Quantification of aqueous cyanogen chloride and cyanogen bromide in environmental samples by MIMS

Membrane introduction mass spectrometry (MIMS) was developed and verified for the direct quantification of cyanogen chloride (CNCl) and cyanogen bromide (CNBr) in environmental samples without any sample workup. Factors including the membrane temperature and the liquid flow rates were examined for system optimization. The MIMS method provided linear responses for three orders of magnitude of concentrations. The instrument detection limits of CNCl and CNBr were 1.2 and 3.8 microg/L, respectively, and the method detection limits of CNCl and CNBr were both 1.7 microg/L. Effects of pH and the water matrix including synthetic water, saline water, natural surface water, and wastewater, on the responses were also examined. A pH ranging from 3 to 10 did not affect the quantification. The average recoveries of CNCl and CNBr in the water matrixes tested were 98.5% and 92.7%, respectively. The use of the MIMS method in on-line monitoring of the formation of cyanogen halide was demonstrated in chlorination of aqueous solutions containing glycine and bromide ions. The results indicated the important role of bromide ions in cyanogen halide speciation.     

On the determination of the chemical reduction factor for PET geogrids

Data from four samples of commercially available PET geogrids (made either of yarns or bars), which were measured by BAM or other institute, are analyzed to discuss the procedure and problems of determining the chemical reduction factor RF_CH associated with a certain service life. Estimates from Arrhenius extrapolation usually have very large statistical errors. The level of confidence must therefore be specified. A reliable estimate requires data from immersion tests below the glass transition temperature of PET. To extrapolate the time of reductions for each reduction factor at such low temperatures, one has to know the functional form of the mechanical degradation curve. It is shown how the degradation curve of the tensile strength may be obtained by determining the relation between increase in concentration of carboxyl end group (CEG) and decrease in tensile strength. Therefore, experimental studies to determine the chemical reduction factor should be accompanied by the measurements of the CEG concentration and the intrinsic viscosity. Furthermore, such measurements allow a non-ambiguous determination of the molecular mass. Hydrolytic molecular degradation will proceed continuously even at 20 °C with half-life of the inverse of the CEG concentration of 40–100 y. Nevertheless, small chemical reduction factors at a lifetime of 100 y are obtained with high level of confidence for materials with low initial CEG concentration and high molecular mass. This is shown by pooling data from samples with comparable CEG concentration, molecular mass and above all comparable intrinsic relation between increase in CEG concentration and decrease in strength. Therefore, the recommendation of ISO TR 20432, Table 2, for chemical reduction factors seems to be applicable to PET geogrids with index properties well below the one specified by the technical report. Whether these index properties are actually a sufficient condition to have small chemical reduction factors even at a very long service life is still an open question. The determination of chemical reduction factor should be based on aging experiments, at least for products with index properties close to the limiting values for the following reasons. (1) Even so standards are available, results of different laboratories on absolute values of CEG concentration and number averaged molecular mass differ to a certain extent. (2) Other factors, like crystallization, affect the mechanical degradation significantly. (3) There is no universally applicable form of the mechanical degradation curve.     

Kinetics of the chemical oxidation of polysulfide anions in aqueous solution

The kinetic properties of the chemical oxidation of aqueous polysulfide solutions have been studied in phosphate-buffered systems at pH 7-12, at temperatures between 20 and 40 degrees C, and ionic strength between 0.05 and 0.50 M. Polysulfide solutions were mixed with a buffer solution of known dissolved oxygen concentration, after which the decrease in the oxygen concentration of the solution was measured in time. The rate of oxygen consumption can be described by the empirical relation d[O2]/dt= -k[Sx(2-)][O2](0.59) . The reaction rate constant k is moderately dependent on pH and goes through a maximum at pH 10. The rate of oxygen consumption for polysulfide solutions is approximately four times higher than for sulfide solutions. At pH values below 9, reaction products were formed according to Sx(2-)+3/2O2-->S2O3(2-)+(x-2)S(0) . At pH values higher than 9, more thiosulfate and additional sulfide were formed, which is attributed to the low chemical stability of the sulfur of oxidation state zero, formed upon polysulfide oxidation. Our results strongly suggest that hydrolysis of this 'nascent' elemental sulfur to HS- and S2O3(2-) is faster than hydrolysis of crystalline inorganic sulfur or colloidal particles of biologically produced sulfur, and has a significant contribution already at 30 degrees C and pH 10.     

混凝土抗氯离子渗透性试验方法综述

混凝土抗氯离子渗透性是混凝土重要的耐久性劣化指标之一,客观准确而实用的试验方法显得尤为重要.对国内外混凝土抗氯离子渗透性的试验方法以及相关标准或规范进行了充分的调研,比较了各种主流试验方法或测试技术的原理和适用范围,并分析了各自的优缺点,突出阐述了试验室和现场均适用的测试方法,为GBJ 82-85<普通混凝土长期性能和耐久性试验方法标准的修订提供参考.     

冻融损伤对混凝土氯离子扩散性能的影响

通过自由氯离子滴定试验和氯离子扩散深度试验研究了冻融损伤对混凝土氯离子扩散性能的影响。结果表明，冻融损伤对混凝土氯离子扩散性能的影响是显著的。当混凝土的损伤为24％时，其氯离子扩散系数和扩散深度分别是未损伤混凝土的6．5倍和2倍，混凝土结构的使用寿命将会缩短75％～85％。回归分析结果表明。混凝土的损伤与氯离子扩散系数、扩散深度之间均可以建立良好的非线性关系。     

对混凝土氯离子渗透性试验评价方法的商榷

概述了目前混凝土氯离子渗透性测试方法当中混凝土氯离子浓度表示和评价方法的不足.指出混凝土毛细孔结构对氯离子渗透和钢筋局部腐蚀(坑蚀)的影响.并对混凝土氯离子渗透性试验的氯离子浓度表示和评价方法提出建议.     

混凝土裂缝表征方法研究进展及裂缝对氯离子传输影响

氯离子侵蚀导致混凝土中钢筋锈蚀,是钢筋混凝土耐久性劣化的主要表现形式,然而混凝土裂缝的存在将加快氯离子在混凝土中的传输并缩短钢筋混凝土的服役寿命。首先对已有的裂缝表征方法进行了介绍,包括线性位移传感器、图像分析法、CT扫描等。然后综述了带有裂缝的混凝土基体中氯离子扩散的影响因素,重点介绍了裂缝的宽度、水灰比、矿物掺合料、龄期、荷载等因素对氯离子扩散行为的影响。结果表明当裂缝宽度在50~200μm之间时,对氯离子扩散系数的影响最大,在此区间内,氯离子扩散系数随着裂缝宽度的增加而增大;其余因素也对氯离子扩散系数有不同程度的影响。     

利用二氯化铁的氧化反应改色花岗石的研究

利用二氯化铁高温氧化反应,对普通灰白色花岗石进行了改色研究。考察了花岗石改色的主要影响因素,确定了较理想的工艺条件,并对改色后的花岗后时行了性能测试。测试结果表明,本方法改色的花岗石耐酸、耐碱、耐有机溶剂、耐沸水、耐紫外光。     

改善氯离子对脱硫石膏制品性能影响的方法研究

研究了有机硅防水剂、矿物掺合料以及水灰比等对氯离子在脱硫石膏制品(以纸面石膏板为例)中的迁移情况以及对制品性能的影响.结果表明,掺加适量的防水剂不仅可以有效提高纸面石膏板的纸板粘接能力,还能改善其耐水性能;掺加适量的矿物掺合料可以在不影响石膏制品性能的前提下提高对氯离子的固化能力;水灰比对石膏板中氯离子的迁移及纸板粘接性能有重要影响,在不影响其工作性的前提下,水灰比越低,对氯离子的固化效果越好.     

Removal of perfluorooctanoate from surface water by polyaluminium chloride coagulation

Perfluorooctanoate (PFOA) has been detected in surface water all over the world, and little is known of its removal by coagulation in water treatment plants. In this study, polyaluminium chloride (PACl) was used to remove PFOA from surface water, and the effects of coagulant dose, solution pH, temperature, and initial turbidity on the removal of both PFOA and suspended solids (SS) from water were investigated. Since the SS had high sorption affinity for PFOA, most PFOA was adsorbed on the particles and removed via the SS removal in the coagulation process. PFOA concentrations in aqueous phase decreased with increasing initial turbidity and PACl dose, while they increased with increasing solution pH and temperature. Other perfluorinated compounds (PFCs) with different C-F chain lengths and functional groups were also compared with PFOA. It was proved that hydrophobic interaction played an important role in the adsorption of PFOA on the SS. The addition of powdered activated carbon (PAC) before the coagulation process significantly enhanced the removal efficiency of PFOA in water, and the residual PFOA concentrations in water were less than 1 μg/L after the addition of 1-16 mg/L PAC and subsequent coagulation when the initial PFOA concentrations were in the range of 0.5-3 mg/L.     

Extraction of chemical impurities for forensic investigations: A case study for indoor releases of a sarin surrogate

A solvent extraction approach was developed and examined for extraction of targeted organophosphorus compounds as well as nerve agent simulants from painted wallboard (PWB). Painted wallboard was chosen as a substrate due to its presence as large surface area media in an indoor environment that is applicable to a chemical agent release scenario. Three different solvent systems were examined with a 1:1 methylene chloride: acetone mixture having the most robust and consistent extraction for four target organophosphorus compounds [dimethyl methyl phosphonate (DMMP), diethyl methyl phosphonate (DEMP), diethyl methyl phosphonothioate (DEMPT), and diisopropyl methyl phosphonate (DIMP)]. An average extraction efficiency of approximately 60% was obtained for these four compounds. The extraction approach was further demonstrated by extracting and detecting the chemical impurities present in neat DMMP that was vapor deposited onto painted wallboard tickets as a simulant to an agent release. Five chemical impurities that were present in DMMP – dimethyl phosphate, trimethyl ester phosphoric acid, ethyl methyl methylphosphonate, O,O,S-trimethyl ester phosphorothioic acid, and biphenyl were detected on the PWB and were utilized to determine the source/supplier of the DMMP.     

Investigation of the noise reduction provided by tree belts

This study investigates the noise reduction effect of 35 evergreen-tree belts. A point source of noise was positioned in front of the tree belts and the noise level at various points in the belts was measured with a noise meter. Factors important for noise reduction include visibility, width, height and length of the tree belts. Stepwise regression was employed to examine the factors associated with noise reduction. A negative logarithmic relationship between the visibility and relative attenuation was found. A positive logarithmic relationship between relative attenuation and the width, length or height of the tee belts was also found. A map showing the relationship between visibility together with width was plotted. The map provides some practical suggestions concerning design of tree belts for noise reduction.     

氯化镁对水泥土早期强度的影响研究

通过水泥加固不同含量的氯化镁污染土室内28 d抗压强度、X射线衍射（XRD）和微观扫描电镜试验（SEM）,研究了氯化镁对水泥土的早期强度影响机理。XRD分析结果表明：氯化镁参与反应生成的M-S-H、M-A-H、氯化钙结晶、轻质氯化镁结晶和水化氯铝酸钙等产物对水泥土产生分解与结晶的复合作用;SEM图象分析表明：氯化镁使水泥土的孔径分布发生改变,当氯化镁含量较低时,水泥土中的水泥水化产物与结晶物将颗粒连结在一起,形成较强的结构联结,使其孔隙率变小,对水泥土的强度增长有利;随着氯化镁含量增大,土颗粒周围的凝胶物被分解,使水泥土的孔隙率增大与胶结程度下降,对水泥土的强度不利。     

边界元法研究混凝土中氯离子的扩散及分布规律

有限元法是分析氯离子在混凝土中扩散常用的方法,但它需要在时间域上做细密的离散网格,增加了计算时间及模型的复杂性.首次采用边界元法建立二维混凝土结构中氯离子一维扩散分析模型,提出了计算长度的概念及其表达式,使得计算模型中避免了对时间域的离散.同时由于边界元法可以将二维问题降低为一维离散问题,所以该计算模型可以大大简化计算过程,提高计算精度.算例分析验证了该方法的计算效率和可行性.     

Influence of chloride corrosion on the effective mechanical properties of steel reinforcement

This paper presents a methodology to develop advanced reduction factors for the effective mechanical properties of corroded steel reinforcement of reinforced concrete (RC) members. The reduction factors (mainly developed for bare steel reinforcement) reported in the literature scatter over a large range. In this regard, critical questions arise, such as the reliability and accuracy of the reduction factors of bare steel bars to evaluate residual capacity of corroded RC structure. This paper will provide answers to these questions based on reviewing past studies and the results observed from experimental inspection of corroded steel reinforcement carried out in this research. The results show using the reduction factors of bare steel bars to estimate residual capacity of corroded RC structures is not safe because they are significantly lower than the reduction that happens in real corroded RC columns.     

《混凝土结构耐久性设计规程》中抗氯离子渗透性检测方法的试验研究

针对山东省《混凝土结构耐久性设计规程》中混凝土抗氯离子渗透性检测方法进行了试验研究.试验结果表明,《规程》中的交流电法和RCM法可以便捷准确的评定混凝土中氯离子的渗透性,有广阔的应用前景.但不同的试块制备方法对氯离子渗透性电测法的试验结果影响很大,考虑到工程上混凝土的实际情况,建议《规程》中的混凝土抗氯离子渗透性试验评定方法应对试块的制备方法应提出更明确的要求.     

Consecutive chemical cleaning of fouled PVC membrane using NaOH and ethanol during ultrafiltration of river water

Chemical cleaning of fouled hollow-fiber polyvinyl chloride (PVC) membrane with the consecutive use of NaOH and ethanol during ultrafiltration of river water was investigated in the study. Results showed that through the chemical cleaning with 1% NaOH for 30 min, a negative cleaning efficiency of −14.6% was observed for the PVC membrane. This might be due to the increase of membrane hydrophobicity, which was reflected by the increase of contact angle from 69.7° to 87.6°. On the other hand, the cleaning efficiency of 85.1% was obtained by the consecutive cleaning with 30 min of 1% NaOH and 30 min of ethanol. Individual ethanol cleaning could remove 48.5% of the irreversible resistance, indicating that NaOH cleaning also made its contribution (36.6%) to the removal of membrane foulants. Scanning electronic microscopy (SEM) and atomic force microscopy (AFM) analyses demonstrated that both NaOH and ethanol were not only able to eliminate the foulants on membrane surface, but also able to remove the in-pore fouling of the PVC membrane. The synergetic effects for removing membrane foulants were observed between the NaOH and ethanol. Furthermore, ethanol could also restore the hydrophilicity of the membrane by decreasing the contact angle from 87.6° to 71.4°. Considering that ethanol is easy to be used and reclaimed, the consecutive chemical cleaning by alkali and ethanol is recommended for PVC membrane in filtration of surface water.     

化学沉淀法去除水中镉的特性研究

考察了氢氧化物沉淀法和硫化物沉淀法对镉的去除效果。结果表明,两种方法均能将0.025mg/L的镉降低到《生活饮用水卫生标准》限值(0.005mg/L)以内,除镉效果稳定。氢氧化物沉淀法中,三氯化铁作为混凝剂对镉的去除效果明显优于聚合氯化铝,能有效去除0.250mg/L的镉,且处理后铁残余浓度未超标;硫化钠沉淀法除镉效果好,但硫化钠投加量增加到0.20mg/L时,上清液硫化物会超标。     

利用微型动物捕食进行污泥减量的研究进展

介绍了目前用来作为污泥减量的微型动物种类,并阐述了在线减量工艺和离线减量工艺两种生物捕食减量工艺,总结了生物捕食污泥减量技术的污泥减量效果,最后提出了其今后的研究方向。     

强度折减有限元法研究开挖边坡的稳定性

用强度折减有限元方法对开挖边坡的稳定性进行了较为全面的研究。分析结果表明 :当折减系数达到某一数值时 ,边坡内一定幅值的广义剪应变自坡底向坡顶贯通 ,认为边坡破坏 ,定义此前的折减系数为安全系数 ;和强度指标相比 ,弹性模量、泊松比、剪胀角和侧压力系数对边坡的安全系数影响不大 ;开挖边坡和天然边坡具有相似的破坏形式 ,表明强度折减有限元方法适用于开挖边坡的稳定性分析。最后指出 ,强度折减有限元法具有广泛的适用性和良好的应用前景