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.     

Occurrence of 1,1′-dimethyl-4,4′-bipyridinium (Paraquat) in irrigated soil of the Lake Chad Basin,Niger

Increased use of agrochemical products to improve yields for irrigated crops in sub-Saharan Africa has been accompanied by a significant increase in the risk of environmental contamination. Detailed examples of the fate of pesticides after initial spreading on crop fields are scarce in tropical regions, where safe practices and related health risks are poorly understood by smallholder farmers. In the semi-arid environment of the Lake Chad Basin, SE Niger, both intrinsic properties of pesticides and extrinsic factors such as soil and climate helped to characterize processes leading to an accumulation of pesticides in soils. Analysis by HPLC-UV of a 6 m deep soil profile showed the presence of Paraquat at concentrations from 953?±?102 μg kg^?1 to 3083?±?175 μg kg^?1 at depths between 0.80 and 2.75 m below the land surface. Soil analysis revealed that up to approximately 15 % of the total soil matrix consists of smectites, a clay mineral capable of retaining cationic pesticides such as Paraquat, and a very low content of organic matter (<0.15 wt.% TOC). Paraquat could be stored and not bioavailable in a clayey barrier at approximately 2-m depth and therefore does not represent an immediate risk for populations or environment in this form. However, if the Paraquat application rate remains constant, the clayey barrier could reach a saturation limit within 150–200 years and 180–220 years if we consider a DT50 in soil of ~1,000 days (FAO). Consequently, it could lead to a deeper infiltration and so a pollution of groundwater. Such a scenario can represent a health risk for drinking water and for the Lake Chad, which is a major resource for this densely populated region of semi-arid Africa. Further analyses should focus on deeper layers and groundwater Paraquat contents to validate or invalidate the hypothesis of storage in this clay-rich layer.     

Ligninase-mediated transformation of 4,4′-dibromodiphenyl ether (BDE 15)

The structurally related hydroxylated polybrominated diphenyl ether (PBDE) like hydroxylated 4,4′-dibromodiphenyl ether widely occur in precipitation, surface water, and biotic media. The origins of hydroxylated PBDEs (OH-PBDEs) are of particular interest due to their greater toxic potencies than the corresponding PBDEs. We studied the transformation behavior and products of 4,4′-dibromodiphenyl ether (BDE 15) mediated by lignin peroxidase (LiP), an extracellular enzyme that is produced by certain white rot fungus and is widely present in the natural environment. We found that BDE 15 can be effectively transformed through the reaction mediated by LiP, and two different mono-OH-dibromodiphenyl ethers were identified by using gas chromatography–mass spectrometry (GC-MS) and GC-MS/MS. In particular, we compared the reaction behavior for systems variously containing natural organic matter (NOM) and/or veratryl alcohol (VA), a metabolite that certain fungus produces along with LiP in nature. It was found that the VA’s enhancement effect on LiP performance was impaired by the presence of NOM. The findings in this study provide useful information for better understanding the origins of OH-PBDEs found in the environment.     

Study of MoO3-γAl2O3 catalysts behavior in selective catalytic reduction of SO2 toxic gas to sulfur with CH4

Environmental Science and Pollution Research - In the present study, a detailed investigation was carried out on MoO3 alumina-supported catalysts behavior in selective catalytic reduction of SO2 to...     

超声协同TiO2光催化降解4,4′-二溴联苯

以纳米TiO2膜为光催化剂,对4,4′-二溴联苯水溶液进行了超声光催化（US＋UV）、光催化（UV）和超声（US）降解,探讨了初始浓度、超声的声强和频率等对降解4,4′-二溴联苯的影响。结果表明,4,4′-二溴联苯的超声光催化降解存在协同效应,降解率随4,4′-二溴联苯初始浓度的增大而下降,随声强和频率的增大而增大。超声光催化过程符合一级动力学方程,反应数率常数为0.011 min^-1。超声光催化与光催化的降解产物不同。     

超声协同TiO_2光催化降解4,4′-二溴联苯

以纳米TiO2膜为光催化剂,对4,4′-二溴联苯水溶液进行了超声光催化(US+UV)、光催化(UV)和超声(US)降解,探讨了初始浓度、超声的声强和频率等对降解4,4′-二溴联苯的影响。结果表明,4,4′-二溴联苯的超声光催化降解存在协同效应,降解率随4,4′-二溴联苯初始浓度的增大而下降,随声强和频率的增大而增大。超声光催化过程符合一级动力学方程,反应数率常数为0.011 min-1。超声光催化与光催化的降解产物不同。     

The effects of 3,3′,4,4′-tetrabromobiphenyl on rats fed diets containing a constant level of copper and varying levels of molybdenum

Copper (Cu) metabolism is altered in rats fed diets high in molybdenum (Mo) and low in Cu. This 10-week study was carried out to examine the effects of supplemental Mo (7.5–240 μg/g diet) on male Sprague–Dawley rats fed diets adequate in Cu (5 μg/g diet) and to determine the susceptibility of Mo-treated animals to the environmental pollutant 3,3′,4,4′-tetrabromobiphenyl (TBB). After 7 weeks of dietary treatment, half of the rats in each group received a single IP injection of TBB (150 μM/kg bw), while the other half received the corn oil vehicle. Rats sacrificed at 10 weeks showed no effects of Mo on growth, feed efficiency, or selected organ or tissue weights. Dose-dependent effects on plasma Mo (0–5.1 μg/mL), plasma Cu (0.95–0.20 μg/mL), and bone Cu (3.4–10 μg/g) in control through the high dose were found. Cu sequestration in the bone of Mo-treated rats is a new finding. TBB treatment resulted in dramatic weight loss and loss of absolute organ mass. Relative organ weights were increased, except for the thymus. TBB altered the concentrations of certain amino acids. Compared to control rats, this polybrominated biphenyl congener significantly decreased plasma Cu and ceruloplasmin at higher concentrations of dietary Mo and promoted the process of plasma Cu decrease by Mo, suggesting a combined effect.     

活性污泥缺氧转化1-2-7-三氨基-8-羟基-3-6-萘二磺酸

1—2-7-三氨基-8-羟基-3—6-萘二磺酸（TAHNDS）作为偶氮染料的脱色产物很难被常规的厌氧-好氧染料废水处理工艺所去除。研究了未经驯化的活性污泥对TAHNDS的缺氧转化效果。结果表明,只有在特定的缺氧条件下（ORP在-50～-150mV之间）,TAHNDS才能被活性污泥所降解转化。当浓度在10—80mg／L范围内,TAHNDS可在72h内转化93％以上。加入100mg／L的硝酸盐和0．64mmol／L的氧化还原介体蒽醌-2-磺酸钠（AQS）可将40mg／L的TAHNDS的转化时间从84h缩短到36h。光谱及HPLC—MS分析表明,TAHNDS在缺氧条件下主要是通过脱氨基和脱磺酸作用生成已知可好氧生物降解的3,5-二氨基4-羟基萘-2-磺酸。因此,缺氧处理有望作为预处理工艺促进废水中TAHNDS的完全降解。     

Catalytic wet oxidation of ammonia: why is N2 formed preferentially against NO3 -?

The role of catalyst and the reason for the preferential formation of N(2) in the catalytic oxidation reaction of ammonia in water over a Ru (3wt.%)/TiO(2) catalyst were elucidated. It was verified that the catalyst in the reaction had no direct relevance to the selective formation of N(2), but was responsible only for the oxidation of aqueous ammonia, NH(3)(aq), finally giving a molecule of nitrous acid. The preferential production of N(2) was experimentally demonstrated due to the homogeneous aqueous phase reaction of the nitrous acid-dissociated NO(2)(-) with NH(4)(+) ions. Even under the highly oxidizing condition, NO(2)(-) was much more likely to react with NH(4)(+) to form N(2) than being oxidized over the catalyst to NO(3)(-) as long as NH(4)(+) was available in solution.     

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。     

Degradation of 3,3′-iminobis-propanenitrile in aqueous solution by Fe0/GAC micro-electrolysis system

The degradation of 3,3′-iminobis-propanenitrile was investigated using the Fe⁰/GAC micro-electrolysis system. Effects of influent pH value, Fe⁰/GAC ratio and granular activated carbon (GAC) adsorption on the removal efficiency of the pollutant were studied in the Fe⁰/GAC micro-electrolysis system. The degradation of 3,3′-iminobis-propanenitrile was affected by influent pH, and a decrease of the influent pH values from 8.0 to 4.0 led to the increase of degradation efficiency. Granular activated carbon was added as cathode to form macroscopic galvanic cells between Fe⁰ and GAC and enhance the current efficiency of the Fe⁰/GAC micro-electrolysis system. The GAC could only adsorb the pollutant and provide buffer capacity for the Fe⁰/GAC micro-electrolysis system, and the macroscopic galvanic cells of the Fe⁰/GAC micro-electrolysis system played a leading role in degradation of 3,3′-iminobis-propanenitrile. With the analysis of the degradation products with GC–MS, possible reaction pathway for the degradation of 3,3′-iminobis-propanenitrile by the Fe⁰/GAC micro-electrolysis system was suggested.     

氧化还原电位对活性污泥合成聚3-羟基丁酸-co-3-羟基戊酸酯组分的影响

分析了低DO下,乙酸钠、丙酸钠或葡萄糖作碳源,不同氧化还原电位(ORP)对活性污泥合成聚3-羟基丁酸-co-3-羟基戊酸酯(PHBV)的组分和产量的影响.结果显示,ORP从-30mV(厌氧)增加到 100mV(好氧),PHBV共聚物的产量增加,PHBV共聚物中3-羟基戊酸(HV)单体的摩尔分数降低,细胞生长量和碳源利用量增加;乙酸钠作单一碳源,ORP为-30mV时,PHBV共聚物中HV摩尔分数达到21.0%,ORP为 30mV时,PHBV共聚物在细胞内的质量分数达到35.0%.因此,DO是影响活性污泥合成PHBV共聚物的产量以及PHBV共聚物中HV摩尔分数的重要影响因素.     

铁炭微电解法降解1-丁基-3-甲基咪唑四氟硼酸盐的研究

1-丁基-3-甲基咪唑四氟硼酸盐([BMIM]BF4)是一种常用的离子液体,被越来越多地应用于精细化学品及药物的合成。由于其对水生生物有毒性的影响且难于生物降解,提出了采用铁炭微电解法来降解[BMIM]BF4,并探讨了影响处理效果的主要因素、工艺条件及其反应动力学。结果表明,影响铁炭微电解降解[BMIM]BF4的因素按从小到大的顺序为:炭铁比、反应时间、pH;铁炭微电解降解[BMIM]BF4的最佳工艺条件是:铁粉用量3 g/L、水样pH2.5、炭铁比2、反应时间为60~90 min;在此条件下,[BMIM]BF的去除率可以达到80%以上,且该降解反应为二级反应。     

羟肟酸类捕收剂2-羟基-3-萘甲羟肟酸的生物降解研究

生物法是处理难降解有机物的一种重要方法,通过投加活性污泥,采用振荡培养法,研究了以2-羟基-3-萘甲羟肟酸(H205)为唯一碳源的单基质条件、外加碳源和氮源的共基质条件下H205的生物降解过程.结果表明:(1)单基质条件下,不同初始质量浓度(10～50 mg/L)H205的生物降解符合一级动力学模型方程.(2)共基质条...     

Simultaneous measurements of ammonia and nitric acid in ambient air at Agra (27°10′N and 78°05′E) (India)

Simultaneous measurements of ammonia and nitric acid in ambient air were conducted at Dayalbagh, Agra using the mist chamber technique. The sampling site is located near a cattle shed. A total of 120 samples were collected during the period July–September and November–February (1997–1998). Sampling was performed during six different times a day. Gas-phase HNO₃ was estimated as NO₃⁻ using ion chromatographic technique while ammonia was determined colorimetrically as NH₄⁺ using indophenol blue method. The mean levels of NH₃ and HNO₃ for the entire data set were 16.3±2.8 and 1.6±1.4 ppbv, respectively. In the monsoon, mean values for NH₃ and HNO₃ averaged to 16.4±3.5 and 0.9±0.7 ppbv while the winter means were 11.8±4.4 and 2.1±1.2 ppbv, respectively. Concentration of both the species (NH₃ and HNO₃) did not show any significant diurnal behaviour in both the seasons. However, concentration of both NH₃ and HNO₃ were lower at dawn than the previous night's value. This has been ascribed to their removal through dew. Concentrations of HNO₃ are observed to increase during the daytime, consistent with its formation by photochemical reactions. Nitric acid and ammonia concentrations show a significant seasonal variation. Levels of HNO₃ are higher in winter but lower in monsoon, while ammonia shows a reverse trend with higher monsoon and lower winter values. Observed trends in nitric acid and ammonia concentration are due to seasonal variation in emission sources, chemistry and meteorology. Gaseous ammonia and nitric acid are in equilibrium with NH₄NO₃ (solid or aqueous) in the atmosphere. The existence of this equilibrium was examined from simultaneous measurements of NH₃ and HNO₃ in the ambient air. It is found that for the monsoon data, measured concentrations are qualitatively below the predicted equilibrium value, while in the winter, concentration product ([NH₃] [HNO₃]) lies consistently above the predicted values. These deviations may be explained due to local sources of both [NH₃] and [HNO₃], presence of coarse nitrate particles and low-temperature and high-humidity conditions.     

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.     

O_3氧化-SO_3~(2-)还原燃煤烟气脱硝

燃煤烟气同时脱硫脱硝是燃煤烟气污染治理技术研究与应用的趋势。提出利用臭氧注入到模拟烟气氧化NO生成NO_2,再利用NO_2氧化亚硫酸盐生成硫酸盐,同时NO_2被还原生成N2的工艺方法。研究了沿面放电法产生臭氧、臭氧氧化NO、NO_2在亚硫酸钠溶液中的转化和溶液中SO_2-4生成及影响因素。结果表明,臭氧投加量对NO氧化过程影响较大,当O_3/NO摩尔比为1.1时,烟气中NO脱除率达到90%;亚硫酸钠溶液中NO_2脱除率达到97%,且在吸收液温度小于80℃、pH小于10的条件下,NO_2脱除率基本保持不变;液相亚硫酸钠溶液中NO_2与SO_2-3离子之间氧化还原反应生成SO_2-4离子和N2是NO_2转化的主导反应。     

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.     

Measurements of JNO3− in snow by nitrate-based actinometry

Chemical actinometry was used to measure nitrate photolysis rate coefficients, J_NO3⁻, on and in snowpack at Summit, Greenland. Sealed glass tubes containing nitrate and a hydroxyl radical trapping system were buried in snow and exposed for between 2 and 24 h. Average J_NO3⁻ values for 2-h midday exposures in early June on surface snow were 10–14×10⁻⁷ s⁻¹. Averages over 24 h were 3.5–4.5×10⁻⁷ s⁻¹. These values reflect the integrated photon flux and also any variation of the nitrate photolysis rate with temperature. Attenuation of J_NO3⁻ within the firn was 0.03–0.04 cm⁻¹ for 24-h exposures and 0.08 cm⁻¹ for a 2-h exposure. Different attenuation coefficients may relate to differential light penetration due to changes in sun angle over the course of 24 h.