Sample preparation followed by high performance liquid chromatographic (HPLC) analysis for monitoring muconic acid as a biomarker of occupational exposure to benzene.

Factors affecting solid phase extraction (SPE) of trans,trans-muconic acid (ttMA), as a benzene biomarker, including sample pH, sample concentration, sample volume, sample flow rate, washing solvent, elution solvent, and type of sorbent were evaluated. Extracted samples were determined by HPLC-UV (high performance liquid chromatography-ultraviolet). The analytical column was C18, UV wave length was 259 nm, and the mobile phase was H(2)O/methanol/acetic acid run at flow rate of 1 ml/min. A strong anion exchange silica cartridge was found successful in simplifying SPE. There was a significant difference between recoveries of ttMA when different factors were used (p < .001). An optimum recovery was obtained when sample pH was adjusted at 7. There was no significant difference when different sample concentrations were used (p > .05). The optimized method was then validated with 3 different pools of samples showing good reproducibility over 6 consecutive days and 6 within-day experiments.     

Solid phase extraction for evaluation of occupational exposure to Pb (II) using XAD-4 sorbent prior to atomic absorption spectroscopy.

Lead is an important constituent widely used in different industrial processes. For evaluation of workers' exposure to trace toxic metal of Pb (II), solid-phase extraction (SPE) was optimized. SPE using mini columns filled with XAD-4 resin was developed with regard to sample pH, ligand concentration, loading flow rate, elution solvent, sample volume, elution volume, the amount of resins, and sample matrix interferences. Lead ions were retained on a solid sorbent and then eluted, followed by a simple determination of analytes with flame atomic absorption spectrometery. The obtained recoveries of metal ions were greater than 92%. This method was validated with 3 different pools of spiked urine samples; it showed a good reproducibility over 6 consecutive days as well as 6 within-day experiments. This optimized method can be considered successful in simplifying sample preparation for a trace residue analysis of lead in different matrices when evaluating occupational and environmental exposures is required.     

Optimization of Headspace Solid Phase Microextraction Procedure for Trace Analysis of Toluene

This study describes optimization of headspace solid phase microextraction followed by gas chromatography equipped with a flame ionization detector for toluene at trace level in spiked urine. The parameters affecting the extraction and gas chromatographic determination of analytes were studied: extraction time and temperature; desorption time and temperature; addition of NaCl; and pH, volume and agitation of the sample. Optimized headspace extraction was carried out at 30 °C for 6 min in the presence of 0.2 g-m^-1of NaCl in the sample solution. Also, sample volume and sample pH were optimized at 5 ml and 7 (neutral pH), respectively. Desorption of the analytes was carried out at 250 °C for 60 s. The optimized procedure was validated with 3 different pools of spiked urine; it showed good reproducibility over 6 consecutive days and 6 within-day experiments. The study also determined the accuracy, linearity and detection limits of this method.     

Recovery of methyl orange and Congo red from aqueous solutions using tri-octyl amine (TOA) in benzene as carrier

The recovery of anionic azo dyes namely Congo red (CR), methyl orange (MO) from acidic aqueous solutions using tri-octyl amine (TOA) as an extractant has been investigated. The percentage of extraction of MO and CR increases with an increasing TOA concentration. The anionic dyes were extracted from aqueous solution at pH 2.0 ± 0.1. The extracted dye has been back extracted into aqueous solutions using sodium hydroxide, sodium carbonate and sodium bicarbonate. The organic phase obtained after the stripping of dyes was washed with dilute sodium hydroxide solution to neutralize any sulphuric acid trapped or adhered to the solvent and then with distilled water. This solvent was reused in succeeding extraction of dyes. The influencing parameters were; the effect of diluents, effect of extractant concentration, effect of pH, effect of interference study, effect of equilibrium time, various stripping reagents and stripping phase ratio. The characterization studies such as UV and IR spectra of extracted and stripped MO and CR was also studied.     

畜牧业污水中大环内酯和拟除虫菊酯类驱虫剂物质的LCMSMS检测

采用无需衍生化的同相萃取为前处理手段,高效液相色谱-串联四极杆质谱联用技术(LCMSMS)为检测手段,在电喷雾电离正离子模式下,对澳大利亚畜牧业污水中常见的大环内酯和拟除虫菊酯两类共7种驱虫剂物质的残留,建立了一次进样下的有效快速分析方法.经一系列优化试验,确定了以50%丙酮+50%乙腈为洗提剂、每次4 mL共8 mL的洗提方法.结果表明,该固相萃取技术(SPE)的加标回收试验结果较好,各化合物的平均回收率为95.50%～108.00%,相对标准差范围为0.73%-8.82%.以含10mmoL/L醋酸铵、0.1%甲酸的超纯水和甲醇混合溶液为流动相,以准分子离子峰[M+NH_4]~+、[M+H]~+作为母离子的定量离子对,所建立的1～500 ng/mL范围内的8点校正曲线中.各物质的相关系数均高于0.998 0,定量限范围为0.03-2.47 ng/mL.实际样品测定时.不同处理流程中各化合物的残留浓度有较好地体现.     

Tl(Ⅰ)与Tl(Ⅲ)在UV - H2O2体系中的价态转化

建立了chelex-100螯合树脂分离技术与石墨炉原子吸收联用测定水体中Tl(Ⅰ)与Tl(Ⅲ)的方法,分别考察了光化学氧化中pH值、H2O2投加量、光照强度对Tl(Ⅰ)的氧化效果。方法的Tl(Ⅰ)与Tl(Ⅲ)检出量均为0.5μg/L。两者共存时各自加标回收率大于95%。结果表明,在偏酸性环境(pH=3.0),投加适量30%H2O2,光照强度大有利于Tl(Ⅰ)的氧化。当pH=2.91,投加30%H2O2为5 mL,UV照射10min后,Tl(Ⅰ)的转化率达90%。研究表明,光化学氧化可有效转化水体中不易被物理化学法去除的Tl(Ⅰ)和容易被物理吸附、化学沉淀方法去除的Tl(Ⅲ)。     

大落差原油管道投产充水过程研究

为了探究大落差管道充水投产过程中存在的不满流及低点超压问题,以中缅原油管道怒江跨越段为例（其最大高差达1 480 m）,基于OLGA多相流瞬态模拟方法,对大落差原油管道充水过程进行仿真研究,重点分析到达管道不同低点位置的最大速度、压力及相应持液率,得到不同输量条件下不同低点位置的水流速度、压力及持液率随时间变化规律。结果表明:当输量为900~2 000 m3/h时该管道中存在的段塞流概率降低57%,同时减少了管压波动以及对管道和设备的破坏,提高了管道输送效率。     

太湖水体中藻蓝蛋白提取的影响因素分析

以室内培养的铜绿微囊藻样品为参照,基于反复冻融法,探讨了滤膜类型、磷酸盐缓冲液加入体积、冻融次数对太湖水体中藻蓝蛋白提取的影响。结果表明:1)GF/C玻璃纤维滤膜(孔径1.2μm)和CN-CA混合纤维素酯微孔滤膜(孔径0.45μm)提取的叶绿素a结果差异不显著(p分别为0.95和0.97),说明二者的生物截留量基本一致;2)在生物截留量相当的情况下,GF/C滤膜和CN-CA滤膜提取的藻蓝蛋白结果差异显著(p均为0.04),GF/C滤膜的提取效率高于CN-CA滤膜;3)加入的缓冲液体积和藻蓝蛋白质量浓度呈良好的负线性关系(r均大于0.85),受藻体包裹效应的影响,太湖水体对比组中的相关系数略低于人工培养的铜绿微囊藻;4)太湖水样和铜绿微囊藻在冻融次数上存在差异,太湖水样冻融9~11次的提取效果较佳,室内培养的铜绿微囊藻冻融次数以5~7次为宜。     

Destruction of methylene blue by mediated electrolysis using two-phase system

The destruction and colour removal of methylene blue were carried out by mediated electrochemical oxidation using cerium(IV) mediator in nitric acid medium using two-phase system and was applied for oxidation of organic compound. Organic compounds and mediator were taken in the organic and aqueous phases respectively. The influence of organic solvent type, cerium(III) concentration, dye concentration, stirring speed and temperature were investigated in order to find the optimum conditions of the system to check the removal of COD and colour in the organic phase. The decolourisation followed the pseudo-first order reaction for electrochemically oxidized cerium(IV). The maximum colour removal efficiency of 95% was achieved within 45 min in dichloromethane solvent system. The COD removal efficiency and colour removal rate were increased with increase in temperature and stirring speed.     

不同pH值下含铁矿物对硫酸侵蚀混凝土的影响研究

硫酸侵蚀为混凝土耐久性损伤的一个重要方面。在硫酸盐侵蚀过程中,含铁矿物等侵蚀产物不断形成,导致混凝土材料形成不同程度的腐蚀。为研究不同pH值环境下含铁矿物对混凝土结构腐蚀的影响,在实验室配置了pH值为2.0、3.0和4.0的稀硫酸溶液,结合不同洗刷作用方式来模拟酸雨环境,采用室内长期浸泡试验方法对混凝土试件进行不同程度腐蚀。用X射线能谱分析(EDS)现代测试技术分析得到腐蚀剩余物质Fe元素。结果表明:浸泡液的pH值对混凝土的腐蚀速度有一定的影响,当浸泡液的pH值小于3以后,硫酸对混凝土的腐蚀速度要考虑含铁矿物的影响;当大量的氢氧化铁参与反应时会消耗更多的H2SO4,腐蚀速度会有小幅度提升,在定期更换浸泡液并清洗试件表面的洗刷作用下更加明显,耗酸速度提升到了10倍。     

三氯杀螨醇生产过程中的DDT环境排放研究

三氯杀螨醇生产工艺流程主要包括缩合、碱解、氯化和水解等步骤。对工作场所中空气样品、生产过程排放的废酸及废水样品进行采集和分析。工作场所空气中DDT总质量浓度均值为6.69×10-3mg/m3。其中,碱解反应工序中质量浓度水平较低,为1.10×10-3mg/m3;包装车间质量浓度水平较高,为16.72×10-3mg/m3。所有空气样品中p,p’-DDE均是主要贡献物质,占DDT杂质总量的80.2%;p,p’-DDT的质量浓度范围为0.053×10-3~1.66×10-3mg/m3,平均为0.49×10-3mg/m3,低于国家标准限值。缩合废酸与水解废酸中DDT杂质总质量比分别为4.84μg/kg和334.83μg/kg;碱解废水与水解废水中的DDT杂质总质量比分别为456.48μg/kg和75.65μg/kg。废水及废酸样品中各种DDT杂质的质量比水平存在差异;生产工艺阶段不同,杂质组成也各具特点。水解废酸的p,p’-DDT的质量比最高,为146.82μg/kg;缩合废酸与水解废水处质量比水平较低,分别为0.33μg/kg和1.41μg/kg。该企业随废水及废酸排放的DDT杂质总量为1234.08 g/a,其中随碱解废水的排放量高达912.95 g/a。p,p’-DDT的年排放总量为163.37 g/a,随碱解废水和水解废酸的排放量分别为86.98 g/a和73.41 g/a。     

浸渍液pH值对V-Mo/Ti脱硝催化剂性能的影响研究

为提升V-Mo/Ti催化剂的脱硝性能,在催化剂制备过程中调节浸渍工艺参数,制备了一系列不同浸渍液pH值的催化剂,采用XRD、N2-吸附脱附、拉曼光谱、UV-Vis、H2-TPR、NH3-TPD等手段对催化剂进行表征,考察了pH值的变化对催化剂物理化学性能的影响,采用固定床微型反应器对催化剂的脱硝性能进行评价。结果表明,降低浸渍液pH值,可以抑制催化剂上VOx物种的聚合,提升催化剂的还原性能,有利于提升催化剂的脱硝效率,降低脱硝反应过程中N2O生成量。同时,浸渍液pH值的变化,也会影响催化剂的酸性性能。当浸渍液pH值低于3.64时,催化剂酸性性能显著降低,造成催化剂脱硝性能降低;当浸渍液pH值控制在3.64时,催化剂的还原性能和酸性性能匹配较好,从而显示了较高的脱硝性能。     

聊城耕地土壤有机氯农药在地域间的残留差异

为确定聊城市耕地土壤中有机氯农药(OCPs)的残留状况与分布特征,采用网格布点法采集了136个耕地土壤样品,利用ASE萃取技术,采用气相色谱-电子捕获检测器(GC-ECD)测定了样品中α-BHC、βBHC、γ-BHC、δ-BHC、p,p′-DDE、p,p′-DDT、p,p′-DDD和o,p′-DDT等8种OCPs的残留状况。采用单因子方差分析和多重比较判断了聊城市8个县市之间OCPs的污染差异。结果表明,该地区各OCPs均有不同的检出率和残留量,其中以β-BHC和p,p’-DDE为首要污染物。东昌府区的β-BHC和临清市的γ-BHC及DDTs残留量明显高于其他各县市,其他各县市之间差异不显著。     

南京市城市污泥和工业污泥中典型矿质元素含量和形态分布研究

采用三态连续提取法研究南京市部分城市污泥和工业污泥中典型矿质元素的含量和形态分布,为污泥资源化的合理利用提供科学参考.结果表明,污泥总体呈高有机质、高氮磷、低K的相似性,但其理化性质如阳离子交换容量(CEC)、pH等有差异.污泥中不同矿质元素含量差异也较大,Fe的浓度最高,其次是Mg、Zn;且不同污泥间同一矿质元素含量的差异也较大.各元素的形态分布有一定差异,Cu主要分布在可氧化态,其酸溶/交换态和可还原态的百分率很低;Zn三态分布均较高;Mg、Mn主要分布在酸溶/交换态;Fe主要分布在残渣态.但三种提取形态百分率之和除Fe外均超过50%.研究同时表明,城市污泥和工业污泥中矿质元素形态分布无显著性差异.     

固体高分子膜电解法(SPE)处理苯并红紫4B废水的研究

采用固体高分子膜作隔膜,以Pt网上附着的β-PbO2作催化剂,建立了一个高效的催化电解装置(SPE).用此装置处理难降解的苯并红紫4B模拟染料废水,苯并红紫4B的质量浓度为0.1 g/L.结果表明,此法对苯并红紫4B废水的色度和TOC具有良好的去除效果,催化电解过程中产生的原子氢对染料分子中发色键的破坏起决定性作用,当电流密度为0.24 A/era2、电压为3.9 V时,对染料苯并红紫废水,处理120min后,废水的色度明显下降,由处理前的红色变为几乎无色,TOC的去除率为42%,SO42-的生成率为78%.催化电解是染料废水绿色降解的重要途径之一.     

硬、软煤样三轴压缩瓦斯流动特征

利用三轴渗流装置对来自不同矿区的硬、软原煤样进行常规三轴压缩渗流试验,对应力、形变、瓦斯流速连续采集,得出流速与主应力差、轴向应变关系曲线,从而得出硬、软煤样不同应力阶段的瓦斯流动特征,并且对瓦斯流动速度与主应力差之间的关系加以分析。结果表明:1)三轴压缩全过程中应力应变曲线变化趋势基本一致,可以被分为加载、破坏和残余阶段,加载阶段内软煤样环向应变高于硬煤样、吸收外界的能量相对较低,破坏阶段硬煤样应力迅速跌落;2)硬、软煤样在加载阶段内瓦斯流速与主应力差关系曲线都呈凹形二次曲线,残余阶段都呈线性增加;3)通过三轴压缩,硬煤与软煤的瓦斯流动规律表现出明显的差异,硬煤样表现为瓦斯流速显著增加,软煤样流速增幅不明显、甚至低于初始流速。     

高锰酸钾去除水中甲硫醚的效能及动力学研究

通过烧杯试验研究水处理常用氧化剂KMnO_4氧化水中甲硫醚的效能,探讨了KMnO_4投加量、甲硫醚初始质量浓度、p H值及腐殖酸质量浓度对氧化反应的影响,并对反应动力学及氧化产物进行了分析。结果表明:不同剂量的KMnO_4氧化甲硫醚反应在t=10 min内已基本完成,去除率达99%;随KMnO_4投加量增加,去除率和反应速率增加;KMnO_4过量条件下甲硫醚初始质量浓度对反应速率和去除率无影响;p H值对反应速率常数影响较显著,当p H=6.85时,反应速率常数达到最大;0~30 mg/L的腐殖酸对甲硫醚去除率基本无影响,但对反应速率有一定的抑制作用。腐殖酸质量浓度在0~15 mg/L变化时,反应速率常数基本不变;腐殖酸质量浓度从15 mg/L增大到20mg/L时,反应速率常数迅速变小,反应进程变慢;而当腐殖酸质量浓度大于等于20 mg/L时,反应速率常数又基本不变。KMnO_4氧化甲硫醚的反应符合二级反应动力学模型,二级反应的动力学常数k=0.647 L/(min·mg)。通过GC/MS对反应产物分析发现,KMnO_4可将甲硫醚氧化为二甲基亚砜。因此,KMnO_4是一种高效、快速的去除水中甲硫醚的氧化剂。     

Will Musculoskeletal,Visual and Psychosocial Stress Change for Visual Display Unit (VDU) Operators When Moving From a Single-Occupancy Office to an Office Landscape?

This study investigated the effect of moving from single-occupancy offices to a landscape environment. Thirty-two visual display unit (VDU) operators reported no significant change in visual discomfort. Lighting conditions and glare reported subjectively showed no significant correlation with visual discomfort. Experience of pain was found to reduce subjectively rated work capacity during VDU tasks. The correlation between visual discomfort and reduced work capacity for single-occupancy offices was r_s = .88 (p = .000) and for office landscape r_s = .82 (p = .000). Eye blink rate during habitual VDU work was recorded for 12 operators randomly selected from the 32 participants in the office landscape. A marked drop in eye blink rate during VDU work was found compared to eye blink rate during easy conversation. There were no significant changes in pain intensity in the neck, shoulder, forearm, wrist/hand, back or headache (.24 < p < .67). Pain levels in different body areas were significantly correlated with reduced work capacity, .77 < r_s < .99 (p = .000).     

理化因素对锰细菌Arthrobacter chlorophenolicus MN1409氧化Mn2+的影响

Arthrobacter chlorophenolicus MN1409是1株分离自锰矿样品的高效锰氧化细菌。为了建立该菌株氧化Mn2+的适宜条件,研究了接种量、装液量、摇床转速、温度、pH值、Fe2+初始质量浓度和Mn2+初始质量浓度等理化因素对其锰氧化效率的影响。结果表明,接种量、装液量、转速和Mn2+初始质量浓度在一定范围内变化对锰氧化率影响不大;而温度、pH值和Fe2+初始质量浓度变化对锰氧化率有较大影响。当接种量为4%,装液量为60 mL,温度为25℃,摇床转速为100r/min,pH值为7,且有一定的Fe2+存在时,Arthrobacter chlorophenolicusMN1409对锰的氧化效率最高。     

低温硫铁化合物氧化诱导期试验研究

以设备腐蚀样品和均相沉淀样品为研究对象,运用差示扫描量热法测定硫铁化合物的氧化诱导期,并考察了粒径、升温速率和空气流量对硫铁化合物氧化诱导期的影响。结果表明,两种样品在125~200℃范围内均处于活跃的自热阶段,热稳定性较差,样品粒径在44~74μm范围内,升温速率越小,空气流量越大,样品自燃倾向性越高。