Bioinformatics analysis of the potential mechanisms of Alzheimer's disease induced by exposure to combined triazine herbicides.

BACKGROUND: The development of Alzheimer's disease (AD) is promoted by a combination of genetic and environmental factors. Notably, combined exposure to triazine herbicides atrazine (ATR), simazine (SIM), and propazine (PRO) may promote the development of AD, but the mechanism is unknown. AIM: To study the molecular mechanism of AD induced by triazine herbicides. METHODS: Differentially expressed genes (DEGs) of AD patients and controls were identified. The intersectional targets of ATR, SIM, and PRO for possible associations with AD were screened through network pharmacology and used for gene ontology (GO) and Kyoto Encyclopaedia of Genes and Genomes (KEGG) enrichment analysis. The binding potentials between the core targets and herbicides were validated by molecular docking and molecular dynamics. RESULTS: A total of 1,062 DEGs were screened between the AD patients and controls, which identified 148 intersectional targets of herbicides causing AD that were screened by network pharmacology analysis. GO and KEGG enrichment analysis revealed that cell cycling and cellular senescence were important signalling pathways. Finally, the core targets EGFR, FN1, and TYMS were screened and validated by molecular docking and molecular dynamics. CONCLUSION: Our results suggest that combined exposure to triazine herbicides might promote the development of AD, thereby providing new insights for the prevention of AD.

Transition metal-doped germanium oxide nanozyme with enhanced enzyme-like activity for rapid detection of pesticide residues in water samples.

Designing highly active nanozymes for bioanalysis and environmental sensing remains a challenge. In this study, transition metal, palladium (Pd) and iron (Fe), doped germanium oxide (GeO2) nanozyme was designed and optimized. Compared with the pristine GeO2 nanozyme, the transition metal doped GeO2 nanozyme have lower Michaelis-Menten constants and higher catalytic activity, indicating that the Pd and Fe doped GeO2 nanozyme not only enhance their affinity for the substrate but also improve its catalytic activity. In addition, a colorimetric sensor based on the GeO2@Pd-H2O2-TMB system was constructed for the visual detection of simazine in water samples due to the good affinity between TMB and simazine. This sensor has good selectivity and sensitivity with a detection limit of 6.21 µM because of the highest catalytic performance of GeO2@Pd nanozyme. This study broadens the application of nanozymes in environmental field and other nanozymes can also be enhanced in activity by simple transition metal doping.

Catchment sourcing urban pesticide pollution using constructed wetlands in Melbourne, Australia.

A survey of 111 urban constructed stormwater wetlands (median watershed area = 86.8 ha) was conducted to identify the major pesticides present and to determine their major catchment sources (residential, industrial, commercial, sporting ovals) and associations with catchment imperviousness. Melbourne, Australia, has separate stormwater and sewerage systems and these wetlands are designed to treat urban stormwater. To maximise the pesticides that could be detected, three types of passive samplers (POCIS, Chemcatcher® SDB-XC and Chemcatcher® C18) were deployed, along with collection of fine sediments. A total of 231 pesticides were screened using these methods. Pesticides that were detected in >5 % of wetlands were checked to determine their registered use in urban areas using an Australian government database (PubCris). Twenty-five pesticides were detected in >5 % of wetlands: 4 pesticides were associated with non-urban land uses (agriculture and forests), another 4 pesticides had no known registered use in urban areas and 17 were associated with urban areas. The pesticides associated with urban areas were the herbicides simazine, diuron, metolachlor, bromacil, propyzamide and paclobutrazol, the fungicides tebuconazole, propiconazole, metalaxyl, trifloxystrobin, iprodione and carbendazim and the insecticides fipronil, bifenthrin, chlorantraniliprole, thiamethoxam and permethrin. Atrazine was also detected in 59 % of wetlands but has not been registered for urban uses in Australia since 2010. It's presence in Melbourne may be due to legacy issues or aerial transportation from rural areas where it's still widely used in crop cultivation. Generally, the major urban catchment source of pesticides is from residential areas (particularly fipronil and simazine), most likely in wood preservatives, paints and from weed or insect control. Many of these widely used pesticides were correlated with increased catchment imperviousness. Some pesticides (bromacil and imidacloprid) were correlated with commercial premises and chlorantraniliprole was correlated with the presence of sporting ovals in the catchment. No pesticides were specifically correlated with industrial areas. The use of passive samplers and fine sediments, in conjunction with detailed land use mapping of stormwater wetland catchments is very effective and efficient in monitoring and sourcing pesticide contamination in urban environments.

National Assessment of Long-Term Groundwater Response to Pesticide Regulation.

Quantitative assessments of long-term, national-scale responses of groundwater quality to pesticide applications are essential to evaluate the effectiveness of pesticide regulations. Retardation time in the unsaturated zone (Ru) was estimated for selected herbicides (atrazine, simazine, and bentazon) and degradation products (desethylatrazine (DEA), desisopropylatrazine (DIA), desethyldesisopropylatrazine (DEIA), and BAM) using a multidecadal time series of groundwater solute chemistry (∼30 years) and herbicide sales (∼60 years). The sampling year was converted to recharge year using groundwater age. Then, Ru was estimated using a cross-correlation analysis of the sales and the frequencies of detection and exceedance of the drinking water standard (0.1 µg/L) of each selected compound. The results showed no retardation of the highly polar, thus mobile, parent compounds (i.e., bentazon), while Ru of the moderately polar compounds (i.e., simazine) was about a decade, and their degradation products showed even longer Ru. The temporal trends of the degradation products did not mirror those of the sale data, which were attributed to the various sale periods of the parent compounds, sorption of the parent compounds, and complex degradation pathways. The longer Ru in clayey/organic sediments than in sandy sediments further confirmed the role of soil-specific retardation as an important factor to consider in groundwater protection.

Surface water contamination from pesticide mixtures and risks to aquatic life in a high-input agricultural region of Brazil.

The environmental risks of pesticides found in surface waters of an important agricultural basin in Brazil were estimated by adopting two approaches: individual pesticides risk quotients (RQ) and concentration addition model for pesticide mixtures (∑RQs) contained in each water sample. Monitoring was carried out in the Mogi Guaçu River basin, Brazil, from October 2017 to May 2018. Four sampling points were selected in the Mogi Guaçu River and seven in its tributaries A multiresidue method with solid-phase extraction and subsequent analysis by UPLC-ESI-QqQ-MS/MS was developed to quantify 19 pesticides. Herbicides, except for simazine, presented the highest detection frequencies with values above 70%. Tebuthiuron was found in all 55 analyzed samples, presenting the highest concentration (6437 ng L-1) over the monitoring period. Fungicides and insecticides showed similar detection frequency (DF) values, ranging from 1.8% to 21.8%. Tebuconazole and carbofuran were the fungicides and insecticides most frequently detected, respectively. January 2018 sampling showed the highest total concentration of pesticides, differing from March 2018 and May 2018 (p < 0.05). The MG2 > TMG8 > MG1 > TMG6 sites showed the highest concentration total of pesticides while MG4 > TMG4 > TMG3 (p < 0.05) sites showed the lowest values: MG4 > TMG4 > TMG3 (p < 0.05). Most pesticide occurrences presented no risks to aquatic organisms. Only 19 out of the 175 pesticide occurrences > LOQ presented individual risks to aquatic biota. Contrary to the results obtained by the individual risk assessment, most pesticide mixtures presented risks to aquatic biota. In 36 out of the 55 samples analyzed during monitoring, pesticide mixtures presented risks to aquatic life.

Combination of microwave-assisted solvent extraction and effervescence-assisted deep eutectic solvent-based in-syringe dispersive liquid-liquid microextraction and its application in the extraction of triazine pesticides from apple samples.

In the current study, a combination of microwave-assisted solvent extraction combined with effervescence-assisted deep eutectic solvent-based in-syringe dispersive liquid-liquid microextraction has been developed as a new sample pretreatment method. The offered method was used for the extraction of five triazine pesticides (atrazine, propazine, cyanazine, ametryn, and simazine) from apple samples before their determination by gas chromatography-flame ionization detection. For this purpose, briefly, the apple sample was contacted with a suitable acidified extraction solvent and the mixture was exposed to microwave irradiations. Then, the supernatant was taken and mixed with a few microliters of a low-density deep eutectic solvent. The supernatant phase containing the extracted analytes was injected into a sodium bicarbonate solution filled into a syringe. Consequently, the effervescence reaction occurs and the analytes were extracted into the fine droplets of extractant dispersed throughout the solution. Afterward, an aliquot of this phase was analyzed by the chromatographic system. Satisfactory outcomes include high enrichment factors (228-261) and extraction recoveries (67-87%), good repeatability (relative standard deviations equal to or less than 3.2% and 5.3% for intra- and inter-day precisions), and low limits of detection (0.4-0.7 ng/g) and quantification (1.4-2.3 ng/g) were acquired under the best experimental situations.

Unraveling the occurrence of contaminants of emerging concern in groundwater from urban setting: A combined multidisciplinary approach and self-organizing maps.

In recent decades, changes in human behavior and new technologies have introduced thousands of new compounds into the environment called "contaminants of emerging concern" (CEC). These compounds have been detected in different environmental compartments such as soil, surface water, air, and groundwater. The presence of these contaminants in groundwater may pose risks to human health when used as potable water. In some urban areas in Brazil, groundwater is normally consumed without previous treatment. This study aimed to use statistical analysis by self-organizing maps (SOM) to evaluate the trends of CEC in urban groundwater systems. A total of 23 CEC compounds including pesticides, pharmaceuticals, and hormones were determined in groundwater samples using solid phase extraction and liquid chromatography-mass spectrometry. The CEC most frequently detected were atrazine and degradation products, fipronil, simazine, tebuconazole, hexazinone, and caffeine in concentrations up to 300 ng L-1. All studied compounds were detected in groundwater at least in one sample. Patterns in the data through SOM have shown a strong positive correlation between atrazine, hexazinone, simazine, tebuthiuron, 2-hydroxyatrazine, and 17ß-estradiol. The hormones estrone and testosterone also show a positive correlation due to their similar chemical properties. On the other hand, caffeine was detected in 90% of the samples, likely due to a population habit of taking daily a hot drink made of yerba mate associated with low rates of treated domestic sewage in the study area.

Household herbicide use as a source of simazine contamination in urban surface waters.

Contamination of urban surface waters by herbicides is an increasing concern; however, sources of contamination are poorly understood, hindering the development of mitigation and regulatory strategies. Impervious surfaces, such as concrete in driveways and paths are considered an important facilitator for herbicide runoff to urban surface waters following applications by residential homeowners. This study assessed the transferability of a herbicide from concrete pavers treated with an off-the-shelf product, containing simazine as the active herbicide, marketed for residential homeowner application to impervious surfaces. Commercially available pavers were treated according to label directions and the effects of exposure time prior to irrigation, repeated irrigations, and dry time between irrigations on transferability of simazine to runoff were assessed. Simazine transferability was greatest when receiving an initial irrigation 1 h after application, with concentrations in runoff reduced by half when exposure times prior to the first irrigation were >2 days. Concentrations remained stable for repeated irrigations up to 320 days and exposures to outdoor conditions of 180 days prior to a first irrigation. Dry time between irrigations significantly influenced simazine transfer to runoff. Dry periods of 140 days resulted in approximately a 4-times increase in simazine transferability to runoff. These results suggest that herbicides used by homeowners, or any other users, on impervious surfaces are available to contaminate runoff for prolonged time periods following application at concentrations that may pose risks to aquatic life and for reuse of harvested runoff on parks and gardens. Regulators should consider the potential of hard surfaces to act as reservoirs for herbicides when developing policies and labelling products.

Isolation of 2 simazine-degrading bacteria and development of a microbial agent for bioremediation of simazine pollution.

Simazine was one of the most commonly used herbicides and was widely used to control broadleaf weeds in agriculture and forestry. Its widespread use had caused wide public concern for its high ecological toxicity. In order to remove simazine residues, 2 strains capable of effectively degrading simazine were isolated from the soil and named SIMA-N5 and SIMA-N9. SIMA-N5 was identified as Bacillus licheniformis by 16SrRNA sequence analysis, and SIMA-N9 was Bacillus altitudinis. According to the degradation ratio of simazine in a certain period of time, the degradation ability of different strains was evaluated. The degradation efficiency of simazine (5 mg/L) by SIMA-N9 could reach about 98% in 5d, and the strain SIMA-N5 could reach 94% under the same conditions. In addition, the addition of Pennisetum rhizosphere soil during the process of degrading simazine by strain SIMA-N9 could effectively improve the degradation efficiency. The strain SIMA-N9 has been developed as a microbial agent for the bioremediation of simazine contamination in soil. The new microbial agent developed by using SIMA-N9 has achieved satisfactory application effects. Based on the research results already obtained in this study, it was considered that strain SIMA-N9 and its live bacterial agent could play an important role in bioremediation of simazine pollution. This study could not only provide a set of solutions to the simazine pollution, but also provide a reference for the treatment of other pesticide pollution.

Bead-immobilized Pseudomonas stutzeri Y2 prolongs functions to degrade s-triazine herbicides in industrial wastewater and maize fields.

Functional durability of bio-augmented microbes in contaminated fields remains a major challenge in bioremediation. In the present study, various immobilization materials and compositional combinations were designed and compared to enhance the functional durability of Pseudomonas stutzeri sp. Y2 for degradation of simazine, one of the most used herbicides, in industrial wastewater and maize fields. Among four combinations of materials tested, the optimal combination obtained from the orthogonal array trials was 14% polyvinyl alcohol (PVA), 1-3% sodium alginate (SA), 2% activated carbon (AC), and 1-2% Y2 cells (PSC-Y2), which yielded 1.7 fold faster degradation of simazine at 50 mg L-1 than that by free Y2 cells in the industrial wastewater. The degradation half-lives (DT50) of simazine (10 mg L-1) by free Y2 cells and PSC-Y2 was 1.1 d and 5.3 d in laboratory soil, respectively. The DT50 of simazine by PSC-Y2 at the recommended and double dosages of simazine (0.45 and 0.9 g ai·m-2) was 17.2 d and 12.4 d in the maize fields, respectively, in comparison with 23 d and 17.4 d by free Y2 cells. In addition, the PSC-Y2 degraded 100% of atrazine and terbuthylazine, and 96% of propazine at an initial concentration of 50 mg L-1 each in 4 days. This study provides an immobilization strategy to stabilize bacteria and prolong bacterial functions to treat s-triazine herbicides contaminated water and soil.

Automated online coupling of robot-assisted single drop microextraction and liquid chromatography.

A high-throughput and innovative setup has been developed to automate the online integration of single drop microextraction (SDME), liquid chromatography (LC) and high-resolution mass spectrometry (QqToF). SDME and LC were online hyphenated for the first time. SDME was carried out by a lab-made cartesian robot actuating a 100 µL syringe, equipped with a three-way solenoid microvalve that allowed the online transference of the enriched extract to the chromatographic system, through a six-port switching valve. The complete method, including the synchronized robot action, valves, and the analytical instruments, was controlled by an Arduino Mega board. The merits of the proposed setup were demonstrated by the triazines determination in coconut water samples. The most relevant extraction parameters, such as drop size, exposure time, stirring effect, salt addition and pH were systematically investigated. Under optimized conditions (60 µL drop volume and 10 min extraction time), the LC-UV enrichment factors (EF) and the extraction recoveries (ER) ranged between 15.2-18.4 and 11.4-13.8%, respectively. Using the SDME-LC-MS setup, the linear range, detection limit (S/N = 3) and precision (RSD, n = 6 at 0.25 µg L-1 level of concentration) were 0.25-25 µg L-1, 0.10 µg L-1 and 16.8% for simazine; 0.25-25 µg L-1, 0.05 µg L-1 and 14.7% for atrazine; and 0.25-25 µg L-1, 0.05 µg L-1 and 18.5% for propazine, respectively. Although none of the analytes were detected in the evaluated commercial samples, the results indicate that the proposed online SDME-LC setup is a competitive analytical strategy for the determination of target organic compounds in complex matrices.

Occurrence, distribution and ecological risk assessment of the herbicide simazine: A case study.

The occurrence and distributions of simazine, and its environmental behaviors were studied in Taizi River, China. Results showed that concentration of simazine in surface water and suspended solids (SS) were in the range of 35-1150 ng L-1and 0.00-1075 ng g-1 with mean value of 240.26 ng L-1 and 311.68 ng g-1, respectively. A significant correlation between the concentrations of simazine and organic carbon was observed in both surface water and SS (r1 = 0.82, n1 = 15, r2 = 0.68, n2 = 10). and organic carbon in SS was more adsorptive to simazine. Moreover, the concentrations of simazine in groundwater were negatively correlated to the well depths and the distances to the corn fields, and higher concentration of simazine corresponds to younger groundwater. The criterion continuous concentration (CCC) of simazine to Chinese native aquatic species was derived based on the species sensitivity distribution (SSD) to assess the ecological risk. The CCC for simazine was derived to be 4.8 µg L-1. Furthermore, Ecological risk assessment through risk quotient (RQ) showed that simazine presented low risk (RQ < 0.1) in some of sampling sites, while simazine posed medium risk (0.1 < RQ < 1) only on a few sampling sites nearby corn fields. The study contributed a better sight on the presence of simazine in river and its ecological risk to native aquatic species, and provided information for further studies of simazine potential hazards to the aquatic ecosystem.

Ecotoxicity thresholds for ametryn, diuron, hexazinone and simazine in fresh and marine waters.

Triazine and urea herbicides are two groups of photosystem II inhibiting herbicides frequently detected in surface, ground and marine waters. Yet, there are few water quality guidelines for herbicides. Ecotoxicity thresholds (ETs) for ametryn, hexazinone and simazine (triazine herbicides) and diuron (a urea herbicide) were calculated using the Australian and New Zealand method for deriving guideline values to protect fresh and marine ecosystems. Four ETs were derived for each chemical and ecosystem that should theoretically protect 99, 95, 90 and 80% of species (i.e. PC99, PC95, PC90 and PC80, respectively). For all four herbicides, the phototrophic species were significantly more sensitive than non-phototrophic species, and therefore, only the former data were used to calculate the ETs. Comparison of the ET values to measured concentrations in 2606 samples from 15 waterways that discharge to the Great Barrier Reef (2011-2015) found three exceedances of the simazine PC99, regular exceedances (up to 30%) of the PC99 in a limited number of rivers for ametryn and hexazinone and frequent (> 40%) exceedances of the PC99 and PC95 ETs in at least four waterways for diuron. There were no exceedances of the marine ETs in inshore reef areas. Further, ecotoxicity data are required for ametryn and hexazinone to fresh and marine phototrophic species, for simazine to marine phototrophic species, for tropical phototrophic species, repeated pulse exposures and long-term (2 to 12 months) exposures to environmentally relevant concentrations.

Simultaneous determination of simazine, cyanazine, and atrazine in honey samples by dispersive liquid-liquid microextraction combined with high-performance liquid chromatography.

A rapid and simple sample preparation method was developed for simultaneous determination of three triazine herbicides in honey samples. The selected herbicides were extracted from honey samples by ionic liquid dispersive liquid-liquid microextraction, separated on a C18 column (250 mm × 4.6 mm id, 5 µm) using acetonitrile and H2 O as the mobile phase with gradient elution, and then detected by high-performance liquid chromatography. The parameters, such as the type and volume of the extraction and disperser solvent, ion strength, pH, extraction time, and centrifuge time were optimized in order to provide the excellent extraction performance. Good linearity was showed for all the target herbicides over the tested concentration range with correlation coefficient higher than 0.994. Three spiked levels (0.005, 0.05, 0.10 mg/kg) were applied for determination of the recoveries of the targets in honey samples in the range of 80-103% with relative standard deviations not larger than 10.6%. The limits of quantification for the analytes ranged between 1.5 and 4.0 µg/kg. The developed method was applied for determination of the target compounds residues in real samples.

Factors controlling spatial and temporal patterns of multiple pesticide compounds in groundwater (Hesbaye chalk aquifer, Belgium).

Factors governing spatial and temporal patterns of pesticide compounds (pesticides and metabolites) concentrations in chalk aquifers remain unclear due to complex flow processes and multiple sources. To uncover which factors govern pesticide compound concentrations in a chalk aquifer, we develop a methodology based on time series analyses, uni- and multivariate statistics accounting for concentrations below detection limits. The methodology is applied to long records (1996-2013) of a restricted compound (bentazone), three banned compounds (atrazine, diuron and simazine) and two metabolites (deethylatrazine (DEA) and 2,6-dichlorobenzamide (BAM)) sampled in the Hesbaye chalk aquifer in Belgium. In the confined area, all compounds had non-detects fractions >80%. By contrast, maximum concentrations exceeded EU's drinking-water standard (100 ng L-1) in the unconfined area. This contrast confirms that recent recharge and polluted water did not reach the confined area, yet. Multivariate analyses based on variables representative of the hydrogeological setting revealed higher diuron and simazine concentrations in the southeast of the unconfined area, where urban activities dominate land use and where the aquifer lacks protection from a less permeable layer of hardened chalk. At individual sites, positive correlations (up to τ=0.48 for bentazone) between pesticide compound concentrations and multi-annual groundwater level fluctuations confirm occurrences of remobilization. A downward temporal trend of atrazine concentrations likely reflects decreasing use of this compound over the last 28 years. However, the lack of a break in concentrations time series and maximum concentrations of atrazine, simazine, DEA and BAM exceeding EU's standard post-ban years provide evidence of persistence. Contrasting upward trends in bentazone concentrations show that a time lag is required for restriction measures to be efficient. These results shed light on factors governing pesticide compound concentrations in chalk aquifers. The developed methodology is not restricted to chalk aquifers, it could be transposed to study other pollutants with concentrations below detection limits.

Plastic antibody based surface plasmon resonance nanosensors for selective atrazine detection.

This study reports a surface plasmon resonance (SPR) based affinity sensor system with the use of molecular imprinted nanoparticles (plastic antibodies) to enhance the pesticide detection. Molecular imprinting based affinity sensor is prepared by the attachment of atrazine (chosen as model pesticide) imprinted nanoparticles onto the gold surface of SPR chip. Recognition element of the affinity sensor is polymerizable form of aspartic acid. The imprinted nanoparticles were characterized via FTIR and zeta-sizer measurements. SPR sensors are characterized with atomic force microscopy (AFM), scanning electron microscopy (SEM), Fourier transform infrared spectrophotometry (FTIR) and contact angle measurements. The imprinted nanoparticles showed more sensitivity to atrazine than the non-imprinted ones. Different concentrations of atrazine solutions are applied to SPR system to determine the adsorption kinetics. Langmuir adsorption model is found as the most suitable model for this affinity nanosensor system. In order to show the selectivity of the atrazine-imprinted nanoparticles, competitive adsorption of atrazine, simazine and amitrole is investigated. The results showed that the imprinted nanosensor has high selectivity and sensitivity for atrazine.

Fast pesticide detection inside microfluidic device with integrated optical pH, oxygen sensors and algal fluorescence.

The necessities of developing fast, portable, cheap and easy to handle pesticide detection platforms are getting attention of scientific and industrial communities. Although there are some approaches to develop microchip based pesticide detection platforms, there is no compact microfluidic device for the complementary, fast, cheap, reusable and reliable analysis of different pesticides. In this work, a microfluidic device is developed for in-situ analysis of pesticide concentration detected via metabolism/photosynthesis of Chlamydomonas reinhardtii algal cells (algae) in tap water. Algae are grown in glass based microfluidic chip, which contains integrated optical pH and oxygen sensors in a portable system for on-site detection. In addition, intrinsic algal fluorescence is detected to analyze the pesticide concentration in parallel to pH and oxygen sensors with integrated fluorescence detectors. The response of the algae under the effect of different concentrations of pesticides is evaluated and complementary inhibition effects depending on the pesticide concentration are demonstrated. The three different sensors allow the determination of various pesticide concentrations in the nanomolar concentration range. The miniaturized system provides the fast quantification of pesticides in less than 10min and enables the study of toxic effects of different pesticides on Chlamydomonas reinhardtii green algae. Consequently, the microfluidic device described here provides fast and complementary detection of different pesticides with algae in a novel glass based microfluidic device with integrated optical pH, oxygen sensors and algal fluorescence.

Spatial distribution of triazine residues in a shallow alluvial aquifer linked to groundwater residence time.

At present, some triazine herbicides occurrence in European groundwater, 13 years after their use ban in the European Union, remains of great concern and raises the question of their persistence in groundwater systems due to several factors such as storage and remobilization from soil and unsaturated zone, limited or absence of degradation, sorption in saturated zones, or to continuing illegal applications. In order to address this problem and to determine triazine distribution in the saturated zone, their occurrence is investigated in the light of the aquifer hydrodynamic on the basis of a geochemical approach using groundwater dating tracers (3H/3He). In this study, atrazine, simazine, terbuthylazine, deethylatrazine, deisopropylatrazine, and deethylterbuthylazine are measured in 66 samples collected between 2011 and 2013 from 21 sampling points, on the Vistrenque shallow alluvial aquifer (southern France), covered by a major agricultural land use. The frequencies of quantification range from 100 to 56 % for simazine and atrazine, respectively (LQ = 1 ng L-1). Total triazine concentrations vary between 15 and 350 ng L-1 and show three different patterns with depth below the water table: (1) low concentrations independent of depth but related to water origin, (2) an increase in concentrations with depth in the aquifer related to groundwater residence time and triazine use prior to their ban, and (3) relatively high concentrations at low depths in the saturated zone more likely related to a slow desorption of these compounds from the soil and unsaturated zone. The triazine attenuation rate varies between 0.3 for waters influenced by surface water infiltration and 4.8 for water showing longer residence times in the aquifer, suggesting an increase in these rates with water residence time in the saturated zone. Increasing triazine concentrations with depth is consistent with a significant decrease in the use of these pesticides for the last 10 years on this area and highlights the efficiency of their ban.

Coupling of multi-walled carbon nanotubes/polydimethylsiloxane coated stir bar sorptive extraction with pulse glow discharge-ion mobility spectrometry for analysis of triazine herbicides in water and soil samples.

An analytical method based on stir bar sorptive extraction (SBSE) coupled with pulse glow discharge-ion mobility spectrometry (PGD-IMS) was developed for analysis of three triazine pesticide residues in water and soil samples. An injection port with sealing device and stir bars hold device were designed and constructed to directly position the SBSE fiber including the extracted samples into the heating device, making desorption and detection of analytes proceeded simultaneously. The extraction conditions such as SBSE solid phase material, extraction time, extraction temperature, pH value and salt concentration were optimized. Mixture of MWCNTs-COOH and PDMS were shown to be effective in enriching the triazines. The LODs and LOQs of three triazines were found to be 0.006-0.015µgkg(-1) and 0.02-0.05µgkg(-1), and the linear range was 0.05-10µgL(-1) with determination coefficients from 0.9987 to 0.9993. The SBSE-PGD-IMS method was environmentally friendly without organic solvent consumption in the entire experimental procedures, and it was demonstrated to be a commendable rapid analysis technique for analysis of triazine pesticide residues in environmental samples on site. The proposed method was applied for the analysis of real ground water, surface water and soil samples.

Hydrochemical profiles in urban groundwater systems: New insights into contaminant sources and pathways in the subsurface from legacy and emerging contaminants.

It has long been known that groundwaters beneath urban areas carry a fingerprint from urban activities but finding a consistent tracer for anthropogenic influence has proved elusive. The varied sources of urban contaminants means that a single consistent and inexpensive means of tracing the fate of urban contaminants is not generally possible and multiple tracers are often required to understand the contaminant sources and pathways in these complex systems. This study has utilized a combination of micro-organic (MO) contaminants and inorganic hydrochemistry to trace recharge pathways and quantify the variability of groundwater quality in multi-level piezometers in the city of Doncaster, UK. A total of 23 MOs were detected during this study, with more compounds consistently detected during higher groundwater table conditions highlighting the importance of sampling under different hydrological conditions. Four of the compounds detected are EU Water Framework Directive priority substances: atrazine, simazine, naphthalene and DEHP, with a maximum concentration of 0.18, 0.03, 0.2, 16µg/l respectively. Our study shows that the burden of the banned pesticide atrazine persists in the Sherwood Sandstone and is detected at two of the three study sites. Emerging contaminants are seen throughout the borehole profiles and provide insights into transient pathways for contaminant migration in the sub-surface. Long term changes in inorganic hydrochemistry show possible changes in contaminant input or the dissolution of minerals. Nitrate was detected above 50mg/l but on the whole nitrate concentrations have declined in the intervening years either due to a reduction of nitrate application at the surface or a migration of peak nitrate concentrations laterally or to greater depth. This study shows that multiple tracers together with multi-level piezometers can give a better resolution of contaminant pathways and variable flow regimes within the relatively uncomplicated aquifer of the Sherwood Sandstone compared with single long screened wells.