聚合硅酸钛铝复合絮凝剂的结构及性能

为了克服有机絮凝剂的二次投加及有毒性的缺点,以硅酸钠、硫酸钛、硫酸铝为原料,制备了聚合硅酸钛铝(PTAS)无机高分子复合絮凝剂处理模拟江水。结果表明,在n(Ti+Al)∶n(Si)=1∶3,n(Ti)∶n(Al)=1∶5,模拟江水pH值为5～9.3,絮凝剂投加量为0.3 mmol/L(以金属离子计)时,PTAS对模拟江水的混凝效果最好,除浊率达到92.5%以上。此外,通过X-射线衍射说明聚硅酸与硫酸铝、硫酸钛不是单纯的原料复合;红外吸收光谱显示钛、铝离子及其水解聚合产物可与共存的聚硅酸生成Si—O—Al键和Ti—O—Si键;激光粒度分析表明PTAS在聚合过程中粒度并没有明显变化,但均比聚硅酸粒径大。     

PATS的制备表征及其处理低浊水效能与残留铝控制

以水玻璃、硫酸铝和硫酸钛为原料,采用共聚法制备了聚硅酸硫酸铝钛(PATS)混凝剂。考察了混凝剂处理模拟低浊水的效能和出水残留铝含量,并且运用FTIR、XRD和SEM对混凝剂的结构形貌进行了表征。研究发现,当Al/Ti摩尔比为10∶1,(Al+Ti)/Si摩尔比为1∶2,水体pH为7~9,水体温度为10℃时,合成的PATS混凝剂对模拟低浊水的混凝性能最好,残留铝含量较低,当该混凝剂投量为0.10 mmol·L~(-1)(以金属离子计)时,余浊和残留铝含量分别可达到0.36 NTU和0.022 mg·L~(-1)。结果表明,PATS中存在铝、钛及其水解产物与硅发生相互作用生成的Al—O—Si键和Ti—O—Si键。PATS不是几种原料的简单混合,而是一种无定形共聚物。与聚合氯化铝、聚硅酸硫酸铝相比,PATS具有更好的混凝效果和更低的残留铝含量。     

聚硅酸锌铝的制备及其性能研究

以硅酸钠、硫酸锌、硫酸铝为原料,通过共聚法制备了无机高分子絮凝剂聚硅酸锌铝（PSZAS）,研究了Na₂SiO₃的摩尔浓度、活化时间、Al/Si、Zn/Si 配比及絮凝剂的投加量对絮凝效果的影响,用X-射线衍射（XRD）和电子扫描电镜（SEM）对该絮凝剂的结构及形貌进行了表征。结果表明：当硅酸钠的浓度为0.4 mol/L,硅酸活化时间为2 h,Si∶Al∶Zn=1∶1∶1.5,絮凝剂投加量为20 mL/L废水时,絮凝剂的电中和能力和吸附架桥能力最强,絮凝剂对含H-酸染料模拟废水的絮凝效果最好。     

聚硅硫酸铝的形貌结构和絮凝机理

以工业水玻璃、工业硫酸铝为原料制得聚硅硫酸铝(PASS)复合絮凝剂,采用电子显微镜观察了不同,nAl/n(Si)的PASS的形貌,借助倒置式生物显微镜分析了PASS所形成絮体的形貌并用激光粒度分析仪对絮体粒度分布进行了测定,通过红外光谱和X-射线衍射研究了PASS中铝与聚硅酸的相互作用情况,考察了模拟江水中胶体颗粒物和PASS水解物的Zeta电位随pH值的变化,在此基础上探讨分析了PASS的絮凝机理和絮凝过程.结果发现:nAl/n(Si)对PASS的形貌有较大影响,絮体粒度分布的数据印证了该结果;红外光谱图表明PASS中有Si-O-Al振动峰出现,峰强度随nAl/n(Si)减小而增大;X-射线衍射图证实了聚硅硫酸铝不是晶体,而是铝水解产物与聚硅酸共同作用形成的无定型聚合物;吸附架桥及粘结卷裹作用是PASS絮凝时的主导作用.     

用褐铁矿制备聚硅氯化硫酸铁的研究

通过正交实验研究了用盐酸、硫酸、褐铁矿和硅酸钠制备聚硅氯化硫酸铁（PSFCS）絮凝剂的工艺条件。实验结果表明,浸取时间为2.5～3 h,浸取温度为110℃,硫酸浓度为6 mol/L,盐酸浓度为3 mol/L,质量液固比为4∶1,铁的浸出率可达95.7%～96.3%。溶液中加入少量聚乙烯醇作稳定剂,亚硝酸钠作氧化催化剂。PSFCS的合成条件：Fe/Si摩尔比为2,硅酸活化pH值为2,硅酸活化时间是30～40 min,陈化时间是2～2.5 h。与聚合硫酸铁（PFS）和聚合氯化铝（PAC）比较了处理印染废水的效果,表明PSFCS具有良好的絮凝性能,COD和浊度的去除率分别可达81.4%和96.1%。     

聚硅酸钛制备及其助凝特性

采用在活化硅酸制备过程中加入适量Ti Cl4的方法,试制了一种新型无机高分子助凝剂—聚硅酸钛。研究了不同[Si]/[Ti]条件下制备的聚硅酸钛在固定p H值的水中分散物的粒径和Zeta电位随着活化时间的变化趋势,并与活化硅酸作比较。结果表明,在Si/Ti=20,活化48 h的条件下能制备出较为稳定的聚硅酸钛。与活化硅酸相比,聚硅酸钛在水中的分散物具有较大的粒径和更高的Zeta电位。通过对比制备的活化硅酸和聚硅酸钛的红外图谱发现,聚硅酸钛中有TiO-Si键,证明钛离子参与了聚合反应,新生成的化学键提高了它的聚合度和稳定性。采用硫酸铝为混凝剂,聚硅酸钛为助凝剂进行混凝除浊实验。测定了絮凝体的Zeta电位和混凝沉淀后的上清液浊度,研究了硫酸铝投加量和混凝p H对聚硅酸钛助凝效果的影响。结果表明,投加适量的聚硅酸钛助凝剂,明显提高了混凝除浊效果且拓宽了有效混凝p H值的范围。     

附载型复合光催化剂TiO2·SiO2/beads降解有机磷农药

研究以四异丙醇钛 [Ti( iso- O C3 H7) 4]、硅酸乙酯为原料 ,以空心玻璃微球为载体 ,用溶胶—凝胶法制备可漂浮附载型复合光催化剂 Ti O2 · Si O2 / beads的过程 ,利用附载型复合光催化剂降解有机磷农药。结果表明 ,复合型光催化剂 Ti O2 · Si O2 摩尔比存在最佳值 ,n ( Ti O2 ) / m ( Si O2 ) =30 / 70时 ,光催化剂活性最高 ,其活性是同样降解条件下、同样含量 Degussa P- 2 5Ti O2 的 2倍左右。该光催化剂比表面大 ,吸附性强。并用 XRD和 SEM对附载型复合光催化剂进行表征     

高浓度复合型聚铁硅絮凝剂PFSS和PSFS的形态分布研究

采用紫外分光光度法、逐时络合比色法和红外图谱从不同角度对高浓度聚合硫酸铁硅和聚合硅酸铁的形态分布及转化规律进行了探讨。紫外吸收表明,聚铁硅絮凝剂中主要以Fe(OH)+2、Fe2(OH)4+2等二聚体为主,而且还有三聚体或其他聚合形态的存在;逐时络合分析显示,复合型聚铁硅体系中硅形态以Si(c)为主,铁形态以Fe(a)和Fe(c)为主;红外图谱证实高浓度聚铁硅是以羟桥为主结构连接的高分子复合物,在1100cm-1附近M—OH—M的振动证明有铁羟基及其聚合态存在,且其形态区别于PFS。     

聚硅基复合氯化铁絮凝剂的制备及其在采油废水处理中的应用

采用硅酸钠制备聚硅酸,探讨了活化pH、活化剂、硅酸钠浓度(以SiO_2质量分数计)及聚合温度等因素对聚硅酸稳定性的影响.利用聚硅酸及氯化铁制备聚硅基复合氯化铁(PSiF),并通过正交试验分析了活化pH、Si/Fe(摩尔比)、OH/Fe(摩尔比)、制备时间对PSiF絮凝性能的影响.综合考虑絮凝性能、稳定性以及经济性等因素,确定PSiF适宜的制备条件为SiO_2质量分数2%～3%;活化pH为2～3;Si/Fe为0.50～0.75;OH/Fe为0.50～0.75;制备时间为0.5 h;聚合温度低于25℃.对比PSiF、PAC、FeCl_3对采油废水的处理效果,PSiF除浊、除COD效果以及经济性最好,是一种应用前景广阔的新型絮凝剂.     

还原剂添加的矿物聚合物对Cr(Ⅵ)的解毒/固化

在对现有Cr(Ⅵ)污染控制方法分析的基础上,提出用还原剂添加的矿物聚合物对Cr(Ⅵ)进行解毒/固化的研究思路。以煤矸石为原料,以水玻璃和Na OH为碱性激发剂,合成矿物聚合物;以Fe Cl2·4H2O为还原剂,用还原剂添加的矿物聚合物对Cr(Ⅵ)进行解毒/固化实验,并采用XRD、TEM/EDS、XPS对固化体进行检测。当添加的Fe(Ⅱ)与Cr(Ⅵ)的摩尔比≥3∶1时,矿物聚合物中总铬的浸出浓度小于1 mg/L,铬固化率大于99%。还原剂添加的矿物聚合物对Cr(Ⅵ)最大固化量为0.8%。在合成过程中,Fe(Ⅱ)和Cr(Ⅵ)添加的矿物聚合物发生了氧化还原反应,Fe(Ⅱ)被氧化成了Fe(Ⅲ),Cr(Ⅵ)被还原成了Cr(Ⅲ),随后Fe(Ⅲ)和Cr(Ⅲ)同时被矿物聚合物中的—OAl(-)(OH)3吸引,并固化在非晶质结构中。     

Use of diffuse reflectance spectrometry in spot test reactions for quantitative determination of cations in water

Diffuse reflectance spectroscopy can be successfully used for the quantitative determination of small amounts of pollutants like metals. The remission function was found to be linearly proportional to the concentration, when we applied the Kubelka–Munk equation. The color reactions of Cu(II), Co(II), and Ni(II) with dithiooxamide, were realised on filter paper. Reaction between Fe(III) and ammonium thiocyanate was realized on filter paper and gelatine matrix. All measurements were accomplished with a laboratory-constructed reflectometer. We have obtained a calibration curve by plotting the optical density of reflectance A_R vs log of the mol l⁻¹ concentration. Limits of detection at the 10⁻⁴ M level were estimated for all the compounds. Linear dynamic range extend over one order of magnitude and shows the potential of device for the quantitative analysis of environmental pollutants.     

Distribution and sources of polyfluoroalkyl substances (PFAS) in the River Rhine watershed

The concentration profile of 40 polyfluoroalkyl substances (PFAS) in surface water along the River Rhine watershed from the Lake Constance to the North Sea was investigated. The aim of the study was to investigate the influence of point as well as diffuse sources, to estimate fluxes of PFAS into the North Sea and to identify replacement compounds of perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA). In addition, an interlaboratory comparison of the method performance was conducted. The PFAS pattern was dominated by perfluorobutane sulfonate (PFBS) and perfluorobutanoic acid (PFBA) with concentrations up to 181 ng/L and 335 ng/L, respectively, which originated from industrial point sources. Fluxes of ΣPFAS were estimated to be ∼6 tonnes/year which is much higher than previous estimations. Both, the River Rhine and the River Scheldt, seem to act as important sources of PFAS into the North Sea.     

Polychlorinated dibenzo-p-dioxins and related compounds: the blood levels of young Japanese women.

We investigated PCDDs and related compounds in the blood of young Japanese women, approximately 20 years of age, who had not yet had children, and discussed how the TEQ level of PCDDs and related compounds in their blood may affect the next generation. Means of total TEQ levels were 0.063 pg/g for whole blood basis and 21 pg/g for lipid basis. TEQ of PCDDs, PCDFs and coplanar PCBs accounted for about 43, 34 and 23% of the total TEQ in the whole blood basis, respectively. In the lipid basis, their values were about 44, 34 and 22%, respectively. Previously, we investigated PCDDs and related compounds levels in mother's breast milk, lymphocyte subpopulation and thyroid function of their children, and found negative correlations between the TEQ level of PCDDs and related compounds and CD4+/CD8+, and/or the TEQ level of PCDDs and related compounds and the T₄ level in 36 mothers and children. Of these cases, the average age was approximately 28 years. PCDDs and related compounds may be related to immunopathy, such as atopic dermatitis. The effects of PCDDs and related compounds on babies of young Japanese women are important and must be further evaluated.     

Effect of vegetation in pilot-scale horizontal subsurface flow constructed wetlands treating sulphate rich groundwater contaminated with a low and high chlorinated hydrocarbon

In order to characterize the effect of vegetation on performance of constructed wetlands (CWs) treating low and high chlorinated hydrocarbon, two pilot-scale horizontal subsurface flow (HSSF) CWs (planted with Phragmites australis and unplanted) treating sulphate rich groundwater contaminated with MCB (monochlorobenzene, as a low chlorinated hydrocarbon), (about 10 mg L⁻¹), and PCE (perchloroethylene, as a high chlorinated hydrocarbon), (about 2 mg L⁻¹), were examined. With mean MCB inflow load of 299 mg m⁻² d⁻¹, the removal rate was 58 and 208 mg m⁻² d⁻¹ in the unplanted and planted wetland, respectively, after 4 m from the inlet. PCE was almost completely removed in both wetlands with mean inflow load of 49 mg m⁻² d⁻¹. However, toxic metabolites cis-1,2-DCE (dichloroethene) and VC (vinyl chloride) accumulated in the unplanted wetland; up to 70% and 25% of PCE was dechlorinated to cis-1,2-DCE and VC after 4 m from the inlet, respectively. Because of high sulphate concentration (around 850 mg L⁻¹) in the groundwater, the plant derived organic carbon caused sulphide formation (up to 15 mg L⁻¹) in the planted wetland, which impaired the MCB removal but not statistically significant. The results showed significant enhancement of vegetation on the removal of the low chlorinated hydrocarbon MCB, which is probably due to the fact that aerobic MCB degraders are benefited from the oxygen released by plant roots. Vegetation also stimulated completely dechlorination of PCE due to plant derived organic carbon, which is potentially to provide electron donor for dechlorination process. The plant derived organic carbon also stimulated dissimilatory sulphate reduction, which subsequently have negative effect on MCB removal.     

BAT and BEP as instruments for reducing emissions of unintentionally produced POPs and development of guidelines under the stockholm convention

The 6th Intergovernmental Negotiating Committee (INC 6), under the Stockholm Convention on POPs, gave an expert group the mandate to develop guidelines for the application and implementation of best available techniques (BAT) and best environmental practices (BEP) for the prevention and reduction of unintentionally produced and emitted POPs, including polychlorinated dibenzodioxins/-furans (PCDD/Fs), polychlorinated biphenyls (PCBs) and hexachlorobenzene (HCB). Measures to reduce or eliminate the release of these POPs to the environment can be found in Article 5 of the Convention. BAT and BEP are already being applied as emission reduction instruments in a number of industrialised countries and are elements of other major international treaties, e.g. the UN ECE Protocol on POPs and the Marine Convention's OSPAR and HELCOM, and of the EU Directive for Integrated Pollution Prevention and Control (IPPC Directive). Existing concepts are presented and compared with the requirements of the Stockholm Convention. Consequences, perspectives and questions for the future intersessional work of the above-mentioned Expert Group are discussed.     

Natural attenuation of trichloroethene and its degradation products at a lake-shore site

Subsurface contamination by trichloroethene (TCE) was detected at a Michigan National Priorities List (NPL) site in 1982. The TCE plume resulted from the disposal of spent solvent and other chemicals at an industrial facility located in the eastern shore of Lake Michigan. TCE degradation products of three dichloroethene (DCE) isomers, vinyl chloride (VC) and ethene were present. The plume was depleted of oxygen and methanogenic at certain depths. Transects of the plume were sampled by slotted auger borings the year after the TCE plume was first discovered. Water samples were also taken from lake sediments to a depth of 12 m about 100 m offshore. Later samples were taken along the shoreline of the lake with a hand-driven probe. Later in 1998 water was taken from sediments about 3-m from the shoreline. The average concentration of each chemical and net apparent base coefficient between appropriate pairs of transects between the lower site and lakeshore were calculated. Loss rates were then calculated from an analytical solution of the two-dimensional advective-dispersive-reactive transport equation. Net apparent rate coefficients and a set of coupled reaction rate equations were used to extract the apparent loss coefficients. This study showed the field evidence for natural attenuation of TCE.     

Reduction in uptake by rice and soybean of aromatic arsenicals from diphenylarsinic acid contaminated soil amended with activated charcoal

Activated charcoal (AC) amendment has been suggested as a promising method to immobilize organic contaminants in soil. We performed pot experiments with rice and soybean grown in agricultural soil polluted by aromatic arsenicals (AAs). The most abundant AA in rice grains and soybean seeds was methylphenylarsinic acid (MPAA). MPAA concentration in rice grains was significantly reduced to 2% and 3% in 0.2% AC treated soil compared to untreated soil in the first year of rice cultivation. In the second year, MPAA concentration in rice grains was significantly reduced to 15% in 0.2% AC treated soil compared to untreated soil. MPAA concentration in soybean seeds was significantly reduced to 44% in 0.2% AC treated soil compared to untreated soil. AC amendment was effective in reducing AAs in rice and soybean.     

Using a Set of Strategic Indicator Systems as a Decision-making Support Implement for Establishing a Recycling-oriented Society - A Taiwanese Case Study (16 pp)

Background Scope and Aims. To realize the vision of sustainable development (SD) originating from the ‘only one earth’ philosophy, and to integrate the conceptions of ecology and sustainability into the planning and decision-making criteria of urban growth management, the establishment of a recycling-oriented society (ROS) is essential. However, before the above intention can be achieved, it is indispensable to develop a system of strategic indicators for supporting a radical reformation of the urban development plan. Therefore, this study, based on the conception of the new urban development pattern ROS, attempted to carefully choose a sample city in Taiwan for launching a preliminary case study, and furthermore designed and proposed a concise and strategy-oriented assessment indicator system termed ROSAIS. ROSAIS, on the one hand, can act as a compass for understanding resource using efficiency and recycling status during city development and, on the other hand, can serve as an implement supporting decision-making for ROS construction.Methods According to the definition and spirit of ROS, the structure of ROSAIS should clearly represent the relationship between resources and environment in human activities. The eco-efficiency indicator system (EEIS) and environmental symbiosis indicator system (ESIS) can be considered two key sub-indicator systems, and are the necessary components of ROSAIS. EEIS chooses the dominant production sectors in urban economic activities to calculate their eco-efficiency (EE). Separately, for obtaining a consensus regarding the framework of ESIS, the questionnaire approaches and expert consultation, together with the research experience and foundation of current relevant studies and indicator systems, are applied when crucial resource and environmental issues and respective indicators are selected.Results and Discussion The calculation results of EEIS in this case study indicated that among the three dominant production activities (agricultural, fishery, and animal husbandry sector) the fishery sector has the highest EE, which indicates that the fishery activities and resources significantly influence the sustainability of the economic-environmental system of the sample city. Furthermore, according to a consensus achieved in ESIS, local green spaces, resource recovery, energy consumption pattern change, freshwater conservation and greenhouse effect abatement were considered as the five crucial issues influencing how the case study city can develop into an ES-city. The rate of local green spaces, resource recycling, freshwater conservation and the rate of reduction of nonrenewable energy use as well as carbon dioxide (CO2) emissions were used to evaluate the above five issues.Conclusion This case study is unparalleled in Taiwan. Even in Japan, where ROS legislation has been implemented, this kind of study remains in the preliminary stages. Furthermore, when communicating the indicator results, it is essential to provide the context and countermeasures of the crucial issues that are faced. The two sub-indicator systems proposed in this case study could comply completely with the above-mentioned requirements. For example, the EEIS provides information for achieving a balance between environmental burden and economic benefits among dominant production sectors; the ESIS provides information for setting strategies for overcoming the crucial issues faced. Recommendation and Outlook This study recommends that urban planers should consider the construction of the corresponding strategic indicator system to be indispensable, and makes further use of the indicator results related to the environmental education of residents for identifying and promoting participation with ROS, and turning them into implements for supporting urban SD decision-making. Furthermore, a successful indicator system depends on data availability and quality. This study recommends that urban planers should pay considerable attention to constructing relevant data collection channels, databases and the data quality.     

Emissions from soil fumigation in two raised bed production systems tarped with low permeability films

Raised beds are used to produce some high-value annual fruit and vegetable crops such as strawberry in California (CA) and tomato in Florida (FL), USA. Pre-plant soil fumigation is an important tool to control soil-borne pests in the raised beds. However, fumigant emissions have detrimental environmental consequences. Field trials were conducted to evaluate emissions of 1,3-dichloropropene (1,3-D) and chloropicrin (CP) in two different production systems with raised beds covered by different tarps. In the CA trial, InLine (60.8% 1,3-D and 33.3% CP) was drip-applied at 340 kg ha⁻¹ to 5 cm deep in the beds (30 cm high and 107 cm wide) tarped with polyethylene (PE) or virtually impermeable film (VIF). In the FL trial, carbonated Telone C35 (63.4% 1,3-D and 34.7% CP) was shank-applied at 151 kg ha⁻¹ to 20 cm deep in the beds (22 cm high and 76 cm wide) tarped with totally impermeable film (TIF). Emissions from tarped beds relative to furrows were contrary between the two trials. For the CA trial, the emission was 47% of applied 1,3-D and 27% of applied CP from PE tarped beds and 31% of applied 1,3-D and 15% of applied CP from VIF tarped beds, while that from uncovered furrows was <0.4% for both chemicals in both fields. In the FL trial, only 0.1% 1,3-D was emitted from the TIF tarped beds, but 27% was measured from the uncovered furrows. Factors contributing to the differences in emissions were chiefly raised-bed configuration, tarp permeability, fumigant application method, soil properties, soil water content, and fumigant carbonation. The results indicate that strategies for emission reduction must consider the differences in agronomic production systems. Modifying raised bed configuration and fumigant application technique in coarse textured soils with TIF tarping can maximize fumigation efficiency and emission reduction.     

机动车尾气中氮氧化物的分析检测技术

为了分析机动车尾气氮氧化物净化催化剂的催化性能 ,建立了一套尾气模拟评价体系 ,分别使用电化学法、化学发光法和比色法 3种氮氧化物分析手段进行检测。结果表明 ,3种方法都能在一定精度范围内测量机动车尾气中的氮氧化物 ,化学发光法测量精度高 ,响应时间短 ,能够及时地反映发动机运转过程中的氮氧化物浓度变化情况 ,是一种较好的分析手段。电化学法随着使用时间推移 ,响应时间变长 ,灵敏度降低 ,需要及时更换传感器。比色法通过化学吸收可以测定氮氧化物的浓度 ,不能实现连续在线分析 ,只能采样测量。在分析中 ,还尝试利用一些辅助设备 ,将尾气中的NO和NO2转化后再通入测量仪器 ,实现测量总氮氧化物或其中某一气体的功能