含硫化合物的气相色谱检测响应特性研究

利用气相色谱（配炎焰光度检测器）对二硫化碳（ＣＳ２）、甲硫醇（ＣＨ３ＣＨ）、甲硫醚（ＤＭＳ）和二甲二硫醚（ＤＭＤＳ）４种含硫物质进行了分析检测，着重讨论了气相色谱仪的各项参数对几种含硫物质响应和分离效果的影响。结果表明：该分析对含硫气体的最小检测浓度达到ｐｐｂ级。在各项参数中，色谱柱温度在Ｎ２压力对各含硫物质响应和分离度影响最大，汽化室和检测器温度及空气压力对它们的影响相对较小。     

天然水体中有机物检测方法的选择与优化

本文选取并优化了一种准确、易行、适合于天然水样中微量有机物的分析技术.天然水样品中有机物通过混合大孔径吸附树脂XAD-2与XAD-7(4:1,V/V)富集并用二氯甲烷洗脱.所有富集的有机物样品中均加入衍生化试剂N,O-双(三甲基硅基)三氟乙酰胺(缩写为BSTFA)硅烷化,最后采用气相色谱-质谱联用仪分析.为了实验的简便,我们的样品为模拟水样(4L添加定量5β-胆烷(挪威Chiron公司)的去离子水).     

水中乙醛、丙烯醛和丙烯腈3种测定方法的对比

对比研究了大体积直接进样填充柱气相色谱法、顶空-气相色谱法和吹扫捕集-气相色谱法等3种测定水中乙醛、丙烯醛和丙烯腈的方法.结果表明,大体积直接进样法设备简单,但手动进样耗力费时,且灵敏度低,精密度差,直接水样分析易影响色谱柱和检测器的使用寿命;顶空法稳定性好,线性范围宽,相关性和精密度好,适合较高浓度水样的分析;吹扫捕集法操作简便,峰形好,检出限低,回收率高,适合低浓度水样的分析.顶空法和吹扫捕集法自动化程度高,均适用于大批量样品分析.     

城市居住区毒气扩散数值模拟

针对某居住区附近氯气储罐连续泄漏,通过求解三维不可压缩Navier-Stokes方程、K-ε湍流模型和物质浓度方程,模拟毒气在建筑物扰动条件下的扩散过程以及浓度时空分布特征,以毒气负载为基础给出近地面毒气危害区域,探讨毒气扩散对周边居民的影响。     

高效液相色谱-电感耦合等离子体质谱联用测定生物样品中的有机汞

建立了酸提取-高效液相色谱-电感耦合等离子体质谱联用技术(HPLC-ICP-MS)测定生物样品中甲基汞、乙基汞、苯基汞等3种有机汞的分析方法。鱼肉和贝类样品经盐酸消解,苯萃取,硫代硫酸钠溶液反萃取后,采用醋酸铵/L-半胱氨酸缓冲盐及甲醇体系组成的流动相按一定比例进行梯度洗脱,经前处理的生物样品在液相色谱中经C18柱分离后,进入电感耦合等离子体质谱检测其甲基汞、乙基汞和苯基汞的浓度。3种有机汞化合物均在0.50~50.0μg/L范围内呈现良好的线性关系,线性相关系数(r)均大于0.9998。方法检出限为0.010~0.038mg/kg;3种有机汞样品加标的RSD均小于12.2%;两个水平的加标回收率在50.8~129%。     

Octanol–air partition coefficients of polybrominated biphenyls

The octanol–air partition coefficients (K_OA) for PBB15, PBB26, PBB31, PBB49, PBB103 and PBB153 were determined as a function of temperature using a gas chromatographic retention time technique with 1,1,1-trichloro-2,2-bis (4-chlorophenyl) ethane (p,p′-DDT) as a reference substance. The internal energies of phase change from octanol to air (Δ_OAU) were calculated for the six compounds and were in the range from 74 to 116 kJ mol⁻¹. Simple regression equations of log K_OA versus relative retention times (RRTs) on gas chromatography (GC), and log K_OA versus molecular connectivity indexes (MCI) were obtained, for which the correlation coefficients (r²) were greater than 0.985 at 283.15 K and 298.15 K. Thus the K_OA values of the remaining PBBs can be predicted by using their RRTs and MCI according to these relationships.     

Gas/particle partitioning of atmospheric PCDD/Fs in a satellite town in Eastern China

Gas/particle partitioning of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in ambient air was investigated in a satellite town in Eastern China from April 2007 to January 2008 comprehending large temperature variations (from 3 to 34 °C, daily average). Molecular weight, molecular structure and ambient temperatures are the three major factors that govern the gas/particle partitioning of atmospheric PCDD/Fs throughout the year. Generally, good agreements were obtained (except for winter) between measured particulate fractions and theoretical estimates of both the Junge–Pankow adsorption model and Harner Bidleman absorption model using different sets of subcooled liquid vapor pressure and octanol–air partition coefficient (K_oa), respectively. Models utilizing estimates, derived from gas chromatographic retention indices (GC-RIs), are more accurate than that of entropy-based. Moreover, during winter, the K_oa-based model using the GC-RIs approach performs better on lower chlorinated PCDD/Fs than that of -based. Furthermore, possible sources of mismatch between measured and predicted values in winter (3–7 °C) were discussed. Gas adsorption artifact was demonstrated to be of minor importance for the phenomena observed. On the other hand, large deviations of slopes (m_r) and intercepts (b_r) in logK_p vs. plots from theoretical values are observed in the literature data and these are found to be linearly correlated with ambient temperatures (P<0.001) in this study. This indicates that the non-equilibrium partitioning of PCDD/Fs in winter may be significantly influenced by the colder temperatures that may have slowed down the exchange between gaseous and particulate fractions.     

Microbial reduction of sulfate injected to gas condensate plumes in cold groundwater

Despite a rapid expansion over the past decade in the reliance on intrinsic bioremediation to remediate petroleum hydrocarbon plumes in groundwater, significant research gaps remain. Although it has been demonstrated that bacterial sulfate reduction can be a key electron accepting process in many petroleum plumes, little is known about the rate of this reduction process in plumes derived from crude oil and gas condensates at cold-climate sites (mean temperature <10 degrees C), and in complex hydrogeological settings such as silt/clay aquitards. In this field study, sulfate was injected into groundwater contaminated by gas condensate plumes at two petroleum sites in Alberta, Canada to enhance in-situ bioremediation. In both cases the groundwater near the water table had low temperature (6-9 degrees C). Monitoring data had provided strong evidence that bacterial sulfate reduction was a key terminal electron accepting process (TEAP) in the natural attenuation of dissolved hydrocarbons at these sites. At each site, water with approximately 2000 mg/L sulfate and a bromide tracer was injected into a low-sulfate zone within a condensate-contaminant plume. Monitoring data collected over several months yielded conservative estimates for sulfate reduction rates based on zero-order kinetics (4-6 mg/L per day) or first-order kinetics (0.003 and 0.01 day(-1)). These results favor the applicability of in-situ bioremediation techniques in this region, under natural conditions or with enhancement via sulfate injection.     

污泥投配率对污泥中温厌氧消化效果影响的试验研究

试验装置采用半连续流污泥中温厌氧消化反应器,污泥培养接近成熟后开始每天按不同污泥投配率加泥和排泥.结果表明:污泥投配率在3%～10%时,有机物分解率先增大后减小,去除率均在30%以上;污泥投配率在15%和20%时,污泥的有机物去除率非常小;污泥投配率在5%时,有机物分解率最大为41.2%;单位VSS产气量随污泥投配率的增大而呈先急剧上升后逐渐下降的趋势,当污泥投配率为5%时,单位VSS产气量为0.60 L/g,符合美国污水处理厂设计手册标准,其他污泥投配率下该指标均小于0.4 L/g.因此,认为实验用污泥中温消化的最佳污泥投配率为5%,这时污泥的可消化性较好.     

水体和甘蓝及土壤中毒死蜱残留检测方法

研究运用不同的样品前处理方式,在装配火焰光度检测器的气相色谱(GC-FPD)上检测,建立了有机磷杀虫剂毒死蜱在水样、土壤和甘蓝中的残留测定方法.研究表明,不同样品中的毒死蜱残留采用本文中介绍的前处理方法是可行的,用石油醚盐析提取和净化水样中毒死蜱,采用丙酮振荡提取甘蓝中毒死蜱,选用索氏提取法提取土壤中毒死蜱,并经液液分配净化后,采用OV-101大口径毛细管柱(30 m×0.53 mm×1.0μm),在装配火焰光度检测器(FPD和磷滤光片)的气相色谱上测定.该分析方法下,毒死蜱的保留时间为1.74 min,线性范围在1.0×10-11—1.0×10-8g之间,其线性相关系数为0.9998,最小检出量为2.0×10-12g.在设定的较低添加浓度的条件下,毒死蜱在水样、土壤与甘蓝上的添加回收率为80%—120%,变异系数均小于5%.该分析方法灵敏、准确、操作简便,适合水样、甘蓝和土壤中低浓度毒死蜱的残留检测.