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.     

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.     

Molecular tools for bathing water assessment in Europe: Balancing social science research with a rapidly developing environmental science evidence-base

The use of molecular tools, principally qPCR, versus traditional culture-based methods for quantifying microbial parameters (e.g., Fecal Indicator Organisms) in bathing waters generates considerable ongoing debate at the science–policy interface. Advances in science have allowed the development and application of molecular biological methods for rapid (~2 h) quantification of microbial pollution in bathing and recreational waters. In contrast, culture-based methods can take between 18 and 96 h for sample processing. Thus, molecular tools offer an opportunity to provide a more meaningful statement of microbial risk to water-users by providing near-real-time information enabling potentially more informed decision-making with regard to water-based activities. However, complementary studies concerning the potential costs and benefits of adopting rapid methods as a regulatory tool are in short supply. We report on findings from an international Working Group that examined the breadth of social impacts, challenges, and research opportunities associated with the application of molecular tools to bathing water regulations.     

Determination of neonicotinoids in Estonian honey by liquid chromatography–electrospray mass spectrometry

The aim of the study was to provide a comprehensive overview of neonicotinoid pesticide residues in honey samples for a single country and compare the results with the import data for neonicotinoid pesticides. The levels of four neonicotinoid pesticides, namely thiamethoxam, imidacloprid, acetamiprid, and thiacloprid, were determined in 294 honey samples harvested from 2005 to 2013 from more than 200 locations in Estonia. For the analyzed honey samples, 27% contained thiacloprid, and its levels in all cases were below the maximum residue level set by the European Union. The other neonicotinoids were not detected. The proportion of thiacloprid-positive samples for different years correlates well with the data on thiacloprid imports into Estonia, indicating that honey contamination with neonicotinoids can be estimated based on the import data.     

Review of receptor modeling methods for source apportionment

Efforts have been made to relate measured concentrations of airborne constituents to their origins for more than 50 years. During this time interval, there have been developments in the measurement technology to gather highly time-resolved, detailed chemical compositional data. Similarly, the improvements in computers have permitted a parallel development of data analysis tools that permit the extraction of information from these data. There is now a substantial capability to provide useful insights into the sources of pollutants and their atmospheric processing that can help inform air quality management options. Efforts have been made to combine receptor and chemical transport models to provide improved apportionments. Tools are available to utilize limited numbers of known profiles with the ambient data to obtain more accurate apportionments for targeted sources. In addition, tools are in place to allow more advanced models to be fitted to the data based on conceptual models of the nature of the sources and the sampling/analytical approach. Each of the approaches has its strengths and weaknesses. However, the field as a whole suffers from a lack of measurements of source emission compositions. There has not been an active effort to develop source profiles for stationary sources for a long time, and with many significant sources built in developing countries, the lack of local profiles is a serious problem in effective source apportionment. The field is now relatively mature in terms of its methods and its ability to adapt to new measurement technologies, so that we can be assured of a high likelihood of extracting the maximal information from the collected data.

Implications: Efforts have been made over the past 50 years to use air quality data to estimate the influence of air pollution sources. These methods are now relatively mature and many are readily accessible through publically available software. This review examines the development of receptor models and the current state of the art in extracting source identification and apportionments from ambient air quality data.     

β-环糊精接枝羧甲基壳聚糖吸附剂的制备及其性能

采用γ-氨丙基三乙氧基硅烷化学修饰活化后的硅胶,以戊二醛为交联剂,接上羧甲基壳聚糖,继而接枝上β-环糊精作为功能单体,制备了一种用于分离富集水样中Cu(Ⅱ)的固相萃取新材料。利用红外光谱(FT-IR)、比表面分析(BET)、X射线衍射光谱(XRD)以及热重分析(TG)等方法对吸附剂进行结构表征。采用火焰原子吸收(FAAS)作为检测手段,考察了溶液pH、振荡时间、吸附剂用量、样品流速、洗脱液浓度和体积等对吸附剂吸附Cu(Ⅱ)的影响。吸附剂饱和吸附容量为9.37 mg/g,最大富集倍数高达350。吸附过程能用准二级动力学模型和Langmuir等温吸附方程进行很好的拟合。应用于环境水样中Cu(Ⅱ)的分离富集与测定,回收率在96.8%~105.2%之间,效果较好。     

某城市污水处理厂废水化学除磷沉淀特性及影响因素

通过对西安市某污水处理厂进水、厌氧池上清液、二沉池出水、污泥浓缩水、污泥脱水进行FeCI3·6H2O、PAC除磷实验,并以FeCI3·6H2O为沉淀剂对厌氧池上清液从pH、Fe/P摩尔比、腐殖酸、挥发性脂肪酸(VFA)等因素进行批次实验分析磷去除状况.实验显示,三氯化铁、PAC对进水除磷效果不佳,厌氧池上清液用FeCI3·6H2O为沉淀剂时磷去除率较低,二沉池出水、污泥浓缩水以及污泥脱水用FeCI3·6H2O、PAC时其正磷去除率均可达到80%左右.通过对比不同pH值、Fe/P摩尔比、腐殖酸和VFA浓度对厌氧池上清液除磷效果的影响,结果表明,在pH=4~5,Fe/P=1.3时磷的去除效果达到78%以上,腐殖酸浓度对磷去除率影响不大,VFA在低于10 mg/L和高于60 mg/L时对磷去除率影响较大.     

Nitrogen fixation by cyanobacteria stimulates production in Baltic food webs

Filamentous, nitrogen-fixing cyanobacteria form extensive summer blooms in the Baltic Sea. Their ability to fix dissolved N₂ allows cyanobacteria to circumvent the general summer nitrogen limitation, while also generating a supply of novel bioavailable nitrogen for the food web. However, the fate of the nitrogen fixed by cyanobacteria remains unresolved, as does its importance for secondary production in the Baltic Sea. Here, we synthesize recent experimental and field studies providing strong empirical evidence that cyanobacterial nitrogen is efficiently assimilated and transferred in Baltic food webs via two major pathways: directly by grazing on fresh or decaying cyanobacteria and indirectly through the uptake by other phytoplankton and microbes of bioavailable nitrogen exuded from cyanobacterial cells. This information is an essential step toward guiding nutrient management to minimize noxious blooms without overly reducing secondary production, and ultimately most probably fish production in the Baltic Sea.