Determination of phenols and pharmaceuticals in municipal wastewaters from Polish treatment plants by ultrasound-assisted emulsification–microextraction followed by GC–MS

A method combining ultrasound-assisted emulsification–microextraction (USAEME) with gas chromatography–mass spectrometry (GC–MS) was developed for simultaneous determination of four acidic pharmaceuticals, ibuprofen, naproxen, ketoprofen, and diclofenac, as well as four phenols, 4-octylphenol, 4-n-nonylphenol, bisphenol A, and triclosan in municipal wastewaters. Conditions of extraction and simultaneous derivatization were optimized with respect to such aspects as type and volume of extraction solvent, volume of derivatization reagent, kind and amount of buffering salt, location of the test tube in the ultrasonic bath, and extraction time. The average correlation coefficient of the calibration curves was 0.9946. The LOD/(LOQ) values in influent and effluent wastewater were in the range of 0.002–0.121/(0.005–0.403) μg L^?1 and 0.002–0.828/(0.006–2.758) μg L^?1, respectively. Quantitative recoveries (≥94 %) and satisfactory precision (average RSD 8.2 %) were obtained. The optimized USAEME/GC–MS method was applied for determination of the considered pharmaceuticals and phenols in influents and treated effluents from nine Polish municipal wastewater treatment plants. The average concentration of acidic pharmaceuticals in influent and effluent wastewater were in the range of 0.06–551.96 μg L^?1 and 0.01–22.61 μg L^?1, respectively, while for phenols were in the range of 0.03–102.54 μg L^?1 and 0.02–10.84 μg L^?1, respectively. The removal efficiencies of the target compounds during purification process were between 84 and 99 %.     

Single and combined effects of aluminum (Al<Subscript>2</Subscript>O<Subscript>3</Subscript>) and zinc (ZnO) oxide nanoparticles in a freshwater fish, <Emphasis Type="Italic">Carassius auratus</Emphasis>

The increasing use of nanoparticles (NPs) worldwide has raised some concerns about their impact on the environment. The aim of the study was to assess the toxicity of metal oxide nanoparticles, singly or combined, in a freshwater fish (Carassius auratus). The fish were exposed for 7, 14, and 21 days to different concentrations of NPs (10 μg Al₂O₃.L^?1, 10 μg ZnO.L^?1, 10 μg Al₂O₃.L^?1 plus 10 μg ZnO.L^?1, 100 μg Al₂O₃.L^?1, 100 μg ZnO.L^?1, and 100 μg Al₂O₃.L^?1 plus 100 μg ZnO.L^?1). At the end of each exposure period, antioxidant enzyme activity (catalase, glutathione-S-transferase, and superoxide dismutase), lipid peroxidation, and histopathology were assessed in the gills and livers of C. auratus. The results show an increase in catalase (CAT) and superoxide dismutase (SOD) activity in the gills and livers of fish, especially after 14 days of exposure to single and combined NPs, followed by a reduction at 21 days. An increase in glutathione S-transferase (GST) was observed in gills after 7 days for all tested NP concentrations (single and combined); while in livers, a significant increase was determined after 14 days of exposure to 100 μg.L^?1 of both single ZnO and Al₂O₃ NPs. Lipid peroxidation (LPO) significantly increased in gills after 7 days of exposure to 100 μg.L^?1 Al₂O₃ NPs (single or combined). In livers, LPO increased significantly after 7 days of exposure to all tested concentrations of both single ZnO and Al₂O₃ (except for 10 μg Al₂O₃.L^?1), and after 14 days of exposure to ZnO (10 and 100 μg.L^?1) and Al₂O₃ (100 μg.L^?1)_. The results from histological observations suggest that exposure to metal oxide NPs affected both livers and gills, presenting alterations such as gill hyperplasia and liver degeneration. However, the most pronounced effects were found in gills. In general, this study shows that the tested NPs, single or combined, are capable of causing sub-lethal effects on C. auratus, but when combined, NPs seem to be slightly more toxic than when added alone.     

Environmental effects of anticholinesterasic therapeutic drugs on a crustacean species,Daphnia magna

The presence of pharmaceutical drugs in the environment is an important field of toxicology, since such residues can cause deleterious effects on exposed biota. This study assessed the ecotoxicological acute and chronic effects of two anticholinesterasic drugs, neostigmine and pyridostigmine in Daphnia magna. Our study calculated 48 h-EC₅₀ values for the immobilization assay of 167.7 μg L^?1 for neostigmine and 91.3 μg L^?1 for pyridostigmine. In terms of feeding behavior, we calculated a 5 h-EC₅₀ for filtration rates of 7.1 and 0.2 μg L^?1 for neostigmine and pyridostigmine, respectively; for the ingestion rates, the calculated EC₅₀ values were, respectively, 7.5 and 0.2 μg L^?1 for neostigmine and pyridostigmine. In the reproduction assay, the most affected parameter was the somatic growth rate (LOECs of 21.0 and 2.9 μg L^?1 for neostigmine and pyridostigmine, respectively), followed by the fecundity (LOECs of 41.9 and 11.4 μg L^?1 for neostigmine and pyridostigmine, respectively). We also determined a 48 h-IC₅₀ for cholinesterase activity of 1.7 and 4.5 μg L^?1 for neostigmine and pyridostigmine, respectively. These results demonstrated that both compounds are potentially toxic for D. magna at concentrations in the order of the μg L^?1.     

Novel pipette-tip graphene/poly (vinyl alcohol) cryogel composite extractor for the analysis of carbofuran and carbaryl in water

A novel pipette-tip extractor of a graphene/poly (vinyl alcohol) cryogel (graphene/PVA) composite sorbent was prepared to preconcentrate carbamate pesticides in environmental water samples before analysis with a gas chromatograph-flame ionization detector (GC-FID). This novel pipette-tip extractor with the graphene/PVA sorbent exhibited a high porosity when observed through a scanning electron micrograph (SEM). Under optimal conditions, using only 1.0 mL of sample and 0.75 mL of eluting solvent, the developed method provided a wide linear range of 10–700 ng mL^?1 and 10–500 ng mL^?1 with limit of detection (LOD) of 6.40 ± 0.18 and 9.17 ± 0.34 ng mL^?1 for carbofuran (2,3-dihydro-2,2-dimethylbenzofuran-7-yl methylcarbamate) and carbaryl (1-naphthyl methylcarbamate), respectively. The pipette-tip extractor provided high extraction efficiency with high accuracy indicated, by good recoveries in the range of 74.5 ± 4.8% to 119.7 ± 1.6% and 76 ± 15% to 114 ± 19% for carbofuran and carbaryl, respectively. In addition, the fabrication procedure showed a good pipette-tip extractor-to-pipette-tip extractor reproducibility with a relative standard deviation of 1.3–9.8% (n = 5). When the developed pipette-tip extractor was applied for the extraction of carbofuran and carbaryl in surface water samples near vegetable plantation areas, 25.9 ± 8.2 ng mL^?1 of carbofuran was found, and carbaryl was also detected in concentrations that ranged from 45.0 ± 4.0 to 191 ± 13 ng mL^?1.     

Differences in response of two model estuarine crustaceans after lethal and sublethal exposures to chlorpyrifos

This study assessed the in vitro and in vivo effects of an acetylcholinesterase enzyme inhibitor (chlorpyrifos) in two estuarine crustaceans: grass shrimp (Palaemonetes pugio) and mysid (Americamysis bahia). The differences in response were quantified after lethal and sublethal exposures to chlorpyrifos and in vitro assays with chlorpyrifos-oxon. Results from the in vitro experiments indicated that the target enzyme, acetylcholinesterase (AChE), in the two species was similar in sensitivity to chlorpyrifos inhibition with IC50s of 0.98 nM and 0.89 nM for grass shrimp and mysids, respectively. In vivo experiments showed that mysids were significantly more sensitive to chlorpyrifos-induced AChE inhibition after 24 h of exposure. The in vivo EC50s for AChE inhibition were 1.23 μg L^?1 for grass shrimp and 0.027 μg L^?1 for mysids.

Median lethal concentrations (24h LC50 values) were 1.06 μg L^?1 for grass shrimp and 0.068 μg L^?1 for mysids. The results suggest that differences in the response of these two crustaceans are likely related to differences in uptake and metabolism rather than target site sensitivity.     

Mine water geochemistry and metal flux in a major historic Pb-Zn-F orefield, the Yorkshire Pennines, UK

Recent studies have shown up to 6 % of rivers in England and Wales to be impacted by discharges from abandoned metal mines. Despite the large extent of impacts, there are still many areas where mine water impact assessments are limited by data availability. This study provides an overview of water quality, trace element composition and flux arising from one such area; the Yorkshire Pennine Orefield in the UK. Mine drainage waters across the orefield are characterised by Ca–HCO₃–SO₄-type waters, with moderate mineralization (specific electrical conductance: 160–525 μS cm^?1) and enrichment of dissolved Zn (≤2003 μg?L^?1), Ba (≤971 μg?L^?1), Pb (≤183 μg?L^?1) and Cd (≤12 μg?L^?1). The major ion composition of the waters reflects the Carboniferous gritstone and limestone-dominated country rock, the latter of which is heavily karstified in parts of the orefield, while sulphate and trace element enrichment is a product of the oxidation of galena, sphalerite and barite mineralization. Contaminant flux measurements at discharge sites highlight the disproportionate importance of large drainage levels across the region, which generally discharge into first-order headwater streams. Synoptic metal loading surveys undertaken in the Hebden Beck sub-catchment of the river Wharfe highlight the importance of major drainage levels to instream baseflow contamination, with diffuse sources from identifiable expanses of waste rock becoming increasingly prominent as river flows increase.     

Dietary arsenic consumption and urine arsenic in an endemic population: response to improvement of drinking water quality in a 2-year consecutive study

We assessed the association between arsenic intake through water and diet, and arsenic levels in first morning-void urine under variable conditions of water contamination. This was done in a 2-year consecutive study in an endemic population. Exposure of arsenic through water and diet was assessed for participants using arsenic-contaminated water (≥50 μg L^?1) in a first year (group I) and for participants using water lower in arsenic (<50 μg L^?1) in the next year (group II). Participants with and without arsenical skin lesions were considered in the statistical analysis. Median dose of arsenic intake through drinking water in groups I and II males was 7.44 and 0.85 μg kg body wt.^?1 day^?1 (p <0.0001). In females, it was 5.3 and 0.63 μg kg body wt.^?1 day^?1 (p <0.0001) for groups I and II, respectively. Arsenic dose through diet was 3.3 and 2.6 μg kg body wt.^?1 day^?1 (p?=?0.088) in males and 2.6 and 1.9 μg kg body wt.^?1 day^?1 (p?=?0.0081) in females. Median arsenic levels in urine of groups I and II males were 124 and 61 μg L^?1 (p?=?0.052) and in females 130 and 52 μg L^?1 (p?=?0.0001), respectively. When arsenic levels in the water were reduced to below 50 μg L^?1 (Indian permissible limit), total arsenic intake and arsenic intake through the water significantly decreased, but arsenic uptake through the diet was found to be not significantly affected. Moreover, it was found that drinking water mainly contributed to variations in urine arsenic concentrations. However, differences between male and female participants also indicate that not only arsenic uptake, but also many physiological factors affect arsenic behavior in the body and its excretion. As total median arsenic exposure still often exceeded 3.0 μg kg body wt.^?1 day^?1 (the permissible lower limit established by the Joint Expert Committee on Food Additives) after installation of the drinking water filters, it can be concluded that supplying the filtered water only may not be sufficient to minimize arsenic availability for an already endemic population.     

Efficiency of a cleanup technology to remove mercury from natural waters by means of rice husk biowaste: ecotoxicological and chemical approach

In the present work, the efficiency of rice husk to remove Hg(II) from river waters spiked with realistic environmental concentrations of this metal (μg L^?1 range) was evaluated. The residual levels of Hg(II) obtained after the remediation process were compared with the guideline values for effluents discharges and water for human consumption, and the ecotoxicological effects using organisms of different trophic levels were assessed. The rice husk sorbent proved to be useful in decreasing Hg(II) contamination in river waters, by reducing the levels of Hg(II) to values of ca. 8.0 and 34 μg L^?1, for an Hg(II) initial concentration of 50 and 500 μg L^?1, respectively. The remediation process with rice husk biowaste was extremely efficient in river waters spiked with lower levels of Hg(II), being able to eliminate the toxicity to the exposed organisms algae Pseudokirchneriella subcapitata and rotifer Brachionus calyciflorus and ensure the total survival of Daphnia magna species. For concentrations of Hg(II) tenfold higher (500 μg L^?1), the remediation process was not adequate in the detoxification process, still, the rice husk material was able to reduce considerably the toxicity to the bacteria Vibrio fischeri, algae P. subcapitata and rotifer B. calyciflorus, whose responses where fully inhibited during its exposure to the non-remediated river water. The use of a battery of bioassays with organisms from different trophic levels and whose sensitivity revealed to be different and dependent on the levels of Hg(II) contamination proved to be much more accurate in predicting the ecotoxicological hazard assessment of the detoxification process by means of rice husk biowaste.     

Online microchannel preconcentrator for carbofuran detection

A simple and rapid online microchannel preconcentrator coupled with an amperometric detection for the analysis of carbofuran using polyethylene glycol coated onto magnetic particle (PEG-magnetic particles) sorbents was developed. This simple-to-prepare microchannel preconcentrator used an external magnet to retain the PEG-magnetic particle sorbents inside the microchannel. Under optimum conditions, the system provided two linear ranges, from 0.01 to 10.0 mg L^?1 and from 10.0 to 130.0 mg L^?1 with a limit of detection of 8.7 ± 0.1 μg L^?1. The microchannel preconcentrator provided very good stability; it can be used for up to 326 consecutive injections of 5.0 mg L^?1 carbofuran with a relative standard deviation of less than 3%. The developed system provided a good microchannel-to-microchannel and a good electrode-to-electrode reproducibility (n = 6, %RSD < 1). It also provided an excellent selectivity when it was tested with two other carbamate pesticides, carbaryl and methomyl, with a 43 and 256 times higher detection sensitivity for carbofuran, respectively. The developed system was successfully applied to detect carbofuran in surface water samples obtained near vegetable plantation areas. The concentrations of carbofuran in these samples were found to be in the range of non-detectable to 0.047 ± 0.001 mg L^?1. The developed system is easy to operate and easy to couple with other analytical instruments and it could be easily adapted for the analysis of other polar organic contaminants.     

Psychotropic drugs in mixture alter swimming behaviour of Japanese medaka (<Emphasis Type="Italic">Oryzias latipes</Emphasis>) larvae above environmental concentrations

Psychiatric pharmaceuticals, such as anxiolytics, sedatives, hypnotics and antidepressors, are among the most prescribed active substances in the world. The occurrence of these compounds in the environment, as well as the adverse effects they can have on non-target organisms, justifies the growing concern about these emerging environmental pollutants. This study aims to analyse the effects of six psychotropic drugs, valproate, cyamemazine, citalopram, sertraline, fluoxetine and oxazepam, on the survival and locomotion of Japanese medaka Oryzias latipes larvae. Newly hatched Japanese medaka were exposed to individual compounds for 72 h, at concentrations ranging from 10 μg L^?1 to 10 mg L^?1. Lethal concentrations 50 % (LC₅₀) were estimated at 840, 841 and 9,136 μg L^?1 for fluoxetine, sertraline and citalopram, respectively, while other compounds did not induce any significant increase in mortality. Analysis of the swimming behaviour of larvae, including total distance moved, mobility and location, provided an estimated lowest observed effect concentration (LOEC) of 10 μg L^?1 for citalopram and oxazepam, 12.2 μg L^?1 for cyamemazine, 100 μg L^?1 for fluoxetine, 1,000 μg L^?1 for sertraline and >10,000 μg L^?1 for valproate. Realistic environmental mixture of the six psychotropic compounds induced disruption of larval locomotor behaviour at concentrations about 10- to 100-fold greater than environmental concentrations.     

Easy and fast extraction methods to determine organochlorine pesticides in sewage sludge,soil, and water samples based at low temperature

Organochlorine pesticides present in sewage sludge can contaminate soil and water when they are used as either fertilizer or agricultural soil conditioner. In this study, the technique solid–liquid extraction with low temperature purification was optimized and validated for determination of ten organochlorine pesticides in sewage sludge and soil samples. Liquid–liquid extraction with low temperature purification was also validated for the same compounds in water. Analyses were performed by gas chromatography-mass spectrometry operating in the selective ion monitoring mode. After optimization, the methods showed recoveries between 70% and 115% with relative standard deviation lower than 13% for all target analytes in the three matrices. The linearity was demonstrated in the range of 20 to 70 µg L^?1, 0.5 to 60 µg L^?1, and 3 to 13 µg L^?1, for sludge, soil, and acetonitrile, respectively. The limit of quantification ranged between 2 and 40 µg kg^?1, 1 and 6 µg kg^?1, and 0.5 µg L^?1 for sludge, soil, and water, respectively. The methods were used in the study of pesticide lixiviation carried out in a poly vinyl chlorine column filled with soil, which had its surface layer mixed with sludge. The results showed that pesticides are not leached into soil, part of them is adsorbed by the sewage sludge (4–40%), and most pesticides are lost by volatilization.     

Assessing the enrichment of heavy metals in surface soil and plant (Digitaria eriantha) around coal-fired power plants in South Africa

Nine metals (Fe, Cu, Mn, Ni, Cd, Pb, Hg, Cr, and Zn) were determined in soil and Digitaria eriantha plants within the vicinity of three coal power plants (Matla, Lethabo, and Rooiwal), using ICP-OES and GFAAS. The total metal concentration in soil ranged from 0.05?±?0.02 to 1836?±?70 μg g^?1, 0.08?±?0.05 to 1744?±?29 μg g^?1, and 0.07?±?0.04 to 1735?±?91 μg g^?1 in Matla, Lethabo, and Rooiwal, respectively. Total metal concentration in the plant (D. eriantha) ranged from 0.005?±?0.003 to 535?±?43 μg g^?1 in Matla, 0.002?±?0.001 to 400?±?269 μg g^?1 in Lethabo, and 0.002?±?0.001 to 4277?±?201 μg g^?1 in Rooiwal. Accumulation factors (A) of less than 1 (i.e., 0.003 to 0.37) at all power plants indicate a low transfer of metal from soil to plant (excluder). Enrichment factor values obtained (2.4–5.0) indicate that the soils are moderately enriched with the exception of Pb that had significant enrichment of 20. Geo-accumulation index (I-geo) values of metals indicate that the soils are moderately polluted (0.005–0.65), except for Pb that showed moderate to strong pollution (1.74–2.53).     

Quantification of ionophores in aged poultry litter using liquid chromatography tandem mass spectrometry

Veterinary anticoccidials, biochemically known as ionophores, are widely used in poultry feed at therapeutic levels to treat Coccidiosis and at sub-therapeutic levels for growth- promotion. Commonly used ionophores in the US poultry industry are monensin, salinomycin, lasalocid and narasin. There is an increasing concern regarding the persistence of these anticoccidials in the environment. However, little attention has been directed to methods development for quantitatively measuring ionophores in complex environmental matrices such as poultry litters that are land applied. Here, we describe a rapid and sensitive liquid chromatography tandem mass spectrometry (LC-MS/MS)-based method developed for simultaneous quantification of monensin, lasalocid, salinomycin, and narasin in aged poultry litter samples. Results show significant level of monensin (97.8 ± 3.2 μg kg^?1), lasalocid (19.2 ± 6.6 μg kg^?1), salinomycin (70 ± 2.7 μg kg^?1) and narasin (57.3 ± 2.6 μg kg^?1) in poultry litter stored for over three years at < 5°C. Our findings indicate that even after several years of unmanaged storage of poultry litter, ionophores may continue to persist in this matrix, raising the possibility of prolonged release into the environment.     

Determination of 2,4-Dichlorophenoxyacetic acid in food and water samples using a modified graphene oxide sorbent and high-performance liquid chromatography

Abstract

In the present work, dispersive micro-solid phase extraction (D-μ-SPE) method using magnetic graphene oxide tert-butylamine (GO/Fe₃O₄/TBA) nanocomposite, as an efficient sorbent, was applied for determining 2,4-dichlorophenoxyacetic acid (2,4-D) in water and food samples. Detection was carried out using high-performance liquid chromatography (HPLC) instrument. Influential parameters of D-μ-SPE such as sorbent and its amount, elution solvent and its volume, adsorption and desorption times and pH of sample solution were investigated and optimized. Under the optimized conditions, limit of detection and quantitation values were 0.007 and 0.02?μg/mL, respectively. Recovery data for several real samples were obtained within the range of 88.0–94.0% with a relative standard deviation (RSD) less than 7.5%. The proposed method was successfully applied to quantitative determination of 2,4-D in several vegetables and water samples.     

Characterization of carbonaceous aerosols over Delhi in Ganga basin: seasonal variability and possible sources

The mass concentration of carbonaceous species, organic carbon (OC), and elemental carbon (EC) using a semicontinuous thermo-optical EC-OC analyzer, and black carbon (BC) using an Aethalometer were measured simultaneously at an urban mega city Delhi in Ganga basin from January 2011 to May 2012. The concentrations of OC, EC, and BC exhibit seasonal variability, and their concentrations were ～2 times higher during winter (OC 38.1?±?17.9 μg m^?3, EC 15.8?±?7.3 μg m^?3, and BC 10.1?±?5.3 μg m^?3) compared to those in summer (OC 14.1?±?4.3 μg m^?3, EC 7.5?±?1.5 μg m^?3, and BC 4.9?±?1.5 μg m^?3). A significant correlation between OC and EC (R?=?0.95, n?=?232) indicate their common emission sources with relatively lower OC/EC ratio (range 1.0–3.6, mean 2.2?±?0.5) suggests fossil fuel emission as a major source of carbonaceous aerosols over the station. On average, mass concentration of EC was found to be ～38 % higher than BC during the study period. The measured absorption coefficient (b_abs) was significantly correlated with EC, suggesting EC as a major absorbing species in ambient aerosols at Delhi. Furthermore, the estimated mass absorption efficiency (σ_abs) values are similar during winter (5.0?±?1.5 m² g^?1) and summer (4.8?±?2.8 m² g^?1). Significantly high aerosol loading of carbonaceous species emphasize an urgent need to focus on air quality management and proper impact assessment on health perspective in these regions.     

Development,validation, and application of a method for the GC-MS analysis of fipronil and three of its degradation products in samples of water,soil, and sediment

A method for the identification and quantification of pesticide residues in water, soil, and sediment samples has been developed, validated, and applied for the analysis of real samples. The specificity was determined by the retention time and the confirmation and quantification of analyte ions. Linearity was demonstrated over the concentration range of 20 to 120 µg L^?1, and the correlation coefficients varied between 0.979 and 0.996, depending on the analytes. The recovery rates for all analytes in the studied matrix were between 86% and 112%. The intermediate precision and repeatability were determined at three concentration levels (40, 80, and 120 µg L^?1), with the relative standard deviation for the intermediate precision between 1% and 5.3% and the repeatability varying between 2% and 13.4% for individual analytes. The limits of detection and quantification for fipronil, fipronil sulfide, fipronil-sulfone, and fipronil-desulfinyl were 6.2, 3.0, 6.6, and 4.0 ng L^?1 and 20.4, 9.0, 21.6, and 13.0 ng L^?1, respectively. The method developed was used in water, soil, and sediment samples containing 2.1 mg L^?1 and 1.2% and 5.3% of carbon, respectively. The recovery of pesticides in the environmental matrices varied from 88.26 to 109.63% for the lowest fortification level (40 and 100 µg kg^?1), from 91.17 to 110.18% for the intermediate level (80 and 200 µg kg^?1), and from 89.09 to 109.82% for the highest fortification level (120 and 300 µg kg^?1). The relative standard deviation for the recovery of pesticides was under 15%.     

The effect of consumption of pork enriched by organic selenium on selenium status and lipid profile in blood serum of consumers

Abstract

The aim of the research was to evaluate the effect of consumption of selenium-enriched pork on selected health indicators of probands. The intake of feed mixture with increased organic selenium at the dose of 0.3?mg.kg^?1 probably increases selenium concentration in MSM (musculus semimembranosus). In the pork enriched with organic selenium, the concentration was higher by 1.045?±?0.10?mg.kg^?1 compared with the control group 0.701?±?0.05?mg.kg^?1 at significance P?<?0.001. Sixteen participants in the experiment were represented by 8 men at the average age of 41.5?±?11.9?years and 8 women at the average age of 41.4?±?7.9?years. All the probands consumed meat enriched with selenium three times a week during one month. By consumption of the enriched pork, there was an increase of the selenium concentration in blood serum of probands traced with selenium increase from 73.19?±?15.68?μg.L^?1 to 73.73?±?15.13?μg.L^?1 (P?>?0.05). From the results we can see that consumption of enriched pork with selenium was significantly manifested in lowering of total cholesterol levels, which was associated with LDL cholesterol lowering (P?<?0.05). Differences among the HDL cholesterol and triglycerides samples were not significant.     

Quantitative modelling to estimate the transfer of pharmaceuticals through the food production system

Use of pharmaceuticals in animal production may cause an indirect route of contamination of food products of animal origin. This study aimed to assess, through mathematical modelling, the transfer of pharmaceuticals from contaminated soil, through plant uptake, into the dairy food production chain. The scenarios, model parameters, and values refer to contaminants in emission slurry production, storage time, immission into soil, plant uptake, bioaccumulation in the animal's body, and transfer to meat and milk. Modelling results confirm the possibility of contamination of dairy cow's meat and milk due the ingestion of contaminated feed by the cattle. The estimated concentration of pharmaceutical residues obtained for meat ranged from 0 to 6 ng kg^?1 for oxytetracycline, from 0.011 to 0.181 μg kg^?1 for sulfamethoxazole, and from 4.70 to 11.86 μg kg^?1 for ketoconazole. The estimated concentrations for milk were: zero for oxytetracycline, lower than 40 ng L^?1 for sulfamethoxazole, and from 0.98 to 2.48 μg L^?1 for ketoconazole. Results obtained for the three selected pharmaceuticals indicate a minor risk for human health. This study showed that supply chain modelling could be an effective tool in assessing the indirect contamination of feedstuff and animal products by residues of pharmaceuticals. The model can easily be adjusted to other contaminants and supply chain and, in this way, present a valuable tool to underpin decision making.     

Comparisons of ambient air particulates concentrations (TSP,PM2.5) and dry depositions during smog and non-smog periods at Luliao,Shalu District sampling site

The concentrations of ambient total suspended particulates (TSP) and PM_2.5, and the dry depositions at a sample site at Luliao Junior High School (Luliao) in central Taiwan were measured during smog and non-smog days between December 2017 and July 2018. The results are compared to those obtained during non-smog periods in the years 2015–2017. The mean TSP and PM_2.5 concentrations and dry deposition flux were 72.41?±?26.40, 41.88?±?23.51?μg/m³, and 797.57?±?731.46?μg/m² min, respectively, on the smog days. The mean TSP and PM_2.5 concentrations and dry deposition flux on the non-smog days were 56.39?±?18.08, 34.81?±?12.59?μg/m³ and 468.93?±?600.57?μg/m² min, respectively. The mean TSP concentration in the smog period was 28% greater than that in the non-smog period, and the mean PM_2.5 concentration was 20% higher. The mean dry deposition flux in the smog period was 70% higher than that in the non-smog period at Luliao. The PM_2.5 concentrations exceeded the standards set by the Taiwan EPA (35?μg/m³ daily, and 15?μg/m³ annually). Therefore, the TSP and PM_2.5 concentrations and dry deposition must be reduced in central Taiwan on smog days. In addition, atmospheric TSP and PM_2.5 concentrations at various sampling sites were compared, and those herein were not higher than those measured in other countries. Finally, apart from the local traffic emissions, during smog periods, the other pollution source originated from the transportation process of traffic pollutants emitted in the northwest side of Taiwan.     

Simultaneous determination of eight metabolites of organophosphate and pyrethroid pesticides in urine

A simultaneous method for quantifying eight metabolites of organophosphate pesticides and pyrethroid pesticides in urine samples has been established. The analytes were extracted using liquid–liquid extraction coupled with WCX solid phase extraction (SPE) cartridges. Eight metabolites were chemically derivatized before analysis using gas chromatography–tandem mass spectrometry (GC–MS–MS). The separation was performed on a HP-5MS capillary column (30 m × 0.25 mm × 0.25 µm) with temperature programming. The detection was performed under electro-spray ionization (ESI) in multiple reaction monitoring (MRM) mode. An internal standard method was used. The extraction solvent, types of SPE cartridges and eluents were optimized by comparing the sample recoveries under different conditions. The results showed that the calibration curves of the five organophosphorus pesticides metabolites were linear in the range of 0.2–200 μg/L (r² ≥ 0.992) and that of the three pyrethroid pesticides metabolites were linear in the range of 0.025–250 μg/L (r² ≥ 0.991). The limits of detection (LODs, S/N ≥ 3) and the limits of quantification (LOQs, S/N ≥ 10) of the eight metabolites were 0.008–0.833 μg/L and 0.25–2.5 μg/L, respectively. The recoveries of the eight metabolites ranged from 54.08% to 82.49%. This efficient, stable, and cost-effective method is adequate to handle the large number of samples required for surveying the exposure level of organophosphorus and pyrethroid pesticides in the general population.