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.     

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...     

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.     

Vertical distributions of COS,CS2, DMS and other sulfur compounds in a loblolly pine forest

Measurements of atmospheric COS, CS₂, DMS, SO₂ and aerosol sulfate and methanesulfonate (MSA) concentrations were conducted in a loblolly pine forest in central Georgia between July and September 1990. The daytime profiles obtained for the reduced sulfur gases (COS, CS₂, DMS) often showed significantly higher concentrations at the canopy level than above the forest canopy, indicating a net emission of these gases from the tree tops. No evidence was found for a net uptake of COS by the canopy during daytime. With one exception, all COS concentrations measured during the day were significantly higher than corresponding nighttime values. These results appear to be in conflict with recent studies suggesting a net uptake of atmospheric COS by plants during photosynthetic activity. Possible explanations for these different findings are discussed. Nighttime profiles indicated no major biosphere-atmosphere exchange of COS, CS₂ or DMS. Nighttime DMS concentrations were significantly higher than corresponding daytime values. A clear inverse relationship between the diel variations of DMS and MSA was observed, consistent with rapid photochemical oxidation of DMS under the given conditions.     

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.     

GC determination of dimethyl selenide and trimethyl selenonium ions in aquatic systems using element specific detection

Dimethyl selenide has been postulated to be an organoselenium compound in seawater. In this study, dimethyl selenide was detected in seawater along with a non-identified sulfur compound other than COS, CH₃SH, CS₂, DMS, and DMDS. Additionally, trimethyl selenonium ions could be detected in a moorland lake water sample.     

Effect of liming on sulfate transformation and sulfur gas emissions in degraded vegetable soil treated by reductive soil disinfestation

Reductive soil disinfestation (RSD), namely amending organic materials and mulching or flooding to create strong reductive status, has been widely applied to improve degraded soils. However, there is little information available about sulfate (SO₄^2 −) transformation and sulfur (S) gas emissions during RSD treatment to degraded vegetable soils, in which S is generally accumulated. To investigate the effects of liming on SO₄^2 − transformation and S gas emissions, two SO₄^2 −-accumulated vegetable soils (denoted as S1 and S2) were treated by RSD, and RSD plus lime, denoted as RSD₀ and RSD₁, respectively. The results showed that RSD₀ treatment reduced soil SO₄^2 − by 51% and 61% in S1 and S2, respectively. The disappeared SO₄^2 − was mainly transformed into the undissolved form. During RSD treatment, hydrogen sulfide (H₂S), carbonyl sulfide (COS), and dimethyl sulfide (DMS) were detected, but the total S gas emission accounted for < 0.006% of total S in both soils. Compared to RSD₀, lime addition stimulated the conversion of SO₄^2 − into undissolved form, reduced soil SO₄^2 − by 81% in S1 and 84% in S2 and reduced total S gas emissions by 32% in S1 and 57% in S2, respectively. In addition to H₂S, COS and DMS, the emissions of carbon disulfide, methyl mercaptan, and dimethyl disulfide were also detected in RSD₁ treatment. The results indicated that RSD was an effective method to remove SO₄^2 −, liming stimulates the conversion of dissolved SO₄^2 − into undissolved form, probably due to the precipitation with calcium.     

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 .     

湿地生态系统还原性硫气体自然释放研究

还原性硫气体是重要的痕量生源气体,对全球硫循环和大气化学具有重要作用。湿地是还原性硫气体的重要排放源,二甲基硫(DMS)、硫化氢(H2S)、羰基硫(COS)和二硫化碳(CS2)是湿地系统释放明显的还原性硫气体。开展湿地生态系统还原性硫气体自然释放的研究,可在全球尺度上估算还原性硫气体对大气循环的具体贡献提供基础数据。DMS、H2S和CS2的日变化规律表现为昼释放率大于夜释放率,COS释放速率表现为夜大于昼,在季节变化上都呈现生长季释放率大于非生长季;空间释放规律上也有较大差异性,水稻田硫气体释放量较为明显。温度通过影响酶活性进而影响硫气体释放,土壤、植被和潮周期等也是影响湿地生态系统还原性硫气体释放的重要因素。在探讨目前该研究领域存在不足的同时,对未来的研究工作进行了展望,以期对湿地生态系统还原性硫气体释放取得更深入的探究。     

青岛环境大气和海洋表层水中挥发性硫化物的测定

建立了采用预浓缩和GC FPD测定环境大气和海洋表层水中挥发性硫化物(COS、DMS和CS2)的方法.该方法对气态COS、DMS和CS2的回收率分别为(95±4)%,(86±3)%和(91±6)%(n=5),精密度分别为4 75%,8 26%和7 55%(n=5).对水体中COS、DMS和CS2的回收率分别为(86±8)%,(80±6)%和(97±12)%(n=5),精密度分别为8 17%,5 59%和11 70%.COS、DMS和CS2检出限分别为33pg,387pg和22pg.采用该方法测定了青岛近岸海域大气和表层海水中COS、DMS和CS2的浓度.结果表明,COS是近岸海域大气中主要挥发性硫化物,DMS是表层海水中最主要的挥发性硫化物.3种挥发性硫化物的浓度有明显的季节差异,夏季浓度远高于冬季浓度.     

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）.     

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.     

Effect of drainage on CO2, CH4, and N2O fluxes from aquaculture ponds during winter in a subtropical estuary of China

Aquaculture ponds are dominant features of the landscape in the coastal zone of China.Generally,aquaculture ponds are drained during the non-culture period in winter.However,the effects of such drainage on the production and flux of greenhouse gases(GHGs)from aquaculture ponds are largely unknown.In the present study,field-based research was performed to compare the GHG fluxes between one drained pond(DP,with a water depth of 0.05 m)and one undrained pond(UDP,with a water depth of 1.16 m)during one winter in the Min River estuary of southeast China.Over the entire study period,the mean CO_2flux in the DP was(0.75±0.12)mmol/(m~2·hr),which was significantly higher than that in the UDP of(-0.49±0.09)mmol/(m~2·hr)(p0.01).This indicates that drainage drastically transforms aquaculture ponds from a net sink to a net source of CO_2in winter.Mean CH_4and N_2O emissions were significantly higher in the DP compared to those in the UDP(CH_4=(0.66±0.31)vs.(0.07±0.06)mmol/(m~2·hr)and N_2O=(19.54±2.08)vs.(0.01±0.04)μmol/(m~2·hr))(p0.01),suggesting that drainage would also significantly enhance CH_4and N_2O emissions.Changes in environmental variables(including sediment temperature,p H,salinity,redox status,and water depth)contributed significantly to the enhanced GHG emissions following pond drainage.Furthermore,analysis of the sustained-flux global warming and cooling potentials indicated that the combined global warming potentials of the GHG fluxes were significantly higher in the DP than in the UDP(p0.01),with values of739.18 and 26.46 mg CO_2-eq/(m~2·hr),respectively.Our findings suggested that drainage of aquaculture ponds can increase the emissions of potent GHGs from the coastal zone of China to the atmosphere during winter,further aggravating the problem of global warming.     

Environmental chamber study of the photochemical reaction of ethyl methyl sulfide and Nox

A series of experiments were conducted in a self-made smog chamber at 300 ± 1 K and 1.01×105 Pa to simulate the photochemical reaction of ethyl methyl sulfide (EMS) and NOx. The results show that the higher the initial concentration of EMS, the more ozone is generated in the simulative reactions. It is found that the light intensity plays a very important role in the evaluation of ozone formation potential for EMS. The parameters of d(O3-NO) and IR (incremental reactivity) were used to quantify the potential of EMS on ozone formation. The obtained maximum IR values in this paper for the five simulative reactions were 1.55×10-2, 0.99×10-2, 1.36×10-2, 2.47×10-2, and 1.65×10-2, respectively. Comparison between the results we obtained here and the results we obtained before for di-tert-butyl peroxide and acetylene was made and it showed that the potential reactivity of EMS on ozone formation is at a relatively low level.     

铅锌硫化矿浮选废水及尾矿库外排水中VOSCs的组成特征及其来源解析

利用臭氧氧化技术对铅锌硫化矿浮选过程各单元作业废水及尾矿库外排水进行处理,根据硫酸根离子浓度增量计算废水中低价态硫(价态小于+6)浓度.采用吹扫捕集-气相色谱质谱联用仪(PTC-GC/MS)检测浮选药剂(丁基二硫代碳酸钠(n-BX)、二乙基二硫代氨基甲酸钠(DDTC)、腐殖酸钠(SH)、松醇油)水溶液的自然降解产物、尾矿库进水及外排水中的挥发性有机硫化物(VOSCs).结果表明,尾矿库主要进水水源中低价态硫浓度为112 mg·L-1,其中,二硫化碳(CS2)在检测组分中所占相对比例为35.60%,是主要的VOSCs物质.各单元作业中浮选作业工段加入大量浮选药剂,浮选药剂水溶液自然降解产物中均检出CS2,而用药量最大的n-BX(C5H9Na OS2)自然降解产物中CS2相对比例最高(80.33%),因此,n-BX是浮选废水中VOSCs主要药剂来源.尾矿库外排水中低价态硫浓度为22 mg·L-1,其中,VOSCs物质主要有3,6-二甲基-1,2,4,5-四硫环己烷(C2H4S4)、N-巯基-甲酰胺(CH2SNO)和2-甲基-3-噻唑啉(C4H7NS),尾矿库外排水中C2H4S4所占相对比例为22.59%,是主要VOSCs物质.尾矿库水体中微生物通过消耗CS2生成C2H4S4进行新陈代谢.本研究结果可为铅锌硫化矿浮选工艺改进和安全排放提供参考.     

Oxygen tolerance capacity of upflow anaerobic solid-state (UASS) with anaerobic filter (AF) system

In order to investigate the oxygen tolerance capacity of upflow anaerobic solid-state(UASS)with anaerobic filter(AF) system, the effect of microaeration on thermophilic anaerobic digestion of maize straw was investigated under batch conditions and in the UASS with AF system. Aeration intensities of 0–431 m L O2/gvswere conducted as pretreatment under batch conditions. Aeration pretreatment obviously enhanced anaerobic digestion and an aeration intensity of 431 m L O2/gvsincreased the methane yield by 82.2%. Aeration intensities of 0–355 m L O2/gvswere conducted in the process liquor circulation of the UASS with AF system. Dissolved oxygen(DO) of UASS and AF reactors kept around 1.39 ±0.27 and 0.99 ± 0.38 mg/L, respectively. p H was relatively stable around 7.11 ± 0.04. Volatile fatty acids and soluble chemical oxygen demand concentration in UASS reactor were higher than those in AF reactor. Methane yield of the whole system was almost stable at 85 ± 7 m L/gvs as aeration intensity increased step by step. The UASS with AF system showed good oxygen tolerance capacity.     

常压和真空下CS2的光氧化反应

利用原位FTIR、XPS 和GC-MS等技术手段,研究了常温紫外光辐照下常压及真空状态中,CS₂的光氧化反应.结果表明,常压及真空状态下CS₂光氧化反应的产物均为COS、SO₂、CO 和 CO₂,反应均遵循表观一级反应动力学规律,但中间产物COS的浓度变化有较大的差异.常压下COS浓度先迅速增大,然后减少; 真空条件下COS浓度增加到常压下COS浓度的 1/10后基本持平,然后逐渐减小,整个变化趋势缓慢; 2种条件下CS₂的半衰期分别为31.6 s和39.8 s, 中间产物COS降解 98% 所需时间分别为 55 min和22 min.在相同的光照条件下,O₂浓度的增加有助于CS₂光氧化反应的进行.以CS₂光氧化中间产物COS为初始物的光氧化反应主要产物为CO₂和SO₂,后者可以进一步被氧化为SO2-4.适量增加O₂的浓度可以促进COS光氧化反应的进行,但O₂的浓度增加至一定程度后反应速率基本保持恒定.以上结论对揭示CS₂和COS的源和汇以及全球S物质循环具有重要价值.     

Performance and microbial community of a membrane bioreactor system——Treating wastewater from ethanol fermentation of food waste

In this study, a lab-scale biological anaerobic/anaerobic/anoxic/membrane bioreactor(A_-~3MBR) was designed to treat wastewater from the ethanol fermentation of food waste,a promising way for the disposal of food waste and reclamation of resources. The 454 pyrosequencing technique was used to investigate the composition of the microbial community in the treatment system. The system yielded a stable effluent concentration of chemical oxygen demand(202 ± 23 mg/L), total nitrogen(62.1 ± 7.1 mg/L), ammonia(0.3 ±0.13 mg/L) and total phosphorus(8.3 ± 0.9 mg/L), and the reactors played different roles in specific pollutant removal. The exploration of the microbial community in the system revealed that:(1) the microbial diversity of anaerobic reactors A_1 and A_2, in which organic pollutants were massively degraded, was much higher than that in anoxic A_3 and aerobic MBR;(2) although the community composition in each reactor was quite different, bacteria assigned to the classes Clostridia, Bacteroidia, and Synergistia were important and common microorganisms for organic pollutant degradation in the anaerobic units, and bacteria from Alphaproteobacteria and Betaproteobacteria were the dominant microbial population in A_3 and MBR;(3) the taxon identification indicated that Arcobacter in the anaerobic reactors and Thauera in the anoxic reactor were two representative genera in the biological process. Our results proved that the biological A_-~3MBR process is an alternative technique for treating wastewater from food waste.     

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.     

Effect of elevated tropospheric ozone on methane and nitrous oxide emission from rice soil in north India

Physiological changes in crop plants in response to the elevated tropospheric ozone (O₃) may alter N and C cycles in soil. This may also affect the atmosphere-biosphere exchange of radiatively important greenhouse gases (GHGs), e.g. methane (CH₄) and nitrous oxide (N₂O) from soil. A study was carried out during July to November of 2007 and 2008 in the experimental farm of Indian Agricultural Research Institute, New Delhi to assess the effects of elevated tropospheric ozone on methane and nitrous oxide emissions from rice (Oryza sativa L.) soil. Rice crop was grown in open top chambers (OTC) under elevated ozone (EO), non-filtered air (NF), charcoal filtered air (CF) and ambient air (AA). Seasonal mean concentrations of O₃ were 4.3 ± 0.9, 26.2 ± 1.9, 59.1 ± 4.2 and 27.5 ± 2.3 ppb during year 2007 and 5.9 ± 1.1, 37.2 ± 2.5, 69.7 ± 3.9 and 39.2 ± 1.8 ppb during year 2008 for treatments CF, NF, EO and AA, respectively. Cumulative seasonal CH₄ emission reduced by 29.7% and 40.4% under the elevated ozone (EO) compared to the non-filtered air (NF), whereas the emission increased by 21.5% and 16.7% in the charcoal filtered air (CF) in 2007 and 2008, respectively. Cumulative seasonal emission of N₂O ranged from 47.8 mg m⁻² in elevated ozone to 54.6 mg m⁻² in charcoal filtered air in 2007 and from 46.4 to 62.1 mg m⁻² in 2008. Elevated ozone reduced grain yield by 11.3% and 12.4% in 2007 and 2008, respectively. Global warming potential (GWP) per unit of rice yield was the least under elevated ozone levels. Dissolved organic C content of soil was lowest under the elevated ozone treatment. Decrease in availability of substrate i.e., dissolved organic C under elevated ozone resulted in a decline in GHG emissions. Filtration of ozone from ambient air increased grain yield and growth parameters of rice and emission of GHGs.