Selective Separation of Chromium Species from Soils by Single-Step Extraction Methods: a Critical Appraisal

A critical appraisal of single-step extraction procedures of chromium species from soil was done in terms of their selectivity towards Cr(III) and Cr(VI) species. Samples of natural mineral and organic soil and samples of soil enriched with different chromium compounds of various solubility (in liquid or solid form) were used to simulate contamination of soil by liquid and solid wastes. The efficiency of extraction of Cr(III) and Cr(VI) species with various reagents, e.g. acetic acid, chelating agents (EDTA, DTPA) or inorganic salts (phosphates and carbonates), was evaluated on the basis of recovery results obtained for enriched samples. None of used reagents allow for quantitative extraction of added Cr(III) form. Procedures based on extraction of soil with Na2CO3 at room and elevated temperature (90–95 °C) were suitable for extraction of Cr(VI) species from mineral soil, whereas for organic soil, the procedure based on extraction with Na2CO3 at room temperature was recommended. The developed extraction procedures were validated using certified reference material (CRM 041 soil) and applied for analysis of contaminated soil samples. The studies showed that the physical state of waste, initial form and oxidation state of chromium and soil properties influenced the final chromium species and their mobility in soil, which have an impact on contamination of environment. The analysis of contaminated soil samples from a tannery area showed that the share of Cr(VI) was very low (only 0.8–4.5%) despite the high total content of chromium, which confirmed that chromium was present in immobile forms.Barbara Leśniewska - Institute of Chemistry, University of Bialystok, Bialystok, PolandMarta Gontarska - Institute of Chemistry, University of Bialystok, Bialystok, PolandBeata Godlewska-Żyłkiewicz - Institute of Chemistry, University of Bialystok, Bialystok, PolandApte, A. D., Verma, S., Tare, V., & Bose, P. (2005). 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Chromium Speciation in Wastewater and Sewage by Solid-Phase Extraction Using a New Diphenylcarbazone-Incorporated Resin

A new procedure for the determination of chromium species in polluted environmental samples by flame atomic absorption spectrometry was developed in this work. A new material containing 1,5-diphenylcarbazone included in a polymeric matrix was prepared and employed as a solid-phase extraction material for selective separation of Cr(III) ions under dynamic conditions. Chromium(III) ions were retained on this sorbent with high efficiency and repeatability (95 %, RSD = 1 %) from solutions with pH 9.0. The quantitative recovery of analyte was obtained with 0.1 mol L−1 EDTA. The concentration of Cr(VI) ions was calculated from the difference between the concentration of total chromium and Cr(III) ions. The prepared sorbent exhibits good chemical and mechanical stability, sorption capacity and selectivity towards Cr(III) ions in the presence of Cu(II), Ni(II), Mn(II) and Ca(II) ions. The accuracy of the separation method was proved by analysis of reference material of wastewater RES 10.2. The developed procedure was applied for chromium speciation analysis in municipal sewage samples.Barbara Leśniewska: [email protected] Leśniewska - Institute of Chemistry, University of BialystokAnna Jeglikowska - Institute of Chemistry, University of BialystokBeata Godlewska-Żyłkiewicz - Institute of Chemistry, University of BialystokAboufazeli, F., Lotfi, Z. Z., Hamid, R., Sadeghi, O., Karimi, M., & Najafi, E. (2013). Novel ion imprinted polymer magnetic mesoporous silica nano-particles for selective separation and determination of lead ions in food samples. Food Chemistry, 141, 3459–3465.Bagheri, A., Behbahani, M., Amini, M. M., Sadeghi, O., Taghizade, M., Baghayi, L., & Salarian, M. (2012). Simultaneous separation and determination of trace amounts of Cd(II) and Cu(II) in environmental samples using novel diphenylcarbazide modified nanoporous silica. Talanta, 89, 455–461.Barałkiewicz, D., Pikosz,B.,Belter,M.,&Marcinkowska,M. (2013). 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Development of Solid Phase Extraction Method Based on Ion Imprinted Polymer for Determination of Cr(III) Ions by ETAAS in Waters

In this work, a new solid phase extraction method for the determination of chromium species in water samples by electrothermal atomic absorption spectrometry was developed. For selective separation of Cr(III) ions under dynamic conditions, two ion imprinted polymers containing Cr(III)-1,10-phenanthroline complex (Cr(III)-phen) were prepared with the use of one (styrene, ST) or two (styrene and 4-vinylpyridine, ST-4VP) functional monomers. The physicochemical properties of those solid sorbents towards Cr(III) ions were studied and compared. It was found that Cr(III) ions were retained on the Cr(III)-phen-ST and Cr(III)-phen-ST-4VP polymers with high efficiency and repeatability (91.6% and 92.9%, RSD < 2%) from solutions at pH 4.5. The quantitative recovery of the analyte (91.7% and 93.9%, RSD < 4%) was obtained with 0.1 mol/L EDTA solution. The introduction of 4VP, an additional functional monomer, improved selectivity of the Cr(III)-phen-ST-4VP polymer towards Cr(III) ions in the presence of Cu(II), Mn(II) and Fe(III) ions, and slightly decreased the sorption capacity and stability of that polymer. The accuracy of procedures based on both polymeric sorbents was proved by analyzing the standard reference material of surface water SRM 1643e. The method using the Cr(III)-phen-ST polymer was applied for determining of Cr(III) ions in tap water and infusion of a green tea.Research work financed by the Ministry of Science and Education as part of a grant for maintaining research potential awarded to the Faculty of Chemistry, University of Bialystok.Laura Trzonkowska: ; [email protected] Leśniewska: : [email protected] Godlewska-Żyłkiewicz: ; [email protected] Trzonkowska - Department of Analytical Chemistry, Faculty of Chemistry, University of BialystokBarbara Leśniewska - Department of Analytical Chemistry, Faculty of Chemistry, University of BialystokBeata Godlewska-Żyłkiewicz - Department of Analytical Chemistry, Faculty of Chemistry, University of BialystokDhal, B.; Thatoi, H.N.; Das, N.N.; Pandey, B.D. Chemical and microchemical remediation of hexavalent chromium from contaminated soil and mining/metallurgical solid waste: A review. J. Hazard. Mater. 2013, 250–251, 272–291.Sawicka, E.; Jurkowska, K.; Piwowar, A. 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A novel ion-imprinted polymeric sorbent for separation and determination of chromium(III) species in wastewater

A new chromium(III) ion-imprinted polymer (IIP) was prepared from a Cr(III)-nicotinate complex (template), acrylamide (functional monomer), and ethylene glycol dimethacrylate (cross-linking agent) using 2,2’-azobisisobutyronitrile as the radical initiator. IIP was characterised and used as a selective sorbent for the solid-phase extraction of Cr(III) ions. The conditions for dynamic separation of Cr(III) on IIP were optimised. Cr(III) ions are selectively retained on the sorbent in a pH range from 9 to 10 and can be eluted with 4 mol L -1 acetic acid. Cr(III) ions were determined by flame atomic absorption spectrometry (FAAS) with a detection limit of 0.08 µg mL −1. The method was successfully applied to determine Cr(III) species in wastewater and reference material RES 25.2 with a reproducibility of 1.8%–3.4%.Beata Godlewska-Żyłkiewicz: [email protected] Leśniewska - Department of Analytical Chemistry, Faculty of Biology and Chemistry, University of Bialystok, Bialystok, PolandIwona Jakubowska - Department of Analytical Chemistry, Faculty of Biology and Chemistry, University of Bialystok, Bialystok, PolandElżbieta Zambrzycka - Department of Analytical Chemistry, Faculty of Biology and Chemistry, University of Bialystok, Bialystok, PolandBeata Godlewska-Żyłkiewicz - Department of Analytical Chemistry, Faculty of Biology and Chemistry, University of Bialystok, Bialystok, PolandThe New Top Six Toxic Threats: A Priority List for Remediation World’s Worst Pollution Problems 2015. Document prepared by Pure Earth and Green Cross Switzerland (http://www.worstpolluted.org/docs/WWPP 2015 Final.pdf).Sterans, D. M. 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Fast and simple procedure for fractionation of zinc in soil using an ultrasound probe and FAAS detection. Validation of the analytical method and evaluation of the uncertainty budget

A new fast method for determination of mobile zinc fractions in soil is proposed in this work. The three-stage modified BCR procedure used for fractionation of zinc in soil was accelerated by using ultrasounds. The working parameters of an ultrasound probe, a power and a time of sonication, were optimized in order to acquire the content of analyte in soil extracts obtained by ultrasound-assisted sequential extraction (USE) consistent with that obtained by conventional modified Community Bureau of Reference (BCR) procedure. The content of zinc in extracts was determined by flame atomic absorption spectrometry. The developed USE procedure allowed for shortening the total extraction time from 48 h to 27 min in comparison to conventional modified BCR procedure. The method was fully validated, and the uncertainty budget was evaluated. The trueness and reproducibility of the developed method was confirmed by analysis of certified reference material of lake sediment BCR-701. The applicability of the procedure for fast, low costs and reliable determination of mobile zinc fraction in soil, which may be useful for assessing of anthropogenic impacts on natural resources and environmental monitoring purposes, was proved by analysis of different types of soil collected from Podlaskie Province (Poland).Barbara Leśniewska: [email protected] Leśniewska - University of Bialystok, Institute of Chemistry, Bialystok, PolandKatarzyna Kisielewska - University of Bialystok, Institute of Chemistry, Bialystok, PolandJózefa Wiater - Bialystok University of Technology, Faculty of Civil and Environmental Engineering, Bialystok, PolandBeata Godlewska-Żyłkiewicz - University of Bialystok, Institute of Chemistry, Bialystok, PolandAlonso Castillo, M. L., Vereda, A. E., Siles Cordero, M. T., Cano Pavon, J. M., & Garcia de Torres, A. (2011). 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Monit., 3, 398–403.Evaluation of measurement data-Guide to the expression of uncertainty in measurement. (2008) JCGM 100.Finžgar, N., Tlustošs, P., & Leštan, D. (2007). Relationship of soil properties to fractionation, bioavailability and mobility of lead and zinc in soil. Plant Soil Environ., 53, 225–238.Garcia, C. D., García-Salgado, S., & Ángeles, Q. M. (2014). Accuracy evaluation of ultrasound probe sonication and microwave-assisted extraction systems for rapid single extraction of metals in soils. Anal. Methods., 6, 8403–8412.Golia, E. E., Tsiropoulos, N. G., Dimirkou, A., & Mitsios, I. (2007). Distribution of heavy metals of agricultural soils of central Greece using the modified BCR sequential extraction method. Int. J. Environ. Anal. Chem., 87, 1053–1063.Kabata-Pendias A. (2011). Trace elements in soils and plants, CRC Press Taylor and Francis Group, LLC, Boca Raton, 4th editionKazi, T. G., Jamali, M. K., Siddiqui, A., Kazi, G. H., Arain, M. B., & Afridi, H. I. (2006). 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An ultrasound-assisted procedure for fast screening of mobile fractions of Cd, Pb and Ni in soil. Insight into method optimization and validation

A fast ultrasound-assisted sequential extraction (UASE) procedure for the determination of cadmium, lead and nickel fractions in soil was developed and fully validated. The working parameters of an ultrasound probe were optimized by comparing the content of metals in soil extracts obtained by the UASE procedure with that obtained by the conventional (with the aid of a vertical rotor) modified Community Bureau of Reference (BCR) procedure. The content of metals in soil fractions was determined by electrothermal atomic absorption spectrometry. The total time of extraction of metals from soil was shorten from 48 h to 27 min (total sonication time). The trueness of the developed method was confirmed by analysis of the certified reference material BCR701. In order to indicate critical points of the developed UASE method, uncertainties of fractionation results were calculated and compared with those calculated for conventional modified BCR procedure. The method usefulness was tested for the determination of metal fractions in different types of soil collected in the Podlasie Province (Poland). The proposed procedure could be used for fast screening of mobile fractions of several heavy metals in soil.Barbara Leśniewska: [email protected] Leśniewska - Institute of Chemistry, University of Bialystok, Białystok, PolandMarta Krymska - Institute of Chemistry, University of Bialystok, Białystok, PolandEwelina Świerad - Institute of Chemistry, University of Bialystok, Białystok, PolandJózefa Wiater - Faculty of Civil and Environmental Engineering, Bialystok University of Technology, Białystok, PolandBeata Godlewska-Żyłkiewicz - Institute of Chemistry, University of Bialystok, Białystok, PolandAhmad MS, Ashraf M (2011) Essential roles and hazardous effects of nickel in plants. Rev Environ Contam Toxicol 214:125–167.Andresen E, Küpper H (2013) Cadmium toxicity in plants. 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Successes and pitfalls of chronic peritoneal dialysis in infants – a Polish nationwide outcome study

Introduction: Peritoneal dialysis (PD) is a preferred method of renal replacement therapy for end-stage renal disease in children. Recent advances have allowed chronic PD to be provided to children of all ages and sizes. Material and methods: The study was designed as a national (10 dialysis centres), multicentre retrospective analysis of the medical history of 33 children who started chronic peritoneal dialysis in their infancy between 1993 and 2005, with a follow-up period of at least 24 months. Results: The nutritional status of the infants was unsatisfactory. The mean SDS of body weight at the start was -2.0, at 1 year of age -1.7. Only 40% of infants were adequately nourished at 1 year of age. Long-term follow-up analysis showed that 12 children received a kidney transplant, 13 were still on dialysis (4 changed method) and 6 died (mortality rate in the first year of life of 9%). In 2 children we observed an improvement of renal function. We observed a relatively high (1/8.8 patient-months) peritonitis rate in the analysed children when compared to 1 : 22 patient-months in all children undergoing PD in Poland. Conclusions: The results of our survey have shown that the management of dialysed infants is still a challenge for the medical team and families, but longterm results of the therapy are encouragin

Fast and simple procedure for fractionation of zinc in soil using an ultrasound probe and FAAS detection. Validation of the analytical method and evaluation of the uncertainty budget

A new fast method for determination of mobile zinc fractions in soil is proposed in this work. The three-stage modified BCR procedure used for fractionation of zinc in soil was accelerated by using ultrasounds. The working parameters of an ultrasound probe, a power and a time of sonication, were optimized in order to acquire the content of analyte in soil extracts obtained by ultrasound-assisted sequential extraction (USE) consistent with that obtained by conventional modified Community Bureau of Reference (BCR) procedure. The content of zinc in extracts was determined by flame atomic absorption spectrometry. The developed USE procedure allowed for shortening the total extraction time from 48 h to 27 min in comparison to conventional modified BCR procedure. The method was fully validated, and the uncertainty budget was evaluated. The trueness and reproducibility of the developed method was confirmed by analysis of certified reference material of lake sediment BCR-701. The applicability of the procedure for fast, low costs and reliable determination of mobile zinc fraction in soil, which may be useful for assessing of anthropogenic impacts on natural resources and environmental monitoring purposes, was proved by analysis of different types of soil collected from Podlaskie Province (Poland). ELECTRONIC SUPPLEMENTARY MATERIAL: The online version of this article (doi:10.1007/s10661-015-5020-6) contains supplementary material, which is available to authorized users

Speciation of Chromium in Alkaline Soil Extracts by an Ion-Pair Reversed Phase HPLC-ICP MS Method

The aim of this work was to study by a hyphenated HPLC-ICP MS technique the chromium species released during alkaline extraction of various soils collected from a contaminated area of an old tannery. An ultrasound-assisted extraction procedure using 0.1 mol L&#8722;1 Na2CO3 solution was developed for the release of chromium species from the soil. The chromium species in the soil extracts were separated on a C8 column using EDTA and TBAH solution as a mobile phase. The use of an ICP-QQQ MS spectrometer in tandem mass configuration (MS/MS) combined with an octopole reaction system (ORS3) pressurized with helium allows one to eliminate spectral interferences during Cr determination in the soil extracts. The detection limit of the procedure was 0.08 &#181;g L&#8722;1 for Cr(III) and 0.09 &#181;g L&#8722;1 for Cr(VI) species. The trueness of the IP RP HPLC-ICP MS method was proved by an analysis of CRM 041 and CRM 060. The advantage of the proposed method is the analysis of soil extracts without their preliminary neutralization, which limits the losses of Cr(VI) due to the reduction process. The analysed soils mainly contained chromium in immobile forms (94.6&#8211;98.5% of the total Cr content). In all alkaline soil extracts mostly the Cr(VI) form was found, but in the extract of organic soils Cr(III) was also present. This arose from the reduction of Cr(VI) species by organic matter (humic acids) and Fe(II). The amount of formed Cr(III) species was dependent on the type of soil (content of organic matter, Mn and Fe) and its moistness. For the first time, the presence of neutral and non-polar chromium fractions in the soil extracts was also demonstrated. It was found that reliable speciation analysis results could be obtained for mineral soils

The Arabidopsis receptor kinase STRUBBELIG regulates the response to cellulose deficiency.

Plant cells are encased in a semi-rigid cell wall of complex build. As a consequence, cell wall remodeling is essential for the control of growth and development as well as the regulation of abiotic and biotic stress responses. Plant cells actively sense physico-chemical changes in the cell wall and initiate corresponding cellular responses. However, the underlying cell wall monitoring mechanisms remain poorly understood. In Arabidopsis the atypical receptor kinase STRUBBELIG (SUB) mediates tissue morphogenesis. Here, we show that SUB-mediated signal transduction also regulates the cellular response to a reduction in the biosynthesis of cellulose, a central carbohydrate component of the cell wall. SUB signaling affects early increase of intracellular reactive oxygen species, stress gene induction as well as ectopic lignin and callose accumulation upon exogenous application of the cellulose biosynthesis inhibitor isoxaben. Moreover, our data reveal that SUB signaling is required for maintaining cell size and shape of root epidermal cells and the recovery of root growth after transient exposure to isoxaben. SUB is also required for root growth arrest in mutants with defective cellulose biosynthesis. Genetic data further indicate that SUB controls the isoxaben-induced cell wall stress response independently from other known receptor kinase genes mediating this response, such as THESEUS1 or MIK2. We propose that SUB functions in a least two distinct biological processes: the control of tissue morphogenesis and the response to cell wall damage. Taken together, our results reveal a novel signal transduction pathway that contributes to the molecular framework underlying cell wall integrity signaling