Vapour pressures, aqueous solubility, Henry's law constants and air/water partition coefficients of 1,8-dichlorooctane and 1,8-dibromooctane

New data on the vapour pressures and aqueous solubility of 1,8-dichlorooctane and 1,8-dibromooctane are reported as a function of temperature between 20 °C and 80 °C and 1 °C and 40 °C, respectively. For the vapour pressures, a static method was used during the measurements which have an estimated uncertainty between 3% and 5%. The aqueous solubilities were determined using a dynamic saturation column method and the values are accurate to within ±10%. 1,8-Dichlorooctane is more volatile than 1,8-dibromooctane in the temperature range covered (p_sat varies from 3 to 250 Pa and from 0.53 to 62 Pa, respectively) and is also approximately three times more soluble in water (mole fraction solubilities at 25 °C of 5.95 × 10⁻⁷ and 1.92 × 10⁻⁷, respectively). A combination of the two sets of data allowed the calculation of the Henry’s law constants and the air water partition coefficients. A simple group contribution concept was used to rationalize the data obtained.     

Formation of dioxins from combustion of polyvinylidene chloride in a well-controlled incinerator

Polyvinylidene chloride (PVDC; polymer of 1,1-dichloroethylene) was combusted with paper in a well-controlled, small-scale incinerator at an average grate temperature of 700 °C, and then dioxins (PCDDs, PCDFs, and coplanar-PCBs) formed in the exhaust gases were analyzed by gas chromatography/mass spectrometry. PVDC lowered the combustion temperature due to its less flammable character. The amount of total dioxins (PCDDs + PCDFs + coplanar-PCBs) formed in the exhaust gas was 58.0 ng/g of a combustion sample and its toxicity equivalency quantity (TEQ) value was 0.64 ng-TEQ/g. The amount of PCDDs formed in the sample ranged from 2.33 ng/g (Cl₈-isomer) to 0.048 ng/g (Cl₁-isomer). The lower the number of chloride, the less production of PCDDs. On the other hand, there was no relation between the number of chloride and PCDF formation. The amount of PCDFs formed in the sample ranged from 8.02 ng/g (Cl₂-isomer) to 4.46 ng/g (Cl₈-isomer). A polyvinylchloride (PVC) sample produced 207 ng/g of total dioxins and a PVDC sample produced 57.4 ng/g of total dioxins when they were combusted under the same conditions. An approximately equal composition of dioxin isomers was formed from PVDC and PVC samples. Paper was found to contribute to PCDF formation when it was combusted with plastics.     

Evaluation of the emission characteristics of PCDD/Fs from electric arc furnaces

Distribution of PCDD/F (polychlorinated dibenzo-p-dioxin and polychlorinated dibenzofuran) congeners at two electric arc furnaces (EAFs) in Taiwan is evaluated via intensive stack sampling and analysis. Two kinds of exhaust system in EAFs including stack system and shutter system are selected for measuring dioxin emissions. In addition, dioxin emissions during oxidation and reduction stages at EAF-A were characterized. Results indicate that the PCDD/F concentration of stack gas in EAF-A was 4.39 ng/N m³ while total Toxic Equivalent Quantity (TEQ) concentration was 0.35 ng I-TEQ/N m³. The PCDD/F concentration of stack gas in EAF-B was 2.20 ng/N m³ and the TEQ concentration was 0.14 ng I-TEQ/N m³. 1,2,3,4,6,7,8-H_pCDF, OCDD and OCDF are the major contributors of the dioxin concentrations for two EAFs investigated and the percentage of PCDD/F in particulate phase increases as the chlorination level of the PCDD/F congener increases. The results obtained on gas/particulate partitioning of PCDD/Fs in flue gases prior to the APCD in EAFs indicate that more than 90% exists in particulate phase. In EAF-A, the PCDD/F concentration during oxidation stage is slightly higher than that measured during reduction stage, including the sampling points of CO converter outlet, prior to bag filter and stack. Majority of PCDD/Fs emitted from steel-making processes exists in particulate-phase (about 60–70%) at both EAFs investigated.     

Broad range analysis of endocrine disruptors and pharmaceuticals using gas chromatography and liquid chromatography tandem mass spectrometry

Endocrine disrupting compounds (EDCs) and pharmaceuticals and personal care products (PPCPs) have been globally detected in impacted natural waters. The detection of trace quantities of EDCs and PPCPs in the environment is of great concern since some of these compounds have known physiological responses at low concentrations. EDCs can have a wide range of polarities, acidic and basic moieties, and exist in trace quantities, which often requires numerous complex extractions, large sample collection volumes, and multiple instrumental analyses. A comprehensive method has been developed allowing for the analysis of 58 potential EDCs in various water matrices using a single solid-phase extraction (SPE) of a 1 L sample with subsequent analyses using both gas chromatography and liquid chromatography, each coupled with tandem mass spectrometry (GC–MS/MS and LC–MS/MS). Instrument detection limits ranged between 0.12–7.5 pg with corresponding method reporting limits of 1–10 ng l⁻¹ in water. Recoveries for most compounds were between 50% and 112% with good reproducibility (RSD 6–22%).     

聚糖菌颗粒污泥基于胞内储存物质的同步硝化反硝化

采用特殊运行方式的厌氧-好氧SBR系统(厌氧后排水),以乙酸钠为有机基质成功富集了聚糖菌颗粒污泥.聚糖菌颗粒污泥厌氧-好氧批式实验表明,聚糖菌颗粒污泥具有较强的SND能力,TOC/N分别为5.0,4.0,2.8时,SND效率分别96.4%、95.3%及96.2%,而周期总氮去除效率随着碳氮比降低而降低,分别为66.0%、61.2%及56.3%.通过对周期氨氮、亚硝酸盐氮、硝酸盐氮、TOC以及胞内糖原、PHB变化的测定分析,证明聚糖菌颗粒污泥SND过程中,污泥以厌氧阶段储存于胞内的多聚物PHB作为反硝化碳源,并且反硝化聚糖菌是系统中反硝化能力的来源.与溶解性基质相比,PHB的降解速率相对较低,因此在SND过程中,反硝化可以与硝化保持相近的速率,从而有助于获得良好的SND效果.     

厌氧水解酸化-好氧氧化A1/A2/O工艺剩余污泥减量

在碱减量印染废水A₁/A₂/O生物处理系统,通过污泥回流、把剩余污泥回流到A₁段,利用A段污泥的水解、酸化和O段微生物的好氧氧化作用可有效实现对回流剩余污泥的减量,同时O段好氧污泥的表观产率系数下降,系统产生的剩余污泥量减少.厌氧水解酸化-好氧氧化A₁/A₂/O工艺实现污泥减量由3段共同完成:A₁段实现回流剩余污泥的“液化”和惰性化;A₂段对系统污泥减量起到了强化作用;而O段微生物的合成作用在逐渐减弱.6个月连续运行的动态试验表明,在A₁段的容积负荷(COD_Cr)为2.54 kg·(m³·d)^-1、水力停留时间为7.56h条件下,A₁段利用水解酸化作用对回流剩余污泥的减量达到67.87%,系统O段好氧污泥的表观产率系数也下降到试验初始时的45.5%.在A₁/A₂/O污泥减量系统中,各段污泥性状发生了变化,A₁段污泥[MLVSS/MLSS]值从试验开始时的0.718 2下降到0.592 2,A₂段污泥[MLVSS/MLSS]值从0.667 3下降到0.526 7,剩余污泥的减量是活性污泥逐渐惰性化过程,污泥的粒度分析也证明了这一点.     

CSM/EVA复合材料的阻燃与伸缩性能研究

采用机械共混法制备了EVA/CSM复合材料.系统地研究了EVA与CSM的混合比率、CSM交联及不同阻燃体系对复合材料阻燃性质的影响.结果表明,掺杂阻燃剂之后,复合材料都具有很好的阻燃性能,其中使用Sb2O3/氯乙醇混合阻燃体系,阻燃效果最好,且复合材料交联后,阻燃性能会进一步增强.同时研究了各种因素,如交联、混合比率和处理温度对复合材料收缩率的影响.当CSM含量较高或拉伸温度处于室温,收缩率都较好;而交联前,加入阻燃剂会使复合材料收缩性能降低;反之,交联后使之增加.     

A/DAT-IAT生物膜法处理高含盐废水

以含盐量为60 000mg/L(以NaCl计)的模拟工业废水为研究对象,利用A/DAT-IAT生物膜反应器,研究A/DAT-IAT工艺对投加悬浮填料后高含盐废水的处理,并以CODCr、NH4 -N、PO43--P等作为指标评价处理效果.试验结果表明,在总水力停留时间(HRT)为13 h、pH=7,5、25℃条件下,进水ρ(CODCr)、ρ(NH4 -N)和ρ(PO43--P)分别为907.4～1 210.0 mg/L、86.2～99.7 mg/L和3.6～5.1 mg/L.CODCr、NH4 -N和PO43--P的平均去除率分别为73.9%、38.6%和93.5%,平均出水SS为198 mg/L,其中CODCr和PO43--P的去除效果较好.研究表明,A/DAT-IAT生物膜法较其他活性污泥法有了较大的提高.     

Perfluorinated Surfactants in Surface and Drinking Waters (9 pp)

Background, Aim and Scope In this paper recent results are provided of an investigation on the discovery of 12 perfluorinated surfactants (PS) in different surface and drinking waters (Skutlarek et al. 2006 a, Skutlarek et al. 2006 b). In the last years, many studies have reported ubiquitous distribution of this group of perfluorinated chemicals, especially perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) in the environment, particularly in wildlife animal and human samples (Giesy and Kannan 2001, Houde et al. 2006, Prevedouros et al. 2006). Perfluorinated surfactants (e.g. PFOS and PFOA) have shown different potentials for reproductory interference and carcinogenity in animal experiments as well as partly long half-lives in humans (Guruge et al. 2006, FSA UK 2006a, FSA UK 2006b, 3M 2005, OECD 2002, Yao and Zhong 2005). They possess compound-dependent extreme recalcitrance against microbiological and chemical degradation and, in addition, they show variable potentials for bioaccumulation in animals and humans (Houde et al. 2006). Materials and Methods: Surface and drinking water samples were collected from different sampling sites: - Surface waters: samples taken from the rivers Rhine, Ruhr, Moehne and some of their tributaries. Further samples were taken from the Rhine-Herne-Canal and the Wesel-Datteln-Canal. - Drinking waters: samples taken in public buildings of the Rhine-Ruhr area. After sample clean-up and concentration by solid-phase extraction, the perfluorinated surfactants were determined using HPLC-MS/MS. Results: All measured concentrations (sum of seven mainly detected components) in the Rhine river and its main tributaries (mouths) were determined below 100 ng/L. The Ruhr river (tributary of the Rhine) showed the highest concentration (94 ng/L), but with a completely different pattern of components (PFOA as major component), as compared with the other tributaries and the Rhine river. Further investigations along the Ruhr river showed remarkably high concentrations of PS in the upper reaches of the Ruhr river and the Moehne river (tributary of the Ruhr) (Ruhr: up to 446 ng/L, Moehne: up to 4385 ng/L). The maximum concentration of all drinking water samples taken in the Rhine-Ruhr area was determined at 598 ng/L with the major component PFOA (519 ng/L). Discussion: The surface water contaminations most likely stem from contaminated inorganic and organic waste materials (so-called 'Abfallgemisch'). This waste material was legally applied to several agricultural areas on the upper reaches of the Moehne. Perfluorinated surfactants could be detected in some suchlike soil samples. They contaminated the river and the reservoir belonging to it, likely by superficial run-off over several months or probably years. Downstream, dilution effects are held responsible for decreasing concentrations of PS in surface waters of the Moehne and the Ruhr river. In analogy to the surface water samples, PS (major component PFOA) can be determined in many drinking water samples of the Rhine-Ruhr area where the water supplies are mainly based on bank filtration and artificial recharge. Conclusions: The concentrations found in drinking waters decreased with the concentrations of the corresponding raw water samples along the flow direction of the Ruhr river (from east to west) and were not significantly different from surface water concentrations. This indicates that perfluorinated surfactants are at present not successfully removed by water treatment steps. Recommendations and Perspectives: Because of their different problematic properties (persistence, mobility, toxicity, bioaccumulation), the concentrations of specific perfluorinated surfactants and their precursors in drinking waters and food have to be minimised. Therefore, it is of utmost importance to take the initiative to establish suitable legal regulations (limitations/ban) concerning the production and use of these surfactants and their precursors. Furthermore, it is indispensable to protect water resources from these compounds. A discussion on appropriate limit values in drinking water and foodstuffs is urgently needed. Concerning the assumed soil contamination, the corresponding regulation (Bioabfall-Verordnung 1998 – Regulation on Organic Waste 1998) should be extended to allow the control of relevant organic pollutants.     

Quantitation of Hydroxyl Radicals from Photolysis of Fe(III)-Citrate Complexes in Aerobic Water (5 pp)

Background For their high photoreactivity, Fe(III)-carboxylate complexes are important sources of H2O2 for some atmospheric and surface waters. Citrate is one kind of carboxylate, which can form complexes with Fe(III). In our previous study, we have applied Fe(III)-citrate complexes to degrade and decolorize dyes in aqueous solutions both under UV light and sunlight. Results have shown that carboxylic acids can promote the photodegradation efficiency. It is indicated that the photolysis of Fe(III)-citrate complexes may cause the formation of some reactive species (e. g. H2O2 and ·OH). This work is attempted to quantify hydroxyl radicals generated in the aqueous solution containing Fe(III)-citrate complexes and to interpret the photoreactivity of Fe(III)-citrate complexes for degrading organic compounds. Methods By using benzene as the scavenger to produce phenol, the photogeneration of ·OH in the aqueous solution containing Fe (III)-citrate complexes was determined by HPLC. Results and Discussion In the aqueous solution containing 60.0/30.0 mM Fe(III)/citrate and 7.0 mM benzene at pH 3.0, 96.66 mM ·OH was produced after irradiation by a 250W metal halide light (l ≥ 313 nm) for 160 minutes. Effects of initial pH value and concentrations of Fe(III) and citrate on ·OH radical generation were all examined. The results show that the greatest photoproduction of ·OH in the aqueous solution (pH ranged from 3.0 to 7.0) was at pH 3.0. The photoproduction of ·OH increased with increasing Fe(III) or citrate concentrations. Conclusion In the aqueous solutions containing Fe(III)-citrate complexes, ·OH radicals were produced after irradiation by a 250W metal halide light. It can be concluded that Fe(III)-citrate complexes are important sources of ·OH radicals for some atmospheric and surface waters. Recommendations and Outlook It is believed that the photolysis of Fe(III)-citrate complexes in the presence of oxygen play an important role in producing ·OH both in atmospheric waters and surface water where high concentrations of ferric ions and citrate ions exist. The photoproduction of ·OH has a high oxidizing potential for the degradation of a wide variety of natural and anthropogenic organic and inorganic substances. We can use this method for toxic organic pollutants such as organic dyes and pesticides.