Colloid facilitated transport of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) to the groundwater at Ma Da Area, Vietnam

PCDD/Fs are hydrophobic organic substances and strongly sorbing to soil particles. Once adsorbed to soil particles they are believed to be virtually immobile. However, research in the last decades confirmed that strong sorbing contaminants may reach the groundwater via colloid-facilitated transport. This pathway has not been investigated before in Vietnam. Ma Da area, 100 km north of Ho Chi Minh City, was repeatedly sprayed during the Vietnam War (1962–1971) with herbicides like Agent Orange containing, beside others, the teratogenic contaminant 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD). 11 surface soil samples and 12 water samples were collected in Ma Da area for analysis of PCDD/Fs in solids. Soil TCDD concentrations ranged from 1–41 ppt with a mean of 8.8 ppt and a mean I-TEQ of 9.7 ppt. Two surface water samples showed colloid bound TCDD (7 and 19 ppt). Groundwater samples showed elevated colloid bound PCDD concentrations (mean 770 ng/kg), mainly octachlorodibenzo-p-dioxin. Groundwater colloids separated by filtration did not show any TCDD. The results support that TCDD/Fs can be relocated from the top soil to the groundwater by colloidal pathway. They did not provide evidence that the dioxins bound to groundwater colloids are leftovers from the Second Indochinese War. However, this study reinforces that the colloidal transport pathway has to be included investigating the relocation of strong sorbing organic contaminants.     

Biofilms coating Schoenoplectus californicus as indicators of water quality in the Río de la Plata Estuary (Argentina)

N-ethyl-3-carbazolecarboxaldehyde-3-thio- semicarbazone (ECCT) as an new analytical reagent used for the development of a highly sensitive extractive spectrophotometric method for the determination of copper(II). The ECCT forms a greenish-yellow colored 1:1 (M:L) complex with copper(II) at pH 3.0, which is well extracted into n-butanol and shows maximum absorbance at 380nm. The color of the complex is stable for more than forty eight hours. The system obey Beer's law in the range 0.4–3.6 with 2.243 × 10⁴lmol⁻¹cm⁻¹, 2.83 × 10^-3μgcm⁻² molar absorptivity and Sandell's sensitivity respectively. The regression coefficient is 0.412 with 0.99 correlation coefficient. The precision and accuracy of the method was checked by finding the relative standard deviation (0.422%). This developed method has been successfully employed for the determination of copper(II) in environmental and pharmaceutical samples. The method is evaluated by analyzing samples from the bureau of analyzed samples (BCS 233, 266, 216/1, 207 and 179) and by inter comparison of experimental values using AAS.     

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.     

Chemical immobilisation of arsenic in contaminated soils using iron(II)sulphate—advantages and pitfalls

Chemical immobilisation of inorganic contaminants by increasing the sorption capacity of soils and/or promoting the formation of sparingly soluble precipitates may be a cost-effective approach to counteract groundwater pollution. This study focuses on the enhanced retention of arsenic in two contaminated soils by addition of solid iron(II)sulphate. Four lab-scale column experiments were performed under unsaturated conditions with subsoil material sampled at a former timber preservation site and a pigment production plant. Arsenic effluent concentrations indicated 89.9 to 99.8% immobilisation in the treated columns. Sequential extractions showed a shift in contaminant binding forms towards the iron(hydr)oxide and residual fractions. Possible immobilisation mechanisms are the precipitation of FeAs phases, the formation of inner sphere complexes, and/or the occlusion of arsenic in newly formed amorphous/crystalline iron oxides. Bromide breakthrough curves point to the fact that the addition of iron(II)sulphate only moderately affects soil hydraulic properties. In contrast to reduced emissions of arsenic, increased seepage water concentrations were observed for other trace elements (e.g., cobalt, nickel, zinc). Mass balances indicate that this effect is primarily related to the temporary pH-drop caused by the oxidation of ferrous iron. The results show that chemical immobilisation using iron(II)sulphate is a promising way to protect groundwater quality at sites contaminated with timber preservation and pigment production remnants. As a prerequisite, optimum amendment levels need to be established and practical/field tests should be accompanied by a monitoring for a broad range of relevant trace elements.     

Prenatal diagnosis of the Hunter syndrome and the introduction of a new fluorimetric enzyme assay

Prenatal diagnosis of the Hunter syndrome (mucopolysaccharidosis type II; MPS II) is preferably achieved by the assay of iduronate-2-sulphate sulphatase (IDS) in uncultured chorionic villi (CV) as this allows early (12th week), rapid (2–3 days) and reliable results. We summarize the results of 174 prenatal analyses in the past 30 years, using various methods such as radiolabelled sulphate incorporation in amniotic fluid (AF) cells, glycosaminoglycan (GAG)-electrophoresis in AF and IDS assay in CV, CV-cells, AF and AF-cells. Twenty-seven fetuses with MPS II were diagnosed after finding clearly abnormal results in pregnancies with a male fetus; very low IDS activity has also been measured in some pregnancies with a (heterozygous) female fetus, emphasizing the need to combine enzyme assay with fetal sex determination. IDS activity has until recently been assessed by a cumbersome radioactive enzyme assay. Here we describe the use of a novel fluorigenic 4-methylumbelliferyl substrate, which allows a sensitive, rapid and convenient assay of IDS activity and reliable early prenatal diagnosis. This novel IDS assay was validated in retrospective analyses of 14 CV, CV-cell, AF and AF-cell samples from affected pregnancies in addition to prospective prenatal diagnosis in eight pregnancies at risk with one MPS II-affected fetus. Copyright © 2002 John Wiley & Sons, Ltd.     

Synthesis of a novel ternary HA/Fe-Mn oxides-loaded biochar composite and its application in cadmium(II) and arsenic(V) adsorption

Cadmium (Cd) and arsenic (As) are two of the most toxic elements. However, the chemical behaviors of these two elements are different, making it challenging to utilize a single adsorbent with high adsorption capacity for both Cd(II) and As(V) removal. To solve this problem, we synthesized HA/Fe-Mn oxides-loaded biochar (HFMB), a novel ternary material, to perform this task, wherein scanning electron microscopy (SEM) combined with EDS (SEM-EDS) was used to characterize its morphological and physicochemical properties. The maximum adsorption capacity of HFMB was 67.11?mg/g for Cd(II) and 35.59?mg/g for As(V), which is much higher compared to pristine biochar (11.06?mg/g, 0?mg/g for Cd(II) and As(V), respectively). The adsorption characteristics were investigated by adsorption kinetics and the effects of the ionic strength and pH of solutions. X-ray photoelectron spectroscopy (XPS) and Fourier-transform infrared spectroscopy (FT-IR) revealed that chelation and deposition were the adsorption mechanisms that bound Cd(II) to HFMB, while ligand exchange was the adsorption mechanism that bound As(V).     

Fe3O4/CeO2复合材料催化降解橙黄G的效能及降解途径

为研究磁性纳米Fe₃O₄/CeO₂复合材料在高浓度难降解有机废水处理中的应用,利用共沉淀法制备Fe₃O₄/CeO₂复合材料,并将其作为非均相类Fenton催化剂降解橙黄G染料废水,利用单因素法优化出最佳降解工艺,同时利用TOF-MS/MS(飞行时间质谱)检测降解中间产物,推测出可能降解途径.结果表明,当Ce/Fe为1 :1(质量比)时制备的Fe₃O₄/CeO₂复合材料催化效果最佳.最佳降解工艺条件:初始pH为2.0,温度为30 ℃,H₂O₂投加量为30 mmol/L,Fe₃O₄/CeO₂复合材料的投加量为2.0 g/L,初始ρ(橙黄G)为50 mg/L.在最佳降解工艺条件下反应120 min后,橙黄G去除率为96.2%,TOC去除率为65.0%,Fe₃O₄/CeO₂复合材料至少可重复利用6次.研究显示,橙黄G降解主要有三条可能的降解途径,包括偶氮键断裂、偶氮键与苯环断开、脱磺酸基、羟基化以及开环等过程,共检测出八种可能的降解中间产物,主要有苯胺、苯酚、萘酚以及羧酸等.      

Zn-LDHs覆膜改性麦饭石对Cd(Ⅱ)吸附性能及其作用机理研究

采用水浴共沉淀法在碱性条件下制备两种Zn系层状双金属氢氧化物(Zn-LDHs),并对天然麦饭石进行覆膜改性得到Zn-LDHs覆膜改性麦饭石.运用能谱分析仪(EDS)配合场发射扫描电子显微镜(FE-SEM)检测改性前后麦饭石,及吸附试验后ZnFe-LDHs覆膜改性麦饭石的形貌和元素变化;采用X射线衍射仪(XRD)对天然麦饭石和ZnFe-LDHs覆膜改性麦饭石的结构进行表征;通过等温吸附试验、解吸附试验、吸附动力学试验、吸附热力学试验、不同pH值条件下的吸附试验和竞争离子吸附试验,探究Zn-LDHs覆膜改性麦饭石对Cd(Ⅱ)的吸附效果及其作用机理.结果表明,Zn-LDHs覆膜改性麦饭石对Cd(Ⅱ)的吸附性能显著提升,其中ZnFe-LDHs覆膜改性麦饭石饱和吸附容量(2500 mg·kg~(-1))较天然麦饭石(714.29 mg·kg~(-1))提高了3.5倍;吸附时间、pH值和温度条件均对吸附容量产生影响;Zn-LDHs覆膜改性麦饭石吸附过程更符合Langmuir等温模型、准二级动力学模型、Elovich模型,为均匀的单分子层化学吸附,而天然麦饭石吸附过程符合Freundlich等温模型和准一级动力学模型,吸附类型为非均匀多分子层物理吸附;Zn-LDHs覆膜改性麦饭石热力学参数ΔG~θ0,ΔH~θ0,ΔS~θ0,说明Zn-LDHs覆膜改性麦饭石对Cd(Ⅱ)的吸附是自发放热过程,天然麦饭石吸附则为自发的吸热过程.研究结果可为ZnFe-LDHs覆膜改性麦饭石有效应用于生态工程除Cd(Ⅱ)提供理论依据和技术参考.     

Screening of factors influencing Cu(II) extraction by soybean oil-based organic solvents using fractional factorial design

This study aimed to identify the significant factors that give large effects on the efficiency of Cu(II) extraction from aqueous solutions by soybean oil-based organic solvents using fractional factorial design. Six factors (mixing time (t), di-2-ethylhexylphosphoric acid concentration ([D2EHPA]), organic to aqueous phase ratio (O:A), sodium sulfate concentration ([Na(2)SO(4)]), equilibrium pH (pH(eq)) and tributylphosphate concentration ([TBP])) affecting the percentage extraction (%E) of Cu(II) were investigated. A 2(6-1) fractional factorial design was applied and the results were analyzed statistically. The results show that only [D2EHPA], pH(eq) and their second-order interaction ([D2EHPA] × pH(eq)) influenced the %E significantly. Regression models for %E were developed and the adequacy of the reduced model was examined. The results of this study indicate that fractional factorial design is a useful tool for screening a large number of variables and reducing the number of experiments.     

Influence of complexation on lead(II) and cadmium(II) percolation through a clay liner

Wastes are usually stocked in waste disposals without any pre-treatment. Runoff waters lead to the formation of leachates containing mineral and organic pollutants. In order to prevent groundwater contamination, a double barrier is placed on the landfill bottom. The first one is an active barrier made up of a draining system and a geomembrane, and the second one, consisting of a clay liner allowing pollutant retention, is considered as a passive system. The aim of this work is to evaluate the complexation impact on the organic and inorganic retention. Percolations on columns filled with clay are performed, which allow a better knowledge of the transfer of metallic pollutants, complexed or not, through a model porous media, considering charge and conditional stability of complexes.