Enhanced Desorption of Phenanthrene from Soils Using Hydroxypropyl‐β‐cyclodextrin: Experimental Results and Model Predictions

Objective of this study was to evaluate the effects of hydroxypropyl‐β‐cyclodextrin (HPCD) on the removal of phenanthrene from solid phase. Batch tests for the phenanthrene distribution between aqueous and solid phase were conducted in the presence of HPCD. Column tests and numerical simulations were conducted to evaluate the roles of HPCD cavities and interaction rates between water, HPCD, and solid phase in the enhanced removal of phenanthrene. Experimental results showed that HPCD was effective in removing sorbed phenanthrene from subsurface environment, primarily due to its negligible sorption to the solid phase and the partitioning of phenanthrene into HPCD cavities. From the numerical simulations, it was found that rate‐limited partitioning of phenanthrene into HPCD cavities was most influential factor in the enhanced elution of phenanthrene. Sorption and desorption rate of phenanthrene between aqueous and solid phase was very fast or near equilibrium state. Interaction rates of contaminant between water, HPCD, and solid phase could be affected by other factors such as soil types and organic matter contents. Results from this study implied that HPCD flushing could be effectively applied for the removal of hydrophobic organic pollutants existing in the soils as sorbed or NAPL state.     

Statistical uncertainty in hazardous terrestrial concentrations estimated with aquatic ecotoxicity data

Since chemicals’ ecotoxic effects depend for most soil species on the dissolved concentration in pore water, the equilibrium partitioning (EP) method is generally used to estimate hazardous concentrations (HC50) in the soil from aquatic toxicity tests. The present study analyzes the statistical uncertainty in terrestrial HC50s derived by the EP-method. For 47 organic chemicals, we compared freshwater HC50s derived from standard aquatic ecotoxicity tests with porewater HC50s derived from terrestrial ecotoxicity tests. Statistical uncertainty in the HC50s due to limited species sample size and in organic carbon–water partitioning coefficients due to predictive error was treated with probability distributions propagated by Monte Carlo simulations. Particularly for specifically acting chemicals, it is very important to base the HC50 on a representative sample of species, composed of both target and non-target species. For most chemical groups, porewater HC50 values were approximately a factor of 3 higher than freshwater HC50 values. The ratio of the porewater HC50/freshwater HC50 was typically 3.0 for narcotic chemicals (2.8 for nonpolar and 3.4 for polar narcotics), 0.8 for reactive chemicals, 2.9 for neurotoxic chemicals (4.3 for AChE agents and 0.1 for the cyclodiene type), and 2.5 for herbicides–fungicides. However, the statistical uncertainty associated with this ratio was large (typically 2.3 orders of magnitude). For 81% of the organic chemicals studied, there was no statistical difference between the hazardous concentration of aquatic and terrestrial species. We conclude that possible systematic deviations between the HC50s of aquatic and terrestrial species appear to be less prominent than the overall statistical uncertainty.     

Atmospheric partitioning and the air–water exchange of polycyclic aromatic hydrocarbons in a large shallow Chinese lake (Lake Chaohu)

The residual levels of polycyclic aromatic hydrocarbons (PAHs) in the atmosphere and in dissolved phase from Lake Chaohu were measured by (GC–MS). The composition and seasonal variation were investigated. The diffusive air–water exchange flux was estimated by a two-film model, and the uncertainty in the flux calculations and the sensitivity of the parameters were evaluated. The following results were obtained: (1) the average residual levels of all PAHs (PAH16) in the atmosphere from Lake Chaohu were 60.85 ± 46.17 ng m⁻³ in the gaseous phase and 14.32 ± 23.82 ng m⁻³ in the particulate phase. The dissolved PAH16 level was 173.46 ± 132.89 ng L⁻¹. (2) The seasonal variation of average PAH16 contents ranged from 43.09 ± 33.20 ng m⁻³ (summer) to 137.47 ± 41.69 ng m⁻³ (winter) in gaseous phase, from 6.62 ± 2.72 ng m⁻³ (summer) to 56.13 ± 22.99 ng m⁻³ (winter) in particulate phase, and 142.68 ± 74.68 ng L⁻¹ (winter) to 360.00 ± 176.60 ng L⁻¹ (summer) in water samples. Obvious seasonal trends of PAH16 concentrations were found in the atmosphere and water. The values of PAH16 for both the atmosphere and the water were significantly correlated with temperature. (3) The monthly diffusive air–water exchange flux of total PAH16 ranged from −1.77 × 10⁴ ng m⁻² d⁻¹ to 1.11 × 10⁵ ng m⁻² d⁻¹, with an average value of 3.45 × 10⁴ ng m⁻² d⁻¹. (4) The results of a Monte Carlo simulation showed that the monthly average PAH fluxes ranged from −3.4 × 10³ ng m⁻² d⁻¹ to 1.6 × 10⁴ ng m⁻² d⁻¹ throughout the year, and the uncertainties for individual PAHs were compared. (5) According to the sensitivity analysis, the concentrations of dissolved and gaseous phase PAHs were the two most important factors affecting the results of the flux calculations.     

Simulation of arsenic partitioning in tributaries to drinking water resevoirs

Arsenic released by bottom sediments was determined by experiments in which the sediments were artificially re-suspended using a particle entrainment simulator (PES) to simulate river conditions. Sediment cores were collected from various tributaries to drinking water reservoirs in Connecticut spiked with arsenic, and run in the PES at simulated bed-flow shear stresses from 0.0 to 0.6 N/m². Under equilibrium conditions, the dissolved fraction of arsenic was found to range from 8.3 to 22.1 μg/l, which in most cases exceeded EPA Maximum Contaminant Level (MCL) of 10 μg/l. Experimental results from these simulations have shown that bed-flow shear stress causes an increased concentration of dissolved arsenic, most notably at shear stresses of 0.4, 0.5, and 0.6 N/m². For the solid phase under equilibrium, the concentrations of arsenic ranged between 71 and 275 mg/kg. The average concentration of arsenic on the solid phase as well as partitioning coefficient values (K _p) were highest at initial shear stress. This was attributed to the higher fraction of colloidal material and finer organic particles in the suspended solid mixture. Particles of such nature proved to have higher affinity to arsenic. K _p values were determined from PES data and were found to range from 4,687 to 24,090 l/kg. However, on a mass load basis, the amount of arsenic found in suspended sediment increased with the increase of shear stress. Similarly, the amount of arsenic in the solid phase increased significantly for sites with high Volatile Organic Carbon (VOC) content. Because of the influence of Total Suspended Solids (TSS) and VOC concentrations on K _p, the use of the PES is more appropriate in obtaining K _p values that would be found under real stream conditions when compared to the traditional way of measuring K _p using a jar study technique.     

Sampling and Analysis of Organic Compounds in Diesel Particulate Matter

The fraction of atmospheric semi-volatile organic compounds (SVOC) is partitioned between the gaseous and particulate phases. Certain of these compounds eg. polynuclear aromatic hydrocarbons (PAH) and their derivatives have been shown to exhibit mutagenic or carcinogenic properties. Emissions from diesel engines are an important source of these contaminants. In a dilution chamber, we studied a diesel engine emissions. It is shown firstly, that the gaseous fraction is predominant (by up to 20 times) with respect to the particulate phase. Secondly, the polar compounds, neglected in the majority of previous studies, are the predominant species. A test campaign was carried out in Paris-Porte d'Auteuil which yielded similar results to the laboratory experiments.     

湘江沉积物镉和汞质量基准的建立及其应用

沉积物质量基准是保护底栖生物免受污染物危害的保护性临界水平,可用来评估与沉积物结合的污染物的影响,并为底栖生物保护和沉积物的科学管理提供依据.分析了湘江43个采样点沉积物、上覆水、间隙水和植物中Cd和Hg含量,选取钩虾做沉积物毒理实验,利用相平衡分配法、加标毒理实验法和背景值法确定湘江沉积物Cd和Hg质量基准低值(SQC-L)分别为1.89 mg·kg-1和0.13 mg·kg-1,基准高值(SQC-H)分别为28.32 mg·kg-1和0.79 mg·kg-1.经与国内外基准值比较,并与底栖生物监测数据和植物监测数据对比分析,表明确定的基准值合理.应用该基准值评价湘江沉积物质量现状发现,湘江沉积物Cd和Hg含量低于SQC-L和高于SQC-H的采样点所占比例较低,74.4%和76.7%的采样点沉积物Cd和Hg含量在SQC-L和SQC-H之间.     

浙北平原富硒土壤资源区硒来源的定量分离

明确硒元素含量不同来源组分(自然背景组分和外源输入组分)贡献率是评价富硒土地资源是否具有可持续利用性的前提.以嘉兴市秀洲富硒土地资源区为研究区域,通过地学分析和多元统计交互验证,将该区域土壤硒来源定性分离为自然背景组分和含外源输入组分,并采用频数分布函数为工具,对硒含量不同来源组分的贡献率进行定量分离.结果表明,秀洲区富硒土地硒含量来源自然背景组分的贡献率占90%,外源输入组分占10%,表明秀洲区富硒土地资源具有可持续开发利用的潜力.     

Simultaneous monitoring of PCB profiles in the urban air of Dalian, China with active and passive samplings

The concentration of polychlorinated biphenyls (PCBs) in the urban air of Dalian, China was monitored from November 2009 to October 2010 with active high-volume sampler and semipermeable membrane device (SPMD) passive sampler. The concentration of PCBs (particle + gas) ( ∑ PCBs) ranged from 18.6 to 91.0 pg/m 3 , with an average of 50.9 pg/m 3 , and the most abundant dioxin-like PCB (DL-PCBs) was PCB118. The WHO-TEQ values of DL-PCBs were 3.6-22.1 fg/m3 , with an average of 8.5 fg/m 3 , and PCB126 was the maximum contributor to ∑ TEQ. There was a much larger amount of PCBs in the gas phase than in the particulate phase. The dominant PCB components were lower and middle molecular weight PCBs. With increasing chlorination level, the concentration of the PCB congeners in the air decreased. The gas-particulate partitioning of PCBs was different for the four seasons. The gas- particulate partitioning coefficients (logK p ) vs. subcooled liquid vapor pressures (logP L 0 ) of PCBs had reasonable correlations for different sampling sites and seasons. The absorption mechanism contributed more to the gas-particulate partitioning process than adsorption. Correlation analysis of meteorological parameters with the concentration of PCBs was conducted using SPSS packages. The ambient temperature and atmospheric pressure were important factors influencing the concentration of PCBs in the air. The distribution pattern of the congeners of PCBs and the dominant contributors to DL-PCBs and TEQ in active samples and SPMDs passive samples were similar. SPMD mainly sequestrated gas phase PCBs.     

Compilation of reaction kinetics parameters determined in the Key Development Project for Air Pollution Formation Mechanism and Control Technologies in China

A compilation of new advances made in the research field of laboratory reaction kinetics in China's Key Development Project for Air Pollution Formation Mechanism and Control Technologies was presented. These advances are grouped into six broad, interrelated categories, including volatile organic compound (VOC) oxidation, secondary organic aerosol (SOA) formation, new particle formation (NPF) and gas-particle partitioning, ozone chemistry, model parameters, and secondary inorganic aerosol (SIA) formation, highlighting the laboratory work done by Chinese researchers. For smog chamber applications, the current knowledge gained from laboratory studies is reviewed, with emphasis on summarizing the oxidation mechanisms of long-chain alkanes, aromatics, alkenes, aldehydes/ketones in the atmosphere, SOA formation from anthropogenic emission sources, and oxidation of aromatics, isoprene, and limonene, as well as SIA formation. For flow tube applications, atmospheric oxidation mechanisms of toluene and methacrolein, SOA formation from limonene oxidation by ozone, gas-particle partitioning of peroxides, and sulfuric acid-water (H₂SO₄-H₂O) binary nucleation, methanesulfonic acid-water (MSA-H₂O) binary nucleation, and sulfuric acid-ammonia-water (H₂SO₄-NH₃-H₂O) ternary nucleation are discussed.     

深圳冬季大气气态硝酸和硝酸盐气粒分配特征

利用双通道在线气体和气溶胶分析仪（MARGA）在深圳冬季同时观测了PM_2.5和PM₁₀中水溶性无机离子及气态前体物浓度变化,以探究气态硝酸（HNO₃）和颗粒态硝酸盐（pNO₃^-）的气粒分配特征.结果表明,气态硝酸和颗粒态硝酸盐总和TNO₃（TNO₃=HNO₃+pNO₃^-）中,气态HNO₃、细颗粒NO₃^-和粗颗粒NO₃^-三个部分的占比分别为9.6%、56.8%和33.6%.TNO₃浓度日变化呈现双峰特征,上午峰值来自于细颗粒态NO₃^-增加,由交通早高峰排放NO_x转化生成所致;白天光化学反应使TNO₃的3个部分浓度均增加,TNO₃在下午17：00达到全天峰值.相关分析表明,低温有利于NO₃^-以NH₄NO₃存在于细颗粒态;TNO₃浓度较高时,细颗粒态NO₃^-占比亦升高.