Mechanistic insights into the specificity of human cytosolic sulfotransferase 2A1 (hSULT2A1) for hydroxylated polychlorinated biphenyls through the use of fluoro-tagged probes

Determining the relationships between the structures of substrates and inhibitors and their interactions with drug-metabolizing enzymes is of prime importance in predicting the toxic potential of new and legacy xenobiotics. Traditionally, quantitative structure activity relationship (QSAR) studies are performed with many distinct compounds. Based on the chemical properties of the tested compounds, complex relationships can be established so that models can be developed to predict toxicity of novel compounds. In this study, the use of fluorinated analogues as supplemental QSAR compounds was investigated. Substituting fluorine induces changes in electronic and steric properties of the substrate without substantially changing the chemical backbone of the substrate. In vitro assays were performed using purified human cytosolic sulfotransferase hSULT2A1 as a model enzyme. A mono-hydroxylated polychlorinated biphenyl (4-OH PCB 14) and its four possible mono-fluoro analogues were used as test compounds. Remarkable similarities were found between this approach and previously published QSAR studies for hSULT2A1. Both studies implicate the importance of dipole moment and dihedral angle as being important to PCB structure in respect to being substrates for hSULT2A1. We conclude that mono-fluorinated analogues of a target substrate can be a useful tool to study the structure activity relationships for enzyme specificity.     

Enrichment of trace elements in the clay size fraction of mining soils

Reactive waste dumps with sulfide minerals promote acid mine drainage (AMD), which results in water and soil contamination by metals and metalloids. In these systems, contamination is regulated by many factors, such as mineralogical composition of soil and the presence of sorption sites on specific mineral phases. So, the present study dedicates itself to understanding the distribution of trace elements in different size fractions (<2-mm and <2-μm fractions) of mining soils and to evaluate the relationship between chemical and mineralogical composition. Cerdeirinha and Penedono, located in Portugal, were the waste dumps under study. The results revealed that the two waste dumps have high degree of contamination by metals and arsenic and that these elements are concentrated in the clay size fraction. Hence, the higher degree of contamination by toxic elements, especially arsenic in Penedono as well as the role of clay minerals, jarosite, and goethite in retaining trace elements has management implications. Such information must be carefully thought in the rehabilitation projects to be planned for both waste dumps.     

Impact of temperature on the dynamics of organic matter and on the soil-to-plant transfer of Cd,Zn and Pb in a contaminated agricultural soil

Predicting the soil-to-plant transfer of metals in the context of global warming has become a major issue for food safety. It requires a better understanding of how the temperature alters the bioavailability of metals in cultivated soils. This study focuses on one agricultural soil contaminated by Cd, Zn and Pb. DGT measurements were performed at 10, 20 and 30 °C to assess how the bioavailability of metals was affected by a rise in soil temperature. A lettuce crop was cultivated in the same conditions to determine if the soil-to-plant transfer of metals increased with a rise in soil temperature. A gradual decline in Cd and Zn bioavailability was observed from 10 to 30 °C, which was attributed to more intense complexation of metals in the pore water at higher temperatures. Together with its aromaticity, the affinity of dissolved organic matter (DOM) for metals was indeed suspected to increase with soil temperature. One main output of the present work is a model which satisfactorily explains the thermal-induced changes in the characteristics of DOM reported in Cornu et al. (Geoderma 162:65–70, 2011) by assuming that the mineralization of initial aliphatic compounds followed a first-order reaction, increased with soil temperature according to the Arrhenius law, and due to a priming effect, led to the appearance of aromatic molecules. The soil-to-plant transfer of Cd and Zn was promoted at higher soil temperatures despite a parallel decrease in Cd and Zn bioavailability. This suggests that plant processes affect the soil-to-plant transfer of Cd and Zn the most when the soil temperature rises.     

Fluoride in weathered rock aquifers of southern India: Managed Aquifer Recharge for mitigation

Climatic condition, geology, and geochemical processes in an area play a major role on groundwater quality. Impact of these on the fluoride content of groundwater was studied in three regions—part of Nalgonda district in Telangana, Pambar River basin, and Vaniyar River basin in Tamil Nadu, southern India, which experience semi-arid climate and are predominantly made of Precambrian rocks. High concentration of fluoride in groundwater above 4 mg/l was recorded. Human exposure dose for fluoride through groundwater was higher in Nalgonda than the other areas. With evaporation and rainfall being one of the major contributors for high fluoride apart from the weathering of fluoride rich minerals from rocks, the effect of increase in groundwater level on fluoride concentration was studied. This study reveals that groundwater in shallow environment of all three regions shows dilution effect due to rainfall recharge. Suitable managed aquifer recharge (MAR) methods can be adopted to dilute the fluoride rich groundwater in such regions which is explained with two case studies. However, in deep groundwater, increase in fluoride concentration with increase in groundwater level due to leaching of fluoride rich salts from the unsaturated zone was observed. Occurrence of fluoride above 1.5 mg/l was more in areas with deeper groundwater environment. Hence, practicing MAR in these regions will increase the fluoride content in groundwater and so physical or chemical treatment has to be adopted. This study brought out the fact that MAR cannot be practiced in all regions for dilution of ions in groundwater and that it is essential to analyze the fluctuation in groundwater level and the fluoride content before suggesting it as a suitable solution. Also, this study emphasizes that long-term monitoring of these factors is an important criterion for choosing the recharge areas.     

Biodegradability of the anticancer drug etoposide and identification of the transformation products

Etoposide susceptibility to microbiological breakdown was studied in a batch biotransformation system, in the presence or absence of artificial wastewater containing nutrients, salts and activated sludge at two concentration levels. The primary focus of the present study was to study etoposide transformation products by ultra-high performance liquid chromatography coupled to high-resolution hybrid quadrupole-Orbitrap tandem mass spectrometry (MS/MS). Data-dependent experiments combining full-scan MS data with product ion spectra were acquired to identify the molecular ions of etoposide transformation products, to propose the molecular formulae and to elucidate their chemical structures. Due to the complexity of the matrix, visual inspection of the chromatograms showed no clear differences between the controls and the treated samples. Therefore, the software package MZmine was used to facilitate the identification of the transformation products and speed up the data analysis. In total, we propose five transformation products; among them, four are described as etoposide transformation products for the first time. Even though the chemical structures of these new compounds cannot be confirmed due to the lack of standards, their molecular formulae can be used to target them in monitoring studies.     

Influence of Al-oxide on pesticide sorption to woody biochars with different surface areas

Biochars’ properties will change after application in soil due to the interactions with soil constituents, which would then impact the performance of biochars as soil amendment. For a better understanding on these interactions, two woody biochars of different surface areas (SA) were physically treated with aluminum oxide (Al-oxide) to investigate its potential influence on biochars’ sorption property. Both the micropore area and mesopore (17～500 Å in diameter) area of the low-SA biochar were enhanced by at least 1.5 times after treatment with Al-oxide, whereas the same treatment did not change the surface characteristics of the high-SA biochar due partly to its well-developed porosity. The enhanced sorption of the pesticide isoproturon to the Al-oxide-treated low-SA biochar was observed and is positively related to the increased mesopore area. The desorption hysteresis of pesticide from the low-SA biochar was strengthened because of more pesticide molecules entrapped in the expanded pores by Al-oxide. However, no obvious change of pesticide sorption to the high-SA biochar after Al-oxide treatment was observed, corresponding to its unchanged porosity. The results suggest that the influence of Al-oxide on the biochars’ sorption property is dependent on their porosity. This study will provide valuable information on the use of biochars for reducing the bioavailability of pesticides.     

Evaluation of the efficacy of a portable LIBS system for detection of CWA on surfaces

Laser-induced breakdown spectroscopy (LIBS) is a laser-based optical technique particularly suited for in situ surface analysis. A portable LIBS instrument was tested to detect surface chemical contamination by chemical warfare agents (CWAs). Test of detection of surface contamination was carried out in a toxlab facility with four CWAs, sarin (GB), lewisite (L1), mustard gas (HD), and VX, which were deposited on different substrates, wood, concrete, military green paint, gloves, and ceramic. The CWAs were detected by means of the detection of atomic markers (As, P, F, Cl, and S). The LIBS instrument can give a direct response in terms of detection thanks to an integrated interface for non-expert users or so called end-users. We have evaluated the capability of automatic detection of the selected CWAs. The sensitivity of our portable LIBS instrument was confirmed for the detection of a CWA at surface concentrations above 15 μg/cm². The simultaneous detection of two markers may lead to a decrease of the number of false positive.