陶瓷膜组合工艺对水中甲硫醚去除效果研究

采用顶空-固相微萃取和色谱质谱联用仪器方法调查严重污染的河流、相关水源中甲硫醚嗅味物质的分布.结果表明,河流中甲硫醚浓度高达2 907 ng/L,受污染的相关水源中甲硫醚浓度达到53 ng/L.单独陶瓷无机膜工艺对DMS去除的效果为20％左右,而臭氧氧化则具有较好的效果,臭氧-陶瓷膜组合工艺对DMS去除率达到50％～9...     

二甲基硫醚光解及二甲基二硫醚生成速率研究

用低压汞灯照射二甲基硫醚（ＤＭＳ）,在２０ｍ的长光池中用富里叶红外光谱仪测量其光解产物,结果表明二甲基硫醚光解生成二甲基二硫醚（ＤＭＤＳ）和乙烷。测量其不同光照时间的光解产物,结果表明Ｉｎ＾ｃ０／ｃｔ在直解坐标上是一条直线,说明了二甲基二硫醚生成按生一极反应进行,其生成的速率常数为８．７０×１０＾－５ｓ＾－１用低压汞灯照射ＤＭＳ＋Ｈ２Ｏ２体系,富里叶红外光谱检测其产物,在有足够的Ｈ２Ｏ２情况下,生     

典型农药污染地块土壤中异味物质的筛查与分布特征研究

针对我国农药污染地块修复过程中异味扰民的突出环境问题,开展地块土壤中异味物质的筛查,明确异味物质在土壤中的分布至关重要. 本文以某典型农药污染地块土壤为研究对象,通过对土壤气样品全扫描分析、异味清单比对、异味活度值计算、累计异味贡献率分析等方法,筛查确定土壤中主要的异味物质;基于筛查结果,通过土壤样品采集,应用GC-MS分析,查明土壤中主要异味物质的污染程度和空间分布. 结果表明:①该典型农药污染地块土壤中涉及二甲基硫醚、二甲基二硫醚、甲苯、三氯乙烯、二硫化碳、氯仿、邻-二甲苯、间/对-二甲苯、苯、噻吩、甲基环己烷、正己烷、四氯乙烯、乙苯和四氯化碳15种异味物质,异味活度值分别为7 287.5、2 755.6、714.8、676.7、438.5、294.5、229.4、74.7、55.4、50.0、49.6、18.9、3.1、1.7和0.6. ②累计异味贡献率超过90%的主要异味物质为二甲基硫醚、二甲基二硫醚、甲苯和三氯乙烯,四者最高含量分别为10.9、48.5、797.7和33 000.0 mg/kg,主要分布在除草剂车间、菊酯车间、敌敌畏车间、氧化制氯车间、百草枯车间和氧乐果车间等生产区域. ③异味物质含量普遍随土壤埋深的增加表现为先增后降,主要分布在1.8~6.8 m的粉质黏土和6.8~10.6 m的粉土中. 研究显示,农药污染地块土壤中异味物质种类复杂,可采用累计异味贡献率分析法进行筛查;地块土壤中异味物质的空间分布主要与生产过程、土壤埋深和土壤性质有关.      

北京市石景山区夏季雨水和大气中PCBs的特征解析

利用气相色谱-质谱联用技术(GC-MS)对北京市石景山城区夏季雨水和大气中多氯联苯(PCBs)的分布特征进行了解析.结果表明,雨水中主要为溶解态PCBs,比例高达65.23%.大气中的PCBs以气态为主,占67.70%.研究表明,雨水对大气中颗粒态和气态PCBs的清除系数相当,分别为6.00×104和5.37×104.8种类二 PCBs同类物的毒性当量总和在大气气相、颗粒相和雨水中分别为0.36pg/m3、0.02pg/m3和0.29ng/L.北京石景山地区8种类二 PCBs同类物对成人呼吸暴露值为0.08pg/(kg·d),说明北京石景山地区人群呼吸暴露风险比较低.     

夏季东海生源硫的分布、通量及其对非海盐硫酸盐的贡献

对2012年6月东海表层海水中二甲基硫（DMS）、二甲巯基丙酸内盐（DMSP）和二甲亚砜（DMSO）的浓度分布特征及其影响因素进行了研究,并估算了DMS的海-气通量及其对大气气溶胶中非海盐硫酸盐（nss-SO₄^2-）的贡献率.结果表明,DMS、溶解态DMSP（DMSPd）、颗粒态DMSP（DMSPp）、溶解态DMSO（DMSOd）和颗粒态DMSO（DMSOp）的浓度平均值±标准偏差为（5.71±5.23）,（5.94±3.68）,（23.84±14.15）,（9.14±10.52）和（11.01±5.81）nmol/L.DMS、DMSP和DMSOp浓度均在28oN~29oN,122°E~123.5°E海域呈现高值中心,沿中心向外扩散降低,并且与叶绿素a（Chl-a）的分布趋势基本一致.除DMSOd外,3种二甲基硫化物与Chl-a表现出显著的相关性,表明浮游植物生物量是影响东海生源有机硫化物生产分布的关键因素.此外,夏季东海DMS海-气通量介于（0.93~101.02）μmol/（m²·d）,平均值±标准偏差为（18.13±21.42）μmol/（m²·d）.夏季东海生源硫释放对nss-SO₄^2-的贡献率仅为2.2%,表明人为排放是东海大气气溶胶中nss-SO₄^2-的主要来源.     

无锡市饮用水嗅味突发事件致嗅原因及潜在问题分析

针对2007年5月底6月初发生的无锡市饮用水嗅味事件,在嗅味层次分析法(FPA)的基础上,利用感官气相色谱法对污染水团、取水口以及管网水中的致嗅物质种类进行了鉴定,并利用GC-MS对主要致嗅物质进行了定量分析,同时,对微囊藻毒素含量以及生物遗传毒性进行了测定.结果表明,此次嗅味事件的主要致嗅物质为以二甲基三硫为主的硫醚类有机体腐败产物,6月4日采集的污染水团中二甲基三硫含量高达11399 ng·L-1.同时,含有一定量的2-甲基异莰醇(MIB)等藻类分泌物,但这些物质的嗅味被二甲基三硫等硫醚类化合物导致的腥臭味所掩盖,不是主要的致嗅物质.另外,6月4日及6月8日采集的取水口样品分析结果表明,原水中微囊藻毒素含量远低于新颁布的生活饮用水卫生标准,而且,利用umu测试得到的水中遗传毒性水平很低.     

硫化物恶臭气体的生物处理机理与应用

致臭的含硫化合物，尤其是二甲基硫化物的生物处理去除率较低，通过分离鉴定或悬浮，附着生长培养等手段，发展能降解气相硫化物的主要是化能自养型和甲基营养型的微生物，它们能将硫化物定量地氧化为SO4^2-和CO2，大部分能降解甲基硫化物的微生物，其适宜PH为中性，甲硫醇和硫化氢是二甲基硫代谢的中间体，参与二甲基硫代的酶系统不稳定，是处理效果不佳的主要原因，利用纯细胞接种，可有效地提高生物过滤器的脱臭效果，今后可从高效菌选育和固定化方式的改进等方面，进一步提高气相含硫恶臭物的生物处理效果。     

珠江三角洲典型生态系统有机含硫气体地气交换通量比较

选取珠江三角洲森林、稻田和城市草地和菜地为研究对象,运用静态箱法,测量土壤COS、DMS、CS2和DMDS通量,并分析了环境因子对含硫气体交换速率的影响。结果表明,稻田和菜地交换速率最大,城市草地次之,森林土壤交换速率最小。森林土壤吸收COS,释放DMS,有凋落物土壤气体交换速率高于无凋落物土壤,CS2和DMDS源与汇存在很大不确定性。森林COS通量受温度、土壤含水量、土壤肥力、土壤微生物和土壤呼吸的共同影响;有水稻稻田吸收COS,无水稻稻田释放COS,有水稻稻田DMS释放速率显著高于无水稻稻田。干旱稻田土壤吸收COS,水淹土壤释放COS,但DMS、CS2和DMDS释放速率两者间无显著影响;城市草地吸收COS释放DMS,CS2和DMDS存在不确定性,有草土壤COS和DMS交换速率高于无草土壤,割草前后气体释放速率无显著变化;菜地释放VOSCs,其中DMDS占75%。     

Comprehensive characterization of ambient nanoparticles collected near an industrial science park: Particle size distributions and relationships with environmental factors

We investigated the characteristics of ambient particles and their relationships with various environmental factors, including gaseous pollutants (CH4, non-methane hydrocarbons (NMHC), total hydrocarbons (THC), NOx, CO, SO2), meteorological parameters (humidity, temperature), and time (day/night, workday/weekend). We used an electrical low-pressure cascade impactor to measure the number and size distributions of ambient particles (0.007–10 m) that were collected approximately 1 km northwest of Hsinchu Science Park in Taiwan between February and May 2007. The number concentrations of particles were enhanced through photochemical reactions during the day. In addition, high traffic flow during workdays increased the formation of particulates. Except for SO2, all of the gaseous pollutants we studied (CH4, NMHC, THC, NOx, CO) correlated positively with the total number concentrations of ambient particles during daytime, indicating that they might contribute to the particulate burden. The poorer relationship between the SO2 level and the total number concentration of particles suggests that SO2 might participate indirectly in the nucleation process during particle formation, The high enrichment factors for Zn, Pb, Cu, and Mn, which mostly comprised the ultrafine particles (diameter: < 0.1 m) and fine particles (diameter: 0.1–1 m), presumably arose from emissions from traffic and high technology factories. Heterogeneous reactions on solid particles might play a role in the removal of SOx and NOx from the atmosphere. Sulfides and nitrides can further react with these local pollutants, forming specific Cu-containing compounds: CuO (39%), CuSO4 (34%), and Cu(NO3)2 (27%), within the ambient particles in this industrial area.     

土壤中发生的挥发性有机硫气体的研究

测定了张北、封丘、鹰潭、吴县、长沙、湛江等地旱地土壤和水稻土在室内培养情况下挥性有机硫气体的释放。结果表明，这些土壤中产生硫化氢、氧硫化碳、甲基硫醇、二甲基硫、二硫化碳和二甲基二硫等含硫气体。水稻土中产生的有机硫气体高于旱地土壤，同时施用有机肥和化肥后，土壤中发生的有机硫气体高于仅施用化肥，在厌氧条件下检测到的有机硫气体高旱地土壤、同时施用有机肥和化肥后，土壤中发赡有机硫气体高于仅施用化肥。在厌氧     

Carbonyl sulfide and dimethyl sulfide fluxes in an urban lawn and adjacent bare soil in Guangzhou, China

Carbonyl sulfide (COS) and dimethyl sulfide (DMS) fluxes from an urban Cynodon dactylon lawn and adjacent bare soil were measured during April–July 2005 in Guangzhou, China. Both the lawn and bare soil acted as sinks for COS and sources for DMS. The mean fluxes of COS and DMS in the lawn (–19.27 and 18.16 pmol/(m2 sec), respectively) were significantly higher than those in the bare soil (–9.89 and 9.35 pmol/(m2 sec), respectively). Fluxes of COS and DMS in mowed lawn were also higher than those in bare soils. Both COS and DMS fluxes showed diurnal variation with detectable but much lower values in the nighttime than in the daytime. COS fluxes were related significantly to temperature and the optimal temperature for COS uptake was 29°C. While positive linear correlations were found between DMS fluxes and temperature. COS fluxes increased linearly with ambient COS mixing ratios, and had a compensation point of 336 ppt.     

水稻土中甲硫氨酸分解释放挥发性含硫气体的影响因素

为了探讨水稻土中含硫气体产生和释放的途径 ,在室内培养条件下 ,测定了南京水稻土中含硫气体的释放 .从该淹水土壤中测出 3种含硫气体 ;羰基硫 (COS)、二甲基硫 (DMS)和少量硫化氢 (H₂S)气体 .当土壤中加入甲硫氨酸后 ,DMS气体的释放量有了明显增加 ,此外还有大量甲硫醇 (CH₃SH)和二甲基二硫 (DMDS)气体测出 .而 COS在好氧条件 (普通大气淹水 )下的释放量明显增加 ,在厌氧条件 (充氮淹水 )下的释放量变化不明显 ;只有 H₂S的释放量几乎没变 .这些结果表明 ,甲硫氨酸的分解可能是 COS、DMS、CH₃SH和 DMDS的产生源之一 ,且释放含硫气体的种类明显不同于胱氨酸和半胱氨酸 .在好氧 (普通大气 )条件下 ,DMDS和 CH₃SH的释放量低于厌氧情况 (充氮气 )下的释放量 ,DMS则高于厌氧条件下的释放量 .这表明 ,水稻土中甲硫氨酸分解产生 DMDS和 CH3SH需较强的还原条件 ,产生这 2种气体的微生物需要严格的厌氧条件 .产生 DMS的微生物则比前者需要高一些的含氧量 .土壤 pH值和含水量及光照对甲硫氨酸分解释放含硫气体均有影响 .各含硫气体在持水率 50%、普通大气、光照条件下的释放量明显高于无光照条件下的释放量 .     

Off-flavor compounds from decaying cyanobacterial blooms of Lake Taihu

The effect of cyanobacterial bloom decay on water quality and the complete degradation of cyanobacterial blooms in a short period were examined by an enclosure experiment in Gonghu Bay of Lake Taihu,China.Water quality parameters as well as taste and odor compounds during the breakdown of cyanobacterial blooms were measured.Results showed that the decay of cyanobacterial blooms caused anoxic water conditions,decreased pH,and increased nutrient loading to the lake water.The highest concentrations of dimethyl sulfide (DMS),dimethyl trisulfide (DMTS),and β-cyclocitral were observed in the anoxic water,at 62331.8,12413.3,and 1374.9 ng/L,respectively.2-Methylisoborneol was dominant during the live growth phase of cyanobacterial blooms,whereas DMS and DMTS were dominant during the decomposition phase.Dissolved oxygen,pH,and chlorophyll a were negatively correlated with DMS,DMTS,and β-cyclocitral,whereas total phosphorus,total nitrogen,and ammonium (NH4+-N) were positively correlated with DMS,DMTS,β-cyclocitral,and β-ionone.The experimental results suggested that preventing the anaerobic decomposition of cyanobacterial blooms is an important strategy against the recurrence of a malodor crisis in Lake Taihu.     

APS-SMPS-WPS对南京夏季气溶胶数浓度的对比观测

为了对比3321型空气动力学粒径谱仪(APS)、3081/3085型气溶胶粒径谱仪(SMPS)和宽范围粒径谱仪(WPS)对气溶胶数浓度的观测性能,于2010年夏季在南京信息工程大学校内使用上述三台仪器进行了同步观测.将得到的数据进行对比,并结合校内自动气象站的气象资料对0.01~10μm气溶胶粒子的数浓度、日变化规律及谱分布特征进行分析.结果表明,3台仪器在总体数浓度变化趋势上表现出较好的一致性,但相同粒径段的粒子浓度NSMPS>NWPS>NAPS.SMPS比WPS尺度分辨率高,粒径范围在0.02~0.2μm时,SMPS与WPS相关性较好;APS测量气溶胶数浓度谱的连续性较WPS好.3种仪器在观测日变化趋势上都表现出双峰型,但SMPS的峰值浓度和出现峰值的粒径范围均高于或大于WPS.各类气象条件及降水对仪器间的测量误差影响不大.     

Sulfur-containing amino acid methionine as the precursor of volatile organic sulfur compounds in algea-induced black bloom

After the application of methionine, a progressive and significant increase occurred in five volatile organic sulfur compounds (VOSCs): methanethiol (MeSH), dimethyl sulfide (DMS), dimethyl disulfide (DMDS), dimethyl trisulfide (DMTS) and dimethyl tetrasulfide (DMTeS). Even in the untreated control without a methionine addition, methionine and its catabolites (VOSCs, mainly DMDS) were found in considerable amounts that were high enough to account for the water’s offensive odor. However, blackening only occurred in two methionine-amended treatments. The VOSCs production was observed to precede black color development, and the reaching of a peak value for total VOSCs was often followed by water blackening. The presence of glucose stimulated the degradation of methionine while postponing the occurrence of the black color and inhibiting the production of VOSCs. In addition, DMDS was found to be the most abundant species produced after the addition of methionine alone, and DMTeS appeared to be the most important compound produced after the addition of methionine+glucose. These results suggest that methionine acted as an important precursor of the VOSCs in lakes suffering from algea-induced black bloom. The existence of glucose may change the transformation pathway of methionine into VOSCs to form larger molecular weight compounds, such as DMTS and DMTeS.     

小麦田中有机硫气体的释放

采用密闭箱法对不同施肥条件下小麦田中羰基硫(COS)、二硫化碳(CS₂)和二甲基硫(DMS)的释放情况进行了监测.结果表明,小麦生长过程对COS、CS₂和DMS释放影响显著,小麦对COS有明显吸收作用,DMS和CS₂是麦田中释放的主要含硫气体.COS和CS₂释放速率昼夜变化明显.仅施用有机肥的麦田,硫释放总量高于其它田块.不同施肥条件的田块,硫释放总量范围在-1.40～0.79mg·ml^-2之间.     

水稻土中硫酸二乙酯分解产生含硫气体的研究

为了探讨水稻土中含硫气体产生和释放的途径，在室内培养条件下，测定了南京水稻土中含硫气体的释放。结果从该淹水土壤中测出3种含硫气体；硫化氢（H2S），羰基硫（COS）和二甲基硫（DMS）气体。当土壤中加入硫酸二乙酯后，不仅上述3种气体的释放量增加了，而且还明显测出甲硫醇（CH3SH）和二硫化碳（CS2）。据此推测，水稻土中硫酸二乙酯的分解可能是CH3SH、CS2、COS、H2S、DMS5种气体产生释放的来源之一。在好氧条件（普通大气）下：（1）H2S和COS的释放量低于厌氧条件（充氮）。（2）CS2和CH3SH的释放量高于厌氧条件。（3）DMS的释放量不受空气中氧气含量的影响。分析了培养前后土壤pH和Eh的变化和影响。     

Photochemical production of carbonyl sulfide, carbon disulfide and dimethyl sulfide in a lake water

Photochemical production of carbonyl sulfide(COS),carbon disulfide(CS_2) and dimethyl sulfide(DMS) was intensively studied in the water from the Aohai Lake of Beijing city.The lake water was found to be highly supersaturated with COS,CS_2 and DMS,with their initial concentrations of 0.91 ± 0.073 nmol/L,0.55 ± 0.071 nmol/L and 0.37 ± 0.062 nmol/L,respectively.The evident photochemical production of COS and CS_2 in the lake water under irradiation of 365 nm and 302 nm indicated that photochemical production of them might be the reason for their supersaturation.The similar dependence of wavelength and oxygen for photochemical production of COS,CS_2 and DMS implied that they might be from the same precursors.The water cage effect was found to favor COS production but inhibit CS_2and DMS formation,indicating that COS photochemical production was mainly from direct degradation of the precursors and the formation of CS_2 and DMS needed intermediates via combination of carbon-centered radicals and sulfur-centered radicals.The above assumptions were further confirmed by simulation experiments with addition of carbonyls and amino acids(cysteine and methionine),and the photochemical formation mechanisms for COS,CS_2 and DMS in water were derived from the investigations.     

含硫化合物对Methylosinus trichosporium OB3b生长和合成聚-β-羟基丁酸酯的影响

为了将人类活动排放的含有甲烷的废气用于聚-β-羟基丁酸酯(PHB)合成过程,以M.trichosporium OB3b为菌种,考察硫化氢(H2S)和甲硫醚(DMS)对甲烷氧化菌生长和PHB合成的影响。实验结果表明,H2S浓度高达2 500μmol/mol时对甲烷氧化菌生长及甲烷单加氧酶(MMO)活性基本无影响,含H2S时的PHB含量和产率比无H2S时高,甲烷氧化菌经H2S培养后PHB合成能力增强。然而,DMS浓度为200μmol/mol时即可明显抑制甲烷氧化菌的生长及MMO活性。在DMS存在条件下,PHB含量和PHB产率都明显降低,经DMS培养后甲烷氧化菌的PHB含量进一步降低。     

南半球海洋大气气溶胶单颗粒的理化特性分析

运用透射电子显微镜-X射线能谱技术分析了中国第29次南极科考期间采集的大气气溶胶单颗粒样品,获得颗粒物的形貌特征、混合状态、成分组成及数量分布等信息.结果表明,航渡区域海洋上空的颗粒物主要表现为4类:海盐颗粒、矿物颗粒、富硫颗粒和含碳颗粒,其中海盐颗粒占主导,本研究将海盐颗粒又分为新鲜、部分老化及完全老化的海盐颗粒.部分和完全老化的海盐颗粒占海盐颗粒总数的86%,且部分老化的海盐颗粒表面及完全老化的海盐颗粒以长条状Na2SO4成分为主.同时,发现两处采样点(印度洋中东部和南极内陆)的样品中富硫颗粒较多,根据后向气团轨迹判断这些富硫颗粒主要来源于海洋地区,推测是由海洋表面浮游生物释放的二甲基硫(dimethyl sulfide,DMS)经过大气氧化形成.本研究表明,南半球海洋大气中海盐颗粒老化是由海洋表面释放的DMS控制,这不同于北半球海洋大气中人为源影响的海盐颗粒老化现象.