Effects of thiol antioxidants on the atropselective oxidation of 2,2′,3,3′,6,6′-hexachlorobiphenyl (PCB 136) by rat liver microsomes

Chiral polychlorinated biphenyl (PCB) congeners, such as PCB 136, are atropselectively metabolized to various hydroxylated PCB metabolites (HO-PCBs). The present study investigates the effect of two thiol antioxidants, glutathione and N-acetyl-cysteine (NAC), on profiles and chiral signatures of PCB 136 and its HO-PCB metabolites in rat liver microsomal incubations. Liver microsomes prepared from rats pretreated with phenobarbital were incubated with PCB 136 (5 μM) in the presence of the respective antioxidant (0–10 mM), and levels and chiral signatures of PCB 136 and its HO-PCB metabolites were determined. Three metabolites, 5-136 (2,2′,3,3′,6,6′-hexachlorobiphenyl-5-ol), 4-136 (2,2′,3,3′,6,6′-hexachlorobiphenyl-4-ol), and 4,5-136 (2,2′,3,3′,6,6′-hexachlorobiphenyl-4,5-diol), were detected in all incubations, with 5-136 being the major metabolite. Compared to microsomal incubations without antioxidant, levels of 4,5-136 increased with increasing antioxidant concentration, whereas levels of PCB 136 and both mono-HO-PCBs were not affected by the presence of either antioxidant. PCB 136, 4-136, and 5-136 displayed significant atropisomeric enrichment; however, the direction and extent of the atropisomeric enrichment was not altered in the presence of an antioxidant. Because 4,5-136 can either be conjugated to a sulfate or glucuronide metabolite that is readily excreted or further oxidized a potentially toxic PCB 136 quinone, the effect of both thiol antioxidants on 4,5-136 formation suggests that disruptions of glutathione homeostasis may alter the balance between both metabolic pathways and, thus, PCB 136 toxicity in vivo.     

Degradation of RPA 202248 [U-14C-phenyl]-α(-(cyclopropylcarbonyl)-2-(methylsulfonyl)-β-oxo-4-(trifluromethyl)benzenepropanenitrile), the Primary Degradation Product of Isoxaflutole,in an Outdoor Aquatic Microcosm System

Abstract

Isoxaflutole, the active ingredient in BALANCE® WDG and BALANCE® PRO corn herbicides and a co-formulant with the herbicide flufenacet in the product EPIC?, is readily degraded in soil and water to RPA 202248 α(-(cyclopropylcarbonyl)-2-(methylsulfonyl)-β-oxo-4-(trifluromethyl)benzenepropanenitrile). Because RPA 202248 is responsible at the molecular level for isoxaflutole's herbicidal activity it is important to understand the environmental behavior of the degradation product. Laboratory studies suggest that RPA 202248 is stable to hydrolysis and photolysis in aqueous systems and hence poses a possible environmental concern. As part of a program of work towards understanding the actual field situation, an outdoor microcosm study was carried out. Over the course of the 29-day study, residues remained predominantly in the aqueous phase. A slow but steady degradation of RPA 202248 was observed leading to the formation of RPA 203328 (2-methylsulfonyl-4-trifluoromethylbenzoic acid), which has no herbicidal activity. The half-life of RPA 202248 was calculated to be 103 days. These findings indicate that aqueous degradation should be considered as a potential route of dissipation when assessing the fate of RPA 202248 in large scale impounded water bodies, such as ponds, lakes, or reservoirs in the Mid-West Corn Belt.     

Aged and bound herbicide residues in soil and their bioavailability part 2: Uptake of aged and non‐extractable (bound) [carbonyl‐14C] methabenzthiazuron residues by maize

Abstract

[Carbonyl‐ C]methabenzthiazuron (MBT) was applied to growing winter wheat in an outdoor lysimeter. The amount applied corresponded to 4 kg Tribunil/ha. 140 days after application the 0–2,5 cm soil layer was removed from the lysimeter. This soil contained about 40 % of the applied radioactivity. Using 0,01 M CaCl₂ solution or organic solvents, the extractable residues were removed from the soil. The bioavailability of the non‐extractable as well as aged residues remaining in the soil was investigated in standardized microecosystems containing 1.5 kg of dry soil. During a 4 weeks period the total uptake (4 maize plants/pot) amounted up to 3,6; 2,2; and 0,9 % of the radioactivity from soils containing aged MBT residues, MBT residues non‐extractable‐with 0,01 MCaCl₂ or MBT residues non‐extractable with organic solvents, respectively. About 20 % of the radioactivity found in maize leaves represented chromatographically characterized parent compound. At the end of the plant experiment the soil was extracted again with 0,01 M CaCl₂ and with organic solvents. The soil extracts and also the organic phases obtained from the aqueous fulvic acid solution contained unchanged parent compound.     

Metabolism of acetaminophen (paracetamol) in plants—two independent pathways result in the formation of a glutathione and a glucose conjugate

Background, aim, and scope  Pharmaceuticals and their metabolites are detected in the aquatic environment and our drinking water supplies. The need for high quality drinking water is one of the most challenging problems of our times, but still only little knowledge exists on the impact of these compounds on ecosystems, animals, and man. Biological waste water treatment in constructed wetlands is an effective and low-cost alternative, especially for the treatment of non-industrial, municipal waste water. In this situation, plants get in contact with pharmaceutical compounds and have to tackle their detoxification. The mechanisms for the detoxification of xenobiotics in plants are closely related to the mammalian system. An activation reaction (phase I) is followed by a conjugation (phase II) with hydrophilic molecules like glutathione or glucose. Phase III reactions can be summarized as storage, degradation, and transport of the xenobiotic conjugate. Until now, there is no information available on the fate of pharmaceuticals in plants. In this study, we want to investigate the fate and metabolism of N-acetyl-4-aminophenol (paracetamol) in plant tissues using the cell culture of Armoracia rusticana L. as a model system. Materials and methods  A hairy root culture of A. rusticana was treated with acetaminophen in a liquid culture. The formation and identification of metabolites over time were analyzed using HPLC-DAD and LC–MSⁿ techniques. Results  With LC–MS technique, we were able to detect paracetamol and identify three of its metabolites in root cells of A. rusticana. Six hours after incubation with 1 mM of acetaminophen, the distribution of acetaminophen and related metabolites in the cells resulted in 18% paracetamol, 64% paracetamol–glucoside, 17% paracetamol glutathione, and 1% of the corresponding cysteine conjugate. Discussion  The formation of two independently formed metabolites in plant root cells again revealed strong similarities between plant and mammalian detoxification systems. The detoxification mechanism of glucuronization in mammals is mirrored by glucosidation of xenobiotics in plants. Furthermore, in both systems, a glutathione conjugate is formed. Due to the existence of P450 enzymes in plants, the formation of the highly reactive NAPQI intermediate is possible. Conclusions  In this study, we introduce the hairy root cell culture of A. rusticana L. as a suitable model system to study the fate of acetaminophen in plant tissues. Our first results point to the direction of plants being able to take up and detoxify the model substrate paracetamol. These first findings underline the great potential of using plants for waste water treatments in constructed wetlands. Recommendations and perspectives  This very first study on the detoxification of a widely used antipyretic agent in plant tissues again shows the flexibility of plant detoxification systems and their potential in waste water treatment facilities. This study covers only the very first steps of acetaminophen detoxification in plants; still, there is no data on long-term exposure as well as the possible impact of pharmaceuticals on the plant health and stress defense. Long-term experiments need to be performed to follow the fate of acetaminophen in root and leaf cells in a whole plant system, and to evaluate possible usage of plants for the remediation of acetaminophen from waste water.     

Dietary intake of hexabromocyclododecane diastereoisomers (α-, β-, and γ-HBCD) in the Belgian adult population

A study was performed to assess exposure of the Belgian population to HBCD diastereoisomers. Measurements of HBCD were performed by UPLC-MS/MS, on 45 composite samples from 5 major food groups: dairy (products), meat (products), eggs, fish (products) and a group of “other” products. The medium bound estimated average daily intake (EDI) of ΣHBCD in the Belgian population was 0.99 ng kg⁻¹ bw d⁻¹. The diastereoisomer contribution to the mean EDI showed a predominance of γ-HBCD at 67%, followed by α-HBCD at 25% and 8% for β-HBCD. These results are consistent with the pattern found in the two food groups contributing the most to the EDI: meat (products) and the group of “other” products. Anyway, it has to be noted that diastereomeric distribution of HBCD can change due to bioisomerisation in biological material. Levels of HBCD diastereoisomers found in Belgian food samples of animal origin were low in comparison with those found in other EU countries and the resulting EDI was substantially below the proposed thresholds.     

Roles of regional hydrodynamic and trophic contamination in cadmium bioaccumulation by Pacific oysters in the Marennes-Oléron Bay (France)

The Marennes-Oléron Bay, hosting the largest oyster production in France, is influenced by the historic polymetallic pollution of the Gironde Estuary. Despite management efforts and decreasing emissions in the Gironde watershed, cadmium levels in oysters from the bay are close to the consumption limit (5 μg g⁻¹ dw, EC). From mid April to mid July 2009, we investigated the role of tidal resuspension and regional hydrodynamics on Cd speciation (seawater, SPM, phytoplankton, sediment, microphytobenthos) and bioaccumulation in 18 month-old oysters (gills, digestive glands, rests of tissues) reared under natural conditions (i) at ∼60 cm above the sediment and (ii) on the sediment surface. Dissolved and particulate Cd concentrations in surface and bottom waters were similar and constant over tidal cycle suggesting the absence of Cd release during sediment resuspension. Temporal dissolved and particulate Cd concentrations were closely related to Gironde Estuary water discharges, showing increasing concentrations during flood situations and decreasing concentrations afterwards. Cd depletion in the water column was associated with increasing Cd in the [20-100 μm] plankton fraction, suggesting Cd bioaccumulation. After 3 months, enrichment factors of Cd in tissues of oysters exposed in the water column and directly on the sediment were respectively 3.0 and 2.2 in gills, 4.7 and 3.2 in digestive glands and 4.9 and 3.4 in remaining tissues. Increasing Cd bioaccumulation in gills, digestive glands and remaining tissues can be related to elevated dissolved Cd in the bay, suggesting gill contamination via the direct pathway and subsequent internal redistribution of Cd to other organs and tissues. Elevated Cd contents in oysters reared on tables could be attributed to different trophic Cd transfer (phytoplankton versus microphytobenthos) or to different oyster metabolisms between the rearing conditions as suggested by metallothionein concentrations.     

Heavy metal bioavailability and effects: I. Bioaccumulation caused by mining activities in the Gulf of Cádiz (SW, Spain)

The bioaccumulation of six metals (Fe, Mn, Zn, Cd, Pb and Cu) was studied as part of the monitoring of the Aznalcóllar mining spill (April 1998) on the Guadalquivir estuary and in other estuaries located in the Gulf of Cádiz. Fish, clams and oysters were collected during different seasonal periods along the years 2000 and 2001 in the Guadalquivir estuary to determine the bioaccumulation of the metals originated by the mining spill. Results were compared to the bioaccumulation of the same metals in fish and clams exposed in the laboratory to sediments collected in the same areas during autumn 2001. The bioaccumulation of these metals was compared to the concentration of metals measured in tissues of same taxas collected in the areas of the ria of Huelva and the Bay of Cádiz. Results show that the bioaccumulation of Zn and Cd in the organisms sampled in the Guadalquivir estuary was associated with the enrichment of these metals in the estuary from the mining spill and decreased along the time reaching the lowest values in autumn 2001. The metal Cu show different trends that are associated with other sources of contamination than the spill and related to the transport of this metal from Huelva to Guadalquivir estuary and/or to the use of this metal as plaguicide in the rice fields located in the area. The comparison between bioaccumulation results under field and laboratory conditions obtained in the different areas of study shows that these data can be used to discriminate between acute and chronic impacts associated with mining activities.     

Determination of the absolute photolysis rate of ozone by sunlight,O3 + hv → O(1D) + O2(1Δg), at ground level

An actinometric technique was used to evaluate half-hourly averaged rate constants k_(1D) for the formation of O(¹D) atoms by ozone photolysis in natural daylight below 310 nm. Sealed quartz bulbs containing a few torr ozone in 2200 torr N₂O were used for the measurements. Molecular nitrogen resulting from the reaction of O(¹D) with the scavenger gas was determined by gas chromatography. The results were corrected for the finite optical density of ozone and for its photochemically induced decay in the actinometer during exposure. Measurements were taken between August 1977 and July 1978, at solar zenith angles of 32–75°, and ozone column densities of 280–400 Dobson k_(1D) values between 7 × 10⁻⁷and 2 × 10⁻⁵s⁻¹ were found under clear sky conditions. The results are shown to depend systematically on both the solar zenith angle and the ozone column density, in accordance with a model calculation. The spatially integrated and spectrally resolved light intensity at 306 nm correlates well with the diurnal variation of k_(1D). The results are compared with literature data.     

The treatment of wastewater containing pharmaceuticals in microcosm constructed wetlands: the occurrence of integrons (int1–2) and associated resistance genes (sul1–3, qacEΔ1)

Environmental Science and Pollution Research - The aim of this study was to analyze the occurrence of sulfonamide resistance genes (sul1–3) and other genetic elements as antiseptic resistance...