50 research outputs found

    Targeted monitoring for human pharmaceuticals in vulnerable source and final waters

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    A range of pharmaceuticals has been detected in soils, surface waters and groundwaters across the world. While the reported concentrations are generally low (i.e. sub μg l-1 in surface waters), the substances have been observed throughout the year across a variety of hydrological, climatic and land-use settings. As a result, questions have been raised over the potential for pharmaceuticals in surface waters to enter drinking water supplies and to affect consumers. In a previous Drinking Water Inspectorate (DWI) funded study, results from a simple exposure model were used alongside information on therapeutic doses of pharmaceuticals to identify pharmaceuticals that are likely to be of most concern in UK drinking water sources. However, this previous study was entirely desk-based and did not involve any experimental measurements of pharmaceutical concentrations. The current study was therefore performed to generate actual measurements on the occurrence of pharmaceuticals in source and treated waters in England. The study considered a range of pharmaceutical compounds and their metabolites that have either a) high predicted exposure concentrations; b) toxicological concerns; or c) a low predicted exposure to therapeutic dose ratio. An illicit drug and its major metabolite were also investigated. The study compounds (in total 17) covered a range of chemical classes and varied in terms of their physico-chemical properties. The study was done at four sites where concentrations in source water at the drinking water treatment abstraction point were predicted to be some of the greatest in England. The study therefore is likely to provide a ‘worst case’ assessment of potential human exposure to pharmaceuticals in drinking water in England and Wales. Ten of the 17 study compounds were detected in untreated source waters at sub-μg/l concentrations. Six of these compounds (namely, benzoylecgonine (a metabolite of cocaine), caffeine, carbamazepine (an antiepileptic medicine), carbamazepine epoxide (a metabolite of carbamazepine), ibuprofen and naproxen (both non-steroidal anti-inflammatory drugs) were also detected in treated drinking water. With the exception of carbamazepine epoxide, concentrations in treated drinking water were generally significantly lower than in source water. Even though England is a densely populated country and in some regions there is limited dilution of wastewater effluents, these observations, made at sites that were predicted to have some of the highest concentrations of pharmaceuticals in England and Wales, are in line with results from similar studies performed in other countries. Comparison of measured concentrations of the study compounds in drinking waters with information on therapeutic doses demonstrated that levels of these compounds in drinking water in England are many orders of magnitude lower than levels that are given to patients therapeutically. It would therefore appear that the low or non-detectable levels of pharmaceuticals and illicit drugs present in drinking waters in England and Wales do not pose an appreciable risk to human health

    Dietary exposure to pesticide residues and associated health risks in infants and young children – Results of the French infant total diet study

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    A total diet study (TDS) was undertaken to estimate the chronic dietary exposure to pesticide residues and health risks for the French infants and young children below 3 years old. As a whole, 516 pesticides and metabolites were analysed in 309 food composite samples including 219 manufactured baby foods and 90 common foods, which cover 97% of infants and young children's diet. These composite samples were prepared using 5,484 food products purchased during all seasons from 2011 to 2012 and processed as consumed. Pesticide residues were detected in 67% of the samples and quantified in 27% of the baby food samples and in 60% of the common foods. Seventy-eight different pesticides were detected and 37 of these quantified at levels ranging from 0.02 to 594 µg/kg. The most frequently detected pesticides (greater than 5% samples) were (1) the fungicides 2-phenylphenol, azoxystrobin, boscalid, captan and its metabolite tetrahydrophthalimide, carbendazim, cyprodinil, difenoconazole, dodine, imazalil, metalaxyl, tebuconazole, thiabendazole, (2) the insecticides acetamiprid, pirimiphos-methyl and thiacloprid, (3) the herbicide metribuzin and (4) the synergist piperonyl butoxide. Dietary intakes were estimated for each of the 705 individuals studied and for 431 pesticides incl. 281 with a toxicological reference value (TRV). In the lower-bound scenario, which tends to underestimate the exposure, the TRV were never exceeded. In the upper-bound scenario that overestimates exposure, the estimated intakes exceeded the TRV for dieldrin and lindane (two persistent organic pollutants) and propylene thiourea, a metabolite of propineb. For these three substances, more sensitive analyses are needed to refine the assessment. For 17 other detected and/or prioritised pesticides, the risk could not be characterised due to the lack of a valid TRV, of certain food analyses or the absence of analytical standards for their metabolites. Keywords: Food safety, Infants and young children, Pesticide residues, Total diet study, Exposure assessment, Risk characterizatio

    Measurement uncertainty from physical sample preparation: estimation including systematic error

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    A methodology is proposed, which employs duplicated primary sampling and subsequent duplicated physical preparation coupled with duplicated chemical analyses. Sample preparation duplicates should be prepared under conditions that represent normal variability in routine laboratory practice. The proposed methodology requires duplicated chemical analysis on a minimum of two of the sample preparation duplicates. Data produced from the hierarchical design is treated with robust analysis of variance (ANOVA) to generate uncertainty estimates, as standard uncertainties (`u¿ expressed as standard deviation), for primary sampling (ssamp), physical sample preparation (sprep) and chemical analysis (sanal). The ANOVA results allow the contribution of the sample preparation process to the overall uncertainty to be assessed. This methodology has been applied for the first time to a case study of pesticide residues in retail strawberry samples. Duplicated sample preparation was performed under ambient conditions on two consecutive days. Multi-residue analysis (quantification by GC-MS) was undertaken for a range of incurred pesticide residues including those suspected of being susceptible to loss during sample preparation procedures. Sampling and analytical uncertainties dominated at low analyte concentrations. The sample preparation process contributed up to 20% to the total variability and had a relative uncertainty (Uprep%) of up to 66% (for bupirimate at 95% confidence). Estimates of systematic errors during physical sample preparation were also made using spike recovery experiments. Four options for the estimation of measurement uncertainty are discussed, which both include and exclude systematic error arising from sample preparation and chemical analysis. A holistic approach to the combination and subsequent expression of uncertainty is advised

    Micellization of alkyltrimethylammonium bromide surfactants in choline chloride:glycerol deep eutectic solvent

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    Deep eutectic solvents have shown the ability to promote the self-assembly of surfactants in solution. However, some differences have been found compared with self-assembly in pure water and other polar organic solvents. The behaviour of alkyltrimethylammonium bromides in choline chloride:glycerol deep eutectic solvent has been studied by means of surface tension, X-ray and neutron reflectivity and small-angle neutron scattering. The surfactants were found to remain surface active and showed comparable critical micelle concentrations to the same surfactants in water. Our scattering studies demonstrate that these surfactants form globular micelles with ellipsoidal shape in solution. The size, shape and aggregation number of the aggregates were found to vary with the chain length of the surfactant. Specific solvent-headgroup interactions were not found in this system, unlike those we have previously postulated for anionic surfactants in choline chloride deep eutectic solvents

    Study of the depletion of tylosin residues in honey extracted from treated honeybee (Apis mellifera) colonies and the effect of the shook swarm procedure

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    Bee colonies were dosed with tylosin tartrate 1.1 g per hive (single dose in sucrose solution) and samples of honey were then collected at intervals over a 20-week period. The samples were analysed for tylosin A and desmycosin (tylosin B) using LC-MS/MS. The mean concentration of tylosin A in the honey (pooled results) 3 days after dosing was 17 μ\mug/g, declining to 0.9 μ\mug/g after 140 days. The mean concentration of desmycosin was 2.3 μ\mug/g, 3 days after dosing declining to 1.1 μ\mug/g after 140 days. The shook swarm procedure was investigated and resulted in a tylosin A concentration in brood honey of 10 μ\mug/g, 3 days after dosing declining to 0.02 μ\mug/g, 140 days after dosing. A corresponding decrease in the mean concentrations of desmycosin in brood honey, 1.1 μ\mug/g, 3 days after dosing to 0.03 μ\mug/g, 140 days after dosing also was observed. Tylosin A depletes to desmycosin in honey and can still be detected 238 days after dosing. Thus a more accurate residue definition is the sum of tylosin A and desmycosin

    Study of the distribution and depletion of chloramphenicol residues in bee products extracted from treated honeybee (Apis mellifera L.) colonies

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    Bee colonies were dosed with chloramphenicol (CAP) 1.0 g per hive (single dose in sucrose solution). Samples of honey were then collected at intervals over a 48-week period and samples of royal jelly, beeswax, honeybees and brood collected at intervals over a 12 week period. The mean concentration of CAP in the honey at 7 days after dosing was 26 μ\mug/g, declining to 1.0 μ\mug/g at 332 days. Application of the shook swarm procedure resulted in a mean concentration of CAP in honey of 26 μ\mug/g at 7 days, declining to 0.1 μ\mug/g at 332 days. The mean concentration of CAP in non-honey samples was in the range of 0.5 to 6.8 μ\mug/g, and 0.2 to 3.3 μ\mug/g at 7 days and 56 days, respectively. These results indicate that use of CAP can be detected up to 332 days after dosing even if the shook swarm procedure is used in an attempt to clean the hives. There was no evidence of any significant formation of bound CAP-glucose conjugates in honey
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