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.     

Mercury species accumulation and trophic transfer in biological systems using the Almadén mining district (Ciudad Real,Spain) as a case of study

The impact of mercury (Hg) pollution in the terrestrial environments and the terrestrial food chains including the impact on human food consumption is still greatly under-investigated. In particular, studies including Hg speciation and detoxification strategies in terrestrial animals are almost non-existing, but these are key information with important implications for human beings. Therefore, in this work, we report on Hg species (inorganic mercury, iHg, and monomethylmercury, MeHg) distribution among terrestrial animal tissues obtained from a real-world Hg exposure scenario (Almadén mining district, Spain). Thus, we studied Hg species (iHg and MeHg) and total selenium (Se) content in liver and kidney of red deer (Cervus elaphus; n?=?41) and wild boar (Sus scrofa; n?=?16). Similar mercury species distribution was found for both red deer and wild boar. Major differences were found between tissues; thus, in kidney, iHg was clearly the predominant species (more than 81 %), while in liver, the species distribution was less homogeneous with a percentage of MeHg up to 46 % in some cases. Therefore, Hg accumulation and MeHg transfer were evident in terrestrial ecosystems. The interaction between total Se and Hg species has been evaluated by tissue and by animal species. Similar relationships were found in kidney for both Hg species in red deer and wild boar. However, in liver, there were differences between animals. The possible underlying mechanisms are discussed.     

Biogenic polycyclic aromatic hydrocarbons in sediments of the San Joaquin River in California (USA), and current paradigms on their formation

Biogenic perylene and higher plant pentacyclic triterpenoid-derived alkylated and partially aromatized tetra- and pentacyclic derivatives of chrysene (3,4,7-trimethyl- and 3,3,7-trimethyl-1,2,3,4-tetrahydrochrysene, THC) and picene (1,2,9-trimethyl- and 2,2,9-trimethyl-1,2,3,4-tetrahydropicene, THP) were two- to four-fold more abundant than pyrogenic PAH in two sediment cores from the San Joaquin River in Northern California (USA). In a core from Venice Cut (VC), located in the river, PAH concentrations varied little downcore and the whole-core PAH concentration (biogenics?+?pyrogenics) was 250.6?±?73.7 ng g^?1 dw; biogenic PAH constituted 67?±?4 % of total PAH. THC were 26?±?9 % of total biogenic PAH, THP were 36?±?7 %, and perylene was 38?±?7 %. PAH distributions in a core from Franks Tract (FT), a former wetland that was converted to an agricultural tract in the late 1800s and flooded in 1938, were more variable. Surface sediments were dominated by pyrogenic PAH so that biogenic PAH were only ~30 % of total PAH. Deeper in the core, biogenic PAH constituted 60–93 % of total PAH; THC, THP and perylene were 31?±?28 %, 24?±?32 %, and 45?±?36 % of biogenic PAH. At 100–103 cm depth, THP constituted 80 % of biogenic PAH and at 120–123 cm perylene was 95 % of biogenic PAH. Current concepts related to precursors and transformation processes responsible for the diagenetic generation of perylene and triterpenoid-derived PAH are discussed. Distributions of biogenic PAH in VC and FT sediments suggest that they may not form diagenetically within these sediments but rather might be delivered pre-formed from the river’s watershed.     

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.     

Release of PCBs from Silvretta glacier (Switzerland) investigated in lake sediments and meltwater

This study is part of our investigations about the release of persistent organic pollutants from melting Alpine glaciers and the relevance of the glaciers as secondary sources of legacy pollutants. Here, we studied the melt-related release of polychlorinated biphenyls (PCBs) in proglacial lakes and glacier streams of the catchment of the Silvretta glacier, located in the Swiss Alps. To explore a spatial and temporal distribution of chemicals in glacier melt, we combined two approaches: (1) analysing a sediment record as an archive of past remobilization and (2) passive water sampling to capture the current release of PCBs during melt period. In addition, we determined PCBs in a non-glacier-fed stream as a reference for the background pollutant level in the area. The PCBs in the sediment core from the Silvretta lake generally complied with trends of PCB emissions into the environment. Elevated concentrations during the most recent ten years, comparable in level with times of the highest atmospheric input, were attributed to accelerated melting of the glacier. This interpretation is supported by the detected PCB fractionation pattern towards heavier, less volatile congeners, and by increased activity concentrations of the radioactive tracer ¹³⁷Cs in this part of the sediment core. In contrast, PCB concentrations were not elevated in the stream water, since no significant difference between pollutant concentrations in the glacier-fed and the non-glacier-fed streams was detected. In stream water, no current decrease of the PCBs with distance from the glacier was observed. Thus, according to our data, an influence of PCBs release due to accelerated glacier melt was only detected in the proglacial lake, but not in the other compartments of the Silvretta catchment.     

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.     

Suitability of passive sampling for the monitoring of pharmaceuticals in Finnish surface waters

The occurrence of five pharmaceuticals, consisting of four anti-inflammatory and one antiepileptic drug, was studied by passive sampling and grab sampling in northern Lake Päijänne and River Vantaa. The passive sampling was performed by using Chemcatcher® sampler with a SDB-RPS Empore disk as a receiving phase. In Lake Päijänne, the sampling was conducted during summer 2013 at four locations near the discharge point of a wastewater treatment plant and in the years 2013 and 2015 at four locations along River Vantaa. The samples were analyzed by liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) in the multiple reaction monitoring mode. The concentrations of carbamazepine, diclofenac, ibuprofen, ketoprofen, and naproxen in Lake Päijänne determined by passive sampling ranged between 1.4–2.9 ng L^?1, 15–35 ng L^?1, 13–31 ng L^?1, 16–27 ng L^?1, and 3.3–32 ng L^?1, respectively. Similarly, the results in River Vantaa ranged between 1.2–40 ng L^?1, 15–65 ng L^?1, 13–33 ng L^?1, 16–31 ng L^?1, and 3.3–6.4 ng L^?1. The results suggest that the Chemcatcher passive samplers are suitable for detecting pharmaceuticals in lake and river waters.     

Effect of feeding dried sweet orange (<Emphasis Type="Italic">Citrus sinensis</Emphasis>) peel and lemon grass (<Emphasis Type="Italic">Cymbopogon citratus</Emphasis>) leaves on growth performance,carcass traits,serum metabolites and antioxidant status in broiler during the finisher phase

The current experiment was conducted to evaluate the effects of feeding dried sweet orange peel (SOP) and lemon grass leaves (LGL) as feed additives on broiler growth performance, serum metabolites, and antioxidant status. A total of 192-day-old (Ross 308) broiler chickens were distributed randomly into 4 dietary treatments with 4 replicates per each treatment. The dietary treatments included a control diet without any feed additive (T1), a diet containing 0.8 % SOP (T2), a diet containing 0.8 % LGL (T3), and a diet containing combination of 0.4 % SOP?+?0.4 % LGL (T4) was fed during the growth period from 22 to 42 days. Feed intake (FI), body weight gain (BWG), feed conversion ratio (FCR), carcass traits, serum components, and antioxidant status were measured. At the end of the experimental period, the results indicated that supplementation of SOP and LGL alone or in combination did not significantly (P?>?0.05) affect BWG, FI, FCR, and carcass characteristics in broiler chickens. Serum total protein was increased significantly (P?<?0.05) in T3 and T4 compared to the other treatments. Also, serum globulin increased significantly (P?<?0.05) in the treated groups. Serum glucose, low density lipoprotein, triglyceride, and very low density lipoprotein decreased significantly (P?<?0.05) in the treatment groups, while cholesterol and high-density lipoprotein decreased in T2 compared to the other groups. Significantly (P?<?0.05) higher total antioxidant status was observed in T2 compared to the other treatments. In conclusion, these results indicate that SOP, LGL, and their combination may positively modify some serum components and the antioxidant status without any beneficial effect on growth performance and carcass traits in broiler chickens.     

Electrospun and functionalized PVDF/PAN nanocatalyst-loaded composite for dechlorination and photodegradation of pesticides in contaminated water

A novel approach for the electrospinning and functionalization of nanocatalyst-loaded polyvinylidene fluoride/polyacrylonitrile (PVDF/PAN) composite grafted with acrylic acid (AA; which form polyacrylic acid (PAA) brush) and decorated with silver (Ag/PAN/PVDF-g-PAA-TiO₂/Fe–Pd) designed for the dechlorination and photodegradation of pesticides was carried out. PAN was used both as a nitrogen dopant as well as a co-polymer. Smooth nanofibers were obtained by electrospinning a solution of 12:2 wt.% PVDF/PAN blend using dimethylformamide (DMF) as solvent. The nanofibers were grafted with AA by free-radical polymerization using 2,2′azobis(2-methylpropionitrile) (AIBN) as initiator. Both bimetallic iron–palladium (Fe–Pd) and titania (TiO₂) nanoparticles (NP) were anchored on the grafted nanofibers via the carboxylate groups by in situ and ex situ synthesis. The Fe–Pd and nitrogen-doped TiO₂ nanoparticles were subsequently used for dechlorination and oxidation of target pollutants (dieldrin, chlorpyrifos, diuron, and fipronil) to benign products. Structural and chemical characterizations of the composites were done using various techniques. These include surface area and porosity analyzer (ASAP) using the technique by Brunner Emmett Teller (BET), Fourier transform infrared (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscope (TEM) analyses were done. After dechlorination, the transformation products (TPs) for dieldrin, chlorpyrifos, diuron, and fipronil were obtained and identified using two-dimensional gas chromatography (time-of-flight) with a mass spectrometer detector (GCxGC-TOFMS). Analysis of total organic carbon (TOC) was carried out and used to extrapolate percentage mineralization. Experimental results showed that dechlorination efficiencies of 96, 93, 96, and 90 % for 1, 2, 2, and 3 h treatment period were respectively achieved for 5 ppm solutions of dieldrin, chlorpyrifos, diuron, and fipronil. The dechlorination of dieldrin, diuron, and fipronil follows first-order kinetics while that of chlorpyrifos followed pseudo-first order. Mineralization performance of 34 to 45 % were recorded when Fe–Pd was used, however upon electrospinning, doping, and grafting (Ag/PAN/PVDF-g-PAA-TiO₂/Fe–Pd composite); it significantly increased to 99.9999 %. This composite reveals great potential for dechlorination and mineralization of pesticides in contaminated water.