超市异味VOCs成分分析及健康风险评估

超市食品容易产生异味,导致顾客产生不愉悦的嗅觉感受,这些异味的主要成分是挥发性有机物(Volatile Organic Compounds,VOCs).为确定超市异味VOCs化学成分及其来源,对超市开展现场采样检测.本研究采用3种不同的VOCs采样检测方法:吸附管采样-热脱附-气相色谱/质谱法(TD-GC/MS)、气袋采样-TD-GC/MS和苏玛罐采样-气相色谱-火焰离子化检测/质谱法(GC-FID/MS),对超市室内空气中的VOCs进行采样检测比较.结果表明,苏玛罐采样法的总挥发性有机物(Total Volatile Organic Compounds,TVOC)体积分数为63.3×10^-9～86.8×10^-9,共检测出26种VOCs,主要包括卤代烃、烷烃和苯系物,但异味贡献较小,未检测出异味较大的VOCs;气袋采样法仅检测出9种VOCs,且φ(TVOC)均小于10.0×10^-9,说明气袋存在显著壁吸附效应,不适用于本次实验;吸附管采样法的检测结果显示,φ(TVOC)为79.5×10^-9～86.1...     

烹调油烟中挥发性有机物的排放初探

挥发性有机化合物(VOCs)是大气臭氧和二次有机气溶胶污染的关键前体物,而烹调油烟排放的VOCs作为大气中VOCs的重要来源之一,对其排放浓度进行研究具有重要意义.从食用油的烧杯加热实验入手,简化模拟烹调油烟发生情景,采用Tenax吸附管采样,热脱附-气相色谱-质谱法(GC-MS)定量检测分析,以加热温度和油品作为变量,对花生油、葵花籽油、大豆油、调和油和橄榄油在不同温度下加热生成的油烟VOCs浓度进行了比较分析,并初步估算了在实验温度范围内典型食用油单位时间内油烟VOCs的排放强度.结果表明,5种典型食用油随着加热温度的升高,排放的油烟中VOCs的浓度也随之升高;而在同一温度下加热5种食用油,调和油产生的油烟中VOCs的浓度最低;对不同温度下典型食用油单位时间内油烟VOCs的排放强度进行拟合,结果为二项式最优,其单位时间内油烟VOCs的排放强度范围为1.6～11.1 mg.(kg.min)-1.     

长白山背景站大气VOCs浓度变化特征及来源分析

挥发性有机物(VOCs)是臭氧和二次有机气溶胶的重要前体物.为研究中国东北背景地区大气中VOCs浓度和变化特征,应用苏码罐采样技术、三步冷冻浓缩和GC/MS联用技术测定了长白山大气本底站中的VOCs组成、浓度及季节变化,并利用PCA(principal component analysis)受体模型初步解析了白山大气中VOCs来源.结果表明,长白山地区TVOCs年平均浓度(体积分数)为10.7×10~(-9)±6.2×10~(-9),其中卤代烃所占比例最高,占VOCs总浓度的37%,其次是烷烃33%、芳香烃15%、烯烃15%.长白山地区TVOCs呈现明显的季节变化,变化特征为春季﹥秋季﹥夏季﹥冬季,春季大气中的TVOCs浓度显著(P﹤0.05)高于其他季节.利用主成分分析VOCs物种,提取出5个因子,分别归纳为交通源、液化石油气(LPG)、生物源、燃烧源和区域工业输送.结合HYSPLIT-4.0后向轨迹模型,分析周边区域传输对VOCs物种浓度的影响,发现来自西南向气团传输是长白山VOCs物种浓度增加的主要原因.     

不同排放标准下机动车挥发性有机化合物排放特征趋势研究

针对机动车挥发性有机物（VOCs）排放特征研究中缺乏含氧VOCs（OVOCs）覆盖、缺乏最新国VI排放标准特征识别等问题,本研究选取了涵盖国I~国VI不同排放标准的轻型汽油车和国Ⅲ~国Ⅴ柴油车为研究对象进行底盘测功机测试,采用SUMMA罐和DNPH管采样相结合的方法,探究了不同排放标准下机动车尾气中VOCs排放特征的变化趋势及启动方式对VOCs排放特征的影响.结果表明,不同排放标准的轻型汽油车尾气组成呈现较大差异.随着排放标准的升级,烷烃、烯炔烃和芳香烃的质量比例逐渐减少,OVOCs逐渐增加,国Ⅰ~国IV轻型汽油车排放以烷烃和芳香烃为主,国V~国Ⅵ轻型汽油车排放以OVOCs为主.国VI轻型汽油车中OVOCs占比高达58.0%,其中,甲醛、乙醛和丙酮合计占47.3%.不同排放标准的柴油车尾气中VOCs均以OVOCs和烯炔烃为主,占79.0%~83.0%.此外,冷启动是机动车尾气VOCs排放的主要阶段,此阶段的VOCs排放因子显著高于热启动,但随着排放标准升级,柴油车在启动阶段的VOCs排放降幅仅有约40%,显著小于全工况排放降幅（77.5%）,表明柴油车启动过程对VOCs排放贡献随排放标准升级逐步加大.本研究凸显了在我国机动车排放标准不断升级的背景下VOCs排放的重要性,需要在制定机动车VOCs排放控制策略中重点关注柴油车尾气中烯炔烃和汽油车尾气中OVOCs减排.     

基于GC-MS的烹调油烟VOCs的组分研究

挥发性有机物(VOCs)是PM2.5和臭氧生成的重要前体物之一,而VOCs组分不同,对大气反应的贡献也不同.烹调油烟排放的VOCs作为大气中VOCs的重要来源之一,其化学成分随所选用的食用油种类、食品种类、烹调方式、加热温度等的不同有很大差异.从对食用油的烧杯加热实验入手,简化模拟烹调油烟发生情景,以油温和油品为变量,采用Tenax吸附管采样,热脱附-气相色谱-质谱法(GC-MS)对不同油品在不同温度下加热产生的VOCs进行组分分析,根据谱库检索和图谱解析,利用面积归一化的半定量法,对各条件下油烟VOCs的具体组分进行了初步的定性和定量.     

机动车排放中挥发性有机污染物的组成及其特征研究

应用大气采样罐采样技术和色谱-质谱联用(GC-MS)技术,对广州市环境空气、交通道路、城市隧道和汽车尾气中55种挥发性有机物(VOCs)的组分及其质量浓度水平进行测试,并研究了广州市机动车VOCs排放特征.结果表明:①城区环境空气质量本底观测点白云山摩星岭的大气样品中ρ(VOCs)数量级为10-1～101 μg/m3,其中烷烃类、烯烃类、乙炔和单环芳香烃类平均质量浓度分别为13.97,15.15,6.16和43.27 μg/m3.市区主要交通干道(东风中路、环市中路和新港西路)旁空气样品的ρ(VOCs)数量级为101～102μg/m3,其中烷烃类、烯烃类、乙炔和单环芳香烃类最高质量浓度相应比环境本底质量浓度高约20～30倍.②在怠速条件下检测了摩托车、出租车、大客车、轻型卡车、小轿车和公交车等6种新车和在用车型VOCs的排放,其组成和质量浓度因机动车类型、功率和燃料不同而不同,一般功率越大VOCs排放越严重,ρ(VOCs)数量级大致为10-1～103mg/m3,为交通干道空气ρ(VOCs)的1 000倍以上.其中LPG车具有最高的烷烃类、烯烃类和乙炔排放量,测试样品的ρ(VOCs)分别为815.79～2 001.66,696.84～1 799.10和53.87～416.13 mg/m3.而柴油车排放的VOCs远远低于其他燃料车型.③通过对广州珠江隧道连续48 h的监测,研究了隧道内交通特征、微气象特征和VOCs组成及其质量浓度水平,能够计算出广州机动车55种VOCs化合物的平均排放因子.      

基于GC-MS对原油装卸VOCs组分的研究

挥发性有机物(VOCs)是二次有机气溶胶(SOA)和光化学烟雾的重要前体物,原油装卸VOCs化学成分随原油种类、伴热温度、搅拌速度等的不同而呈现很大差异。本文以伴热温度和搅拌速度为变量,采用Tenax吸附管采样并利用热脱附-气相色谱-质谱法(GC-MS)对原油在不同伴热和搅拌速度下产生的VOCs进行组分分析。根据谱库检索和图谱解析,利用面积归一化的半定量法分析原油VOCs的具体组分。结果表明:通过热脱附GC-MS法分析检测出54种VOCs,其中,含氧有机物19种,含氮硫化合物13种,碳氢化合物22种;碳氢化合物占VOCs总量的44.75%～50.75%,含氧有机物占VOCs总量的29.47%～37.63%,含氮硫化合物占VOCs总量的15.34%～22.63%。     

罐采样与气相色谱/质谱结合在VOCs监测中的应用

气态挥发性有机物(VOCs)引起的污染严重威胁人们的健康,因而对其监测技术的研究也越来越多。其中罐采样与气相色谱/质谱联用的检测技术在VOCs气态污染物测定中的应用逐步受到关注。对罐采样技术进行了综述,重点介绍了罐采样与气相色谱/质谱联用技术在环境空气、室内空气、废气中VOCs检测的应用。     

电子产品加工制造企业挥发性有机物(VOCs)排放特征

根据美国EPA挥发性有机物标准检测法TO-11及TO-14/15,采用VOCs快速检测仪、Summa罐及DNPH吸附管,对我国某大型电子产品加工制造企业中不同工艺环节生产车间内部及生产线最终废气排放管道中VOCs含量水平及组分特征进行检测.结果表明,该企业涉及VOCs排放工艺中压铸车间总挥发性有机物(TVOCs)浓度为0.1~0.5 mg·m-3、机加工车间TVOCs浓度为1.5~2.5 mg·m-3、喷涂车间中TVOCs浓度为20~200 mg·m-3,各车间VOCs组分主要包括烷类、烯炔类、芳香类、酮类、酯类和醚类,共20余种.其中涂装车间内苯系物及酮类物质为主要VOCs组分,各物质浓度分别为苯0.02~0.34 mg·m-3、甲苯0.24~3.35 mg·m-3、乙苯0.04~1.33 mg·m-3、对二甲苯0.13~0.96 mg·m-3、邻/间二甲苯0.02~1.18mg·m-3、丙酮0.29~15.77 mg·m-3、2-丁酮0.06~22.88 mg·m-3、环己酮0.02~25.79 mg·m-3、甲基异丁基甲酮0~21.29mg·m-3.根据该企业生产特征及工艺数据计算,其单条生产线VOCs年排放量为14 t,整个厂区年排放量约为840 t.结合生产流程及生产工艺分析,喷涂过程中的溶剂使用是电子产品加工制造企业的VOCs主要排放来源,废气排放口是重点排放点.     

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.     

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.     

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.     

Potential of plant polyphenol oxidases in the decolorization and removal of textile and non-textile dyes

In this study an effort has been made to use plant polyphenol oxidases; potato （Solanum tuberosum） and brinjal （Solanum melongena）, for the treatment of various important dyes used in textile and other industries. The ammonium sulphate fractionated enzyme preparations were used to treat a number of dyes under various experimental conditions. Majority of the treated dyes were maximally decolorized at pH 3.0. Some of the dyes were quickly decolorized whereas others were marginally decolorized. The initial first hour was sufficient for the maximum decolorization of dyes. The rate of decolorization was quite slow on long treatment of dyes. Enhancement in the dye decolorization was noticed on increasing the concentration of enzymes. The complex mixtures of dyes were treated with both preparations of polyphenol oxidases in the buffers of varying pH values. Potato polyphenol oxidase was significantly more effective in decolorizing the dyes to higher extent as compared to the enzyme obtained from brinjal polyphenol oxidase. Decolorization of dyes and their mixtures, followed by the formation of an insoluble precipitate, which could be easily removed simply by centrifugation.     

Removal of heavy metals from sewage sludge by low costing chemical method and recycling in agriculture

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Single and joint effects of pesticides and mercury on soil urease

The influence of two pesticides including chlorimuron-ethyl and furadan and mercury （Hg） on urease activity in 4 soils （meadow burozem and phaeozem） was investigated. The soils were exposed to various concentrations of the two pesticides and Hg individually and simultaneously. Results showed that there was a close relationship between urease activity and organic matter content in soil. Chlorimuron-ethyl and furadan could both activate urease in the 4 soils. The maximum increment of urease activity by chlorimuronethyl was up to 14%-18%. There was almost an equal increase （up to 13%-21%） in the urease activity by furadan. On the contrary, Hg markedly inhibited soil urease activity. A logarithmic equation was used to describe the relationship （P〈0.05） between the concentration of Hg and the activity of soil urease in the 4 tested soils. Semi-effect dose （ED50） values by the stress of Hg based on the inhibition of soil urease in the 4 soils were 88, 5.5, 24 and 20 mg/kg, respectively, according to the calculation of the corresponding equations. The interactive effect of chlorimuron-ethyl or furadan with metal Hg on soil urease was mainly synergic at the highest tested concentrations.     

Isolation and preliminary characterization of a 3-chlorobenzoate degrading bacteria

A study was conducted to compare the diversity of 2-, 3-, and 4-chlorobenzoate degraders in two pristine soils and one contaminated sewage sludge. These samples contained strikingly different populations of mono-chlorobenzoate degraders. Although fewer cultures were isolated in the uncontaminated soils than contaminated one, the ability of microbial populations to mineralize chlorobenzoate was widespread. The 3- and 4-chlorobenzoate degraders were more diverse than the 2-chlorobenzoate degraders. One of the strains isolated from the sewage sludge was obtained. Based on its phenotype, chemotaxonomic properties and 16S rRNA gene, the organism S-7 was classified as Rhodococcus erythropolis. The strain can grow at temperature from 4 to 37℃. It can utilize several （halo）aromatic compounds. Moreover, strain S-7 can grow and use 3-chlorobenzoate as sole carbon source in a temperatures range of 10-30℃ with stoichiometric release of chloride ions. The psychrotolerant ability was significant for bioremediation in low temperature regions. Catechol and chlorocatechol 1,2-dioxygenase activities were present in cell free extracts of the strain, but no （chloro）catechol 2,3- dioxygenase activities was detected. Spectral conversion assays with extracts from R. erythropolis S-7 showed accumulation of a compound with a similar UV spectrum as chloro-cis,cis-muconate from 3-chlorobenzoate. On the basis of these results, we proposed that S-7 degraded 3-chlorobenzoate through the modified ortho-cleave pathway.     

Organochlorine pesticides in soils under different land usage in the Taihu Lake region, China

A field study was conducted in the Taihu Lake region, China in 2004 to reveal the organochlorine pesticide concentrations in soils after the ban of these substances in the year 1983. Thirteen organochlorine pesticides (OCPs) were analyzed in soils from paddy field, tree land and fallow land. Total organochlorine pesticide residues were higher in agricultural soils than in uncultivated fallow land soils. Among all the pesticides, ΣDDX (DDD, DDE and DDT) had the highest concentration for all the soil samples, ranging from 3.10 ng/g to 166.55 ng/g with a mean value of 57.04 ng/g and followed by ΣHCH, ranging from 0.73 ng/g to 60.97 ng/g with a mean value of 24.06 ng/g. Dieldrin, endrin, HCB and α-endosulfan were also found in soils with less than 15 ng/g. Ratios of p,p'-(DDD DDE)/DDT in soils under three land usages were: paddy field ＞ tree land ＞ fallow land, indicating that land usage inlfuenced the degradation of DDT in soils. Ratios of p,p'-(DDD DDE)/DDT ＞1, showing aged residues of DDTs in soils of the Taihu Lake region. The results were discussed with data from a former study that showed very low actual concentrations of HCH and DDT in soils in the Taihu Lake region, but according to the chemical half-lives and their concentrations in soils in 1980s, the concentration of DDT in soils seemed to be underestimated. In any case our data show that the ban on the use of HCH and DDT resulted in a tremendous reduction of these pesticide residues in soils, but there are still high amounts of pesticide residues in soils, which need more remediation processes.     

Sorption of 1-naphthol by plant cuticular fractions

The contribution of aliphatic-rich plant biopolymer to sorption of hydrophobic organic compounds is significantly important because of their preservation and accumulation in the soil environment,but sorption mechanism is still not fully understood.In this study, sorption of 1-naphthol by plant cuticular fractions was examined to better understand the contributions of respective fraction.Toward this end,cuticular materials were isolated from the fruits of tomato by chemical method.The tomato cuticle sheet consisted of waxes (6.5 wt%),cuticular monomer (69.5 wt%),and polysaccharide (24.0 wt%).Isotherms of l-naphthol to the cuticular fractions were nonlinear (N value (0.82-0.90)) at the whole tested concentration ranges.The KodKow ratios for bulk cuticle (TC1),dewaxed cuticle (TC2),cutin (TC4),and desugared cuticle (TC5) were larger than unity,suggested that tomato bulk cuticle and cutin are much powerful solption medium.Sorption capability of cutin (TC4) was 2.4 times higher than the nonsaponifiable fraction (TC3).The 1-naphthol interactions with tomato cuticular materials were governed by both hydrophobic-type interactions and polar (H-bonding) interactions. Removal of the wax and polysaccharide materials from the bulk tomato cuticle caused a significant increase in the sorption ability of the cuticular material.There was a linear negative trend between K_(oc) values and the amount of polysaccharides or fraction's polarities ((N O)/C);while a linear positive relationship between K_(oc) values and the content of cutin monomer (linear R~2=0.993) was observed for present in the cuticular fractions.Predominant sorbent of the hydrophobic organic compounds (HOCs) in the plant cuticular fraction was the cutin monomer,contributing to 91.7% of the total sorption of tomato bulk cuticle.     

Alterations of organ histopathology and metallolhionein mRNA expression in silver barb, Puntius gonionotus during subchronic cadmium exposure

Common silver barb,Puntius gonionotus,exposed to the nominal concentration of 0.06 mg/L Cd for 60 d,were assessed for histopathological alterations(gills,liver and kidney),metal accumulation,and metallothionein(MT)mRNA expression.Fish exhibited pathological symptoms such as hypertrophy and hyperplasia of primary and secondary gill lamellae,vacuolization in hepatocytes,and prominent tubular and glomerular damage in the kidney.In addition,kidney accumulated the highest content of cadmium,more than gills and liver.Expression of MT mRNA was increased in both liver and kidney of treated fish.Hepatic MT levels remained high after fish were removed to Cd-free water.In contrast,MT expression in kidney was peaked after 28 d of treatment and drastically dropped when fish were removed to Cd-free water.The high concentrations of Cd in hepatic tissues indicated an accumulation site or permanent damage on this tissue.     

Seed selections for crystallization of calcium phosphate for phosphorus recovery

Seed induces and promotes the crystallization of calcium phosphate, and acts as carrier of the recovered phosphorus （P）. In order to select suitable seed for P recovery from wastewater, three seeds including Apatite （AP）, Juraperle （JP） and phosphate-modified Juraperle （M-JP） were tested and compared. Batch and fixed-bed column experiments of seeded crystallization of calcium phosphate were undertaken by using synthetic wastewater with 10 mg/L P phosphate. It shows that AP has bad enduring property in the crystallization process, while JP has better performance for multiple uses, and M-JP is a hopeful seed for P recovery by crystallization of calcium phosphate.