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The objective of this study is to investigate the use of coffee waste (CW) to remove the 4-chloro-2-methyl phenoxy acetic acid (MCPA) from aqueous solutions. To prepare CW, it was first washed and boiled to remove color and impurities then it was air dried at room temperature for 48 h. Afterward the particle size distribution and zeta potential of the CW ground were determined. The porous texture of coffee was proved by scanning and transition electron microscopy. Batch adsorption tests were performed at 298 K. The effects of contact time, MCPA concentration, and pH were investigated. It was observed that the adsorption of MCPA by using CW is independent of the solution pH level. The Langmuir isotherm provided the best correlation for MCPA adsorption onto CW, showing that the adsorption was favorable. The Langmuir adsorption capacity was found to be 0.34 g/g. The second-order model provided the best description of MCPA adsorption onto CW when compared with the first order model. Infrared spectral studies revealed that acidic groups carboxyl and hydroxyl, are predominant contributors to MPCA adsorption by coffee.

MnO2-modified carbon paste (CP) electrodes and Mn-modified glassy carbon (GC) electrodes show the electrochemistry of Mn species which strongly depends on the solution pH. Both types of modified electrodes are capable of catalytically reducing monochlrophenoxy acetic acid (MCPA), a herbicide. However, the catalytic wave appears at a lower potential at the MnO2-modified CP electrode than that at the Mn-modified GC electrode, thus enabling the modified CP electrode for the determination of MCPA. Amperometric determination of MCPA at the MnO2-modified CP electrode results in a very low detection limit of 0.20 ppm. The application of the proposed method for quantitative analysis of an MCPA formulation provides reliable results. Interaction of MCPA with MnO2 is observed even in the absence of applied potentials mimicking the real situation in the environment where MCPA, when introduced to farmland, would interact with MnO2 if present in soil.

In river catchments used as drinking water sources, high pesticide concentrations in abstracted waters require an expensive treatment step prior to supply. The acid herbicide 2-methyl-4-chlorophenoxyacetic acid (MCPA) is particularly problematic as it is highly mobile in the soil-water environment following application. Here, an agri-environmental scheme (AES) was introduced to a large-scale catchment (384 km 2 ) to potentially reduce the burden of pesticides in the water treatment process. The main measure offered was contractor application of glyphosate by weed wiping as a substitute for boom spraying of MCPA, supported by educational and advisory activities. A combined innovation applied in the assessment was, i) a full before-after-control-impact (BACI) framework over four peak application seasons (April to October 2018 to 2021) where a neighbouring catchment (386 km 2 ) did not have an AES and, ii) an enhanced monitoring approach where river discharge and MCPA concentrations were measured synchronously in each catchment. During peak application periods the sample resolution was every 7 h, and daily during quiescent winter periods. This sampling approach enabled flow- and time-weighted concentrations to be established, and a detailed record of export loads. These loads were up to 0.242 kg km -2 yr -1 , and over an order of magnitude higher than previously reported in the literature. Despite this, and accounting for inter-annual and seasonal variations in river discharges, the AES catchment indicated a reduction in both flow- and time-weighted MCPA concentration of up to 21% and 24%, respectively, compared to the control catchment. No pollution swapping was detected. Nevertheless, the percentage of MCPA occurrences above a 0.1 μg L -1 threshold did not reduce and so the need for treatment was not fully resolved. Although the work highlights the advantages of catchment management approaches for pollution reduction in source water catchments, it also indicates that maximising participation will be essential for future AES., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 The Authors. Published by Elsevier B.V. All rights reserved.)

The molecularly imprinted polymers (MIPs) with the following herbicides used as templates 2,4-dichlorophenoxyacetic acid (2,4-D) or 4-chloro-2-methylphenoxy- acetic acid (MCPA) were synthesized by precipitation polymerization technique using 4-vinylpyridine (4-VP) as a functional monomer, ethylene glycol dimethacrylate (EGDMA) as a cross-linking agent, and 2,2'-azobisisobutyronitrile (AIBN) as an initiator in methanol solvent. For the flavonoid MIPs, rutin (Ru) and quercetin (Q) were used as templates and synthesized via a similar technique, utilizing acrylamide (AA) as a functional monomer. Analysis of binding in the molecularly imprinted and non-imprinted polymer (NIP) has proved that MIP shows a higher affinity towards the analytes, compared to NIP. MIP was used to determine analytes in water using the Flowing Atmospheric-Pressure Afterglow Mass Spectrometry (FAPA-MS) technique. In this approach, the method limit of detection (MLOD) of 2,4-D, MCPA, Ru, and Q in MIP was 4, 3, 10, and 5 μg in 1 g MIP, respectively. The release kinetics of the analytes from MIP and their stability in water was studied. The cultures of Tetradesmus obliquus (Turpin) M.J. Wynne and Daphnia magna Straus were used for in vivo toxicity studies revealing that only Ru-MIP and Q-MIP had negative effect on the living organisms used in the bioassays., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Freshwater occurrences of the selective acid herbicide 2-methyl-4-chloro-phenoxyacetic acid (MCPA) are an ongoing regulatory and financial issue for water utility industries as the number and magnitude of detections increase, particularly in surface water catchments. Assessments for mitigating pesticide pollution in catchments used as drinking water sources require a combination of catchment-based and water treatment solutions, but approaches are limited by a lack of empirical data. In this study, an enhanced spatial (11 locations) and temporal (7-hourly to daily sampling) monitoring approach was employed to address these issues in an exemplar surface water source catchment (384 km 2 ). The spatial sampling revealed that MCPA was widespread, with occurrences above the 0.1 μg L -1 threshold for a single pesticide being highly positively correlated to sub-catchments with higher proportions of 'Improved Grassland' land use (r = 0.84). These data provide a strong foundation for targeting catchment-based mitigation solutions and also add to the debate on the ecosystems services provided by such catchments. Additionally, of the 999 temporal samples taken over 12 months from the catchment outlet, 25% were above the drinking water threshold of 0.1 μg L -1 . This prevalence of high concentrations presents costly problems for source water treatment. Using these data, abstraction shutdowns were simulated for five scenarios using hydrometeorological data to explore the potential to avoid intake of high MCPA concentrations. The scenarios stopped abstraction for 4.2-9.3% of the April-October period and reduced intake of water containing over 0.1 μg L -1 of MCPA by 16-31%. This represents an important development for real-time proxy assessments for water abstraction in the absence of more direct pesticide monitoring data., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 The Authors. Published by Elsevier B.V. All rights reserved.)

Leptospira is a genus of spirochete bacteria highly motile that includes pathogenic species responsible to cause leptospirosis disease. Chemotaxis and motility are required for Leptospira infectivity, pathogenesis, and invasion of bacteria into the host. In prokaryotes, the most common chemoreceptors are methyl-accepting chemotaxis proteins that have a role play to detect the chemical signals and move to a favorable environment for its survival. Here, we report the first crystal structure of CACHE domain of the methyl-accepting chemotaxis protein (McpA) of L. interrogans. The structural analysis showed that McpA adopts similar α/β architecture of several other bacteria chemoreceptors. We also found a typical dimerization interface that appears to be functionally crucial for signal transmission and chemotaxis. In addition to McpA structural analyses, we have identified homologous proteins and conservative functional regions using bioinformatics techniques. These results improve our understanding the relationship between chemoreceptor structures and functions of Leptospira species., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Inc. All rights reserved.)

Data on chlorophenoxy herbicides (CPHs) in drinking water from China are scarce. This study was designed to describe the occurrence of CPHs in drinking water in China. In June 2019, drinking water samples including 789 tap water and 95 groundwater samples were collected from 31 provinces in mainland China and Hong Kong. Raw source, treated, and tap water samples (n = 20, 20, and 170, respectively) in Wuhan, Central China were also analyzed. 2,4-dichlorophenoxyacetic acid (2,4-D) and 2-methyl-4-chlorophenoxyacetic acid (MCPA) were found in 71.2% and 74.9% of the samples nationwide, respectively. The cumulative concentration of CPHs (ΣCPHs) in tap water in China was up to 125 ng/L (median: 1.38 ng/L), and regional variations were found for ΣCPHs. The highest median ΣCPHs (3.95 ng/L) was found in Northeast China, followed by Central (3.40), South (2.71), East (2.43), Southwest (1.58), North (0.42), and Northwest China (0.30). The median ΣCPHs in groundwater was approximately five times lower than that in tap water. In addition, ΣCPHs were found in all the raw source water samples collected in Wuhan, Central China (median: 6.69 ng/L, range: 2.66-43.1 ng/L). The removal of 2,4-D and MCPA during conventional drinking water treatment was not efficient, removing approximately 0.91% and 17.4%, respectively. In a water plant with advanced treatment, they were efficiently removed. Seasonal variations were found in ΣCPHs in tap water from Wuhan, with the highest found in July (median: 21.2 ng/L), and the lowest in October (1.96 ng/L). The intake of CPHs via water ingestion was estimated as below 5 ng/kg-bw/day, much lower than the reference doses for 2,4-D (5 μg/kg-bw/day) and MCPA (4 μg/kg-bw/day). This is the first study to demonstrate the fate of CPHs during drinking water treatment and seasonal variations of CPHs in water from Wuhan, China. Moreover, this study provides an overview of ΣCPHs in tap water for many areas in China., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

The present study was focused on the application of an electrochemical oxidation process combined with biodegradation for the removal of novel Herbicidal Ionic Liquids (HILs) -promising protection plant products which incorporate herbicidal anions and ammonium cations. The influence of carbon chain length (n = 8, 10, 12, 14, 16, 18) in the dialkyldimethylammonium cations on electrochemical oxidation kinetics, degradation efficiency and biodegradation by activated sludge was investigated. It was established that the applied cation influenced the heterogeneous rate constant and diffusion coefficient of electrochemical oxidation. The oxidation efficiency ranged from 17% in case of HILs with C8 alkyl chain to approx. 60% in case of HILs comprising C14 and C16 alkyl chains after 3 h of electrochemical treatment. Subsequent biodegradation studies revealed that electrochemical oxidation improved the mineralization efficiency of the studied HILs. The mineralization efficiency of electrochemically-treated HILs ranged from 28% in case of HILs comprising the C8 alkyl chain to 57% in case of HILs with C14 and C16 alkyl chains after 28 days. In case of untreated HILs, the corresponding mineralization efficiency ranged from 0 to 8%, respectively. This confirms the feasibility of a hybrid electrochemical-biological approach for treatment of herbicidal ionic liquids based on MCPA., (Copyright © 2019 Elsevier Inc. All rights reserved.)

Limited knowledge and experimental data exist on pesticide leaching through partially frozen soil. The objective of this study was to better understand the complex processes of freezing and thawing and the effects these processes have on water flow and pesticide transport through soil. To achieve this we conducted a soil column irrigation experiment to quantify the transport of a non-reactive tracer and the herbicide MCPA in partially frozen soil. In total 40 intact topsoil and subsoil columns from two agricultural fields with contrasting soil types (silt and loam) in South-East Norway were used in this experiment. MCPA and bromide were applied on top of all columns. Half the columns were then frozen at -3 °C while the other half of the columns were stored at +4 °C. Columns were then subjected to repeated irrigation events at a rate of 5 mm artificial rainwater for 5 h at each event. Each irrigation was followed by 14-day periods of freezing or refrigeration. Percolate was collected and analysed for MCPA and bromide. The results show that nearly 100% more MCPA leached from frozen than unfrozen topsoil columns of Hov silt and Kroer loam soils. Leaching patterns of bromide and MCPA were very similar in frozen columns with high concentrations and clear peaks early in the irrigation process, and with lower concentrations leaching at later stages. Hardly any MCPA leached from unfrozen topsoil columns (0.4-0.5% of applied amount) and concentrations were very low. Bromide showed a different flow pattern indicating a more uniform advective-dispersive transport process in the unfrozen columns with higher concentrations leaching but without clear concentration peaks. This study documents that pesticides can be preferentially transported through soil macropores at relatively high concentrations in partially frozen soil. These findings indicate, that monitoring programs should include sampling during snow melt or early spring in areas were soil frost is common as this period could imply exposure peaks in groundwater or surface water., (Copyright © 2018 The Authors. Published by Elsevier B.V. All rights reserved.)

Sorption and degradation are the primary processes controlling the efficacy and runoff contamination risk of agrochemicals. This study assessed the influence of two biochars, made from woodchips and straw at a pyrolysis temperature of 725°C and applied to a loamy sand and a sandy soil in the concentration of 5.3 g 100 g(-1) sandy soil and 4.1 g 100 g(-1) loamy sand soil, or 53 t ha(-1) for both soil types, on degradation of the herbicide 4-chloro-2-methylphenoxyacetic acid (MCPA). Soils were spiked with 50 mg MCPA kg(-1) soil. In the sandy soil, significantly more MCPA remained after 100 days if amended with straw-derived biochar in comparison to wood-derived biochar. Both biochars types significantly increased urease activity (p<0.05) after 37 days in the loamy sand soil, but these differences disappeared after 100 days. A root and shoot elongation test demonstrated that the soils containing straw-derived biochar and spiked with MCPA, showed the highest phytotoxicity. Both biochars were found to retard MCPA degradation in loamy sand and sandy soils. This effect could not be explained only by sorption processes due to comparatively low developed micro/mesoporous structure of both biochars shown by BET surface analysis. However, an enhanced MCPA persistence and soil toxicity in sandy soil amended with straw biochar was observed and further studies are needed to reveal the responsible mechanisms., (Copyright © 2014 Elsevier Inc. All rights reserved.)

This study aimed to determine the leaching potential of MCPA and the contribution of major soil components to its retention in 27 profiles of common Polish arable soils. Results of experiments and modeling of the pH-dependent adsorption indicated that the adsorption of the neutral and anionic forms of MCPA on soil organic matter are the predominant adsorption mechanisms, even in soil horizons with very low organic matter contents. The third most important mechanism was the adsorption of MCPA anions, most likely through the water bridging mechanism on sorption sites created by exchangeable Fe cations adsorbed in soil. It was found that in acidic soils with very low organic matter contents, the neutral form of MCPA was also adsorbed on the quartz and silica sorption sites of silt and sand. The value of r(2) was 78% when it was assumed that MCPA was adsorbed only on organic matter and 93% when all indicated mechanisms of adsorption on mineral soil components were included in the model fitted to data from all soil profiles. Simulations using FOCUS PELMO indicated that in two profiles, the 80th percentiles of the average yearly concentrations of MCPA in the leachate exceeded the European Union (EU) contamination limit of 0.1 μgL(-1). It was shown that when an assumption was made in the model of pH-dependent adsorption that MCPA was adsorbed only on organic matter, the leaching potential of MCPA was overestimated in the examined soils. Much better predictions were obtained when adsorption on mineral soil components was also included in the model., (Copyright © 2014 Elsevier B.V. All rights reserved.)

For improved early detection and assessment of severe acute kidney damage following accidental or intentional ingestion of the herbicide MCPA, we compared a panel of 14 novel kidney injury biomarkers with plasma creatinine. Male Wistar rats received four different oral doses of MCPA and plasma and urine biomarker levels were measured at 8, 24 and 48 h after MCPA exposure. Diagnostic performances using absolute levels, urine levels normalized to urine creatinine or urinary excretion rate were determined by ROC analysis. Plasma creatinine remained the best early biomarker for predicting histological changes at 48 h. The performance of plasma cystatin C in mirroring kidney function was similar to that of plasma creatinine. While urine concentrations were generally less predictive, normalization by urine creatinine greatly improved the performance of several biomarkers. This may be due to an apparent amplification of the biomarker signal on normalizing to creatinine, in the presence of a declining glomerular filtration rate prior to reaching steady state. Normalized 8 h osteopontin and albumin concentrations outperformed other normalized biomarkers in predicting histological changes at later times. Normalized urinary kidney injury molecule-1 at 48 h also correlated well with the degree of kidney damage., (Copyright © 2014 Elsevier Ireland Ltd. All rights reserved.)

Constructed wetlands (CWs) are receiving a renewed attention as a viable phytotechnology for treating agricultural wastewaters and for the removal of more specific pollutants, in particular recalcitrant ones. In this work, the performance of CW mesocosms using light expanded clay aggregates (LECA) as the bed's substrate and planted with Phragmites australis was investigated for treatment of olive mill wastewater (OMW), swine wastewater (SW) contaminated with oxytetracycline and water contaminated with herbicide MCPA (2-methyl-4-chlorophenoxyacetic acid). Both wastewaters (OMW and SW) initially presented high organic matter content and total suspended solids which were removed by the system with efficiencies higher than 80%. Removal of polyphenols in OMW and nitrogen compounds in SW also showed similar or higher efficiencies in comparison with other treatment systems reported in the literature. The antibiotic oxytetracycline was completely removed from SW within the assay period in unplanted LECA beds, but planted beds allowed a significantly faster removal. In regard to water contaminated with MCPA, the results showed that LECA has a large sorption capacity for this herbicide (removal efficiencies of 56-97%). In general, considerably higher pollutant removal efficiencies were obtained when plants were used (up to 28% higher). The results obtained are indicative that CWs with LECA as substrate may be an adequate option for agricultural wastewater treatment., (Copyright © 2013 Elsevier B.V. All rights reserved.)

An evaluation was made of the impact of olive mill waste and its organic matter transformation on the sorption, desorption, leaching, and degradation of the herbicide MCPA when the waste was applied to four Mediterranean soils. The soils were amended in the laboratory with fresh, composted, and field-aged olive mill waste (OW, COW, and AOW treatments, respectively). It was found that the greater the amount of OW applied to the soils, but especially the greater its organic matter maturity, the greater the adsorption of MCPA. Compared with unamended soils, at the 5% rate of application the adsorption capacity increased by between 9.8% and 40%, 148% and 224%, and by 258% for the OW, COW, and AOW amended soils, respectively. The hysteresis coefficients were significantly lower in the OW-amended soils than in AOW or COW-amended soils, indicating that the adsorbed MCPA could be easily desorbed in OW-amended soils if the amendment is not aged or composted. While the OW addition greatly extended the persistence of MCPA, the application of COW enhanced MCPA degradation in all the soils, as corresponded to the increased soil microbial activity indicated by the higher levels of soil dehydrogenase activity. Fresh OW amendment significantly increased the amount of MCPA leached (from 13.7% in the most alkaline soil to 36.7% in the most acidic, at the 5% rate of application), favored by the higher levels of water soluble organic carbon content. However, leaching losses of the herbicide were reduced by up to 39.9% and 55.3% in the COW- and AOW-amended soils at the 5% loading rate, respectively. The use of OW with a high degree of organic matter maturity may be regarded as a potentially useful management practice to reduce MCPA leaching in soils with low organic matter content. The application of fresh OW, however, could well increase the risk of groundwater contamination by this herbicide, especially in acidic soils., (© 2013.)