provided the best prediction of IMI degradation in the Krk sandy clay soil, while in the Istria clay soil biphasic degradation was observed. At the lower concentration level (0.5 mg/kg), the biphasic models Gustafson and Holden models as well as the first-order double exponential model fitted the best experimental data in both soils. The disappearance time (DT₅₀) values estimated by the single first-order double exponential model (from 50 to 132 days) proved that IMI can be categorized as a moderately persistent pesticide. In the Krk sandy clay soil, resulting DT₅₀ values tended to increase with an increase of initial IMI concentration, while in the Istria clay soil, IMI persistence did not depend on the concentration. Organic matter of both experimental soils provided an accelerating effect on the degradation rate. The logistic model demonstrated that the effect of microbial activity was not the most important parameter for the biodegradation of IMI in the Istria clay soil, where IMI degradation could be dominated by chemical processes, such as chemical hydrolysis. The results pointed that mathematical modeling could be considered as the most convenient tool for predicting IMI persistence and contributes to the establishment of adequate monitoring of IMI residues in contaminated soil. Furthermore, IMI usage should be strictly controlled, especially in soils with low organic matter content where the risk of soil and groundwater contamination is much higher due to its longer persistence and consequent leaching and/or moving from soil surface prior to its degradation.     

Remediation of alachlor and atrazine contaminated water with zero-valent iron nanoparticles

Zero-valent iron nanoparticles (nZVI, diameter < 90 nm, specific surface area = 25 m² g^?1) have been used under anoxic conditions for the remediation of pesticides alachlor and atrazine in water. While alachlor (10, 20, 40 mg L^?1) was reduced by 92–96% within 72 h, no degradation of atrazine was observed. The alachlor degradation reaction was found to obey first-order kinetics very closely. The reaction rate (35.5 × 10^?3–43.0 × 10^?3 h^?1) increased with increasing alachlor concentration. The results are in conformity with other researchers who worked on these pesticides but mostly with micro ZVI and iron filings. This is for the first time that alachlor has been degraded under reductive environment using nZVI. The authors contend that nZVI may prove to be a simple method for on-site treatment of high concentration pesticide rinse water (100 mg L^?1) and for use in flooring materials in pesticide filling and storage stations.     

Sorption of metolachlor and atrazine in fly ash amended soils: comparison of optimized isotherm models

Adsorption of metolachlor and atrazine was studied in the fly ash (Inderprastha and Badarpur)- amended Inceptisol and Alfisol soils using batch method. Results indicated that sorption of both the herbicides in soil+fly ash mixtures was highly nonlinear and sorption decreased with a higher herbicide concentration in the solution. Also, nonlinearity increased with an increase in the level of fly ash amendment from 0-5%. Three two-parameter monolayer isotherms viz. Langmuir, Temkin, Jovanovic and one imperical Freundlich models were used to fit the experimental data. Data analysis and comparison revealed that the Temkin and the Freundlich isotherms were best-suited to explain the sorption results and the observed and the calculated adsorption coefficient values showed less variability. The study suggested that sorption mechanism of metolachlor and atrazine involved the physical association at the sorbate surface and the nonlinearity in the sorption at higher pesticide or fly ash concentration was due to a decrease in the heat of adsorption and higher binding energy.     

Modelling the dissipation kinetics of six commonly used pesticides in two contrasting soils of New Zealand

We used three non-linear bi-phasic models, bi-exponential (BEXP), first-order double exponential decay (FODED), and first-order two-compartment (FOTC), to fit the measured degradation data for six commonly used pesticides (atrazine, terbuthylazine, bromacil, diazinon, hexazinone and procymidone) in two New Zealand soils. Corresponding DT₅₀ and DT₉₀ values for each compound were numerically obtained and compared against those estimated by simple first-order kinetic (SFOK) model. All 3 non-linear models gave good fit of the measured data under both soil depths and were well supported by the values obtained for the respective statistical indices (RMSE, CRM and r ²). The FOTC model gave by far the best fit for most compounds, followed by the FODED and BEXP models. Overall, DT₅₀ values derived by non-linear models for the six compounds in soils from both sites were lower than the values obtained by the SFOK model. Differences in the SFOK and the three non-linear models derived DT₉₀were, however, an order of magnitude higher for some compounds, while for others differences were very small. Although all three non-linear models described most data by giving excellent fits, in a few instances > 5–10% asymptotes hindered the estimation of DT₉₀ values. This work shows that when degradation deviates from first-order kinetic, application of non-linear decay models to describe the kinetics of degradation becomes important in order to derive the true end-points for pesticides in soil.     

Multicompartmental fate of persistent substances

Background, Aim and Scope Modelling of the fate of environmental chemicals can be done by relatively simple multi-media box models or using complex atmospheric transport models. It was the aim of this work to compare the results obtained for both types of models using a small set of non-ionic and non-polar or moderately polar organic chemicals, known to be distributed over long distances. Materials and Methods Predictions of multimedia exposure models of different types, namely three multimedia mass-balance box models (MBMs), two in the steady state and one in the non-steady state mode, and one non-steady state multicompartment chemistry-atmospheric transport model (MCTM), are compared for the first time. The models used are SimpleBox, Chemrange, the MPI-MBM and the MPI-MCTM. The target parameters addressed are compartmental distributions (i.e. mass fractions in the compartments), overall environmental residence time (i.e. overall persistence and eventually including other final sinks, such as loss to the deep sea) and a measure for the long-range transport potential. These are derived for atrazine, benz-[a]-pyrene, DDT, α and γ-hexachlorocyclohexane, methyl parathion and various modes of substance entry into the model world. Results and Discussion Compartmental distributions in steady state were compared. Steady state needed 2–10 years to be established in the MCTM. The highest fraction of the substances in air is predicted by the MCTM. Accordingly, the other models predict longer substance persistence in most cases. The results suggest that temperature affects the compartmental distribution more in the box models, while it is only one among many climate factors acting in the transport model. The representation of final sinks in the models, e.g. burial in the sediment, is key for model-based compartmental distribution and persistence predictions. There is a tendency of MBMs to overestimate substance sinks in air and to underestimate atmospheric transport velocity as a consequence of the neglection of the temporal and spatial variabilities of these parameters. Therefore, the long-range transport potential in air derived from MCTM simulations exceeds the one from Chemrange in most cases and least for substances which undergo slow degradation in air. Conclusions and Perspectives MBMs should be improved such as to ascertain that the significance of the atmosphere for the multicompartmental cycling is not systematically underestimated. Both types of models should be improved such as to cover degradation in air in the particle-bound state and transport via ocean currents. A detailed understanding of the deviations observed in this work and elsewhere should be gained and multimedia fate box models could then be ‘tuned in’ to match better the results of comprehensive multicompartmental transport models. ESS-Submission Editor: Prof. Dr. Michael Matthies (matthies@uos.de)     

Uncertainty in Nonpoint Source Pollution Models and Associated Risks

The usefulness of water quality simulation models for environmental management is explored with a focus on prediction uncertainty. The specific objective is to demonstrate how the usability of a flow and transport model (here: MACRO) can be enhanced by developing and analyzing its output probability distributions based on input variability. This infiltration-based model was designed to investigate preferential flow effects on pollutant transport. A statistical sensitivity analysis is used to identify the most uncertain input parameters based on model outputs. Probability distribution functions of input variables were determined based on field-measured data obtained under alternative tillage treatments. Uncertainty of model outputs is investigated using a Latin hypercube sampling scheme (LHS) with restricted pairing for model input sampling. Probability density functions (pdfs) are constructed for water flow rate, atrazine leaching rate, total accumulated leaching, and atrazine concentration in percolation water. Results indicate that consideration of input parameter uncertainty produces a 20% higher mean flow rate along with two to three times larger atrazine leaching rate, accumulated leachate, and concentration than that obtained using mean input parameters. Uncertainty in predicted flow rate is small but that in solute transport is an order of magnitude larger than that of corresponding input parameters. Macropore flow is observed to contribute to the variability of atrazine transport results. Overall, the analysis provides a quantification of prediction uncertainty that is found to enhance a user's ability to assess risk levels associated with model predictions.     

Uncertainty in Nonpoint Source Pollution Models and Associated Risks

The usefulness of water quality simulation models for environmental management is explored with a focus on prediction uncertainty. The specific objective is to demonstrate how the usability of a flow and transport model (here: MACRO) can be enhanced by developing and analyzing its output probability distributions based on input variability. This infiltration-based model was designed to investigate preferential flow effects on pollutant transport. A statistical sensitivity analysis is used to identify the most uncertain input parameters based on model outputs. Probability distribution functions of input variables were determined based on field-measured data obtained under alternative tillage treatments. Uncertainty of model outputs is investigated using a Latin hypercube sampling scheme (LHS) with restricted pairing for model input sampling. Probability density functions (pdfs) are constructed for water flow rate, atrazine leaching rate, total accumulated leaching, and atrazine concentration in percolation water. Results indicate that consideration of input parameter uncertainty produces a 20% higher mean flow rate along with two to three times larger atrazine leaching rate, accumulated leachate, and concentration than that obtained using mean input parameters. Uncertainty in predicted flow rate is small but that in solute transport is an order of magnitude larger than that of corresponding input parameters. Macropore flow is observed to contribute to the variability of atrazine transport results. Overall, the analysis provides a quantification of prediction uncertainty that is found to enhance a user's ability to assess risk levels associated with model predictions.     

饮用水原水中微量阿特拉津去除方法试验研究

饮用水中微量有机物的污染是关系饮用水生态安全的重要问题。以饮用水中微量的内分泌干扰类除草剂阿特拉津为研究对象，分别采用微生物降解技术和光催化氧化技术对其进行降解，考察温度对阿特拉津降解效果的影响。研究结果表明：阿特拉津浓度为1 mg/L时，3种温度条件下，除锰功能菌MB4对阿特拉津均有明显的去除效果，降解时间为7 d时，阿特拉津的去除率达到65%。底物浓度为200 μg/L，3种温度条件下，活性炭负载二氧化钛（TiO₂/PAC）催化剂光降解阿特拉津30 min时，其去除率均达到90%。光催化氧化技术协同微生物降解技术在饮用水中微量的内分泌干扰物的去除中有广阔的应用前景。     

Biodegradation of atrazine by Rhodococcus sp. BCH2 to N-isopropylammelide with subsequent assessment of toxicity of biodegraded metabolites

Atrazine is a persistent organic pollutant in the environment which affects not only terrestrial and aquatic biota but also human health. Since its removal from the environment is needed, atrazine biodegradation is achieved in the present study using the bacterium Rhodococcus sp. BCH2 isolated from soil, long-term treated with atrazine. The bacterium was capable of degrading about 75 % atrazine in liquid medium having pH 7 under aerobic and dark condition within 7 days. The degradation ability of the bacterium at various temperatures (20–60 °C), pH (range 3–11), carbon (glucose, fructose, sucrose, starch, lactose, and maltose), and nitrogen (ammonium molybdate, sodium nitrate, potassium nitrate, and urea) sources were studied for triumph optimum atrazine degradation. The results indicate that atrazine degradation at higher concentrations (100 ppm) was pH and temperature dependent. However, glucose and potassium nitrate were optimum carbon and nitrogen source, respectively. Atrazine biodegradation analysis was carried out by using high-performance thin-layer chromatography (HPTLC), Fourier transform infrared spectroscopy (FTIR), and liquid chromatography quadrupole time-of-flight (LC/Q-TOF-MS) techniques. LC/Q-TOF-MS analysis revealed formation of various intermediate metabolites including hydroxyatrazine, N-isopropylammelide, deisopropylhydroxyatrazine, deethylatrazine, deisopropylatrazine, and deisopropyldeethylatrazine which was helpful to propose biochemical degradation pathway of atrazine. Furthermore, the toxicological studies of atrazine and its biodegraded metabolites were executed on earthworm Eisenia foetida as a model organism with respect to enzymatic (SOD and Catalase) antioxidant defense mechanism and lipid peroxidation studies. These results suggest innocuous degradation of atrazine by Rhodococcus sp. BCH2 in nontoxic form. Therefore the Rhodococcus sp.BCH2 could prove a valuable source for the eco-friendly biodegradation of atrazine pesticide.     

Multi-process herbicide transport in structured soil columns: experiments and model analysis

Model predictions of pesticide transport in structured soils are complicated by multiple processes acting concurrently. In this study, the hydraulic, physical, and chemical nonequilibrium (HNE, PNE, and CNE, respectively) processes governing herbicide transport under variably saturated flow conditions were studied. Bromide (Br-), isoproturon (IPU, 3-(4-isoprpylphenyl)-1,1-dimethylurea) and terbuthylazine (TER, N2-tert-butyl-6-chloro-N4-ethyl-1,3,5-triazine-2,4-diamine) were applied to two soil columns. An aggregated Ap soil column and a macroporous, aggregated Ah soil column were irrigated at a rate of 1 cm h(-1) for 3 h. Two more irrigations at the same rate and duration followed in weekly intervals. Nonlinear (Freundlich) equilibrium and two-site kinetic sorption parameters were determined for IPU and TER using batch experiments. The observed water flow and Br- transport were inversely simulated using mobile-immobile (MIM), dual-permeability (DPM), and combined triple-porosity (DP-MIM) numerical models implemented in HYDRUS-1D, with improving correspondence between empirical data and model results. Using the estimated HNE and PNE parameters together with batch-test derived equilibrium sorption parameters, the preferential breakthrough of the weakly adsorbed IPU in the Ah soil could be reasonably well predicted with the DPM approach, whereas leaching of the strongly adsorbed TER was predicted less well. The transport of IPU and TER through the aggregated Ap soil could be described consistently only when HNE, PNE, and CNE were simultaneously accounted for using the DPM. Inverse parameter estimation suggested that two-site kinetic sorption in inter-aggregate flow paths was reduced as compared to within aggregates, and that large values for the first-order degradation rate were an artifact caused by irreversible sorption. Overall, our results should be helpful to enhance the understanding and modeling of multi-process pesticide transport through structured soils during variably saturated water flow.     

Constructed wetlands for mitigation of atrazine-associated agricultural runoff

Atrazine was amended into constructed wetlands (59-73x14x0.3 m) for the purpose of monitoring transport and fate of the pesticide to obtain information necessary to provide future design parameters for constructed wetlands mitigation of agricultural runoff. Following pesticide amendment, a simulated storm and runoff event equal to three volume additions was imposed on each wetland. Targeted atrazine concentrations were 0 microg/l (unamended control), 73 microg/l, and 147 microg/l. Water, sediment, and plant samples were collected weekly for 35 days from transects longitudinally distributed throughout each wetland and were analyzed for atrazine using gas chromatography. Between 17 and 42% of measured atrazine mass was within the first 30-36 m of wetlands. Atrazine was below detection limits (0.05 microg/kg) in all sediment and plant samples collected throughout the duration of this study. Aqueous half lives ranged from 16 to 48 days. According to these data, conservative buffer travel distances of 100-280 m would be necessary for effective runoff mitigation.     

Controls on atrazine leaching through a soil-unsaturated fractured limestone sequence at Brévilles, France

The objective of this study was to identify the main controls on atrazine leaching through luvisols and calcisols overlying fissured limestone using the dual-permeability model MACRO. The model parameterisation was based on a combination of direct measurements (e.g. hydraulic properties, adsorption and degradation), literature data and calibration against bromide leaching experiments in field plots. A Monte Carlo sensitivity analysis was carried out for a typical application pattern, considering two different depths of unsaturated limestone (15 and 30 m). MACRO calibrations to the field experiments demonstrated the occurrence of strong macropore flow in the luvisol, while transport in the calcisol could be described by the advection-dispersion equation. MACRO simulations of tritium and atrazine leaching qualitatively matched tritium concentration profiles measured in the limestone and atrazine concentrations measured in piezometers and in aquifer discharge via a spring. The sensitivity analysis suggested that the thickness of the limestone, as well as the transport properties and processes occurring in the unsaturated rock (e.g. matrix vs. fissure flow) will have little significant long-term effect on atrazine leaching, mainly because degradation is very slow in the limestone. No mineralization of atrazine was detected in one-year incubations and a mean half-life of 10 years was assumed in the simulations. Instead, processes occurring in the soil exerted the main control on predicted atrazine leaching, especially variations in the degradation rate and the strength of sorption and macropore flow. However, fissure flow in unsaturated rock is expected to exert a much more significant control on groundwater contamination for compounds that degrade more readily in the deep vadose zone.     

Influence of humic substances on the photolysis of aqueous pesticide residues

The present work investigated the direct and indirect photolysis of pesticide residues (atrazine, imazaquin, iprodione), in aqueous solutions and under UV-visible radiation (280-480nm). Different kinds of humic substances (HS) were added to samples in order to evaluate their behaviour as possible photocatalysts and their effect on the photolysis of pesticides. The fulvic acids were purchased from the International Humic Substances Society, and they were added to samples in concentrations ranging from 1 to 150 mgl(-1). Titanium dioxide was used as the photocatalyst, in concentration ranging from 10 to 150 mgl(-1). Pesticides photolysis were measured by UV-visible absorption spectroscopy and differential pulse polarography with all used pesticides, reaching total degradation after 2h of irradiation, thus indicating a fast direct photolysis. Photocatalysis by TiO(2) could increase the pesticides photolysis rate up to 40%. This effect, however, was not observed for imazaquin photolysis. Again, except for imazaquin, HS presence showed a positive effect in increasing pesticide degradation, but only within specific concentration ranges (below 10mg l(-1) for iprodione and about 30mgl(-1) for atrazine). Above these ranges HS induce a decrease in the pesticides photolysis rate. Spin-trapping measurements by electronic paramagnetic resonance spectroscopy, using the spin-trap DMPO, showed that HS are able to photogenerate hydroxyl radicals, increasing the pesticides molecule degradation. However, the HS also react with the photogenerated hydroxyl radical, influencing the pesticide photolysis, leading to a decrease in the photolysis rate and causing it to be strongly dependent on the nature and concentration of residues in the water to be treated.