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%。     

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.     

外源含硫化合物对土壤挥发性有机硫化合物交换通量的影响

通过静态箱采样和Entech7100预浓缩仪-GC-MS分析了半胱氨酸、硫化钠和硫酸钠对土壤吸收或释放羰基硫（COS）、二甲基硫醚（DMS）、二硫化碳（CS2）和二甲二硫醚（DMDS）等4种挥发性有机硫化合物（VOSCs）的影响.结果表明,添加半胱氨酸后,土壤由COS和CS2汇转变为源,DMS和DMDS通量显著增加,且...     

春季东海挥发性有机硫化物(VSCs)分布的研究

于2017年3~4月首次对东海表层海水及大气中3种主要挥发性有机硫化物（VSCs）即羰基硫（COS）、二甲基硫（DMS）、二硫化碳（CS₂）的浓度分布进行观测,研究了海水中3种主要VSCs的相关性,并估算了3种VSCs的海-气通量.结果表明,东海表层海水COS、DMS和CS₂的浓度平均值分别为（1.0±0.4）、（6.8±6.8）和（0.6±0.4）nmol/L,总体来看东海表层水中3种VSCs呈现出近岸高、远海低的分布趋势.相关性分析表明DMS与Chl-a存在显著相关性,表明浮游植物生物量是影响东海海水中DMS分布的主要因素;同时DMS与CS₂存在着显著的相关性,表明这2种物质的来源有着一定的共性.大气中COS、DMS和CS₂的浓度平均值分别为：（294.7±158.8）、（22.7±18.0）和（108.8±88.1）×10^-12,分布呈现出近岸高,远海低的趋势,主要受到人为活动等陆源输入的影响.此外春季东海COS、DMS和CS₂的海-气通量平均值分别为（4.0±3.4）、（25.8±33.8）和（2.6±2.9）μmol/（m²⋅d）,表明春季东海是大气中3种VSCs重要的源.     

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.     

水稻土中胱氨酸分解产生含硫气体的研究

测定在室内培养情况下南京水稻土中挥发性含硫气体的释放．结果表明,该土壤中产生Ｈ２Ｓ、羰基硫（ＣＯＳ）和二甲基硫（ＭＤＳ）气体．当土壤中加入胱氨酸后,检测到甲硫醇（ＣＨ３ＳＨ）、二硫化碳（ＣＳ２）、ＣＯＳ、Ｈ２Ｓ和ＤＭＳ气体．除ＤＭＳ之外,这些气体的释放量随胱氨酸添加量增加而增加．据此推测,水稻土中胱氨酸的分解可能是ＣＨ３ＳＨ、ＣＳ２、ＣＯＳ、Ｈ２Ｓ等４种气体产生释放的来源之一．在厌氧条件（充氮淹水）下检测到的含硫气体低于好氧条件（普通大气淹水）．光照、ｐＨ值、土壤含水量等对含硫气体的释放量均有影响     

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 .     

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。     

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     

Characteristics and anthropogenic sources of carbonyl sulfide in Beijing

Atmospheric mixing ratios of carbonyl sulfide (COS) in Beijing were intensively measured from March 2011 to June 2013. COS mixing ratios exhibited distinct seasonal variation, with a maximum average value of 849 ± 477 pptv in winter and a minimal value of 372 ± 115 pptv in summer. The seasonal variation of COS was mainly ascribed to the combined effects of vegetation uptake and anthropogenic emissions. Two types of significant linear correlations (R² > 0.66) were found between COS and CO during the periods from May to June and from October to March, with slopes (ΔCOS/ΔCO) of 0.72 and 0.14 pptv/ppbv, respectively. Based on the emission ratios of COS/CO from various sources, the dominant anthropogenic sources of COS in Beijing were found to be vehicle tire wear in summer and coal burning in winter. The total anthropogenic emission of COS in Beijing was roughly estimated as 0.53 ± 0.02 Gg/year based on the local CO emission inventory and the ΔCOS/ΔCO ratios.     

Potential particulate pollution derived from UV-induced degradation of odorous dimethyl sulfide

UV-induced degradation of odorous dimethyl sulfide (DMS) was carried out in a static White cell chamber with UV irradiation. The combination of in situ Fourier transform infrared (FT-IR) spectrometer, gas chromatograph-mass spectrometer (GC-MS), wide-range particle spectrometer (WPS) technique, filter sampling and ion chromatographic (IC) analysis was used to monitor the gaseous and potential particulate products. During 240 min of UV irradiation, the degradation e ciency of DMS attained 20.9%, and partially oxidized sulfur-containing gaseous products, such as sulfur dioxide (SO2), carbonyl sulfide (OCS), dimethyl sulfoxide (DMSO), dimethyl sulfone (DMSO2) and dimethyl disulfide (DMDS) were identified by in situ FT-IR and GC-MS analysis, respectively. Accompanying with the oxidation of DMS, suspended particles were directly detected to be formed by WPS techniques. These particles were measured mainly in the size range of accumulation mode, and increased their count median diameter throughout the whole removal process. IC analysis of the filter samples revealed that methanesulfonic acid (MSA), sulfuric acid (H2SO4) and other unidentified chemicals accounted for the major non-refractory compositions of these particles. Based on products analysis and possible intermediates formed, the degradation pathways of DMS were proposed as the combination of the O(1D)- and the OH- initiated oxidation mechanisms. A plausible formation mechanism of the suspended particles was also analyzed. It is concluded that UV-induced degradation of odorous DMS is potentially a source of particulate pollutants in the atmosphere.     

Temperature dependence of the absolute rate constant for the reaction of ozone with dimethyl sulfide

Absolute rate constants for the reaction of ozone with dimethyl sulfide (DMS) were measured in a 200-L Teflon chamber over the temperature range of 283-353 K. Measurements were carried out using DMS in large excess over ozone of 10 to 1 or greater. Over the indicated temperature range,the data could be fit to the simple Arrhenius expression as KDMS = (9.96±3.61)×10-11exp(-(7309.7±1098.2)/T)cm3/(molecule·s). A compared investigation of the reaction between ozone and ethene had a kc2H4 value of(1.35±0.11)×10-18 cm3/(molecule·s) at room temperature.     

三江平原小叶章湿地H2S和COS排放动态

利用静态箱/气相色谱法，观测了生长季（5～9月）三江平原小叶章沼泽化草甸H₂S和COS的释放动态，结果表明，H₂S、COS的排放通量具有季节和日变化规律，小叶章沼泽化草甸H2S的平均释放通量为0.34 μg·(m²·h)^-1，COS的平均释放通量为－0.29μg·(m²·h)^-1；在生长季，小叶章沼泽化草甸表现为H₂S的源，COS的汇。小叶章的生长过程对H₂S、COS的排放影响显著，在小叶章生长旺盛期，H₂S出现排放峰值，COS出现吸收高峰，H₂S和COS的释放通量呈负相关。     

水稻土中挥发性含硫气体的释放

通过建立野外采样系统,对一个生长周期内水稻土释放的挥发性含硫气体进行了检测.研究结果表明:水稻土中释放的含硫气体主要为COS、CS₂和DMS,并有少量的DMDS.估算出的各含硫气体的释放通量分别为81.11、6.33和10.71 mg·(m²·a)^-1.我国水稻土释放含硫气体的通量为(S)0.013662 Tg/a,全球为(S)0.07992Tg/a     

黄、东海二甲基硫海气交换通量时空分布及影响因子

二甲基硫（dimethyl sulfide,DMS）海气交换对全球气候和环境变化有重要贡献。本文利用已发表的2005－2017年文献数据,结合ERA-interim（European Centre for Medium-Range Weather Forecasts Interim Re-Analysis）风速数据,估算了黄、东海DMS海气通量,并分析了其季节变化和空间差异。结果表明:南黄海和东海DMS年平均海气通量分别为（8.63±4.90）μmol/(m2·d)和（12.77±8.42）μmol/(m2·d),除秋季外,东海海气通量高于南黄海;DMS海气通量季节变化显著,夏季最大,冬季最小,南黄海秋季高于春季,东海春季高于秋季。基于方差分解,本文讨论了各因子方差对DMS海气通量方差的贡献,在南黄海,春季表层DMS浓度和交换速率均对海气通量有主要影响,夏季和冬季交换速率对海气通量影响较大;在东海,春季海气通量受到交换速率和DMS浓度交互作用的影响较大,夏季海气通量主要由DMS浓度控制,秋季和冬季交换速率对海气通量的影响较大。南黄海和东海占全球海洋面积的0.30%,其DMS排放量为0.1461 TgS/a,占全球海洋DMS排放量的0.52%。     

贵阳市2种不同类型草地的汞释放通量

利用动态通量箱法对贵阳市人工草坪和天然草地的汞释放通量进行了野外实测. 结果表明:春季和夏季的草地是大气中汞的来源,并未出现明显的季节性变化,其平均汞释放通量为(7.8±15.7)～(41.5±15.2) ng/(m2·h),且天然草地的汞释放通量明显高于人工草坪. 草地的汞释放通量具有明显的日变化特征,白天汞释放通量显著高于夜间,最大值通常出现在午后,最小值则出现在夜间. 草地的汞释放通量与光照强度、土壤温度、大气温度呈显著的正线性关系,与大气相对湿度呈负线性关系. 大气中气态总汞的质量浓度是影响草地汞释放通量的另一个重要因素. 大气中气态总汞质量浓度的升高能够抑制草叶片向大气中释放汞,而高质量浓度的气态总汞可导致大气中的汞向草叶片的强烈沉降.      

Effect of operating parameters on sulfide biotransformation to sulfur

A laboratory-scale bioreactor with polyethylene semi-soft packing was constructed and utilized to determine the efficlency of sulfide biotransformation to sulfur under various operating parameters. Sodium sulfide dissolved in tap water was pumped into the bioreactor as sulfide for biological desulfurization. The sulfide, sulfur and sulfate-S in the effluent and the sulfide purged as gas-phase HzS were determined to investigate the effects of operating parameters, such as pH, DO, hydraulic retention time （HRT）, temperature and salinity, on the sulfide oxidation products. The activity of bacteria was highest at pH 7.8-8.2. The maximal sulfide removal load was 7.25 kg/（m^3·day）, with a 322.07 mg/L influent sulfide concentration and 4.80 mg/L DO. The increase of DO value corresponds to a decrease in the sulfur yield. The reactor had the highest sulfide removal load and sulfur yield at 2.55 mg/L DO. HRT had little effect on desulfurization efficiency when the sulfide removal load was kept constant. The most effective desulfurization temperature was 33℃. The sulfide removal load decreased from 2.85 to 0.51 kg/（m^3.day） with increasing salinity from 0.5% to 2.5% （m/m）.     

Adsorption and desorption of lanthanum at sulfide mineral surface

Batch adsorption experiment with four sulfide minerals - Chalcocite galena, pyrite and sphalerite - were used to study for the adsorption and desorp-tion behavior of La (III) in the presence of EDTA, a model humic matter. Linear adsorption was found in all cases.The presence of soluble organic complexing ligand should reduce the mobility of La (III) in porous media and its transport to groundwater in the percolating soil solution. Binding mechanism is proposed to account for this preferential binding behavior.     

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。     

臭氧与二甲硫醚和乙烯的反应速率常数测定

在室温和1.01×105 Pa条件下,利用烟雾箱以及气相色谱和臭氧分析仪研究手段,采用绝对方法(准一级反应)获得了臭氧与二甲硫醚(DMS)和乙烯(C2H4)的反应速率常数,分别为:kDMS=(1.48±0.12)×10-20 cm3·molecule-1·s-1;kC2H4=(1.35±0.10)×10-18cm3·molecule-1·s-1.其中,臭氧与乙烯的反应速率常数与文献报道吻合较好,臭氧与DMS的反应速率常数比文献报道的上限值低约两个数量级.