Absolute configuration of 2,2′,3,3′,6-pentachlorinatedbiphenyl (PCB 84) atropisomers

Nineteen polychlorinated biphenyl (PCB) congeners, such as 2,2′,3,3′,6-pentachlorobiphenyl (PCB 84), display axial chirality because they form stable rotational isomers, or atropisomers, that are non-superimposable mirror images of each other. Although chiral PCBs undergo atropselective biotransformation and atropselectively alter biological processes, the absolute structure of only a few PCB atropisomers has been determined experimentally. To help close this knowledge gap, pure PCB 84 atropisomers were obtained by semi-preparative liquid chromatography with two serially connected Nucleodex β-PM columns. The absolute configuration of both atropisomers was determined by X-ray single-crystal diffraction. The PCB 84 atropisomer eluting first and second on the Nucleodex β-PM column correspond to (aR)-(?)-PCB 84 and (aS)-(+)-PCB 84, respectively. Enantioselective gas chromatographic analysis with the β-cyclodextrin-based CP-Chirasil-Dex CB gas chromatography column showed the same elution order as the Nucleodex β-PM column. Based on earlier reports, the atropisomers eluting first and second on the BGB-172 gas chromatography column are (aR)-(?)-PCB 84 and (aS)-(+)-PCB 84, respectively. An inversion of the elution order is observed on the Cyclosil-B gas chromatography and Cellulose-3 liquid chromatography columns. These results advance the interpretation of environmental and human biomonitoring as well as toxicological studies.     

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.     

Atropisomers of 2,2′,3,3′,6,6′-hexachlorobiphenyl (PCB 136) exhibit stereoselective effects on activation of nuclear receptors in vitro

PCB 136 is an environmentally relevant chiral PCB congener, which has been found in vivo to be present in form of rotational isomers (atropisomers). Its atropselective biotransformation or neurotoxic effects linked with sensitization of ryanodine receptor suggest that it might interact also with other intracellular receptors in a stereospecific manner. However, possible atropselective effects of PCB 136 on nuclear receptor transactivation remain unknown. Therefore, in this study, atropselective effects of PCB 136 on nuclear receptors controlling endocrine signaling and/or expression of xenobiotic and steroid hormone catabolism were investigated. PCB136 atropisomers were found to exert differential effects on estrogen receptor (ER) activation; (+)-PCB 136 was estrogenic, while (?)-PCB 136 was antiestrogenic. In contrast, inhibition of androgen receptor (AR) activity was not stereospecific. Both PCB136 stereoisomers induced the constitutive androgen receptor (CAR)-dependent gene expression; however, no significant stereospecificity of PCB 136 atropisomers was observed. PCB136 was a partial inducer of the pregnane X receptor (PXR)-dependent gene expression. Here, (?)-PCB 136 was a significantly more potent inducer of PXR activity than (+)-PCB 136. Taken together, the present results indicate that at least two nuclear receptors participating in endocrine regulation or metabolism, ER and PXR, could be regulated in an atropselective manner by chiral PCB 136. The enantioselective enrichment of PCB atropisomers in animal and human tissues may thus have significant consequences for endocrine-disrupting effects of chiral ortho-substituted PCB congeners.     

PCB污染及其治理(综述)

一九六八年三月,日本九州等地有几十万只鸡突然死亡,不久又在爱知县发现一种奇怪的病,患者轻则眼皮发肿,手掌出汗,全身起红疙瘩,疆则恶心呕吐,肝功能下降,全身肌肉疼痛,咳嗽不止,有的甚至医治无效而死,造成了世界闻名的米糠油事件。它就是多氯联苯简称 PCB)在米糠油脱臭过程中混入而造成     

The ‘Storm of the Century’ (December 1999) and the accidental escape of Siberian sturgeons (Acipenser baerii) into the Gironde estuary (Southwest France)

GOAL, SCOPE AND BACKGROUND: The Gironde estuary is considered as a reference ecosystem with a large fish assemblage (75 species) and the presence of eleven diadromous species. However, geochemical studies and biomonitoring using oysters have shown high metal pollution levels. During the December 1999 hurricane, more than 5,000 young Siberian sturgeons (Acipenser baerii) accidentally escaped from a fish farm into the estuary, where this species had not been present until then. METHODS: In 2002/2003, thirteen sturgeons were collected from the estuary and twelve were obtained from the fish farm, from the same initial batch. Analysis of five metals (cadmium, zinc, copper, lead, mercury) measured in the gills, muscle, liver and kidneys, revealed significantly higher levels of cadmium, lead and mercury in the sturgeon collected from the estuary compared with those from the fish farm. RESULTS AND DISCUSSION: Metal analysis of the stomach contents of fish collected from the estuary and artificial food used in the fish farm indicated that dietary exposure might account for the differences observed. Nevertheless, metal concentrations in sturgeons that had spent about three years in the Gironde estuary may be considered low when compared with other species (mullets, eels) or with data in the literature regarding concentrations able to induce structural and functional perturbations in fish. As the introduced Siberian sturgeons live in the same place and feed on the same prey as the juveniles of the endangered A. sturio, our results indicate in the short-term that this strictly protected species does not appear to be much affected by the polymetallic pollution in the Gironde estuary. Marked differences in the concentrations of three metals (Cd, Pb, Hg) were established in four organs (gills, liver, skeletal muscle, kidneys) of Siberian sturgeons between specimens that had accidentally escaped into the Gironde estuary (France) during the December 1999 hurricane and were collected in March/June 2003 and specimens from the same initial batch at the fish farm. RECOMMENDATIONS AND PERSPECTIVES: Based on these results, a programme will be set up, with sampling campaigns carried out in the estuary every two years, with systematic monitoring of age in order to check the origin of individuals, in conjunction with sampling of sturgeon from the fish farm. This programme will complement other studies on several biological species representative of the main trophic levels in the estuary, especially the plankton component, benthic macroinvertebrates and oysters.     

氢氧化铝胶体对2,2′,4,4′-四溴联苯醚的吸附

溴代阻燃剂多溴联苯醚(polybrominated diphenyl ethers,PBDEs)是一种被广泛使用的阻燃剂,其对神经、甲状腺、肝脏等具有潜在毒性。其中,2,2′,4,4′-四溴联苯醚(BDE-47)作为一种重要单体,在环境介质中被广泛检出。胶体是环境中污染物迁移过程中的重要载体,它对有机污染物在土壤-地下水系统中的迁移有不可忽略的影响。开展典型无机胶体氢氧化铝胶体对BDE-47的吸附动力学和吸附热力学研究,以期为BDE-47在土壤-地下水中的迁移提供理论依据。结果表明:Sips等温吸附方程对该吸附过程拟合效果最佳(R_(adj)~2=0.943 94),计算得出氢氧化铝胶体对BDE-47的饱和吸附量为609.37 mg·g~(-1);吸附动力学实验结果显示,准二级反应动力学方程拟合氢氧化铝胶体对BDE-47吸附反应过程最佳(R_(adj)~20.95),同时该吸附反应速率随BDE-47浓度的升高逐渐减小;Van't Hoff方程拟合表明,吸附热力学参数标准反应焓变△H~0=40.506 kJ·mol~(-1)、标准反应熵变△S~0=0.075 7 kJ·(mol·K)~(-1),标准反应吉布斯自由能△G~0(298 K)=17.98 kJ·mol~(-1)。此外,反应体系的pH和阳离子种类及浓度均会影响氢氧化铝胶体对BDE-47的吸附过程。     

Does the wood-borer Sphaeroma terebrans (Crustacea) shape the distribution of the mangrove Rhizophora mucronata?

Field surveys were conducted to evaluate the occurrence of the isopod borer Sphaeroma terebrans (Crustacea) in aerial roots (prop roots) of the red mangrove Rhizophora mucronata on several different spatial scales (m to 100 km) in East Africa. In 6 out of 17 sites studied in Kenya and on Zanzibar Island, Tanzania, no signs of the isopods were found. When the isopods were present the frequency of infestation was high. Trees in muddy substrates in the lower intertidal, in particular at fringing channels or the open sea, showed high prevalence and intensity of infestation, with large part of their roots damaged or dead. Trees at the upper range of Rhizophora, in sandy and muddy areas, showed no signs of isopod infestation. This pattern recurred in mangrove forests on large spatial scales and there was no indication that island forests differed from the mainland forests. This indicates that sediment characteristics, vertical height in the tidal zone, and direct exposure to incoming water are the major factors controlling the abundance of S. terebrans. The isopod may play an important role in determining the lower intertidal limits of R. mucronata. Trees with numerous dead or nongrowing roots, as result of Sphaeroma attack, are likely to tumble due to a lack of root support and this is most likely to occur along channels at the lower, muddy intertidal. Tumbled trees were frequently observed along channels in the lower, muddy intertidal, but rarely in the mid or high intertidal. Implications for management of mangrove forests are discussed.     

Dioxin?hnliche polychlorierte Biphenyle (PCB) in der Umwelt

Zusammenfassung Ziel und Absicht  Der derzeitige Kenntnisstand zu Quellen, Verbleib in der Umwelt, Exposition des Menschen und gesundheitlicher Bewertung von dioxin?hnlichen polychlorierten Biphenylen (PCB) und nicht dioxin?hnlichen PCB wird mit Fokus auf den deutschsprachigen Raum dargestellt und zusammengefasst. Methoden  Grundlage für den aktuellen Kenntnisstand sind die Vortr?ge und Diskussionsergebnisse eines zweit?gigen bundesweiten Statuskolloquiums. Die Bedeutung der dioxin?hnlichen PCB wird insbesondere in Relation zu den polychlorlerten Dibenzo-p-dioxinen (PCDD) und Dibenzofuranen (PCDF) betrachtet. Dazu dient in erster Linie ein Vergleich der Toxizit?ts?quivalentkonzentrationen (TEQ) beider Stoffgruppen in den betrachteten Umweltmatrices. Ergebnisse und Schlussfolgerungen  In vielen Umweltmedien sind die TEQ-Werte der dioxin?hnlichen PCB ?hnlich hoch wie die PCDD/PCDF-Gehalte, in den meisten Lebensmitteln tierischen Ursprungs sogar h?her. In den meisten Medien hat das nichtortho substituierte PCB 126 aufgrund seines hohen Toxizit?ts?quivalenzfaktors von 0,1 den mit Abstand h?chsten Beitrag zum PCB-TEQ. Für die gro?fl?chige Umweltbelastung mit PCB ist offensichtlich der atmosph?rische (Fern) Transport wesentlich. Für den Eintritt der dioxin?hnlichen, PCB in terrestrische Nahrungsketten ist der Transfer Atmosph?re-Pflanze wahrscheinlich der entscheidende Schritt. Empfehlungen und Ausblick  Trotz des Rückgangs der Umweltbelastung mit PCB und PCDD/PCDF überschreitet ein erheblicher Teil der Bev?lkerung in Deutschland und anderen europ?ischen Staaten gegenw?rtig noch die duldbare Aufnahme an, dioxin?hnlichen Substanzen. Aber auch aufgrund einer aktuellen toxikologischen Neubewertung der nicht-dioxin?hnlichen PCB muss die Verminderung der PCB-Exposition weiter betrieben werden. OnlineFirst: 11. April 2005     

The sea–air exchange of mercury (Hg) in the marine boundary layer of the Augusta basin (southern Italy): Concentrations and evasion flux

The first attempt to systematically investigate the atmospheric mercury (Hg) in the MBL of the Augusta basin (SE Sicily, Italy) has been undertaken. In the past the basin was the receptor for Hg from an intense industrial activity which contaminated the bottom sediments of the Bay, making this area a potential source of pollution for the surrounding Mediterranean. Three oceanographic cruises have been thus performed in the basin during the winter and summer 2011/2012, where we estimated averaged Hg_atm concentrations of about 1.5 ± 0.4 (range 0.9–3.1) and 2.1 ± 0.98 (range 1.1–3.1) ng m⁻³ for the two seasons, respectively. These data are somewhat higher than the background Hg_atm value measured over the land (range 1.1 ± 0.3 ng m⁻³) at downtown Augusta, while are similar to those detected in other polluted regions elsewhere. Hg evasion fluxes estimated at the sea/air interface over the Bay range from 3.6 ± 0.3 (unpolluted site) to 72 ± 0.1 (polluted site of the basin) ng m⁻² h⁻¹. By extending these measurements to the entire area of the Augusta basin (∼23.5 km²), we calculated a total sea–air Hg evasion flux of about 9.7 ± 0.1 g d⁻¹ (∼0.004 t yr⁻¹), accounting for ∼0.0002% of the global Hg oceanic evasion (2000 t yr⁻¹). The new proposed data set offers a unique and original study on the potential outflow of Hg from the sea–air interface at the basin, and it represents an important step for a better comprehension of the processes occurring in the marine biogeochemical cycle of this element.     

Water quality of the Guadiamar River after the Aznalcóllar spill (SW Spain)

In April 1998, a spill of 6 hm3 of pyritic mud and acidic water was released into the Guadiamar River due to the rupture of the Aznalcóllar tailings dam. Before the spill, the river was already strongly affected by acid mine drainage (AMD). In this study, the water quality of the Guadiamar River is analysed from a periodic sampling started after the spill. Previous data of the water quality have also been obtained. A recovery of the water quality is observed from 2002 on. The distribution of arsenic is opposed to that of the rest of metals, with the lowest concentrations to the north, due to the adsorption and/or coprecipitation on ferric oxyhydroxides. In the southern area, when pH values are close to 8, arsenic desorption occurs. There is a seasonal pattern of the trace metal content evolution, different in the northern and southern zones of the river. In the northern area the highest polluting levels occur in summer, due to a lower dilution of the mining leachates. In the southern area, the highest metal levels occur during the winter, since during the summer metals remain held by surface sorption processes in the hyporheic zone of the river.     

Mathematical model of Boltzmann’s sigmoidal equation applicable to the spreading of the coronavirus (Covid-19) waves

Environmental Science and Pollution Research - Currently, investigations are intensively conducted on modeling, forecasting, and studying the dynamic spread of coronavirus (Covid-19) new pandemic....     

Current State of the Altai Glaciers (Russia) and Trends Over the Period of Instrumental Observations 1952–2008

Results of research into climate and glacier dynamics in the Altai Mountains (Russia) over the period of instrumental observations (1952–2008) are presented in this article. About 1030 glaciers with a total area of 805 km² and volume of 42.5 km³ have been recorded in the Altai Region. The average summer air temperature in different regions of the Altai has increased during the study period from about 0.2°C (Aktru) to 1.1°C (Akkem). The annual atmospheric precipitation rate has also increased, by 8–10%. Since 1952, the glacier area in different regions of the Altai has decreased by 9–27%, and volume by 12–24%. By 2008, as a result of degradation, the total number of glaciers was 953 with an area of 724 km² and volume of 38 km³.     

A straightforward synthesis in aqueous medium of enantiomerically enriched S(-)2,2′-dihydroxy-1,1′-binaphthyl

Chiral, atropisomeric 2,2'-dihydroxy-1,1'-binaphthyl has been extensively used to direct asymmetric processes. Its key role in asymmetric catalysis has spurred efforts to synthesize it in the optically pure form, but the reported synthetic routes have a significant environmental impact. In an aqueous peroxydase-cyclodextrin system the oxidative coupling of 2-naphthol took place very rapidly in almost quantitative yield and resulted in an enantiomeric excess. This one-pot synthesis do not require any organic solvents and oxidising metal cations.     

Spatio-temporal geostatistical modelling of sulphate concentration in the area of the Reocín Mine (Spain) as an indicator of water quality

Environmental Science and Pollution Research - Water stored in open-pit lakes can be a water resource when the mine is closed. This study aimed to develop a reliable model to evaluate the water...     

Effect of neem limonoids on lactate dehydrogenase (LDH) of the rice leaffolder, Cnaphalocrocis medinalis (Guenée) (Insecta: Lepidoptera: Pyralidae)

Neem is derived from the neem tree Azadirachta indica A. Juss. (Meliaceae), and its primary insecticidal component is the tetranortriterpenoid azadirachtin and other limonoids. The effect of neem limonoids azadirachtin, salannin, deacetylgedunin, gedunin, 17-hydroxyazadiradione and deacetylnimbin on enzyme lactate dehydrogenase (LDH) activity of the rice leaffolder (RLF) Cnaphalocrocis medinalis (Lepidoptera: Pyralidae) larvae was investigated. There was a decrease in enzyme activity relative to the control at all concentrations tested. When fed a diet of rice leaves treated with neem limonoids in bioassays, gut tissue enzyme, LDH levels in rice leaffolder larvae are affected. These results indicate neem limonoids affect LDH activity. These effects are most pronounced in early instar larvae. Azadirachtin was the most potent in of all the limonoids in all experiments indicating strong enzyme inhibition. Clear dose-response relationships were established with respect to LDH activity.     

Occurrence of polybrominated diphenyl ethers (PBDEs) and 2,2’,4,4’,5,5’-hexabromobiphenyl (BB-153) in water samples from the Diep River, Cape Town, South Africa

Until recently, studies reporting the concentrations of polybrominated diphenyl ethers (PBDEs) as well as polybrominated biphenyls (PBBs) are generally scarce in the literature. Consequently, this study was aimed to investigate the occurrence and concentrations of certain PBDE congeners (BDE 28, 47, 100, 99, 154, 153, 183 and 209) and BB 153 in river water samples collected bi-monthly from the Diep River. The routine analyses of the target compounds were performed using a high-capillary GC–microelectron capture detection, while their structural elucidation was assessed using GC-TOF-MS technique. The overall mean concentrations of the sum of the eight PBDE congeners were 2.60, 4.83 and 4.29 ng/L for the upstream, point of discharge and downstream sampling points, respectively. Similarly, the overall mean concentrations of BB 153 were 0.25, 4.85 and 1.56 ng/L for the upstream, point of discharge and downstream sampling points, respectively. BDE 47 was the dominant congener found in these samples contributing between 19 and 26 % to the total PBDEs across the sampling points. The statistical analyses performed on the results obtained showed that all the congeners, except BDE 209 in certain instances, had strong positive correlations with one another, thus suggesting that these contaminants could be emanating from the same source. In this study, potential sources of these pollutants other than WWTP discharges into the investigated river were also identified. However, the relatively high concentrations of the target compounds found at the point of discharge sampling point coupled with the large volume of treated effluent being discharged suggested that the contributions from this source could be very significant over time.     

Metabolism of the Nonylphenol Isomer [Ring-U-14c]-4-(3′,5′-Dimethyl-3′-Heptyl)-Phenol by Cell Suspension Cultures of Agrostemma githago and Soybean

Abstract

The biotransformation of the nonylphenol isomer [ring-U-¹⁴C]-4-(3′,5′-dimethyl-3′-heptyl)-phenol (4-353-NP, consisting of two diastereomers) was studied in soybean and Agrostemma githago cell suspension cultures. With the A. githago cells, a batch two-liquid-phase system (medium/n-hexadecane 200:1, v/v) was used, in order to produce higher concentrations and amounts of 4-353-NP metabolites for their identification; 4-353-NP was applied via the n-hexadecane phase. Initial concentrations of [¹⁴C]-4-353-NP were 1 mg L^?1 (soybean), and 5 and 10 mg L^?1 (A. githago). After 2 (soybean) and 7 days (A. githago) of incubation, the applied 4-353-NP was transformed almost completely by both plant species to four types of products: glycosides of parent 4-353-NP, glycosides of primary 4-353-NP metabolites, nonextractable residues and unknown, possibly polymeric materials detected in the media. The latter two products emerged especially in soybean cultures. Portions of primary metabolites amounted to 19–22% (soybean) and 21–42% of applied ¹⁴C (A. githago). After liberation from their glycosides, the primary 4-353-NP metabolites formed by A. githago were isolated by HPLC and examined by GC-EIMS as trimethylsilyl derivatives. In the chromatograms, eight peaks were detected which due to their mass spectra, could be traced back to 4-353-NP. Seven of the compounds were side-chain monohydroxylated 4-353-NP metabolites, while the remaining was a (side-chain) carboxylic acid derivative. Unequivocal identification of the sites of hydroxylation/oxidation of all transformation products was not possible. The main primary metabolites produced by A. githago were supposed to be four diastereomers of 6′-hydroxy-4-353-NP (about 80% of all products identified). It was concluded that plants contribute to the environmental degradation of the xenoestrogen nonylphenol; the toxicological properties of side-chain hydroxylated nonylphenols remain to be examined.     

Impact of chemical exposure on the fish Pomatoschistus microps Krøyer (1838) in estuaries of the Portuguese Northwest coast

Juveniles of the estuarine fish Pomatoschistus microps were collected from autumn 2001 to summer 2002 in five stations along the Portuguese Northwest coast with different types and/or levels of environmental contamination: two reference sites with low levels of contamination (R1 and R2) and three differently impacted areas with higher levels of contamination. UI is located in an estuary under the influence of urban and industrial effluents, AA in a channel that receives intensive agriculture run-off and IE in a highly impacted industrial area. The activity of the enzymes acetylcholinesterase (AChE), lactate dehydrogenase (LDH), 7-ethoxyresorufin O-deethylase (EROD) and glutathione S-transferases (GST) were used as environmental biomarkers on P. microps. A significant seasonality effect on all the enzymatic activities was found, lower levels being registered in winter and spring on AChE, in autumn on LDH, and in winter on GST and EROD. The battery of biomarkers used was capable of discriminating sites with different types and/or levels of contamination, R1 and UI being the highest discriminated (91.7% and 66.7%, respectively). At R1 significantly lower levels of AChE and LDH were found, and EROD was significantly inducted at UI. Furthermore, IE presented higher levels of GST, and R2 and AA an inhibition of AChE in winter and spring. The results indicated that the battery of biomarkers used in this study seems to be a useful tool to distinguish between different types of environmental contamination in estuarine systems, and that P. microps is a suitable species to be used as bioindicator.     

Diurnal variation in the concentration of α- and β-pinene in the landes forest (France)

The study deals with the identification and the determination of the main monoterpenes (α- and β-pinene) released by the pines in the Landes Forest in France. The measurements were taken after preconcentration using TENAX-GC and thermal desorption. The diurnal variation of atmospheric concentration of α- and β-pinene is established; it is less than 0.5 ppbV in the daytime and varies from 2 to 4 ppbV in the night-time. These variations are explained by the fact that the photochemical reactions and the turbulence phenomena to which the terpenes are exposed change quite radically from day to night. The terpene concentration, higher at 5 m than at 25 m, would seem to confirm the existence of a terpene source at ground level.