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

Publication history: Accepted - 30 September 2020; Published online - 8 October 2020Freshwater 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.This work was funded by the Source to Tap project (project reference IVA5018 – www.sourcetotap.eu). The Source to Tap project is supported by the European Union's INTERREG VA Programme, managed by the Special EU Programmes Body (SEUPB)

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

Publication history: Accepted - 13 September 2022; Published online - 30 September 2022Passive 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 0.05). 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.This work was funded in part by the Source to Tap project (project reference IVA5018 – http://www.sourcetotap.eu), supported by the European Union’s INTERREG VA Programme which is managed by the Special EU Programmes Body (SEUPB). The work was also part-funded by the FAIRWAY project (project reference 727984 - http://www.fair way-project.eu/). supported by the European Union’s HORIZON 2020 Programme

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

Publication history: Accepted - 13 September 2022; Published online - 30 September 2022Passive 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 0.05). 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.This work was funded in part by the Source to Tap project (project reference IVA5018 – http://www.sourcetotap.eu), supported by the European Union’s INTERREG VA Programme which is managed by the Special EU Programmes Body (SEUPB). The work was also part-funded by the FAIRWAY project (project reference 727984 - http://www.fair way-project.eu/). supported by the European Union’s HORIZON 2020 Programme

Impact of cooking on vitamin D-3 and 25(OH)D-3 content of pork products

Publication history: Accepted - 29 July 2022; Published online - 2 August 2022Little is known regarding the impact of cooking on vitamin D content in pork, despite meat being a major contributor to vitamin D intakes. This paper investigated the effect of household cooking (pan-fry/roast/grill/sous-vide/sauté), on the vitamin D3 and 25-hydroxyvitamin D3 (25(OH)D3) concentration/retention in pork loin, mince and sausages. We hypothesised that vitamin D concentrations would be higher in cooked vs raw pork, and retention would differ between products. Cooking significantly increased vitamin D3 (+49 %) and 25(OH)D3 (+33 %) concentrations. All cooked loin vitamin D3 concentrations were significantly lower than mince/sausage. Vitamin D3 retention was > 100 % for all samples (102–135 %), except sauté mince (99 %) which still did not differ significantly from 100 % retention. Sous-vide cooking resulted in the highest vitamin D3 retention (135 %). Likely owing to water/fat loss, household cooking of pork results in favourable retention of vitamin D3 and 25(OH)D3. The type of pork product has greater influence than cooking method.This work was funded as part of a Department for the Economy (DfE; Northern Ireland) Co-operative Awards in Science and Technology (CAST) PhD studentship, supported by Devenish Nutrition Limited

Improving vitamin D content in pork meat by UVB biofortification

Publication history: Accepted - 11 January 2023; Published online - 14 January 2023Vitamin D deficiency is prevalent worldwide and identification of alternative food-based strategies are urgently warranted. In two studies, 12-week old crossbred pigs (Duroc x (Large White x Landrace)) were exposed daily to narrowband UVB radiation for ∼10 weeks or control (no UVB exposure) until slaughter. In Study 1 (n = 48), pigs were exposed to UVB for 2 min and in Study 2 (n = 20), this duration was tripled to 6 min. All pigs were fed the maximum permitted 2000 IU vitamin D3/kg feed. Loin meat was cooked prior to vitamin D LC-MS/MS analysis. In Study 1, pork loin vitamin D3 did not differ between groups. Study 2 provided longer UVB exposure time and resulted in significantly higher loin vitamin D3 (11.97 vs. 6.03 μg/kg), 25(OH)D3 (2.09 vs. 1.65 μg/kg) and total vitamin D activity (22.88 vs. 14.50 μg/kg) concentrations, compared to control (P < 0.05). Pigs remained healthy during both studies and developed no signs of erythema. Biofortification by UVB radiation provides an effective strategy to further safely increase the naturally occurring vitamin D content of pork loin, alongside feed supplementationThis work was funded as part of a Department for the Economy (DfE) Co-operative Awards in Science and Technology (CAST) PhD studentship, supported by Devenish Nutrition Limited and Agri-Food Quest Competence Centre (AFQCC)

Vitamin D Biofortification of Pork May Offer a Food-Based Strategy to Increase Vitamin D Intakes in the UK Population

Publication history: Accepted - 3 November 2021; Published online - 3 December 2021.Hypovitaminosis D is prevalent worldwide, with many populations failing to achieve the recommended nutrient intake (RNI) for vitamin D (10–20 µg/day). Owing to low vitamin D intakes, limited exposure to ultraviolet-B (UVB) induced dermal synthesis, lack of mandatory fortification and poor uptake in supplement advice, additional food-based strategies are warranted to enable the UK population to achieve optimal vitamin D intakes, thus reducing musculoskeletal risks or suboptimal immune functioning. The aims of the current study were to (1) determine any changes to vitamin D intake and status over a 9-year period, and (2) apply dietary modeling to predict the impact of vitamin D biofortification of pork and pork products on population intakes. Data from the UK National Diet and Nutrition Survey (Year 1–9; 2008/09–2016/17) were analyzed to explore nationally representative mean vitamin D intakes and 25-hydroxyvitamin D (25(OH)D) concentrations (n = 13,350). Four theoretical dietary scenarios of vitamin D pork biofortification were computed (vitamin D content +50/100/150/200% vs. standard). Vitamin D intake in the UK population has not changed significantly from 2008 to 2017 and in 2016/17, across all age groups, 13.2% were considered deficient [25(OH)D < 25 nmol/L]. Theoretically, increasing vitamin D concentrations in biofortified pork by 50, 100, 150, and 200%, would increase vitamin population D intake by 4.9, 10.1, 15.0, and 19.8% respectively. When specifically considering the impact on gender and age, based on the last scenario, a greater relative change was observed in males (22.6%) vs. females (17.8%). The greatest relative change was observed amongst 11–18 year olds (25.2%). Vitamin D intakes have remained stable in the UK for almost a decade, confirming that strategies are urgently required to help the population achieve the RNI for vitamin D. Biofortification of pork meat provides a proof of concept, demonstrating that animal-based strategies may offer an important contribution to help to improve the vitamin D intakes of the UK population, particularly adolescentsThis work was funded as part of a Department for the Economy (DfE) Co-operative Awards in Science and Technology (CAST) PhD studentship, supported by Devenish Nutrition Limited

Bacterial dioxygenase- and monooxygenase-catalysed sulfoxidation of benzo[b]thiophenes

Asymmetric heteroatom oxidation of benzo[b]thiophenes to yield the corresponding sulfoxides was catalysed by toluene dioxygenase (TDO), naphthalene dioxygenase (NDO) and styrene monooxygenase (SMO) enzymes present in P. putida mutant and E. coli recombinant whole cells. TDO-catalysed oxidation yielded the relatively unstable benzo[b] thiophene sulfoxide; its dimerization, followed by dehydrogenation, resulted in the isolation of stable tetracyclic sulfoxides as minor products with cis-dihydrodiols being the dominant metabolites. SMO mainly catalysed the formation of enantioenriched benzo[b] thiophene sulfoxide and 2-methyl benzo[b] thiophene sulfoxides which racemized at ambient temperature. The barriers to pyramidal sulfur inversion of 2- and 3-methyl benzo[b] thiophene sulfoxide metabolites, obtained using TDO and NDO as biocatalysts, were found to be ca.: 25-27 kcal mol(-1). The absolute configurations of the benzo[b] thiophene sulfoxides were determined by ECD spectroscopy, X-ray crystallography and stereochemical correlation. A site-directed mutant E. coli strain containing an engineered form of NDO, was found to change the regioselectivity toward preferential oxidation of the thiophene ring rather than the benzene ring