Peracetic acid activated by nickel cobaltite as effective oxidizing agent for BPA and its analogues degradation.

The presented research concerns the use of nickel cobaltite nanoparticles (NiCo2O4 NPs) for the heterogeneous activation of peracetic acid and application of NiCo2O4-PAA system for degradation 10 organic micropollutants from the group of bisphenols. The bisphenols removal (initial concentration 1 µM) process was optimized by selecting the appropriate process conditions. The optimal amount of catalyst (115 mg/L), peracetic acid (PAA) concentration (7 mM) and pH (7) were determined using response surface analysis in the Design of Experiment. Then, NiCo2O4 NPs were used to check the possibility of reuse in subsequent oxidation cycles. The work also attempts to explain the mechanism of oxidation of the studied micropollutants. The participation of the sorption process on the catalyst was excluded and based on the experiments with radical scavengers it can be concluded that the oxidation proceeds in a radical pathway, mainly with participation of O2•- radicals. Experiments conducted in real water matrices exhibit low impact on degradation efficiency. Toxicity tests with green alga Acutodesmus obliquus and aquatic plant Lemna minor showed that post-reaction mixture influenced growth and the content of photosynthetic pigments in concentration dependent manner.

Comparison of benzotriazole ultraviolet stabilizers (BUVs) removal from wastewater after subsequent stages of sequencing batch reactor (SBR) treatment process.

The research focused on benzotriazole ultraviolet stabilizers (BUVs) which are commonly used compounds despite being found dangerous, e.g. promoting breast cancer cell proliferation, damaging vital organs such as hearts, brains livers and kidneys. The aim of the study was to analyse the efficiency and removal rate of BUVs from wastewater depending on the quantity of tested compounds and SBR anaerobic-aerobic conditions. The study was conducted in sequencing batch reactors (SBRs - 17 L) with real flocculent activated sludge (8 L) and model wastewater (5 L) containing UV-326, UV-327, UV-328, UV-329 and UV-P from 50 to 600 µg∙L-1. The SBR were operated in 390 cycles of 7 h and 10 min over 130 days. The similarity of the technological parameters of the treatment process to those used in a real wastewater treatment plant was maintained. Efficiency removal of individual BUVs was strictly dependent on the dose of compounds introduced into wastewater and ranged from 68.2 to 97 %. Removal of UV-329 occurred with lowest efficiency (from 68.2 to 85.2 %) while UV-326 was most efficiently removed from the wastewater (from 94.1 to 97 %). UV-329 was removed from wastewater with the lowest (0.0968-0.9524 µg∙L-1∙min-1) average removal rate while UV-327 with the highest (0.16-1.3357 µg∙L-1∙min-1), irrespective of BUVs dose in the influent. Secondary release of BUVs into the wastewater occurred in SBR during the settling phase and was dependent on the type and concentration of the BUVs in the raw wastewater. This occurrence was noted for UV-326 ≥ 100; UV-327 = 600; UV-328 ≥ 200; UV-329 ≥ 50 and UV-P ≥ 100 µg∙L-1. The settling phase needs to be shortened to the required minimum. This is an important conclusion for WWTPs in regards to SBR cycle duration and technological parameters of the treatment process.

Removal of benzotriazole micropollutants using Spirodela polyrhiza (L.) Schleid. And Azolla caroliniana Willd.

Phytoremediation of benzotriazoles (BTR) from waters by floating macrophytes is not well understood, but it seems to have the potential to be used in conjunction with conventional wastewater treatment plants. The effectiveness of removing four compounds from the benzotriazole group by floating plants Spirodela polyrhiza (L.) Schleid. And Azolla caroliniana Willd. From the model solution, was studied. The observed decrease in the concentration of studied compounds was in the range 70.5%-94.5% using S. polyrhiza, and from 88.3% to 96.2% for A. caroliniana. It was determined using chemometric methods that the effectiveness of the phytoremediation process is mainly influenced by three parameters: exposure time to light, pH of the model solution and the mass of plants. Using the design of experiments (DoE) chemometric approach, the optimal conditions for removing BTR were selected: plant weight 2.5 g and 2 g, light exposure 16 h and 10 h, and pH 9 and pH 5 for S. polyrhiza and A. caroliniana, respectively. Studies on the mechanisms of BTR removal have shown that the reduction in concentration is mainly due to the process of plant uptake. Toxicity studies have proved that the tested BTR affected the growth of S. polyrhiza and A. caroliniana and induced changes in the levels of chlorophyllides, chlorophylls as well as carotenoids. More dramatic loss in plant biomass and photosynthetic pigment contents was observed in A. caroliniana cultures exposed to BTR.

Advanced oxidation of bisphenols by peracetic acid activated by light and ultrasound.

Light and ultrasound have been tested as physical factors activating peracetic acid (PAA) to oxidize bisphenols (BPs). Based on the chemometric approach of the Taguchi method, UV irradiation with a wavelength of 254 nm was selected as the optimal type of PAA activator. The effectiveness of the UV/PAA system was also compared with other oxidation methods. Under optimal conditions ([BPs]0 = 1 mg/L, 1 mM PAA, pH 9, UV 254 nm) the tested bisphenols are completely degraded within 15-60 min. The influence of the matrix on the process of organic micropollutants removal in the UV/PAA system was also investigated. Toxicity assessment leads to the conclusion that the reaction mixture shows limited toxicity towards living organisms.

USAEME-GC/MS Method for Easy and Sensitive Determination of Nine Bisphenol Analogues in Water and Wastewater.

A new, simple and sensitive method for isolating nine compounds from the bisphenol group (analogues: A, B, C, E, F, G, Cl2, Z, AP) based on one-step liquid-liquid microextraction with in situ acylation followed by gas chromatography-mass spectrometry was developed and validated using influent and effluent wastewaters. The chemometric approach based on the Taguchi method was used to optimize the main conditions of simultaneous extraction and derivatization. The recoveries of the proposed procedure ranged from 85 to 122%, and the repeatability expressed by the coefficient of variation did not exceed 8%. The method's limits of detection were in the range of 0.4-64 ng/L, and the method's limits of quantification ranged from 1.3 to 194 ng/L. The developed method was used to determine the presence of the tested compounds in wastewater from a municipal wastewater treatment plant located in northeastern Poland. From this sample, eight analytes were detected. Concentrations of bisphenol A of 400 ng/L in influent and 100 ng/L in effluent were recorded, whereas other bisphenols reached 67 and 50 ng/L for influent and effluent, respectively. The removal efficiency of bisphenol analogues in the tested wastewater treatment plant ranged from 7 to approximately 88%.

Mechanisms, toxicity and optimal conditions - research on the removal of benzotriazoles from water using Wolffia arrhiza.

In the presented work, phytoremediation with the use of floating plant Wolffia arrhiza (L.) Horkel ex Wimm. was proposed as a method of removing the selected benzotriazoles (BTRs): 1H-benzotriazole (1H-BTR), 4-methyl-1H-benzotriazole (4M-BTR), 5-methyl-1H-benzotriazole (5M-BTR) and 5-chlorobenzotriazole (5Cl-BTR) from water. The efficiency of phytoremediation depends on three factors: daily time of exposure to light, pH of the model solution, and the amount of plans. Using a design of experiment (DoE) methods the following optimal values were selected: plant amount 1.8 g, light exposure 13 h and pH 7 per 100 mL of the model solution. It was found that the loss of BTRs in optimal conditions ranged from 92 to 100 % except for 4M-BTR, for which only 23 % of removal was achieved after 14 days of cultivation of W. arrhiza. The half-life values for studied compounds ranged from 0.98 days for 5Cl-BTR to 36.19 for 4M-BTR. The observed rapid vanishing of 5M-BTR is supposed by the simultaneous transformation of 5M-BTR into 4M-BTR. The detailed study of BTRs degradation pointed that the plant uptake is mainly responsible for the benzotriazoles concentration decrease. Toxicity tests showed that the tested organic compounds induce oxidative stress in W. arrhiza, which manifested among others, in reduced levels of chlorophyll in cultures with benzotriazoles compared to control.

Environmental risk assessment of low molecule benzotriazoles in urban road rainwaters in Poland.

This study aimed to identify and quantify benzotriazoles (BTRs) emissions from road traffic and paved areas in an urban environment. Heterocyclic organic compounds BTRs are an emerging threat, under-recognized and under-analyzed in most environmental and water legislation. They are hazardous, potentially mutagenic, and carcinogenic micropollutants, not susceptible to effective biodegradation, and they move easily through the trophic chain, contaminating the environment and water resources. Traffic activities are a common source of BTR emissions in the urban environment, directly polluting human habitats through the different routes and numerous vehicles circulating in the cities. Using twelve heterogeneous locations scattered over a metropolitan area in Poland as a case study, this research analyzed the presence of BTRs in water samples from runoff produced from rainwater and snowmelt. 1H-BTR, 4Me-BTR, 5Me-BTR and 5Cl-BTR were detected in the tested runoff water. 5Cl-BTR was present in all samples and in the highest concentrations reaching 47,000 ng/L. Risk quotients calculated on the basis of the determined concentrations indicate that the highest environmental risk is associated with the presence of 5Cl-BTR and the sum of 4Me-BTR and 5Me-BTR, and the most sensitive organisms are bacteria and invertebrates. The results indicate that it is possible to associate the occurrence of these contaminants with the type of cover, traffic intensity, and vehicle type.

Degradation of Benzotriazole UV Stabilizers in PAA/d-Electron Metal Ions Systems-Removal Kinetics, Products and Mechanism Evaluation.

Benzotriazole UV stabilizers (BUVs) have gained popularity, due to their absorption properties in the near UV range (200-400 nm). They are used in the technology for manufacturing plastics, protective coatings, and cosmetics, to protect against the destructive influence of UV radiation. These compounds are highly resistant to biological and chemical degradation. As a result of insufficient treatment by sewage treatment plants, they accumulate in the environment and in the tissues of living organisms. BUVs have adverse effects on living organisms. This work presents the use of peracetic acid in combination with d-electron metal ions (Fe2+, Co2+), for the chemical oxidation of five UV filters from the benzotriazole group: 2-(2-hydroxy-5-methylphenyl)benzotriazole (UV-P), 2-tert-butyl-6-(5-chloro-2H-benzotriazol-2-yl)-4-methylphenol (UV-326), 2,4-di-tert-butyl-6-(5-chloro-2H-benzotriazol-2-yl)phenol (UV-327), 2-(2H-benzotriazol-2-yl)-4,6-di-tert-pentylphenol (UV-328), and 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol (UV-329). The oxidation procedure has been optimized based on the design of experiments (DoE) methodology. The oxidation of benzotriazoles follows first order kinetics. The oxidation products of each benzotriazole were investigated, and the oxidation mechanisms of the tested compounds were proposed.

Peracids - New oxidants in advanced oxidation processes: The use of peracetic acid, peroxymonosulfate, and persulfate salts in the removal of organic micropollutants of emerging concern - A review.

In recent years, there has been increasing interest in using of advanced oxidation processes in water and wastewater decontamination. As a new oxidants peracids, mainly peracetic acid (PAA) and peracid salts, i.e. peroxymonosulfate (PMS) and persulfate (PS) are used. The degradation process of organic compounds takes place with the participation of radicals, including hydroxyl (•OH) and sulfate (SO4•-) radicals derived from the peracids activation processes. Peracids can be activated in homogeneous systems (UV radiation, d-electron metal ions, e.g. Fe2+, Co2+, Mn2+, base, ozonolysis, thermolysis, radiolysis), or using heterogeneous activation (metals with zero oxidation state, metal oxides, quinones, activated carbon, semiconductors). As a result of oxidation, products of a lower mass than the parent compounds, less toxic, and more susceptible to biodegradation are formed. An important task is to investigate the effect of the peracid activation method and matrix composition on the efficiency of contamination removal. The article presents the latest information about the application of peracids in the removal of organic micropollutants of emerging concern (mainly focuses on endocrine disrupted compounds). The most important information on peracetic acid, peroxymonosulfate and persulfate salts, and methods of their activation are presented. Current uses of these oxidants in organic micropollutants removal are also described. Information was collected on the factors influencing the oxidation process and the effectiveness of pollutant removal. This paper compares PAA, PMS and PS-based processes for the first time in terms of kinetics and efficiency.

Simultaneous determination of low molecule benzotriazoles and benzotriazole UV stabilizers in wastewater by ultrasound-assisted emulsification microextraction followed by GC-MS detection.

A rapid, sensitive, economically and ecologically friendly method based on one-step ultrasound-assisted emulsification microextraction and in situ derivatization followed by gas chromatography-mass spectrometry for simultaneous determination of low molecular benzotriazoles and benzotriazole-based ultraviolet filters was developed. The optimized method allows quantification of benzotriazole, 4-methylbenzotriazole, 5-methylbenzotriazole; 5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzortriazole and 2-(2'-hydroxy-5'-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole in municipal and industrial (dairy) wastewater. The method was validated using real influent and effluent wastewater and samples at various stages of the purification process. Relative recoveries obtained using wastewater as sample matrix were between 77 and 137%, method limits of detection from 0.001 to 0.035 µg/L, method limits of quantification from 0.003 to 0.116 µg/L, the repeatability expressed by the coefficient of variation did not exceed 12%. The use of the method for the determination of tested compounds in municipal and industrial wastewater showed their presence in most of the tested samples, in concentrations from LoD to 6.110 µg/L. The conducted studies of samples from municipal wastewater treatment plant located in north-east Poland showed that the effectiveness of benzotriazole removal by this plant wasfrom 29 to 84%. The load of tested compounds released into the environment by this facility ranges from 2 to 269 mg/day/1000 inhabitants.

Model of Hydraulic Resistance When Forecasting Reverse Osmosis in Water Treatment.

The article presents research on the treatment of infiltration water with increased ammonium ion and nitrate(V) content through reverse osmosis. Then, research was conducted on the phenomena related to the decrease in the permeability of the membrane used for the research. The search for an appropriate interpretation of the phenomena was carried out using mathematical modeling. Based on the assumptions of the hydraulic model of the filtration resistance, calculations were made to forecast the efficiency of the osmotic membrane used in the discussed process. For this purpose, the following indicators were determined experimentally for the membrane: change in the volumetric flow of treated wastewater during low-pressure filtration, total hydraulic resistance, and component resistances, i.e., the resistance of the "new" membrane and resistances resulting from the reversible and irreversible fouling phenomena. It has been observed that irreversible resistance arises in the short and early stages of the process. The efficiency is determined by reversible resistance, which is confirmed by the literature.

Exopolysaccharide Carbohydrate Structure and Biofilm Formation by Rhizobium leguminosarum bv. trifolii Strains Inhabiting Nodules of Trifoliumrepens Growing on an Old Zn-Pb-Cd-Polluted Waste Heap Area.

Heavy metals polluting the 100-year-old waste heap in Boleslaw (Poland) are acting as a natural selection factor and may contribute to adaptations of organisms living in this area, including Trifolium repens and its root nodule microsymbionts-rhizobia. Exopolysaccharides (EPS), exuded extracellularly and associated with bacterial cell walls, possess variable structures depending on environmental conditions; they can bind metals and are involved in biofilm formation. In order to examine the effects of long-term exposure to metal pollution on EPS structure and biofilm formation of rhizobia, Rhizobium leguminosarum bv. trifolii strains originating from the waste heap area and a non-polluted reference site were investigated for the characteristics of the sugar fraction of their EPS using gas chromatography mass-spectrometry and also for biofilm formation and structural characteristics using confocal laser scanning microscopy under control conditions as well as when exposed to toxic concentrations of zinc, lead, and cadmium. Significant differences in EPS structure, biofilm thickness, and ratio of living/dead bacteria in the biofilm were found between strains originating from the waste heap and from the reference site, both without exposure to metals and under metal exposure. Received results indicate that studied rhizobia can be assumed as potentially useful in remediation processes.

Occurrence, removal, and environmental risk of phthalates in wastewaters, landfill leachates, and groundwater in Poland.

Phthalates or phthalic acid esters (PAEs) are chemical compounds whose use is exceptionally widespread in everyday materials but, at the same time, have been proven to have harmful effects on living organisms. Effluents from municipal wastewater treatment plants (WWTP) and leachates from municipal solid waste (MSW) landfills are important sources of phthalates with respect to naturally occurring waters. The main aim of this research was determination, mass loads, removal rates and ecological risk assessment of eight phthalates in municipal wastewaters, landfill leachates and groundwater from Polish WWTPs and MSW landfills. Solid-phase microextraction and gas chromatography with mass spectrometry were used for the extraction and determination of analytes. Summed up concentrations of eight phthalates ranged from below LOD to 596 µg/L in influent wastewater with the highest concentration found for bis-2-ethylhexyl phthalate (DEHP) (143 µg/L). The average degree of phthalate removal varies depending on the capacity of a given treatment plant with larger treatment plants coping better than smaller ones. The highest treatment efficiency for all tested treatment plants, over 90%, was reported for dimethyl phthalate (DMP) and diethyl phthalate (DEP). Overall concentrations of phthalates in leachates ranged from below LOD to 303 µg/L while the highest maximum concentration was registered for DEHP (249 µg/L). Overall concentrations of phthalic acid esters in groundwater from upstream monitoring wells ranged from below LOD to 1.8 µg/L and from LOD to 27.9 µg/L in samples from wells downstream of MSW landfills. The obtained data shows that diisobutyl phthalate (DIBP), dibutyl phthalate (DBP), DEHP, and diisononyl phthalate (DINP) pose a high risk for all trophic levels being considered in effluent wastewaters. In the case of groundwater high environmental risk was recorded for DBP and DEHP for all tested trophic levels. Phthalates, in concentrations that pose a high environmental risk, are present in Polish municipal after-treatment wastewater as well as in groundwater under municipal solid waste landfills.

Auxins and Cytokinins Regulate Phytohormone Homeostasis and Thiol-Mediated Detoxification in the Green Alga Acutodesmus obliquus Exposed to Lead Stress.

Phytohormones, such as auxins and cytokinins, take part in the integration of growth control and stress response, but their role in algal adaptation to heavy metal remains to be elucidated. The current research indicated that lead (Pb), one of the most toxic metals in nature, causes severe depletion of endogenous cytokinins, auxins, and gibberellin and an increase in abscisic acid content in the green alga Acutodesmus obliquus. Exogenous auxins and cytokinins alleviate Pb toxicity through the regulation of the endogenous phytohormones' levels. Exogenously applied auxins provoked the coordinated activation metal tolerance mechanisms leading to the increase in phytochelatin synthase activity and accumulation of phytochelatins and their precursors, which are essential for Pb sequestration. On the other hand, phytochelatin synthesis decreased in algal cells treated with cytokinins. Significant changes in the levels of low molecular weight metabolites, mainly involved in metal chelation and glutathione synthesis pathway under the influence of phytohormones in algal cells growing in the presence of Pb stress, were observed. This is the first report showing that auxins and cytokinins are important regulatory factors in algal adaptation strategies to heavy metal stress based on thiol-mediated compounds and the maintenance of phytohormone homeostasis.

Investigation of lipoic acid - 4-methoxybenzyl alcohol reaction and evaluation of its analytical usefulness.

The presented work is aimed to synthesize a new UV active derivative of α-lipoic acid (ALA) by its esterification with 4-methoxybenzyl alcohol (4-MBA, anise alcohol). The formation of ester was confirmed by 1HNMR, FTIR and UV spectroscopy. The analytical usefulness of the obtained compound for quantification of ALA in food items was examined using HPLC-UV and GC-MS systems. It was found that it is possible to assay ALA in the ester form in the concentration ranges: 5·10-6-1·10-4 mol L-1 by HPLC-UV and 1∙10-7-5∙10-5 mol L-1 by GC-MS techniques. The GC-MS procedure was applied for the determination of ALA in the food samples.

Determination of personal care products and hormones in leachate and groundwater from Polish MSW landfills by ultrasound-assisted emulsification microextraction and GC-MS.

Determination of the endocrine disrupting compounds (EDCs) in leachate and groundwater samples from the landfill sites is very important because of the proven harmful effects of these compounds on human and animal organisms. A method combining ultrasound-assisted emulsification microextraction (USAEME) and gas chromatography-mass spectrometry (GC-MS) was developed for simultaneous determination of seven personal care products (PCPs): methylparaben (MP), ethylparaben (EP), propylparaben (PP), buthylparaben (BP), benzophenone (BPh), 3-(4-methylbenzylidene)camphor (4-MBC), N,N-diethyltoluamide (DEET), and two hormones: estrone (E1) and ß-estradiol (E2) in landfill leachate and groundwater samples. The limit of detection (LOD)/limit of quantification (LOQ) values in landfill leachate and groundwater samples were in the range of 0.003-0.083/0.009-0.277 µg L(-1) and 0.001-0.015/0.002-0.049 µg L(-1), respectively. Quantitative recoveries and satisfactory precision were obtained. All studied compounds were found in the landfill leachates from Polish municipal solid waste (MSW) landfills; the concentrations were between 0.66 and 202.42 µg L(-1). The concentration of pollutants in groundwater samples was generally below 0.1 µg L(-1).

Determination of phenols and pharmaceuticals in municipal wastewaters from Polish treatment plants by ultrasound-assisted emulsification-microextraction followed by GC-MS.

A method combining ultrasound-assisted emulsification-microextraction (USAEME) with gas chromatography-mass spectrometry (GC-MS) was developed for simultaneous determination of four acidic pharmaceuticals, ibuprofen, naproxen, ketoprofen, and diclofenac, as well as four phenols, 4-octylphenol, 4-n-nonylphenol, bisphenol A, and triclosan in municipal wastewaters. Conditions of extraction and simultaneous derivatization were optimized with respect to such aspects as type and volume of extraction solvent, volume of derivatization reagent, kind and amount of buffering salt, location of the test tube in the ultrasonic bath, and extraction time. The average correlation coefficient of the calibration curves was 0.9946. The LOD/(LOQ) values in influent and effluent wastewater were in the range of 0.002-0.121/(0.005-0.403) µg L(-1) and 0.002-0.828/(0.006-2.758) µg L(-1), respectively. Quantitative recoveries (≥94%) and satisfactory precision (average RSD 8.2%) were obtained. The optimized USAEME/GC-MS method was applied for determination of the considered pharmaceuticals and phenols in influents and treated effluents from nine Polish municipal wastewater treatment plants. The average concentration of acidic pharmaceuticals in influent and effluent wastewater were in the range of 0.06-551.96 µg L(-1) and 0.01-22.61 µg L(-1), respectively, while for phenols were in the range of 0.03-102.54 µg L(-1) and 0.02-10.84 µg L(-1), respectively. The removal efficiencies of the target compounds during purification process were between 84 and 99%.

Studies on photodegradation of levomepromazine and olanzapine under simulated environmental conditions.

The present study discusses the influence of sunlight on the photostability of levomepromazine (LV) and olanzapine (OLA) hydrochlorides in river water. Four samples of water from different rivers were used in the research. In their course, it turned out that levomepromazine easily underwent photooxidation under simulated environmental conditions, resulting in the generation of its sulphoxide. Olanzapine, on the other hand, appeared to be more resistant to sunlight, as its photodecomposition proceeded slowly, and only one product of its decomposition was detected spectrophotometrically during the process. The photodegradation was analyzed in detail using principal component analysis (PCA) and multivariate curve resolution alternating least squares (MCR-ALS) chemometric methods, and the outcomes verified by HPLC and GC-MS analysis. It can be stated that the rates of the observed processes heavily depended on the chemical composition of the fresh water used in the experiments.

HS-SPME/GC-MS analysis of volatile and semi-volatile organic compounds emitted from municipal sewage sludge.

The aim of the research involved identification and semi-quantitative determination of unknown volatile and semi-volatile organic compounds emitted to air by sewage sludge formed in the process of municipal wastewater treatment in a sewage treatment plant. Samples taken directly after completion of the technological process as well as the sludge stored on the premise of the sewage treatment plant were analyzed. A simple method using off-line headspace solid-phase microextraction combined with gas chromatography-mass spectrometry has been proposed for extraction and detection of organic pollutants. For reliable identification of compounds, combination of two independent parameters: mass spectra and linear temperature programmed retention indices were employed. Over 170 compounds of different structure were identified including aliphatic and aromatic hydrocarbons, alcohols, esters, carbonyls, as well as sulfur, nitrogen, and chlorine containing compounds. The prevailing substances included: ethyl ether, n-hexane, p-xylene, o-xylene, mesitylene, m-ethylbenzene, limonene, n-decane, n-undecane, and n-dodecane. A few compounds such as methanetiol, dimethyl polisulfide, octaatomic sulfur, phthalic anhydride, and indoles were identified in the sludge for the first time.

Macro-porosity and leaching of atrazine in tilled and orchard loamy soils.

Atrazine is the most commonly detected herbicide in the groundwater. Leaching of atrazine largely depends on soil management practices. The aim of this study was to examine leaching of atrazine in tilled and orchard silty loam soils. The experimental objects included: conventionally tilled field (CT) with main tillage operations including pre-plow (10 cm)+harrowing, mouldboard ploughing (20 cm), and a 35 year-old apple orchard (OR) with a permanent sward. To determine leaching of atrazine soil columns of undisturbed structure were taken with steel cylinders of 21.5 cm diameter and 20 cm high from the depth of 0-20 cm. All columns were equilibrated at water content corresponding to field capacity (0.21 kg kg(-1)). Atrazine suspended in distilled water was dripped uniformly onto the surface of each column. Then water was infiltrated and breakthrough times of leachates were recorded. Atrazine concentration in the leachates was determined by means of HPLC Waters. Macro-porosity and percolation rate were higher in OR than CT soil. Cumulative recovery % of the atrazine applied was 1.267% for OR and approximately one third more from the CT soil but the rate of leaching (per unit of time) was greater from the OR soil. The lower leaching under OR than CT can be due to a greater SOM and the presence of earthworm burrows with organic burrow linings that could adsorb atrazine and contribute to preferential flow allowing solutes to bypass parts whereas the greater rate of leaching due to a greater infiltration rate. The results indicate potential of management practices for minimizing atrazine leaching.