Removal of selected pesticides from water using granular activated carbon

Pesticides are intensively used for the protection of field crops, orchards and vineyards, but they are also used in the removal of undesirable stands on non-agricultural land (railway embankments, playgrounds, handling areas, etc.), in water management (in coastal management, destruction of growths in irrigation canals), in forestry, etc. Regular application of pesticides increases their content in the aquatic environment and agricultural products. Their occurrence in water is relatively common and it follows that these substances are used in large quantities. Residues of these substances can persist in soils for 2 to 12 weeks. Due to their good solubility in water, they are easily transported from the soil to aquifers. Several methods can be used to remove pesticides from water, e.g., coagulation, filtration, precipitation, ozonation, adsorption, ion exchange, nanofiltration, reverse osmosis and advanced oxidation processes. Their effectiveness varies considerably and depends mainly on the chemical nature of the pesticide being removed. This article studies adsorption on two granular activated carbons Filtrasorb 400 and Norit 1240. Mixture of the pesticide standards (acetochlor, alachlor, dimethachlor, propachlor, metazachlor and metolachlor) was added to drinking water with concentration of approximately 1 µg/L. The experiments were performed in the glass bottles with the volume of 200 mL of water. The granular activated carbons (200 mg) were added to the bottles. Subsequently these bottles were regularly stirred, and the samples were taken out at times 0, 30, 60, 90, 120, 180, 240 and 360 minutes. Samples were taken by pipette into the 40 ml glass vials with added thiosulphate for preservation. Analyses of target pesticides were performed in laboratories of ALS Czech Republic in Prague. LC-MS using the internal standard method was used to determine chlorinated pesticides in water samples. The adsorption efficiency of pesticides removal and the adsorption capacity of granular activated carbon depends on the time of contact of water with the material. The results showed that the efficiency of selected pesticides removal and adsorption capacity for two granular activated carbons used varied. Filtrasorb F400 proved to be a better sorption material than Norit 1240. The efficiency of this material ranged from 18 to 60%, while the efficiency of Norit 1240 was significantly lower. Adsorption capacity of activated carbons for selected pesticides and reaction kinetics of 0th, 1st, 2nd and 3rd order was also studied.

An Internal Standard High-Performance Liquid Chromatography Method for Simultaneous Quantification of Candesartan and Hydrochlorothiazide in Combined Formulations

The internal standard method is a versatile procedure that avoids misleading results caused by the instability of the chromatographic system or inexperienced workers. It is an effective way to judge the accuracy of any obtained data. As the detector responses of chlorzoxazone (CZN) resemble those of candesartan (CDZN) and hydrochlorothiazide (HCTZ), CZN was employed as an internal standard. Herein, a simple chromatographic method was established for quantification of CDZN and HCTZ. Isocratic elution was conducted using 1% premixed acetonitrile/formic acid (7:3 v/v) at a 0.8 mL/min flowrate. The separation of the three components was maintained using the universal 20 µL loop, and for further simplicity in application, the analysis was optimized at 25 °C. CDZN, HCTZ, and CZN were simultaneously monitored and quantified at 270 nm. The method developed here complies with all the validation limits according to the British Pharmacopoeia (BP), United States Pharmacopoeia (USP), and the guidelines of the International Council ForHarmonisation (ICH). The method proved to be linear in the range of 6.4 to 25.6 µg/mL and 5.0–20 µg/mL for CDZN and HCTZ, respectively, while the quantitation detection limits were less than 1.0µg/mL for both.

Simultaneous quantification of oxcarbazepine and its active metabolite in spiked human plasma using ultra performance liquid chromatography–MS/MS

Aim: Clinical monitoring of oxcarbazepine (OXC) and its metabolite licarbazepine (MHD) in biological matrix requires a sensitive and validated analytical method. The aim of this study is to develop and validate an optimized ultra performance liquid chromatography–MS/MS based bioanalytical method for the simultaneous estimation of OXC and its metabolite MHD in human plasma, using deuterated internal standard method. Materials & methods: A reverse phase ultra performance liquid chromatography analysis and mass spectrometric detection was performed using electrospray ionization in positive ion mode as interface, multiple reaction monitoring as mode of acquisition. Results & conclusion: The linearity range was 10–4011 ng/ml for OXC and 40–16061 ng/ml for MHD. The kinetic parameters were calculated and compared for bioequivalence. This method fulfilled the validation guidelines, could be employed for determining bioavailability and in new formulation development studies.

In-situ TEM Investigation of Solid Phase Transformations and Reactions

In this paper, an example of phase analysis during annealing is presented using in-situ TEM. The example is demonstrated on amorphous Cu-Mn/C thin films focusing on phase identification in a multicomponent system. The transient states following the crystallization of the amorphous Cu-Mn alloy and the reaction with the C substrate were analyzed by evaluating the diffraction patterns recorded at different temperatures. The camera constant was calibrated using the internal standard method. The change in composition of the Cu(Mn) solid solution was calculated by separating the effect of thermal expansion and solute concentration. Identification of the forming phases was aided by analyzing and comparing the probability of formation of all phases in the Cu-Mn-C-O system. After the crystallization of amorphous Cu-Mn alloy into Cu(Mn) and α-Mn-based solid solutions, the formation of the following carbide phases was observed: Mn23C6, Mn5C2 and Mn7C3.

Crystallization of simonkolleite (Zn5Cl2(OH)8 ∙ H2O) in powder samples prepared for mineral composition analysis by quantitative X-ray diffraction (QXRD)

The analysis of mineralogical composition by quantitative X-ray diffraction (QXRD) is one of the standard research methods used in hydrocarbon exploration. In order to improve it and to obtain better results, the methodology of quantitative analysis used at Well Logging Department is being periodically (more or less) modified. After the introduction of the improvements, comparative analyses were performed on archival samples. Reflections from an unidentified phase which did not occur in the tested Rotliegend sandstone samples were noticed on X-ray diffractograms of archival samples. Reflections of a mineral called simonkolleite were identified in the X-ray diffraction database. Chemically it is a hydrated zinc chloride of the formula: Zn5Cl2(OH)8 × H2O. Analysis of the composition of samples in which simonkolleite crystallised, indicated that the mineral is being formed in the result of the slow reaction of zinc oxide with halite (NaCl) and water vapour. An attempt was made to determine the influence of the presence of this mineral on the results of the quantitative analysis of mineralogical composition. The above methodology was applied on a group of ten samples. The results of the quantitative analysis conducted for archival samples stored with added zincite standard containing simonkolleite and for new, freshly grinded (without artifact) samples were compared. The comparison of the obtained results showed a slight influence of this mineral on the quantitative composition of the remaining components. The difference between the results usually did not exceed the method error. At the same time a significant difference in the calculated content of the internal standard was noted – on average 1% less in archival than in new samples. This shows that the reaction occurring in the archival samples will affect the evaluation of the quality of the obtained quantitative analysis, at the same time excluding the possibility of determining the rock’s amorphous substance content with the internal standard method.

A stable isotope dilution method for a highly accurate analysis of karrikins

Background Karrikins (KARs) are recently described group of plant growth regulators with stimulatory effects on seed germination, seedling growth and crop productivity. So far, an analytical method for the simultaneous targeted profiling of KARs in plant tissues has not been reported. Results We present a sensitive method for the determination of two highly biologically active karrikins (KAR1 and KAR2) in minute amounts of plant material (< 20 mg fresh weight). The developed protocol combines the optimized extraction and efficient single-step sample purification with ultra-high performance liquid chromatography-tandem mass spectrometry. Newly synthesized deuterium labelled KAR1 was employed as an internal standard for the validation of KAR quantification using a stable isotope dilution method. The application of the matrix-matched calibration series in combination with the internal standard method yields a high level of accuracy and precision in triplicate, on average bias 3.3% and 2.9% RSD, respectively. The applicability of this analytical approach was confirmed by the successful analysis of karrikins in Arabidopsis seedlings grown on media supplemented with different concentrations of KAR1 and KAR2 (0.1, 1.0 and 10.0 µmol/l). Conclusions Our results demonstrate the usage of methodology for routine analyses and for monitoring KARs in complex biological matrices. The proposed method will lead to better understanding of the roles of KARs in plant growth and development.