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 %.     

Vegetation development and nutrients supply of trees in habitats with high sulfur concentration in reclaimed former sulfur mines Jeziórko (Southern Poland)

Environmental Science and Pollution Research - The paper presents an assessment of vegetation (composition and cover-abundance), nutrient supply, and especially sulfur accumulation in the trees...     

Comparison of linuron degradation in the presence of pesticide mixtures in soil under laboratory conditions

It is widely recognised that complex interactions occur between chemicals in mixtures. In many agricultural situations, the use of tank mixes and complex spray programs is a common practice. Insecticides, fungicides and a herbicide being applied in potato protection were used in this research. Interactions between linuron and insecticides, such as thiamethoxam or clothianidin, and fungicides, such as mancozeb or chlorothalonil, were examined in soil. The degradation rate of linuron in soil during laboratory incubation in six treatments was studied. Mixtures of linuron with mancozeb in sandy loam and clay loam soils had a significant effect on the persistence of this herbicide. For example, for the same herbicide, t _1/2 values for linuron were from 37 days in sandy loam to 44 days in clay loam. These values changed (64–67 days) when thiamethoxam and mancozeb were in soil. When mancozeb was added only, the half-life values were from 59 to 62 days, respectively. Other mixtures with chlorothalonil, thiamethoxam and clothianidin did not have any effect. In order to compare linuron degradation rates in soils, a single first-order model and expanded statistical analysis were used.     

Speciation of scandium and gallium in soil

A method for the speciation of scandium and gallium in soil has been developed. The sequential extraction scheme of Tessier et al. for heavy metals was examined for the scandium and gallium separation. The regents proposed by Tessier were used for the extraction, and only for the residual fraction the HClO(4) was replaced with H(2)SO(4). The optimum conditions for leaching scandium and gallium from the soil were chosen for each fraction. Very sensitive, spectrophotometric methods based on the mixed complexes of Sc(III) and Ga(III) with Chrome Azurol S and benzyldodecyldimethylammonium bromide were applied for the scandium and gallium determination after their separation by solvent extraction. 100% mesityl oxide and a 0.5M solution of 2-thenoyltrifluoroacetone in xylene were chosen for the extraction of scandium and butyl acetate was selected for gallium. Soil samples from two different regions of Poland were the object of this research. The content of scandium and gallium found in the individual fractions of Upper Silesia soil (industrial region) was [in mugg(-1)] Sc: I, 1.52; II, 0.53; III, 7.78; IV, 1.79; V, 0.20; Ga: I, 24.7; III, 29.2; IV, 35.4; V, 6.9. In Podlasie soil (agricultural region), the content of both elements was clearly lower. The total content of scandium and gallium in the five soil fractions was in good correlation with the total content of these elements in the soils found after HF-H(2)SO(4) digestion. Analysis using the ICP-OES method gave comparable results.     

Pyrethroid residue dynamics in insects depends on the circadian clock

Many factors may affect pesticide effectiveness against pests. One of the factors that should be considered is circadian rhythmicity. In this study, we evaluated daily variations in pyrethroid susceptibility in the house cricket, Acheta domesticus L. Crickets were exposed to a standard dose of ß-cyfluthrin at different times of a day, and pesticide residue levels were evaluated using gas chromatography. Results demonstrate that the time of pyrethroid disappearance is correlated with the circadian clock, with the highest decomposition rate at night. Furthermore, crickets also showed the highest resistance to the insecticide at night, expressed as a high survival rate. Moreover, ß-cyfluthrin induced significant changes in thermal preferences of intoxicated crickets. This is the first report showing that pyrethroid residue levels in the crickets' body depend on its circadian clock.     

LC-MS/MS method validation for determination of selected neonicotinoids in groundwater for the purpose of a column experiment

The work was carried out to develop and validate a method based on liquid chromatography tandem mass spectrometry (LC-MS/MS) for the simultaneous detection and quantification of five neonicotinoid insecticides: acetamiprid, clothianidin, imidacloprid, thiacloprid and thiamethoxam in groundwater samples for the purpose of a further column experiment. This experiment will be used to analyze breakthrough curves of neonicotinoids under a saturated water flow to set transport parameters, where the reliability of the results of chemical analysis plays an important role. The validation was performed in a concentration range from 0.09?µg L^?1 to 100?µg L^?1 using an Infinity 1290 (Agilent, USA) chromatograph coupled with a QTrap 5500 mass spectrometer (Sciex, Canada). The calibration curves were obtained on the basis of the results of six standard solution analyses. Linearity was not lower than 0.998. The limit of detection was set at the lowest concentration which can be determined with an acceptable accuracy and precision. All pesticides had recoveries in the range 85–109% with relative standard deviation values less than 8.1%. The estimated measurement uncertainty did not exceed 30%, so the LC-MS/MS method fits for the intended purpose.     

Pb remobilization by bacterially mediated dissolution of pyromorphite Pb5(PO4)3Cl in presence of phosphate-solubilizing Pseudomonas putida

Remediation of lead (Pb)-contaminated sites with phosphate amendments is one of the best studied and cost-effective methods for in situ immobilization. In this treatment, a very stable mineral, pyromorphite Pb₅(PO₄)₃Cl, is formed. Several studies propose to improve this treatment method with the addition of phosphate-solubilizing bacteria (PSB). The effect of bacteria on solubilization of pyromorphite is unknown. In this study, the effect of the soil microorganisms on the stability of pyromorphite Pb₅(PO₄)₃Cl has been investigated in a set of batch solution experiments. The mineral was reacted with Pseudomonas putida, a common soil microorganism. Dissolution of pyromorphite was enhanced by the presence of P. putida, resulting in an elevated Pb concentration in the solution. This occurred even when the bacteria were provided with an additional source of phosphate in the solution. Pyromorphite has been shown to be a potential source of nutrient phosphorus for common soil bacteria. Thus, the use of PSB in remediation treatments of Pb contaminated sites may have adverse long-term impacts on Pb immobilization. Conscious phosphate management is suggested for long-term sustainability of the in situ Pb immobilization by pyromorphite formation.     

In vitro effects of pesticides and metals on the activity of acetylcholinesterase (AChE) from different tissues of the blue mussel,Mytilus trossulus L.

The objective of this study was to conduct a comprehensive comparison of the effect on acetylcholinesterase (AChE) from various tissues of Mytilus trossulus caused by in vitro exposure to several pesticides and metals, because results available in the literature are inconsistent, difficult to compare, and sometimes contradict each other. For this purpose, fraction S10 extracted from gills, digestive gland, mantle and muscles, and the whole soft tissue of the mussel was exposed to several pesticides (dichlorvos, chlorpyrifos, fenitrothion, carbofuran and carbaryl) and metals (Cu, Zn, Cd, Hg, Pb) at a wide range of concentrations. AChE was inhibited in 50% or more in all the tissues exposed to dichlorvos, Cu, Hg and the mixture of Cu+Cd, and in some tissues exposed to carbaryl and carbofuran. The IC₅₀ was calculated where possible. No inhibition was found in the case of chlorpyrifos, Cd, Pb, and Zn.     

Potential fresh water saving using greywater in toilet flushing in Syria

Greywater reuse is becoming an increasingly important factor for potable water saving in many countries. Syria is one of the most water scarce countries in the Middle East. However, greywater reuse is still not common in the country. Regulations and standards for greywater reuse are not available. Recently, however, several stakeholders have started to plan for greywater reuse. The main objective of this paper is to evaluate the potential for potable water saving by using greywater for toilet flushing in a typical Syrian city. The Sweida city in the southern part of Syria was chosen for this purpose. Interviews were made in order to reflect the social acceptance, water consumption, and the percentage of different indoor water uses. An artificial wetland (AW) and a commercial bio filter (CBF) were proposed to treat the greywater, and an economic analysis was performed for the treatment system. Results show that using treated greywater for toilet flushing would save about 35% of the drinking water. The economic analyses of the two proposed systems showed that, in the current water tariff, the payback period for AW and CBF in block systems is 7 and 52 years, respectively. However, this period will reduce to 3 and 21 years, respectively, if full water costs are paid by beneficiaries. Hence, introducing artificial wetlands in order to make greywater use efficient appears to be a viable alternative to save potable water.