Evaluation of Chemcatcher® passive samplers for pesticide monitoring using high-frequency catchment scale data.

Passive samplers (PS) have been proposed as an enhanced water quality monitoring solution in rivers, but their performance against high-frequency data over the longer term has not been widely explored. This study compared the performance of Chemcatcher® passive sampling (PS) devices with high-frequency sampling (HFS: 7-hourly to daily) in two dynamic rivers over 16 months. The evaluation was based on the acid herbicides MCPA (2-methyl-4-chlorophenoxyacetic acid), mecoprop-P, fluroxypyr and triclopyr. The impact of river discharge parameters on Chemcatcher® device performance was also explored. Mixed effects modelling showed that time-weighted mean concentration (TWMC) and flow-weighted mean concentration (FWMC) values obtained by the HFS approach were both significantly higher (p < 0.001) than TWMC values determined from PS regardless of river or pesticide. Modelling also showed that TWMCPS values were more similar to TWMCHFS than FWMCHFS values. However, further testing revealed that MCPA TWMC values from HFS and PS were not significantly different (p > 0.05). There was little indication that river flow parameters altered PS performance-some minor effects were not significant or consistent. Despite this, the PS recovery of very low concentrations indicated that Chemcatcher® devices may be used to evaluate the presence/absence and magnitude of acid herbicides in hydrologically dynamic rivers in synoptic type surveys where space and time coverage is required. However, a period of calibration of the devices in each river would be necessary if they were intended to provide a quantitative review of pesticide concentration as compared with HFS approaches.

Quantifying MCPA load pathways at catchment scale using high temporal resolution data.

Detection of the agricultural acid herbicide MCPA (2-methyl-4-chlorophenoxyacetic acid) in drinking water source catchments is of growing concern, with economic and environmental implications for water utilities and wider ecosystem services. MCPA is poorly adsorbed to soil and highly mobile in water, but hydrological pathway processes are relatively unknown at the catchment scale and limited by coarse resolution data. This understanding is required to target mitigation measures and to provide a framework to monitor their effectiveness. To address this knowledge gap, this study reports findings from river discharge and synchronous MCPA concentration datasets (continuous 7 hour and with additional hourly sampling during storm events) collected over a 7 month herbicide spraying season. The study was undertaken in a surface (source) water catchment (384 km2-of which 154 km2 is agricultural land use) in the cross-border area of Ireland. Combined into loads, and using two pathway separation techniques, the MCPA data were apportioned into event and baseload components and the former was further separated to quantify a quickflow (QF) and other event pathways. Based on the 7 hourly dataset, 85.2 kg (0.22 kg km-2 by catchment area, or 0.55 kg km-2 by agricultural area) of MCPA was exported from the catchment in 7 months. Of this load, 87.7 % was transported via event flow pathways with 72.0 % transported via surface dominated (QF) pathways. Approximately 12 % of the MCPA load was transported via deep baseflows, indicating a persistence in this delayed pathway, and this was the primary pathway condition monitored in a weekly regulatory sampling programme. However, overall, the data indicated a dominant acute, storm dependent process of incidental MCPA loss during the spraying season. Reducing use and/or implementing extensive surface pathway disconnection measures are the mitigation options with greatest potential, the success of which can only be assessed using high temporal resolution monitoring techniques.

Reducing MCPA herbicide pollution at catchment scale using an agri-environmental scheme.

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 km2) 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 km2) 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.

Approaches to herbicide (MCPA) pollution mitigation in drinking water source catchments using enhanced space and time monitoring.

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 km2). 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.

Toluene dioxygenase-catalyzed synthesis and reactions of cis-diol metabolites derived from 2- and 3-methoxyphenols.

Using toluene dioxygenase as biocatalyst, enantiopure cis-dihydrodiol and cis-tetrahydrodiol metabolites, isolated as their ketone tautomers, were obtained from meta and ortho methoxyphenols. Although these isomeric phenol substrates are structurally similar, the major bioproducts from each of these biotransformations were found at different oxidation levels. The relatively stable cyclohexenone cis-diol metabolite from meta methoxyphenol was isolated, while the corresponding metabolite from ortho methoxyphenol was rapidly bioreduced to a cyclohexanone cis-diol. The chemistry of the 3-methoxycyclohexenone cis-diol product was investigated and elimination, aromatization, hydrogenation, regioselective O-exchange, Stork-Danheiser transposition and O-methylation reactions were observed. An offshoot of this technology provided a two-step chemoenzymatic synthesis, from meta methoxyphenol, of a recently reported chiral fungal metabolite; this synthesis also established the previously unassigned absolute configuration.

Initial studies on the occurrence of cyanobacteria and microcystins in Irish lakes.

We report the results of a synoptic survey at 14 sites across the north of Ireland undertaken to determine the occurrence of cyanobacteria and their constituent microcystin cyanotoxins. Seven microcystin toxins were tested for, and five of which were found, with MC-LR, MC-RR, and MC-YR being the most prevalent. Gomphosphaeria spp and Microcystis aeruginosa were the most dominant cyanobacterial species encountered. Together with Aphanizomenon flos-aquae, these were the cyanobacteria associated with the highest microcystin concentrations. The occurrence of several microcystin toxins indicates that there may potentially be more than one cyanobacteria species producing microcystins at many sites. Total microcystin concentrations varied over three orders of magnitude dividing the sites into two groups of high (>1000 ngMC/µgChla, six sites) or low toxicity (<200 ngMC/µgChla, eight sites).