咪唑类离子液体用于处理油田污水的研究

采用油浴法合成了疏水性咪唑类离子液体[omim]PF6。研究了这种离子液体对油田污水的萃取,考察了萃取时间、离子液体加量、pH值对萃取效果的影响。实验结果表明,萃取15 min就可以达到平衡。污水COD的去除率随pH值的增大而减小,同时对再生离子液体处理油田污水的效果进行了探讨,离子液体的循环使用次数对处理污水的效果影响不大。     

Tissue S/N ratios and stable isotopes (δS and δN) of epilithic mosses (Haplocladium microphyllum) for showing air pollution in urban cities in Southern China

In urban cities in Southern China, the tissue S/N ratios of epilithic mosses (Haplocladium microphyllum), varied widely from 0.11 to 0.19, are strongly related to some atmospheric chemical parameters (e.g. rainwater SO₄²⁻/NH₄⁺ ratios, each people SO₂ emission). If tissue S/N ratios in the healthy moss species tend to maintain a constant ratio of 0.15 in unpolluted area, our study cities can be divided into two classes: class I (S/N > 0.15, S excess) and class II (S/N < 0.15, N excess), possibly indicative of stronger industrial activity and higher density of population, respectively. Mosses in all these cities obtained S and N from rainwater at a similar ratio. Sulphur and N isotope ratios in mosses are found significantly linearly correlated with local coal δ³⁴S and NH₄⁺-N wet deposition, respectively, indicating that local coal and animal NH₃ are the major atmospheric S and N sources.     

The effect of alkyl chain length on the degradation of alkylimidazolium- and pyridinium-type ionic liquids in a Fenton-like system

Background, aim, and scope  Ionic liquids are regarded as essentially “green” chemicals because of their insignificant vapor pressure and, hence, are a good alternative to the emissions of toxic conventional volatile solvents. Not only because of their attractive industrial applications, but also due to their very high stability, ionic liquids could soon become persistent contaminants of technological wastewaters and, moreover, break through into natural waters following classical treatment systems. The removal of harmful organic pollutants has forced the development of new methodologies known as advanced oxidation processes (AOPs). Among them, the Fenton and Fenton-like reactions are usually modified by the use of a higher hydrogen peroxide concentration and through different catalysts. The aim of this study was to assess the effect of hydrogen peroxide concentration on degradation rates in a Fenton-like system of alkylimidazolium ionic liquids with alkyl chains of varying length and 3-methyl-N-butylpyridinium chloride. Materials and methods  The ionic liquids were oxidized in dilute aqueous solution in the presence of two different concentrations of hydrogen peroxide. All reactions were performed in the dark to prevent photoreduction of Fe(III). The concentrations of ionic liquids during the process were monitored with high-performance liquid chromatography. Preliminary degradation pathways were studied with the aid of ¹H NMR. Results  Degradation of ionic liquids in this system was quite effective. Increasing the H₂O₂ concentration from 100 to 400 mM improved ionic liquid degradation from 57–84% to 87–100% after 60 min reaction time. Resistance to degradation was weaker, the shorter the alkyl chain. Discussion  The compound omimCl was more resistant to oxidation then other compounds, which suggests that the oxidation rates of imidazolium ionic liquids by OH· are structure-dependent and are correlated with the n-alkyl chain length substituted at the N-1-position. The level of degradation was dependent on the type of head group. Replacing the imidazolium head group with pyridinium increased resistance to degradation. Nonetheless, lengthening the alkyl chain from four to eight carbons lowered the rate of ionic liquid degradation to a greater extent than changing the head group from imidazolium to pyridinium. 1H-NMR spectra show, in the first stage of degradation, that it is likely that radical attack is nonspecific, with any one of the carbon atoms in the ring and the n-alkyl chain being susceptible to attack. Conclusions  The proposed method has proven to be an efficient and reliable method for the degradation of imidazolium ionic liquids by a Fenton-like reagent deteriorated with lengthening n-alkyl substituents and by replacing the imidazolium head group with pyridinium. The enhanced resistance of 1-butyl-3-methylpyridinium chloride when the resistance of imidazolium ionic liquids decreases with increasing H₂O₂ concentration is probably indicative of a change in the degradation mechanism in a vigorous Fenton-like system. H-NMR spectra showed, in the first stage of degradation, that radical attack is nonspecific, with any one of the carbon atoms in the ring and the n-alkyl chain being susceptible to attack. Recommendations and perspectives  Since ionic liquids are now one of the most promising alternative chemicals of the future, the degradation and waste management studies should be integrated into a general development research of these chemicals. In the case of imidazolium and pyridinium ionic liquids that are known to be resistant to bio- or thermal degradation, studies in the field of AOPs should assist the future structural design as well as tailor the technological process of these chemicals     

Association of plutonium with sediments from the Ob and Yenisey Rivers and Estuaries

The present study applied sequential extraction techniques to investigate the binding and mobility of plutonium (Pu) in sediments from the rivers and estuaries of the Ob and Yenisey. As a study site, the Ob and Yenisey are particularly interesting as both rivers have weapons-grade Pu sources in their catchment areas, including the Russian Pu production and reprocessing plants at Mayak, Tomsk-7 and Krashnoyarsk, and the Semipalantinsk nuclear weapons testing site in Kazakhstan. Plutonium activity and ²⁴⁰Pu/²³⁹Pu ratios were determined using accelerator mass spectrometry (AMS). Sequential extractions showed that between 47 and 80% of the Pu in Yenisey River sediments and 35–53% of the Pu in soils around the Techa River are mobilized with weak oxidising agents, which can indicate that Pu is bound to organic material. In contrast, Pu in Ob and Yenisey Estuarine sediments was more strongly bound, with 60–100% being found in the HNO₃-extractable fraction. This change in speciation could reflect either that Pu bound to organic material in the Techa and Yenisey River sediments becomes more fixed to the sediments with time, or that organic-bound Pu is mobilized and released to the water when the sediments encounter the more saline water of the Ob and Yenisey estuaries. In general, ²⁴⁰Pu/²³⁹Pu ratios were relatively consistent between different extraction fractions, although, in whole sediments, an increase in ratio was observed with distance from the source. This reflects the increased influence of weapon fallout from catchment runoff within the river systems, as compared to the weapons-grade sources close to the production and reprocessing plants. Knowledge of Pu speciation in the Ob and Yenisey Rivers, and the processes controlling its behaviour in estuarine systems, can improve predictions of its transfer and subsequent environmental impact to Arctic Seas.     

Isotopic composition (C & N) of the suspended particles and N uptake by phytoplankton in a shallow tropical coastal lagoon

The spatial distribution of the C/N ratios and variations in δ¹³C and δ¹⁵N of suspended particulate matter were used to characterise their source in Asia’s largest brackish water lagoon, Chilika, India. In addition, the significance of re-mineralised nutrients in the primary productivity of the shallow lagoon was also determined through quantification of the subsurface nitrogen uptake conditions at two relatively stable locations in the lagoon. The results indicated that the influence of terrestrial organic matter was the maximum in the northern sector and was relatively limited at the central and southern part of the lagoon. In situ ¹⁵N uptake experiments (daytime) under biogeochemically stable conditions revealed that the N uptake by phytoplankton ranged between 0.24 and 1.01?mM?m^?3?h^?1 during pre-monsoon and post-monsoon seasons. New production and regenerated production in the shallow lagoon was also estimated by calculating f-ratios (ratio of nitrate assimilation by phytoplankton to total nitrogenous nutrient assimilation, have been estimated), which varied from 0.52 in the post-monsoon to 0.38 in the pre-monsoon. Lowering of the f-ratio from post- to pre-monsoon indicated a dominance of mineralisation over the new production.     

不同流量分配比对多级A/O工艺去除有机物及脱氮的影响

采用三级A/O工艺分段进水工艺处理低碳源生活污水,考察了进水流量分配比对系统去除有机物、硝化反硝化能力以及去除TN的影响。通过对水质指标沿程监测结果表明,不同流量分配比(4∶3∶3,5∶3∶2,6∶3∶1)对系统去除有机物及硝化效率影响不大,出水COD、氨氮分别均在30 mg/L、1 mg/L以下。但反硝化效果受流量分配比的影响较大,在流量比为5∶3∶2时,有效利用原水中碳源进行反硝化,反硝化效果最好。在流量比为5∶3∶2的情况下,TN出水为5.7 mg/L去除率为82.9%,优于流量分配比为6∶3∶1和4∶3∶3时的脱氮效果。总体而言,分段进水工艺在对碳源的有效利用及能耗节省方面优于单点进水。     

Ambient nitrogen oxides exposure and early childhood respiratory illnesses

Acute respiratory infections are common in children below 5 years and recent studies suggest a possible link with air pollution. In this study, we investigated the association between ambient nitrogen oxides (NO_x) and bronchitis or upper airway inflammation.This longitudinal study was conducted in Teplice and Prachatice districts, Czech Republic. Children were followed from birth to 4.5 years of age. Data were compiled from medical records at delivery and at follow up, and from self-administered questionnaires from the same two time points. Air pollution monitoring data were used to estimate exposure over five different averaging periods ranging from three to 45 days prior to an episode. To quantify the association between exposure and outcome, while accounting for repeated measure correlation we conducted logistic regression analysis using generalized estimating equations.During the first 2 years of life, the adjusted rate ratio for bronchitis associated with interquartile increase in the 30-day average NO_x was 1.31 [95% confidence interval (CI): 1.07, 1.61] and for two to 4.5 year olds, it was 1.23 (95% CI: 1.01, 1.49). The 14-day exposure also had stable association across both age groups: below 2 years it was 1.25 (95% CI: 1.06, 1.47) and for two to 4.5 years it was 1.21 (95% CI: 1.06, 1.39). The association between bronchitis and NO_x increased with child's age in the under 2 years group, which is a relatively novel finding.The results demonstrate an association between NO_x and respiratory infections that are sufficiently severe to come to medical attention. The evidence, if causal, can be of public health concern because acute respiratory illnesses are common in preschool children.     

Parental phenols exposure and spontaneous abortion in Chinese population residing in the middle and lower reaches of the Yangtze River

Widespread use of phenols has led to ubiquitous exposure to phenols. In experimental animals, phenols increased resorptions, reduced live litter size and fetal body weights. However, there are limited epidemiological evidences of the relationships between exposure to phenols and pregnancy outcomes. We evaluated the associations between parental urinary levels of various phenols and spontaneous abortion in a Chinese population residing in the middle and lower reaches of the Yangtze River. A case-control study was conducted that included 70 case couples with medically unexplained spontaneous abortion and 180 control couples who did not have a history of spontaneous abortion and had at least one living child. Both parental urinary phenols were measured by ultra-high performance liquid chromatography-tandem mass spectrometry including bisphenol A (BPA), benzophenone-3 (BP-3), 2,3,4-trichlorophenol (2,3,4-TCP), pentachlorophenol (PCP), 4-n-octylphenol (4-n-OP) and 4-n-nonylphenol (4-n-NP). Compared with the low exposure group, there was an increased risk of spontaneous abortion with high paternal urinary PCP concentration [odds ratio (OR) = 2.09, 95% Confidence Interval (CI), 1.05–4.14], and maternal exposure to 4-n-OP and alkylphenol(s) also significantly increased the risk of spontaneous abortion (OR = 2.21, 95% CI, 1.02–4.80; OR = 2.81, 95% CI, 1.39–5.65, respectively). Our study firstly provides the evidence that paternal PCP exposure, maternal 4-n-OP and alkylphenol(s) exposure are associated with spontaneous abortion in humans.     

UASB反应器降解活性染料废水的特性

中温（35±1）℃条件下,采用上流式厌氧污泥床（upflowanaerobicsludgebed,简称UASB）反应器处理了含蒽醌类-活性艳蓝（c．I．ReactiveBlue5,简称K—GR）或偶氮类-活性艳红（C．I．ReactiveRed20,简称KD-8B;C．I．ReactiveRed2,简称X-3B）模拟染料废水,重点研究了回流比对染料脱色率和COD去除率的影响,在最佳回流比的条件下,探讨HRT（hydraulicretentiontime）对脱色的影响和不同结构染料的脱色效果,并初步分析了脱色机理。结果表明,适宜的回流比有利于提高系统的脱色率;控制回流比和HRT分别为2和24h,当模拟废水中染料的浓度为100mg／L时,COD去除率和脱色率分别为90％～96％和85％～92％;蒽醌和偶氮类染料的脱色是通过偶氮键和葸醌共轭结构的断裂来实现的。     

Should Habitat Trading Be Based on Mitigation Ratios Derived from Landscape Indices? A Model-Based Analysis of Compensatory Restoration Options for the Red-Cockaded Woodpecker

Many species of conservation concern are spatially structured and require dispersal to be persistent. For such species, altering the distribution of suitable habitats on the landscape can affect population dynamics in ways that are difficult to predict from simple models. We argue that for such species, individual-based and spatially explicit population models (SEPMs) should be used to determine appropriate levels of off-site restoration to compensate for on-site loss of ecologic resources. Such approaches are necessary when interactions between biologic processes occur at different spatial scales (i.e., local [recruitment] and landscape [migration]). The sites of restoration and habitat loss may be linked to each other, but, more importantly, they may be linked to other resources in the landscape by regional biologic processes, primarily migration. The common management approach for determining appropriate levels of off-site restoration is to derive mitigation ratios based on best professional judgment or pre-existing data. Mitigation ratios assume that the ecologic benefits at the site of restoration are independent of the ecologic costs at the site of habitat loss. Using an SEPM for endangered red-cockaded woodpeckers, we show that the spatial configuration of habitat restoration can simultaneously influence both the rate of recruitment within breeding groups and the rate of migration among groups, implying that simple mitigation ratios may be inadequate.