红外法测定土壤中石油烃的改进研究

通过气相色谱-质谱法定性解析红外法测定土壤中石油烃的各前处理阶段萃取物组分变化情况,探讨了用石油醚萃取土壤中石油烃空白高的原因,发现采用二氯甲烷为萃取剂,空白值低且精密度提高.     

某人工湿地系统对水中持久性有机污染物去除效果的分析

采用固相萃取样品前处理技术和气相色谱/电子捕获检测器(GC/ECD)及气相色谱/质联联用(GC/MS)分析方法,对某人工湿地系统进、出水中持久性有机污染物(包括多环芳烃、多氯联苯、有机氯农药)的质量浓度进行了分析和对比,以研究该湿地水中持久性有机物的污染水平及湿地对它们的处理效果.结果表明,多环芳烃检出19种,以二环为主,萘及其同系物约占总量的71%;有机氯农药只检出HCH的4种异构体和七氯;多氯联苯检出5种,以二氯代为主.这3类物质的浓度水平明显低于以往的研究结果,且低于国家地表水环境质量标准(GB 3838-2002).对于持久性有机物浓度较低的水源水,湿地对以上3类物质的去除效果不明显.     

芳香类有机物生成氯化消毒副产物特性及其与化学结构的关系

选择与腐殖酸有相似芳香结构的有机物进行氯化试验,测定其卤乙酸及三卤甲烷生成量,研究前体物化学结构与氯化消毒副产物生成特性的关系.结果表明:①主要卤乙酸生成活性排序为:对羟基苯甲酸>4-氨基苯乙酮>邻苯二酚>间苯二酚;主要三卤甲烷生成活性排序为:间苯二酚>4-氨基苯乙酮>2-羟基-4-氨基甲苯>对羟基苯甲酸.②卤乙酸的前期氯化反应速度排序为:间苯二酚>4-氨基苯乙酮>对羟基苯甲酸>邻苯二酚;三卤甲烷的前期氯化反应速度排序为:对羟基苯甲酸>2-羟基-4-氨基甲苯>间苯二酚>4-氨基苯乙酮.③对位或邻位取代基结构物质以生成卤乙酸为主;间位取代基结构物质以生成三卤甲烷为主.④苯环上羟基官能团生成消毒副产物的活性最高,酮基官能团次之;氨基官能团主要起到与其它活性官能团形成对位、邻位或间位结构的辅助作用;醛基和羧基官能团为惰性官能团;甲基官能团的作用有待深入考察.     

Pilot study on road traffic emissions (PAHs,heavy metals) measured by using mosses in a tunnel experiment in Vienna,Austria

BACKGROUND, AIMS AND SCOPE: Over the last few years there has been extensive research for new indicators providing information about deposition resulting from road traffic and tunnel experiments received special attention in emission research. Mosses have been used for the estimation of atmospheric heavy metal and PAH depositions for more than three decades, although they were used only a few times for estimating ambient air pollution caused by traffic. In the current study, the suitability of using a moss species for monitoring road traffic emissions inside a tunnel was evaluated. This was a first-time ever attempt to use plants (mosses) as bioindicators in a tunnel experiment. Specifically, two relevant questions were examined: 1) Do mosses accumulate toxic substances derived from road traffic emissions under the extremely adverse conditions which can be found in a tunnel, and 2) Which substances can mainly be attributed to road traffic emissions and therefore be taken as efficient and reliable indicators for motor vehicles? METHODS: For the first time a biomonitor (the moss species Hylocomium splendens (Hedwig) B.S.G.) was used in a road tunnel experiment to analyse emissions from road traffic. Moss samples were exposed for four weeks in wooden frames (size 10 cm x 10 cm), covered by a thin plastic net with a mesh size of 1 cm x 1 cm. 17 elements, mainly heavy metals, and the 16 EPA-PAHs together with coronene were analysed by ICP-AES, AAS and GC-MSD. RESULTS: Enrichment factors, calculated by comparing post-experiment concentrations to those of a background site, were high for most PAHs, especially benzo(g,h,i)perylene (150.7), coronene (134.7), benzo(a)anthracene (125.0), indeno(1,2,3-c,d)pyrene (79.8), chrysene (78.1), pyrene (69.6) and benzo(b)-fluoranthene (67.4), and among the other elements for Sb (73.1), Mo (59.6), Cr (33.9), As (24.1), Cu (19.6), and Zn (17.1). All these substances can thus be taken as indicators for road traffic pollution. Concentrations were also significantly higher in the tunnel mosses for all investigated substances than along busy roads outside tunnels. Cluster analysis revealed groups of substances which could sensibly be attributed to various sources (abrasion processes, Diesel combustion) and enrichment in the various particle size classes. DISCUSSION: The extreme high concentrations in the analysed moss samples from inside the tunnel were due to higher concentrations in the ambient tunnel air, and the fact that already deposited chemical substances are not lost by rain, as well as efficient uptake capacities even under the extremely adverse conditions in a tunnel. In accordance with previous studies our results suggest that PAHs are better indicators for emissions from the burning process than heavy metals. CONCLUSIONS: As in open fields, mosses are suitable indicators for monitoring traffic emissions in tunnels. In addition to biomonitoring in open fields, in tunnel experiments mosses are even better indicators, because the confounding effects of other sources of pollution and the 'noise' in the accumulation process (e.g. washout through wet deposition) are minimised. The results of our study demonstrate the usefulness of mosses for surveying heavy metals and PAH emissions and deposition arising from road traffic sources, even under the extremely adverse conditions of the tunnel environment. RECOMMENDATION: It can be considered that biomonitors like mosses are a suitable alternative to technical particle filters inside tunnels. They are easy to handle, low in costs and valuable information regarding traffic emissions can be obtained. PERSPECTIVE: The results of this pilot-study proved the feasibility of the method, however, should be corroborated by further investigations based on a sample set that allows for generalization of the findings and might even include other moss species. A comparison of technical measurements with the biomonitoring method could lead to a more general acceptance of the results.     

Combined effect of nonionic surfactant Tween 80 and DOM on the behaviors of PAHs in soil--water system

Batch experiments were performed to examine the desorption behavior of phenanthrene and pyrene in soil–water system in the presence of nonionic surfactant Tween 80 and dissolved organic matter (DOM) derived from pig manure or pig manure compost. Addition of 150 mg l⁻¹ Tween 80 desorbed 5.8% and 2.1% of phenanthrene and pyrene from soil into aqueous phase, respectively, while the addition of both Tween 80 and DOM derived from pig manure compost and pig manure could further enhance the desorption of phenanthrene to 15.8% and 16.2%, respectively, and 6.4% and 10.9%, respectively, for pyrene. In addition, our finding also suggested that subsequent addition of Tween 80 into the soil–water system could further enhance PAHs desorption. The enhancement effect of the co-existence of Tween 80 and DOM was more than the additive effect of the Tween 80 and DOM individually. It is likely that the formation of DOM–surfactant complex in the soil–water system may be a possible reason to explain such desorption enhancement phenomenon. Therefore, it is anticipated that the coexistence of both Tween 80 and DOM derived from pig manure or pig manure compost in soil environment will enhance the bioavailability of PAHs as well as other hydrophobic organic contaminants (HOCs) by enhancing the desorption during remediation process.     

The effect of clay catalyst on the chemical composition of bio-oil obtained by co-pyrolysis of cellulose and polyethylene

Cellulose/polyethylene (CPE) mixture 3:1, w/w with and without three clay catalysts (K10 – montmorillonite K10, KSF – montmorillonite KSF, B – Bentonite) addition were subjected to pyrolysis at temperatures 400, 450 and 500 °C with heating rate of 100 °C/s to produce bio-oil with high yield. The pyrolytic oil yield was in the range of 41.3–79.5 wt% depending on the temperature, the type and the amount of catalyst. The non-catalytic fast pyrolysis at 500 °C gives the highest yield of bio-oil (79.5 wt%). The higher temperature of catalytic pyrolysis of cellulose/polyethylene mixture the higher yield of bio-oil is. Contrarily, increasing amount of montmorillonite results in significant, almost linear decrease in bio-oil yield followed by a significant increase of gas yield. The addition of clay catalysts to CPE mixture has a various influence on the distribution of bio-oil components. The addition of montmorillonite K10 to cellulose/polyethylene mixture promotes the deepest conversion of polyethylene and cellulose. Additionally, more saturated than unsaturated hydrocarbons are present in resultant bio-oils. The proportion of liquid hydrocarbons is the highest when a montmorillonite K10 is acting as a catalyst.     

Single-solute and bi-solute sorption of phenanthrene and pyrene onto pine needle cuticular fractions

To better understand interaction mechanisms of pine needles with persistent organic pollutants, single-solute and bi-solute sorption of phenanthrene and pyrene onto isolated cuticular fractions of pine needle were investigated. The structures of cuticular fractions were characterized by elemental analysis, Fourier transform infrared spectroscopy and solid-state ¹³C NMR. Polymeric lipids (cutin and cutan) exhibited notably higher sorption capabilities than the soluble lipids (waxes), while cellulose showed little affinity with sorbates. With the coexistence of the amorphous cellulose, the sorption of cutan (aromatic core) was completely inhibited, so the cutin components (nonpolar aliphatic moieties) dominated the sorption of bulk needle cuticle. By the consumption of the amorphous cellulose under acid hydrolysis, sorption capacities of the de-sugared fractions were dramatically enhanced, which controlled by the exposed aromatic cores and the aliphatic moieties. Furthermore, the de-sugared fractions demonstrated nonlinear and competitive sorption due to the specific interaction between aromatic cores and polycyclic aromatic hydrocarbon.     

自动进样及气体分流技术测定气体中非甲烷总烃

采用自动进样和气体分流技术,双柱双FID检测器气相色谱法测定气体中的非甲烷总烃,实现了非甲烷总烃的连续自动分析,同时一次进样即可得到甲烷和总烃的数据。方法的检出限为0.05 mg/m3,测定的相对标准偏差在0.7%~1.8%内,非甲烷总烃的加标回收率为96.0%~98.5%。与传统手动进样法相比,本方法具有重复性好、操...     

大气降尘中多环芳烃的分布特征及源解析

为探讨大气降尘中多环芳烃的污染水平和来源的解析,于2008年冬、春、夏、秋四个季节采集了北京昌平地区大气降尘样品,采用超声抽提方法,使用GC/MS测定了样品中PAHs的含量。结果表明,冬、春、夏、秋四个季节样品中多环芳烃总量分别为18.6μg/g、17.3μg/g、15.1μg/g和11.0μg/g,单体化合物均值分别为1.04μg/g、0.96μg/g、0.84μg/g和0.61μg/g。与其他城市监测结果比较可知:昌平地区大气降尘中PAHs含量相对较低。使用多种方法对降尘中的PAHs来源进行解析,结果表明:化石燃料燃烧在不同季节中的贡献相对稳定,燃煤在冬季为多环芳烃主要来源之一,在其他季节贡献相对较低。     

新乡市机动车排放对道路灰尘中重金属与多环芳烃污染的影响

以新乡市主要道路的地表灰尘为样本,采用电感耦合等离子体质谱仪和气相色谱质谱联用仪分别测定所含5种重金属(Cd、Pb、Cr、Cu和Zn)和15种多环芳烃(polycyclic aromatic hydrocarbons,PAHs)的含量,并探究了机动车排放对其污染特征的影响.结果显示,重金属和PAHs的含量范围分别为2. 58～1 560 mg·kg~(-1)和ND～1. 30 mg·kg~(-1),其含量总体上随灰尘粒径减小而增高.组成上,重金属以Zn为主,PAHs主要以高环为优势组分.空间分布上,重金属和PAHs含量存在差异:人民路、小店工业园区和水泥厂附近道路灰尘中的重金属总含量最高,而PAHs含量的高值出现在人民路、高速上口和107国道的灰尘中.Pearson相关分析表明,5种重金属与15种PAHs间基本不存在正相关关系.通过聚类分析和因子分析发现,新乡市道路灰尘中的重金属基本不受机动车排放影响,而PAHs受机动车排放影响较大.