Transformation Of Atrazine Research Articles

Impact of superabsorbent hydrogels on microbial community and atrazine fate in soils by 14C-labeling techniques

The accumulation of atrazine in soils can create environmental challenges, potentially posing risks to human health. Superabsorbent hydrogel (SH)-based formulations offer an eco-friendly approach to accelerate herbicide degradation. However, the impact of SHs on soil microbial community structure, and thus on the fate of atrazine, remains uncertain. In this study, a radioactive tracer was employed to investigate the influence of SHs on microbial communities and atrazine transformation in soils. The results revealed that the mineralization of atrazine in active soils was considerably greater than that in sterilized soils. Atrazine degradation proceeded rapidly under SH treatment, indicating the potential of SH to accelerate atrazine degradation. Furthermore, SH addition did not alter the atrazine degradation pathway in soils, which included dealkylation, dechlorination and hydroxylation. The relative abundance of dominant microbial population was influenced by the presence of SHs in the soil. Additionally, SH application led to an increased relative abundance of Lysobacter, suggesting its potential involvement in atrazine degradation. These findings reveal the significance of soil microorganisms and SH in atrazine degradation, offering crucial insights for the development of effective strategies for atrazine remediation and environmental sustainability.

Carbon-14 labeled transformation of atrazine in soils: Comparison of superabsorbent hydrogel coating and technical material

Atrazine exhibits adverse effects on diverse organisms in both terrestrial and aquatic environments, even though it effectively targets specific organisms. This study employed superabsorbent hydrogels to coat 14C-atrazine coupled with a four-compartment model to determine the fate of this herbicide in three oxic soils over a 100-day incubation period. Mineralization of atrazine was limited in all soils, with rates remaining below 3.5 %. The encapsulation treatment reduced mineralization of atrazine in soil A and soil B. Bound residues ranged from 26.1 to 43.6 % at 100 d. The encapsulation treatment enhanced the degradation of atrazine and reduced the content of deethylatrazine in soil A, but significantly increased the content of deisopropylatrazine in soil A and hydroxyatrazine in soil C. Using the obtained data, we also constructed a four-compartment model to clarify the relationships among the parent compound, degradation products, bound residues, and mineralization. This model accurately fits the fate of atrazine in the present work. Additionally, the correlation study suggested that both soil parameters and superabsorbent hydrogels played significant roles in influencing atrazine transformation. These findings serve as a reference for evaluating the environmental impact of superabsorbent hydrogels in atrazine pollution reduction and offer a foundational model approach for a comprehensive understanding of organic pollutants.

Understanding atrazine elimination via treatment of the enzyme-based Fenton reaction: Kinetics, mechanism, reaction pathway, and metabolites toxicity

The degradation kinetics and mechanism of atrazine (ATZ) via an enzyme-based Fenton reaction were investigated at various substrate concentrations and pH values. Toxicological assessment was conducted on ATZ and its degradation products, and the associated reaction pathway was examined. The in situ production of hydrogen peroxide (H2O2) was monitored within the range of 3–15 mM, depending on the increase in glucose concentration, while decreasing the pH to 3.2–5.1 (initial pH of 5.8) or 6.5–7.4 (initial pH of 7.7). The degradation efficiency of ATZ was approximately 2–3 times higher at an initial pH of 5.8 with lower glucose concentrations than at an initial pH of 7.7 with higher substrate concentrations during the enzyme-based Fenton reaction. The apparent pseudo-first-order rate constant for H2O2 decomposition under various conditions in the presence of ferric citrate was 1.9–6.3 × 10−5 s−1. The •OH concentration ([•OH]ss) during the enzyme-based Fenton reaction was 0.5–4.1 × 10−14 M, and the second-order rate constant for ATZ degradation was 1.5–3.3 × 109 M−1 s−1. ATZ intrinsically hinders the growth and development of Arabidopsis thaliana, and its inhibitory effect is marginal, depending on the reaction time of the enzyme-based Fenton process. The ATZ transformation during this process occurs through dealkylation, hydroxylation, and dechlorination via •OH-mediated reactions. The degradation kinetics, mechanism, and toxicological assessment in the present study could contribute to the development and application of enzyme-based Fenton reactions for in situ pollutant abatement. Moreover, the enzyme-based Fenton reaction could be an environmentally benign and applicable approach for eliminating persistent organic matter, such as herbicides, using diverse H2O2-producing microbes and ubiquitous ferric iron with organic complexes.

Differential interference of copper with endophytic bacterial inoculation: Atrazine decontamination in Acorus tatarinowii and culture solution

To clarify the interference effects of inorganic ions, Acorus tatarinowii and endophytic bacterium Herbaspirillum huttiense (Hh) were combined to decontaminate atrazine pollution under different copper levels. This study verified inoculation effects and revealed the complicated processes of atrazine transformation in solutions. 35.9% leaf biomass was promoted by Hh inoculation, and the value was lowered to 7.87% by high doses of copper. The changing trend of leaf N, K, and S contents, and tiller numbers were consistent with that of leaf biomass. Hh injection improved atrazine accumulation by 43.5% in roots, and under copper interference, this value lowered to 10.6%. Hh promoted atrazine deethylation in plants, which was copper-dose dependent in different plant organs. In solutions, atrazine was conjugated with small-molecule secretions at m/z 118, detoxicated into 2-hxydroatrazine and 2-hydroxy-4-acetamido-atrazine, then the triazine ring opened. Copper interference had a more significant impact on residual atrazine conversion products than Hh inoculation treatments. Hh treatment promoted the ring-opening degradation of atrazine in water. The addition of high doses of copper ions promoted the oxidative process of atrazine while inhibiting its ring-opening transformation process in water.

Kinetic and Mechanistic Insights into the Oxidative Transformation of Atrazine by Aqueous Fe(IV): Comparison with Hydroxyl and Sulfate Radicals

Kinetic and Mechanistic Insights into the Oxidative Transformation of Atrazine by Aqueous Fe(IV): Comparison with Hydroxyl and Sulfate Radicals

Promoted dissipation and detoxification of atrazine by graphene oxide coexisting in water.

The herbicide atrazine (ATZ) has a detrimental effect on the health of aquatic ecosystems and has become a global concern in recent years. But the understanding of its persistence and potential toxicity under combined pollution, especially in the coexistence of other emerging pollutants, remains limited. In this work, the dissipation and transformation of ATZ in combination with graphene oxide (GO) in water were investigated. Results showed that dissipation rates of ATZ dramatically increased by 15-95% with half-lives shortened by 15-40% depending on initial concentrations of ATZ, and the products were mainly toxic chloro-dealkylated intermediates (deethylatrazine (DEA) and deisopropylatrazine (DIA)), but their contents were significantly lower under the coexistence of GO compared to ATZ alone. In the presence of GO, the nontoxic dechlorinated metabolite hydroxyatrazine (HYA) was detected earlier than 2-9days, and ATZ transformation into HYA was increased by 6-18% during 21-day incubation periods. This study indicated that the coexistence of GO enhanced the dissipation and detoxification of ATZ. From a remediation standpoint, GO-induced hydrolytic dechlorination of ATZ can reduce its ecological toxicity. But the environmental risks of ATZ for aquatic ecosystem under the coexistence of GO should still be given the necessary prominence due to the potential hazard of ATZ adsorbed on GO and the predominant degradation products (DEA and DIA).

New insights into atrazine degradation by the novel manganese dioxide/bisulfite system: Product formation and Mn reuse

Fenton and Fenton-like systems have been successfully applied in treatment of refractory pollutants in water and wastewater, but the formation and disposal of large amounts of ferric sludge is a matter of concern. This study demonstrated that Mn(IV)/HSO3− system could effectively degrade atrazine (ATZ) through generation of Mn(III) and SO4•− as primary reactive intermediates and meanwhile the sludge could be well controlled. Mn(IV) could be in situ regenerated from oxidation of Mn(II) (i.e., Mn(IV) final transformation product in Mn(IV)/HSO3− system) by oxygen under alkaline condition, and was reused for efficiently catalyzing HSO3− to degrade ATZ. The metal ions (e.g., Ca(II), Mg(II), Zn(II) and Al(III)) commonly used as coagulant had negligible effects on ATZ degradation by Mn(IV)/HSO3− system. The oxidation products of ATZ were identified to further clarify the role of various reactive intermediates in Mn(IV)/HSO3− system. Deethyl-atrazine (DEA) and atrazine amide (CDIT) were two primary products during ATZ transformation by Mn(IV)/HSO3− system. The molar ratio of CDIT to DEA ([CDIT]/[DEA]) was quantified to be 3.0–4.0 during ATZ transformation by Mn(IV)/HSO3− system, which was much higher than those (∼2.3 and ∼0.7) obtained in the cases of authentic SO4•− and •OH oxidation (i.e., UV/PDS and UV/H2O2 system), respectively. This result indicated that Mn(III) was a more selective reactive intermediate than SO4•−, which was also proved by tertiary butanol scavenging experiments. Based on these findings, the Mn(IV)/HSO3− system may be operated in a sequencing batch reactor (SBR) as a durable, efficient, and recyclable technology to treat recalcitrant contaminants in water and meanwhile to achieve ‘zero discharge’ of sludge.

Abiotic transformation of atrazine in aqueous phase by biogenic bixbyite-type Mn2O3 produced by a soil-derived Mn(II)-oxidizing bacterium of Providencia sp.

Recently, biogenic Mn oxides (BioMnOx) are considered as the promising degradation agents for environmental organic contaminants. However, little information is available for the degradation of atrazine by BioMnOx. In this work, BioMnOx, generated by a soil-derived Mn(II)-oxidizing bacterium, Providencia sp. LLDRA6, was explored to degrade atrazine. To begin with, collective results from mineral characterization analyses demonstrated that this BioMnOx was biogenic bixbyite-type Mn2O3. After that, purified biogenic Mn2O3 was found to exhibit a much higher removal efficiency for atrazine in aqueous phase, as compared to unpurified biogenic Mn2O3 and LLDRA6 biomass. During the atrazine removal by biogenic Mn2O3, six intermediate degradation products were discovered, comprising deethylatrazine (DEA), hydroxylatrazine (HA), deethylhydroxyatrazine (DEHA), ammeline, cyanuric acid, and 5-methylhexahydro-1,3,5-triazine-2-thione (MTT). Particularly, the intermediate, MTT, was considered as a new degradation product of atrazine, which was not described previously. Meanwhile, Mn(II) ions were released from biogenic Mn2O3, and on the surface of biogenic Mn2O3, the content of hydroxyl O species increased at the expense of that of lattice and water O species, but the fundamental crystalline structure of this Mn oxide remained unchanged. Additionally, no dissociative Mn(III) was found to involve in atrazine degradation. In summary, these results demonstrated that both the non-oxidative and oxidative reactions underlay the degradation of atrazine by biogenic Mn2O3.

Asymmetric interaction and concurrent remediation of copper and atrazine by Acorus tatarinowii in an aquatic system

To clarify the influence of organic pesticides on phytoremediation of potentially toxic metal elements, hydroponically-grown Acorus tatarinowii was used to repair copper pollution at six concentration levels with and without atrazine. Removal outcomes and processes exhibited asymmetry in an aquatic system. In plants, the addition of atrazine brought as much as 20.5% copper than control. Total amounts, percentage of protein or pectin combined copper and leaf: root ratio of copper were enhanced correspondingly. In solutions, cupric ions (Cu2+) were eliminated as much as 95.6% in plant remediation system. Though atrazine resulted in a quarter more absorption equilibrium concentration, the absorption reaction rate half declined. Copper removal in the system was contributed by both bound copper in solution and plant accumulation, and atrazine magnified contribution weight of the later one. Concurrent copper decreased absolute and relative amounts of atrazine in A. tatarinowii, indicating the influence of copper was mainly to reduce atrazine uptake by A. tatarinowii rather than to change the transformation of atrazine in plants. Copper exhibited antagonistic effects with atrazine in term of plant biomass, photosynthesis and oxidative-related responses (malondialdehyde, Ca, Fe and Mn), which might give support to asymmetry interaction between copper and atrazine accumulation in A. tatarinowii.

Novel catalytic ceramic membranes anchored with MnMe oxide and their catalytic ozonation performance towards atrazine degradation

In the present study, MnMe oxide (Me = Fe, Co, Ce) were in situ embedded on the surface and inside micropores of membranes by redox reaction to fabricate novel catalytic ceramic membranes. The synergistic effect of membrane filtration and catalytic ozonation were evaluated towards atrazine degradation. MnCe-CM owned the best performance with 99.99% atrazine removal in 40 min among four catalytic membranes because of the oxygen vacancies created by Ce 3+ /Ce 4+ and Mn 2+ /Mn 3+ . MnCe-CM was subsequently chosen to explore the optimized operating conditions with a finding of ozone concentration 0.8 mg/min and pH 7. As the catalysts were successfully embedded on the surface and inside the micro-pores of MnCe-CM, the catalytic ozonation took place both on the surface and inside micropores. The reactions on the surface and inside micropores were proved very effective considering that the high specific surface provided sufficient reaction sites while the confined space facilitated the contact between •OH and the reactants. In addition, atrazine degradation pathways were proposed based on the identified byproducts. The reaction sites and the biotoxicity evaluation were calculated by density function theory (DFT) and Toxicity Estimation Software Tool (T.E.S.T), respectively. The present study provides a novel MnCe-CM with dual functions of filtration and catalytic ozonation and outlines the synergistic effect of separation and catalytic ozonation. • Novel catalytic ceramic membranes impregnated with MnMe oxide (Me = Fe, Co, Ce) were successfully fabricated. • MnCe-CM owned the highest atrazine removal because of the oxygen vacancies created by Ce 3+ /Ce 4+ and Mn 2+ /Mn 3+ . • The catalytic ozonation throughout membrane was very effective because of the high specific surface area and the confined space. • The atrazine transformation pathways and the biotoxicity of its products were determined.

π-π Stacked step-scheme PDI/g-C3N4/TiO2@Ti3C2 photocatalyst with enhanced visible photocatalytic degradation towards atrazine via peroxymonosulfate activation

In this study, a novel π-π stacked PDI/g-C3N4/TiO2@Ti3C2 photocatalyst with step-scheme (S-scheme) heterojunction was constructed to boost the atrazine (ATZ) photocatalytic degradation by activating peroxymonosulfate (PMS). The π-π interaction in the PDI/g-C3N4 induced the delocalization of the photoelectrons, therefore promoted their migration. Meanwhile, the intimate contact and the staggered band configurations between the PDI/g-C3N4 and TiO2@Ti3C2 results in the S-scheme heterojunction thus declined the recombination of photocarriers. The π-π interaction and S-scheme heterojunction synergistically promoted the ATZ removal rate to 75% within one hour and can be well-adapted in a variety of environments. It was found that 1O2 domain the photocatalysis, and the H2O2 generated during the reaction may also be helpful for the process. The transformation of ATZ, intermediates, and three pathways during the process were also investigated via LC-MS. Moreover, the total organic carbon analysis shows that the mineralization of ATZ reached 46.08%.

Transformation of Atrazine to Hydroxyatrazine with Alkali-H2O2 Treatment: An Efficient Dechlorination Strategy under Alkaline Conditions

Transformation of Atrazine to Hydroxyatrazine with Alkali-H₂O₂ Treatment: An Efficient Dechlorination Strategy under Alkaline Conditions

A novel diagnostic method for distinguishing between Fe(IV) and •OH by using atrazine as a probe: Clarifying the nature of reactive intermediates formed by nitrilotriacetic acid assisted Fenton-like reaction

In this work, we found that the distribution of two specific atrazine (ATZ) oxidation products (desethyl-atrazine (DEA) and desisopropyl-atrazine (DIA)) was different in oxidation processes involving aqueous ferryl ion (Fe(IV)) species and •OH. Specifically, the molar ratio of produced DEA to DIA (i.e., [DEA]/[DIA]) increased from 7.5 to 13 with increasing pH from 3 to 6 when ATZ was oxidized by Fe(IV), while the treatment of ATZ by •OH led to the [DEA]/[DIA] value of 2 which was independent of pH. Moreover, ATZ showed high reactivity towards Fe(IV) over a wide pH range, especially at near-neutral pH, at which ATZ oxidation in Fe(II)/peroxydisulfate system was even much faster than another well-defined Fe(IV) scavenger, the sulfoxides. By using this approach, it was obtained that the [DEA]/[DIA] value remained at 2 during ATZ transformation by the nitrilotriacetic acid (NTA) assisted Fenton-like (Fe(III)/H2O2) system, which was independent of solution pH and reactants dosage. This result clarified that •OH was the primary reactive intermediate formed in the NTA assisted Fe(III)/H2O2 system. This study not only developed a novel sensitive diagnostic tool for distinguishing Fe(IV) from •OH, but also provided more credible evidence to the nature of reactive intermediate in a commonly controversial system.

Aquaculture-derived distribution, partitioning, migration, and transformation of atrazine and its metabolites in seawater, sediment, and organisms from a typical semi-closed mariculture bay.

Atrazine (ATR) is one of the most commonly used herbicides that could directly impair the growth and health of organisms in mariculture areas and adversely affect human health through the food chain. This study investigated the contaminant occurrence, migration, and transformation of ATR and three of its chlorinated metabolites, namely deethylatrazine (DEA), deisopropylatrazine (DIA), and didealkylatrazine (DDA), in surface seawater, sediment, and aquatic organisms from the Xiangshan Harbor. ATR was detected in all samples, while DIA and DDA were only respectively detected in aquatic and seawater samples. The distribution of ATR and its metabolites presented different patterns depending on the geographic location and showed a higher level in the aquaculture area than that in the non-aquaculture area. The bioaccumulation of ATR in aquaculture organisms showed that benthic organisms, such as Ditrema, and Sinonovacula constricta (Sin), had increased levels. The ecological risks indicated that ATR posed medium or high risks to algae in the water phase of the study area. The microcosm experiment showed that the main fate of ATR in the simulated microenvironment was sedimentation, which followed the first-order kinetic equation. The ATR in the sediment could be enriched 3-5 times in Sin, and its major metabolites were DEA and DIA.

Transformation of iopamidol and atrazine by peroxymonosulfate under catalysis of a composite iron corrosion product (Fe/Fe3O4): Electron transfer, active species and reaction pathways

Cast iron pipes are commonly applied in drinking water distribution systems (DWDSs); peroxymonosulfate (PMS) is a promising alternative for drinking water disinfection; organic micropollutants is still present in drinking water after waterworks' treatment. However, iron corrosion products may affect the reactions between a disinfectant and organic micropollutants. The study investigated the transformation of iopamidol (IPM) and atrazine (ATZ) by PMS under the catalysis of a composite iron corrosion product (Fe/Fe3O4). The pseudo-first-order rate constants (k) for the degradation of IPM and ATZ were 1.47 and 1.03 min-1, respectively. Electron paramagnetic resonance (EPR) experiments indicated that PMS was effectively activated to yield sulfate radical (SO4•-) and hydroxyl radical (HO•), mainly via the reduction by Fe component, dissolved Fe2+ and generated Feocta2+. SO4•- contributed more than HO• to the degradation of IPM and ATZ, and the radical yield achieved 0.97 mol/mol. The k values reached maximum with Fe/Fe3O4 and PMS doses of 2.5 g L-1 and 25 mg L-1, respectively. The optimum mass fraction of Fe3O4 in Fe/Fe3O4 (MFmag) and pH were 10% and 7.0, respectively. The k values increased with increasing temperature, while decreased in the presence of water matrix. Most of the iodine released from IPM was oxidized to IO3-, and NH4+ was the dominant species of nitrogen released from ATZ. The identification of transformation intermediates showed that the radical chain reactions of IPM was mainly initiated from single electron transfer and radical adduct formation, while those of ATZ was primarily initiated from hydrogen atom abstraction and radical adduct formation.

Solar irradiation combined with chlorine can detoxify herbicides

The solar/chlorine process is an energy-efficient advanced oxidation process that can produce reactive species such as hydroxyl radical, reactive chlorine species and ozone. This study investigated the process’ ability to detoxify the typical herbicides atrazine and mecoprop (methylchlorophenoxypropionic acid). Both herbicides are resistant to direct solar photolysis or chlorination alone, but they can be degraded by the solar/chlorine process effectively. Atrazine inhibited the development of Arabidopsis thaliana, but such inhibition was negligible after solar/chlorine treatment of an atrazine solution. The transformation of atrazine in the process was shown to be through hydroxylation, hydrogen abstraction and dechlorination but did not involve chlorine substitution or addition. Cl• reacts with atrazine and mecoprop with rate constants of 6.87 × 109 M−1s−1 and 1.08 × 1010 M−1s−1, respectively, while ClO• reacts with mecoprop with a rate constant of 1.11 × 108 M−1s−1. The degradation kinetics of atrazine and mecoprop by solar/chlorine was simulated by modeling, which fitted the experimental results well. Hydroxyl radicals (HO•) mainly contributed to the degradation of atrazine by solar/chlorine at pH 7 with the contribution of 65%, whereas ClO• and O3 were main species responsible for the degradation of mecoprop with the contribution of 72% and 17%, respectively. The pseudo-first-order rate constants (k′s) of the two degradations increased substantially (by 28.8% for atrazine and by 198% for mecoprop) when the chlorine dosage was increased from 50 μM to 200 μM. The k′s decreased with increasing pH. The presence of natural organic matter inhibited the degradation of both herbicides, while the presence of bromide enhanced their degradation. This work reveals a feasible method for the detoxifying herbicides by combining chlorine with solar radiation.

Transformation of atrazine by photolysis and radiolysis: kinetic parameters, intermediates and economic consideration

Four techniques, UV254 nm photolysis, vacuum ultraviolet (VUV172 nm) photolysis, combined UV254 nm/VUV185 nm photolysis and gamma (γ) radiolysis were used to induce the transformation of atrazine in aqueous solution. The effects of dissolved oxygen (atrazine concentration 1 × 10-4molL-1 and 4.6 × 10-7molL-1) and matrix (high purity water/purified wastewater, atrazine concentration 4.6 × 10-7molL-1) and the electric energy requirements were investigated. The calculation of the energy input in cases of the photolyses was based on the lamp's power. In radiolysis, the absorbed dose (Jkg-1) was the basis. In UV photolysis, atrazine transforms to atrazine-2-hydroxy; this product practically does not degrade during UV photolysis; due to this reason, the mineralisation is very slow. This and some other products of atrazine decomposition degrade only in radical reactions. Dissolved oxygen usually slightly enhances the degradation rate. At 10-7molL-1 concentration level, the matrix, high purity water/purified wastewater, has not much influence on the degradation rates in UV photolysis and radiolysis. In the VUV and UV/VUV systems, considerable matrix effects were observed. Comparing the electric energy requirements of the four degradation processes, radiolysis was found to be the economically most feasible method, requiring 1-2 orders of magnitude less electric energy than UV/VUV, VUV and UV photolysis.

Photo-transformation of atrazine in aqueous solution in the presence of Fe3+-montmorillonite clay and humic substances

As one of the most troublesome herbicides, the natural behavior of atrazine has drawn great attentions. Currently, most studies investigated the adsorption of atrazine on clay minerals and humic substances (HSs), whereas, the transformation of atrazine catalyzed by clay and HSs was still unknown. In the present study, photo-degradation of atrazine in the presence of Fe3+-montmorillonite and Suwannee river fulvic acid (SRFA) in aqueous solution was systematically studied. In the Fe3+-montmorillonite system, the hydroxyl radical (OH) induced removal of atrazine was strongly pH-dependent and the reaction rate increased with the decrease of pH. The presence of SRFA suppressed the atrazine degradation by Fe3+-montmorillonite at pH 3 but promoted its removal rate in the pH range of 4–6. Our results demonstrated that both OH and singlet oxygen are responsible for the degradation process in the Fe3+-montmorillonite/SRFA hybrid system. The degradation of atrazine followed the cleavage of the CN bonds in aliphatic chains of atrazine, and three major products, desethylatrazine, desisopropylatrazine and desethyldesisopropylatrazine were detected. The toxicity assessment showed that the toxicity of the reaction solution significantly decreased after the radical reactions, indicating that the transformation of atrazine on natural clay minerals with/without HSs could be considered as a detoxification pathway, which might be important to evaluate the environmental risk of atrazine in a natural system.

Pesticide residues remaining in soils from previous growing season(s) - Can they accumulate in non-target organisms and contaminate the food web?

Epoxiconazole, tebuconazole, flusilazole, prochloraz, pendimethalin, and the atrazine transformation product (2-hydroxyatrazine) have been found in Czech arable soils at high detection frequencies and/or concentrations. As they have been shown to persist from one growing season to following ones, the question arises of whether they can be taken up by non-target soil organisms and by subsequently planted crops. To reveal this, soils field-contaminated with pesticide residues were subjected to laboratory microcosm studies to measure i) dissipation rates, ii) accumulation in earthworms and lettuce, and iii) exposure by means of solid-phase microextraction (SPME). In parallel, tests with a freshly laboratory-contaminated soil were performed and represented the worst case scenario to be compared with. It was observed that at the residual levels (≤0.1 mg/kg), the behavior of field aged and fresh residues was similar, except for bioaccumulation in earthworms that was significantly lower for aged residues than for fresh residues. Residues' potential for bioconcentration was generally low, i.e., below the maximum residue limits (MRLs) of lettuce. This is in line with SPME results showing low levels of exposure via soil porewater. It follows that these pesticide residues are not likely to pose significant threats to the soil environment, the food web and, consequently, human health if present in soils at levels of ≤0.1 mg/kg.

Application of a ceramic membrane contacting process for ozone and peroxone treatment of micropollutant contaminated surface water

This study investigates the performance of membrane-based ozonation and peroxone processes, regarding the transformation of carbamazepine (CBZ), benzotriazole (BZT), p-chlorobenzoic acid (pCBA) and atrazine (ATZ) in natural surface waters, as well as the formation of bromates. Ozonation, performed with the use of ceramic membrane contactor, was able to diminish CBZ concentration below 0.1 μM at 0.4 mg O3/mg DOC, i.e. presenting >90% removal rate, whereas the transformation of BZT, pCBA and ATZ was not exceeded 70%, 57% and 49%, respectively, under the same experimental conditions. The addition of H2O2 reduced the removal efficiency of CBZ, since up to -8% transformation values were observed at 0.1 mg O3/mg DOC. In contrast, the transformation of ozone-resistant compounds pCBA and ATZ was slightly improved by approximately 5–10%, at 0.8 mg O3/mg DOC. Membrane-based oxidative treatment of surface water resulted to high bromate concentrations (49 μg/L and 28 μg/L for ozone and peroxone process, respectively, at 0.8 mg O3/mg DOC). The results obtained by using the membrane contactor were also compared with the corresponding from conventional batch experiments. These results suggest that the implementation of membrane contactors with the highest possible inner surface per volume along with the use of low ozone gas concentration are required to improve the removal of micropollutants and diminish bromate formation.