浅谈串联四极杆质谱（GC—QqQ-MS／MS）在土壤样品有机污染物分析中的应用

建立了ASE-GPC—GC-QqQ—MS／MS测定土壤中17种有机氯农药和19种多氯联苯以及MAE-SPE—GC-QqQ—MS／MS测定土壤中16种多环芳烃和18种邻苯二甲酸酯的方法。多环芳烃和邻苯二甲酸酯定量限在0．02～2．81μg／kg之间,有机氯农药和多氯联苯定量限在0．01～0．51μg/kg之间。样品加标浓度在5μg/kg时多环芳烃和邻苯二甲酸酯的平均回收率在66．6％～122．1％之间,相对标准偏差均小于20％;有机氯农药和多氯联苯平均回收率在79．6％～93．2％之间,相对标准偏差均小于15％。     

Analysis of accumulation, extractability, and metabolization of five different phenylarsenic compounds in plants by ion chromatography with mass spectrometric detection and by atomic emission spectroscopy

Phenylated arsenic compounds occur as highly toxic contaminants in former military areas where they were formed as degradation products of chemical warfare agents. Some phenylarsenic compounds such as roxarsone and aminophenylarsonic acids were applied as food additive and veterinary drugs in stock-breeding and therefore pose an environmental risk in agricultural used sites. Very few data exist in the literature concerning uptake and effects of phenylarsenic compounds in plants growing on contaminated soils. In this study, the accumulation, extractability, and metabolization of five different phenylarsenic compounds, phenylarsonic acid, p- and o-aminophenylarsonic acid, phenylarsine oxide, and 3-nitro-4-hydroxyphenylarsonic acid called roxarsone, by the terrestrial plant Tropaeolum majus were investigated. Ion chromatography coupled to inductively coupled plasma mass spectrometry was used to differentiate these arsenic compounds, and inductively coupled plasma atomic emission spectroscopy was used for total arsenic quantification. All compounds considered were taken up by the roots and transferred to stalks, leaves, and flowers. The strongest accumulation was observed for unsubstituted phenylarsonic acid followed by its trivalent analogue phenylarsine oxide that was mostly oxidized in soil whereas the amino- or nitro- and hydroxy-substituted phenylarsonic acids were accumulated to a smaller degree.The highest extraction yield of 90% for ground leaf material was achieved by 0.1 M phosphate buffer, pH 7.7, in a two-step extraction with a total extraction time of 24 h. The extraction of higher amounts of arsenic (50–70% of total arsenic present in leaves depending on arsenic species application) from non-ground intact leaves with deionized water in comparison with the buffer (20–40% of total arsenic) is ascribed to osmotic effects. The arsenic species analysis revealed a cleavage of the amino groups from the phenyl ring for plants treated with aminophenylarsonic acids. A further important metabolic effect consisted in the production of inorganic arsenate and arsenite from the phenylated arsonic acid groups.     

Laboratory longitudinal diffusion tests: 1. Dimensionless formulations and validity of simplified solutions

To obtain reliable diffusion parameters for diffusion testing, multiple experiments should not only be cross-checked but the internal consistency of each experiment should also be verified. In the through- and in-diffusion tests with solution reservoirs, test interpretation of different phases often makes use of simplified analytical solutions. This study explores the feasibility of steady, quasi-steady, equilibrium and transient-state analyses using simplified analytical solutions with respect to (i) valid conditions for each analytical solution, (ii) potential error, and (iii) experimental time. For increased generality, a series of numerical analyses are performed using unified dimensionless parameters and the results are all related to dimensionless reservoir volume (DRV) which includes only the sorptive parameter as an unknown. This means the above factors can be investigated on the basis of the sorption properties of the testing material and/or tracer. The main findings are that steady, quasi-steady and equilibrium-state analyses are applicable when the tracer is not highly sorptive. However, quasi-steady and equilibrium-state analyses become inefficient or impractical compared to steady state analysis when the tracer is non-sorbing and material porosity is significantly low. Systematic and comprehensive reformulation of analytical models enables the comparison of experimental times between different test methods. The applicability and potential error of each test interpretation can also be studied. These can be applied in designing, performing, and interpreting diffusion experiments by deducing DRV from the available information for the target material and tracer, combined with the results of this study.     

可变电荷土壤和恒电荷土壤Cl-吸附特性的研究

对不同浓度KCl和不同pH下,3种可变电荷土壤和4种恒电荷土壤Cl-吸附量进行了测定。结果表明,土壤Cl-吸附量随平衡Cl-浓度C（e）增加而增大,恒电荷土壤呈线性,可变电荷土壤在添加Cl-0.5~5.0mmol/L下,符合Langmuir吸附等温式。同一浓度下的Cl-吸附量及其随浓度增加的速率均为砖红壤>红壤>赤红壤>黄棕壤>棕壤、暗棕壤和黑土,与这些土壤所带正电荷量顺序相一致。Langmuir方程K值较小且几种土壤差异不大。恒电荷土壤对Cl-的吸附量很小,在浓度较低时常出现负吸附,其吸附机理可能更多的是与K+吸附时的同时吸附。7种土壤Cl-吸附量均随pH增加而降低,但降低强度可变电荷土壤远大于恒电荷土壤。     

Temporal variations of airborne particles concentration in the Brussels environment

We report and analyze data on the PM10 fraction of airborne particles measured at five recording stations in the Brussels region from October 2002 till September 2003. These stations are representative of the various activity sectors of the Brussels urban area. The objective was the determination of the origin of the PM10 particles (particles up to 10 μm) that are recorded in that region in order to follow the EU directives concerning tolerance level of airborne particles concentration. In order to evaluate the impacts of local and external factors that inject solid particles in the atmosphere of Brussels we compared concentration data from working and not working (holidays) periods. Moreover, we also compared concentrations from periods of agricultural activity and rest in the Brabant provinces surrounding the Brussels region for various crop types. The results lead to the conclusion that the impact or urban traffic is rather limited while that of the agricultural activities is important. Moreover, there appears a clear-cut distinction between different types of crops.     

Estimating nutrient loadings using chemical mass balance approach

The river Hindon is one of the important tributaries of river Yamuna in western Uttar Pradesh (India) and carries pollution loads from various municipal and industrial units and surrounding agricultural areas. The main sources of pollution in the river include municipal wastes from Saharanpur, Muzaffarnagar and Ghaziabad urban areas and industrial effluents of sugar, pulp and paper, distilleries and other miscellaneous industries through tributaries as well as direct inputs. In this paper, chemical mass balance approach has been used to assess the contribution from non-point sources of pollution to the river. The river system has been divided into three stretches depending on the land use pattern. The contribution of point sources in the upper and lower stretches are 95 and 81% respectively of the total flow of the river while there is no point source input in the middle stretch. Mass balance calculations indicate that contribution of nitrate and phosphate from non-point sources amounts to 15.5 and 6.9% in the upper stretch and 13.1 and 16.6% in the lower stretch respectively. Observed differences in the load along the river may be attributed to uncharacterized sources of pollution due to agricultural activities, remobilization from or entrainment of contaminated bottom sediments, ground water contribution or a combination of these sources.     

Evaluation of the Impact of Long-range Transport and Aerosol Concentration Temporal Variations at the Eastern Coast of the Baltic Sea

Ambient particles vary greatly in their ability to affect visibility, climate and human health. The fine fraction of aerosol is responsible for greater and wider effects on human health; thus, investigation of this fraction is very important. Continuous measurements of PM2.5 (particulate matter below 2.5 μm in size) concentrations at the Preila monitoring station started in 2003. During a period of 2 years, the episodes of high daily and semi-hourly concentrations of PM2.5 were measured. These episodes did not depend on the season or time of day. The substantial role of long-range transport of pollutants to these increases in concentration was shown using chemical and statistical analysis. It was found that most of the severe episodes occurred when air masses came from a specific site besides it was established that air masses of different origin were characterized by different mixing layer depth. Lower mixing depth was observed in air masses characterized by higher observed concentrations at the measuring site and vice versa. PM2.5 concentrations showed diurnal and seasonal variations whose pattern reflected the regional origin of the aerosol. The regional pollution level was evaluated by the statistical analysis of PM2.5 concentrations. The background annual average of PM2.5 mass concentration for the eastern coast of the Baltic Sea was 15.1 ± 0.8 μg m⁻³.     

DO C/N对同步硝化反硝化影响的试验研究

在序批式活性污泥反应器(SBR)内,以模拟的城市污水为处理对象,研究DO、C/N等因素对同步硝化反硝化脱氮效率的影响。研究表明:采用连续曝气工艺,在进水COD=200mg/L,NH4+-N=30mg/L条件下,控制DO在0.5～1.5mg/L范围内时,出水TN浓度为1.98～6.3mg/L,TN的平均去除率在80%以上,最高去除率达到93.74%,并可推断出在反应系统内存在好氧反硝化菌;C/N在3.3～10之间时,C/N越高,出水NO3--N浓度越低,SND效果越好。     

基于EOS/MODIS资料的太湖藻类动态模拟

建立了太湖藻类生长的动态模型,并将其与水动力模型和水质模型相耦合,利用2001年7～8月太湖的实测资料对模型进行了率定。借助该模型,对2004年8月太湖水体中TN、TP的变化以及藻类生长过程进行了模拟。利用中分辨率成像光谱仪EOS/MODIS的数据对太湖叶绿素a浓度进行遥感定量,将遥感监测数据和模型计算结果进行了比较。结果表明:该模型可进行风生湖流、TN、TP的模拟,以叶绿素a浓度描述的藻类浓度的模拟值能较好地拟合遥感监测值,且遥感监测图和模型模拟图所反映的全太湖叶绿素浓度分布基本一致。最后根据遥感和模拟对太湖全区的藻类分布作了具体的分析。     

梯形渠道岸边排污浓度分布的理论分析

从无限区域圆形瞬时源扩散的浓度分布公式人手,推导出梯形区域内瞬时线源扩散的近似浓度计算公式,进而得到了梯形渠道岸边排污的浓度分布公式计算公式表明,边坡倾角对污染物的浓度分布影响较大,浓度值随边坡倾角的增加而减小,近似遵循双曲线的递减规律.浓度分布解析解得到了扩散方程数值解的良好验证,两者在污染源附近有所差异,但随着距污染源距离的增加,计算结果愈加吻合,该解析公式可为天然河流岸边污染混合区的污染物浓度估算提供有力的工具.