新型环境测试舱研制、性能评价及释放模拟

研制了一种新型环境测试舱,此舱系统可用于研究室内材料中挥发性有机物（VOCs）释放特征和释放机理。详细介绍舱的设计,讨论舱系统的优缺点,并对舱的性能进行评价测试。结果表明,温度和相对湿度的准确性分别为≤0.5℃和≤3.1%,空气混合水平达到92.9%,回收率达到85.2%。根据回收率实验结果,用经验模型和VB模型模拟对二氯苯（p-DCB）释放,模拟结果与实测值吻合很好。     

硝基清漆膜厚度对硝基清漆VOCs释放的影响

利用自制的小型环境测试舱,研究了硝基清漆膜厚度对挥发性有机物(VOCs)释放的影响.漆膜厚度分别为296,508,715,799,960μm,测试条件为:温度为25.0℃,相对湿度为23.9%,空气流量为0.75m3/h,空气流速为3.4cm/s,支持板为不锈钢盘.采用真空采样罐采集舱出口空气,用气相色谱(GC-FID)分析测试.确定了5种主要VOCs(甲基环乙烷、甲苯、乙苯、间/对二甲苯和邻二甲苯)的浓度,并以一阶衰减模型对浓度进行模拟计算得到释放速率.结果表明,漆膜厚度并不影响VOCs的峰值浓度和初始释放速率,但漆膜越厚,VOCs的浓度衰减越慢,衰减速率越小.     

沈阳市雪与水中对二氯苯的挥发污染行为

应用气相色谱法对对二氯苯(p-DCB)在雪与水中残留动态进行测定,探讨了不同气候下水中p-DCB的挥发污染行为.结果表明,雪与水中p-DCB的挥发速率都相当迅速,并服从一级反应动力学.在自然条件下,雪与水中p-DCB半减期分别为2.32～3.25d和0.76～1.20d.雪与水中p-DCB在投加浓度分别为0.1～100.0μg/g,0.1～100.0μg/mL范围时,投加浓度越高挥发速率越快,挥发半减期越短.     

应用环境舱研究室内混凝土墙体中氨的释放规律

采用环境舱模拟研究了随温度(T)、相对湿度(RH)和空气交换率(AER)变化墙体试块中氨的释放规律,并将现场实验结果与环境舱的模拟实验结果进行对比.研究发现:T和RH一定,随着AER的增大,舱内氨气平衡浓度下降,氨气挥发速率和完全释放时间呈现出一定的规律性;AER和RH一定,舱内氨气平衡浓度和挥发速率随T升高而变大,完全释放时间减小;与AER和T相比,RH对氨气释放的影响有限;通过与现场通风实验和浓度监测结果比较,考虑到室内墙体老化时间等因素,环境舱实验与实际住宅测试得到的结论基本一致.在一般的情况下,使用含尿素防冻剂的住宅,其墙体中氨释放完全大约需要10～32年.     

室内环境对人造板甲醛释放规律影响分析研究

为了研究不同温湿度条件下人造板甲醛的释放规律,利用环境舱模拟人造板在室内特征温湿度下甲醛的散发过程,测量甲醛的逐时散发浓度。结果表明,温度升高,木板中甲醛的释放浓度增大,环境舱内木板甲醛释放达到稳定的时间越长;相对湿度增加,木板中甲醛释放浓度随之增加。改变温湿度对环境舱内板材甲醛的释放趋势影响小。夏季工况的温湿度均高于冬季和过渡季,所以甲醛释放浓度为夏季＞过渡季＞冬季,其峰值浓度高于其他两季约3～5倍。     

板材甲醛释放实验及其释放参数的测定

采用1m3的小型环境模拟舱,测试了不同温度和装载度条件下胶合板、密度板、细木工板和复合地板中甲醛释放规律.研究发现:甲醛浓度在初始阶段(0~3h)均迅速增大,随后速度慢慢减小,最后浓度趋于恒定值;温度升高会促进板材内甲醛释放,温度每升高5℃,甲醛释放量会增加10%~30%;而装载度增大则会减少单位体积板材内甲醛的释放量.利用不同装载度条件下板材在密闭环境舱散发过程和平衡状态浓度,求解了影响板材释放特性的关键释放参数:可散发初始浓度Cm,0、扩散系数Dm和分配系数K;模拟计算的浓度结果与实验测试数据吻合良好,为研究板材甲醛释放规律提供了一种有效手段.     

板材甲醛释放实验及其释放参数的测定

采用1m3的小型环境模拟舱,测试了不同温度和装载度条件下胶合板、密度板、细木工板和复合地板中甲醛释放规律.研究发现:甲醛浓度在初始阶段(0~3h)均迅速增大,随后速度慢慢减小,最后浓度趋于恒定值;温度升高会促进板材内甲醛释放,温度每升高5 ℃,甲醛释放量会增加10%~30%;而装载度增大则会减少单位体积板材内甲醛的释放量.利用不同装载度条件下板材在密闭环境舱散发过程和平衡状态浓度,求解了影响板材释放特性的关键释放参数:可散发初始浓度Cm,0、扩散系数Dm和分配系数K;模拟计算的浓度结果与实验测试数据吻合良好,为研究板材甲醛释放规律提供了一种有效手段.     

大芯板中甲醛的释放规律及影响因素分析

以大芯板为试材,在模拟气候舱中研究密闭状态下甲醛的释放规律及影响因素。发现板材中甲醛的释放为短时间内剧烈释放,约24h后甲醛释放呈缓慢上升状态直至饱和,且板材的不同来源对甲醛的释放规律无显著影响;甲醛的释放速率在释放初期随温度的升高而加快,释放后期受温度影响不显著;湿度对甲醛的释放速率影响不显著;新风的通入会促进短时内甲醛的释放,20h后释放仍符合原规律曲线。     

汽车涂料废物挥发性有机物气相释放特征

汽车涂料废物作为有机污染物类典型固废,在全过程管理各环节都存在挥发性有机物(VOCs)释放的环境风险. 本文选取同一涂装工段下不同漆雾捕集技术产生的漆渣与干式石灰石粉,采用环境测试舱-气相色谱/质谱法,研究涂料废物中VOCs的气相释放特征. 结果表明:①相同工艺下漆渣与干式石灰石粉释放的VOCs种类相似,但漆渣中各组分释放速率和累计释放量远高于干式石灰石粉. ②漆渣与干式石灰石粉均在1 h左右达到VOCs的释放速率峰值,在检出的7种主要VOCs中,最高者同为正丁醇,分别为245.37、22.67 mg/(m2·h);最低者同为邻-甲乙苯,分别为11.49、2.50 mg/(m2·h). ③经过130 h(漆渣)和24 h(干式石灰石粉)的长期散发试验,试验结束时漆渣累计释放量最大的是正丁醇和1,2,4-三甲基苯,分别为4.76×103、2.86×103 mg/m2;干式石灰石粉累计释放量最大的是1,2,4-三甲基苯和正丁醇,分别为77.26、63.75 mg/m2;二者累计释放最低的同为邻-甲乙苯,分别为467.91、11.29 mg/m2. ④两种样品中VOC释放周期均分为释放初始期(峰值期)、过渡期和缓慢衰减期(准稳态期)3个阶段. 除漆渣中浓度最高的正丁醇外,其余各组分均具有一致的过渡期(1~9 h)和缓慢衰减期(9 h之后),但干式石灰石粉达到稳态的时间远低于漆渣. 研究显示,干式漆雾捕集技术所产生的干式石灰石粉相较传统湿式工艺产生的漆渣,二者所释放的VOCs组分种类相似,存在相同的释放阶段,但释放周期和累计释放量大幅降低,在VOCs减排上具有显著优势.      

空冷塔对大气环境温度湿度影响的数值模拟

运用FLUENT建立空冷塔模型进行数值模拟,研究不同出口温度、环境温度和侧风速度下空冷塔与大气环境之间的传热.结果表明：不同出口温度及环境温度对空冷塔与大气环境间的换热有显著影响.其中,当出口温度升高到328K时,空冷塔近地面层空气温度上升6.22K,而其相对湿度由47.7%降至31.78%,空气干燥程度增大;随着环境温度与排气温度间温差增大,换热效果更为显著,表现为冬季空气干燥程度变化最大,春秋次之,夏季最小.不同环境风速对空冷塔与大气环境间换热区域影响显著,其中,当侧风风速为7m/s时,热交换影响区域可达11.17km,且空冷塔近处相对湿度由47.7%降至39.47%.     

Effects of two sludge application on fractionation and phytotoxicity of zinc and copper in the soil

The potential harm of heavy metals is a primary concern in application of sludge to the agricultural land. A pot experiment was conducted to evaluate the effect of two sludges on fractionation of Zn and Cu in soil and their phytotoxicity to pakchoi. The loamy soil was mixed with 0%, 20%, 40%, 60% and 80% (by weight) of digested sewage sludge (SS) and composted sludge (SC). The additions of both sludges caused a significant raise in all fractions, resulting in that exchangeable (EXCH) and organic bound (OM) became predominance of Zn and organic bound Cu occupied the largest portion. There was more available amount of Zn and Cu in SS treatments than SC treatments. During the pot experiment, the concentration of Zn in EXCH, carbonate (CAR) and OM and Cu in EXCH and OM fractions decreased in all treatments, so their bioavailability reduced. Germination rate and plant biomass decreased when the addition rate was high and the best yield appeared in 20% mixtures at the harvest of pakchoi. The two sludges increased tissue contents of Zn and Cu especially in the SS treatments. Zn in pakchoi was not only in relationship to ΔEXCH and ΔCAR forms but also in ΔOM forms in the sludge-soil mixtures. Tissue content of Cu in pakchoi grown on SC-soils could not be predicted by ΔEXCH. These correlation rates between Zn and Cu accumulation in pakchoi and variation of different fractions increased with time, which might indicate that sludges represented stronger impacts on the plant in long-term land application.     

Intraspecific differences in effects of co-contamination of cadmium and

A hydroponic experiment was carried out to study intraspecific differences in the effects of different concentrations of cadmium (Cd)(0-10 mg/L) and arsenate (As(V)) (0-8 mg/L) on the growth parameters and accumulation of Cd and As in six wheat varieties Jing-9428, Duokang-1, Jingdong-11, Jing-411, Jingdong-8 and Zhongmai-8. The endpoints of wheat seedlings, including seed germination,biomass, root length and shoot height, decreased with increasing the Cd and As concentrations. Significant differences in seed germination, biomass, root length, shoot height and the accumulation of Cd and As were observed between the treatments and among the varieties (p ＜ 0.05). The lethal dosage 50% were about 20, 80, 60, 60, 80 and 20 mg As/L for Jing-9428, Duokang-1, Jingdong-11,Jing-411, Jingdong-8 and Zhongmai-8, respectively, and the corresponding values for Cd were about 30, 80, 20, 40, 60 and 10 mg Cd/L, respectively. Among the six varieties, Duokang-1 was found to be the most resistant to Cd and As toxicity, and Zhongmai-8 was the most sensitive to Cd and As co-contamination. The resistance of the six varieties was found dependant on the seedling uptake of Cd and As. Duokang-1 was the most suitable for cultivation in Cd and As co-contaminated soils.     

Toxic effects of acetochlor, methamidophos and their combination on nifH gene in soil

Toxic effects of two agrochemicals on nifH gene in agricultural black soil were investigated using denaturing gradient gel electrophoresis （DGGE） and sequencing approaches in a microcosm experiment. Changes of soil nifH gene diversity and composition were examined following the application of acetochlor, methamidophos and their combination. Acetochlor reduced the nifH gene diversity （both in gene richness and diversity index values） and caused changes in the nifH gene composition. The effects of acetochlor on nifH gene were strengthened as the concentration of acetochlor increased. Cluster analysis of DGGE banding patterns showed that nifH gene composition which had been affected by low concentration of acetochlor （50 mg/kg） recovered firstly. Methamidophos reduced nifH gene richness that except at 4 weeks. The medium concentration of methamidophos （150 mg/kg） caused the most apparent changes in nifH gene diversity at the first week while the high concentration of methamidophos （250 mg/kg） produced prominent effects on nifH gene diversity in the following weeks. Cluster analysis showed that minimal changes of nifH gene composition were found at 1 week and maximal changes at 4 weeks. Toxic effects of acetochlor and methamidophos combination on nifH gene were also apparent. Different nifH genes （bands） responded differently to the impact of agrochemicals： four individual bands were eliminated by the application of the agrochemicals, five bands became predominant by the stimulation of the agrochemicals, and four bands showed strong resistance to the influence of the agrochemicals. Fifteen prominent bands were partially sequenced, yielding 15 different nifH sequences, which were used for phylogenetic reconstructions. All sequences were affiliated with the alpha- and beta-proteobacteria, showing higher similarity to eight different diazotrophic genera.     

EDTA-enhanced phytoremediation of lead contaminated soil by Bidens maximowicziana

Phytoremediation is a potential cleanup technology for the removal of heavy metals from contaminated soils.Bidens maximowicziana is a new Pb hyperaccumulator,which not only has remarkable tolerance to Pb but also extraordinary accumulation capacity for Pb.The maximum Pb concentration was 1509.3 mg/kg in roots and 2164.7 mg/kg in overground tissues.The Pb distribution order in the B. maximowicziana was:leaf>stem>root.The effect of amendments on phytoremediation was also studied.The mobility of soil Pb and the Pb concentrations in plants were both increased by EDTA application.Compared with CK(control check),EDTA application promoted translocation of Pb to overground parts of the plant.The Pb concentrations in overground parts of plants was increased from 24.23-680.56 mg/kg to 29.07-1905.57 mg/kg.This research demonstrated that B.maximowicziana appeared to be suitable for phytoremediation of Pb contaminated soil,especially,combination with EDTA.     

Distribution and ecological effect of mercury in Laogang landfill, Shanghai, China

Laogang landfill near Shanghai is the largest landfill in China, and receives about 10000 t of daily garbage per day, Samples of topsoil and plants were analyzed to evaluate mercury pollution from the landfill. For topsoil samples, there were significant correlations among total mercury （HgT）, combinative mercury （Hgc） and gaseous mercury （HgG）, and content of total organic carbon （TOC）, but, no significantly relationship was found between Hg content and filling time. Hg content changes in vertical profiles with time showed that the average Hgv of profiles 1992, 1996, and 2000 was similar, but their average HgG was quite different. HgT was significantly correlated with Hgc in profile 1992 and 2000, and Hgv was significantly correlated with Hg6 in profile 1996. HgG/Hgv ratio in profile samples decreased in the order of （HgG,/HgT）1992〉（HgG/HgT）1996〉〉（HgG/HgT）2000. A simple outline of Hg release in landfill could be drawn： with increasing of filling time, degradation undergoes different biodegradation, accordingly, gaseous mercury goes through small, more, and small proportion to total mercury. Distribution of Hg in plants was inhomogeneous, following the order of leaf〉root〉stem. The highest value of leaf may be associated with higher atmospheric Hg from landfill. Ligneous plants （e.g. Phyllostachys glanca, Prunus salicina and Ligustrum lucidum） are capable of enriching more Hg than herbaceous plants.     

Arsenic uptake by arbuscular mycorrhizal maize （Zea mays L.） grown in an arsenic-contaminated soil with added phosphorus

The effects of arbuscular mycorrhizal (AM) fungus (Glomus mosseae) and phosphorus (P) addition (100 mg/kg soil) on arsenic (As) uptake by maize plants (Zea mays L.) from an As-contaminated soil were examined in a glasshouse experiment.Non-mycorrhizal and zero-P addition controls were included.Plant biomass and concentrations and uptake of As,P,and other nutrients,AM colonization,root lengths,and hyphal length densities were determined.The results indicated that addition of P significantly inhibited root colonization and development of extraradical mycelium.Root length and dry weight both increased markedly with mycorrhizal colonization under the zero-P treatments,but shoot and root biomass of AM plants was depressed by P application.AM fungal inoculation decreased shoot As concentrations when no P was added,and shoot and root As concentrations of AM plants increased 2.6 and 1.4 times with P addition,respectively.Shoot and root uptake of P,Mn,Cu,and Zn increased,but shoot Fe uptake decreased by 44.6%,with inoculation, when P was added.P addition reduced shoot P,Fe,Mn,Cu,and Zn uptake of AM plants,but increased root Fe and Mn uptake of the nonmycorrhizal ones.AM colonization therefore appeared to enhance plant tolerance to As in low P soil,and have some potential for the phytostabilization of As-contaminated soil,however,P application may introduce additional environmental risk by increasing soil As mobility.     

Enzymatic oxidation of aqueous pentachlorophenol

The influence of the nonionic surfactant Tween 80 on pentachlorophenol （PCP） oxidation catalyzed by horseradish peroxidase was studied. The surfactant was tested at concentrations below and above its critical micelle concentration （CMC）. Enhancement of PCP removal was observed at sub-CMCs. The presence of Tween 80 in the reaction mixture reduced enzyme inactivation which occurred through a combination of free radical attack and sorption by precipitated products. A simple first-order model was able to simulate time profiles for enzyme inactivation in the presence or absence of Tween 80. At supra-CMCs, the surfactant caused noticeable reductions in PCP removal, presumably through micelle partitioning of PCP which precluded the hydrophobic PCP molecule from interacting with the enzyme.     

Decomposition of alachlor by ozonation and its mechanism

Decomposition and corresponding mechanism of alachlor, an endocrine disruptor in water by ozonation were investigated. Results showed that alachlor could not be completely mineralized by ozone alone. Many intermediates and final products were formed during the process, including aromatic compounds, aliphatic carboxylic acids, and inorganic ions. In evoluting these products, some of them with weak polarity were qualitatively identified by GC-MS. The information of inorganic ions suggested that the dechlorination was the first and the fastest step in the ozonation of alachlor.     

Degradation of metabolites accumulated of benzo[a]pyrene by coupling Penicillium Chrysogenum with KMnO4

Several main metabolites of benzo[a]pyrene （BaP） formed by Penicillium chrysogenum, Benzo[a]pyrene-1,6-quinone （BP 1,6- quinone）, trans-7,8-dihydroxy-7,8-dihydrobenzo[a]pyrene （BP 7,8-diol）, 3-hydroxybenzo[a]pyrene （3-OHBP）, were identified by high-performance liquid chromatography （HPLC）. The three metabolites were liable to be accumulated and were hardly further metabolized because of their toxicity to microorganisms. However, their further degradation was essential for the complete degradation of BaP. To enhance their degradation, two methods, degradation by coupling Penicillium chrysogenum with KMnO4 and degradation only by Penicillium chrysogenum, were compared; Meanwhile, the parameters of degradation in the superior method were optimized. The results showed that （1） the method of coupling Penicillium chrysogenum with KMnO4 was better and was the first method to be used in the degradation of BaP and its metabolites; （2） the metabolite, BP 1,6-quinone was the most liable to be accumulated in pure cultures; （3） the effect of degradation was the best when the concentration of KMnO4 in the cultures was 0.01% （w/v）, concentration of the three compounds was 5 mg/L and pH was 6.2. Based on the experimental results, a novel concept with regard to the bioremediation of BaP-contaminated environment was discussed, considering the influence on environmental toxicity of the accumulated metabolites.     

Impact of atrazine and nitrogen fertilizers on the sorption of chlorotoluron in soil and model sorbents

Sorption of chlorotoluron in ammonium sulfate, urea and atrazine multi-solutes system was investigated by batch experiments. The results showed application of nitrogen fertilizers to the soil could affect the behavior of chlorotoluron. At the same concentration of N, sorption of chlorotoluron decreased as the concentration of atrazine increased on the day 0 and 6 in soil, respectively. The sorption of chlorotoluron increased from 0 to 6 d when soils were preincubated with deionized water, ammonium sulfate and urea solution for 6 d. That indicated incubation time was one of the most important factors for the sorption of chlorotoluron in nitrogen fertilizers treatments. The individual sorption isotherms of chlorotoluron in rubbery polymer and silica were strictly linear in single solute system, but there were competition sorption between pesticides or between pesticides and nitrogen fertilizers. That indicated the sorption taken place by concurrent solid-phase dissolution mechanism and sorption on the interface of water-organic matter or water-mineral matter.