Potential of secondary aerosol formation from Chinese gasoline engine exhaust

Light-duty gasoline vehicles have drawn public attention in China due to their significant primary emissions of particulate matter and volatile organic compounds(VOCs). However,little information on secondary aerosol formation from exhaust for Chinese vehicles and fuel conditions is available. In this study, chamber experiments were conducted to quantify the potential of secondary aerosol formation from the exhaust of a port fuel injection gasoline engine. The engine and fuel used are common in the Chinese market, and the fuel satisfies the China V gasoline fuel standard. Substantial secondary aerosol formation was observed during a 4–5 hr simulation, which was estimated to represent more than 10 days of equivalent atmospheric photo-oxidation in Beijing. As a consequence, the extreme case secondary organic aerosol(SOA) production was 426 ± 85 mg/kg-fuel, with high levels of precursors and OH exposure. The low hygroscopicity of the aerosols formed inside the chamber suggests that SOA was the dominant chemical composition. Fourteen percent of SOA measured in the chamber experiments could be explained through the oxidation of speciated single-ring aromatics. Unspeciated precursors, such as intermediate-volatility organic compounds and semi-volatile organic compounds, might be significant for SOA formation from gasoline VOCs. We concluded that reductions of emissions of aerosol precursor gases from vehicles are essential to mediate pollution in China.     

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.     

Metals in sediment/pore water in Chaohu Lake: Distribution, trends and flux

Nine metals, Cd, Cu, Ni, Pb, As, Cr, Zn, Fe, and Mn in sediment and pore water from 57 sampling sites in Chaohu Lake (Anhui Province, China) were analyzed for spatial distribution, temporal trends and diffuse flux in 2010. Metals in the surface sediment were generally the highest in the western lake center and Nanfei-Dianbu River estuary, with another higher area of As, Fe, and Mn occurring in the Qiyang River estuary. Metal contamination assessment using the New York sediment screening criteria showed that the sediment was severely contaminated in 44% of the area with Mn, 20% with Zn, 16% with Fe, 14% with As, and 6% with Cr and Ni. An increasing trend of toxic metals (Cd, Cu, Ni, Pb, As, Cr, Zn) and Mn with depth was shown in the western lake. Compared with metal content data from the sediment survey conducted in 1980s, the metal content of surface sediment in 2010 was 2.0 times that in the 1980s for Cr, Cu, Zn, and As in the western lake, and less than 1.5 times higher for most of the metals in the eastern lake. Among the metals, only Mn and As had a widespread positive diffuse flux from the pore water to overlying water across the whole lake. The estimated flux in the whole lake was on average 3.36 mg/(m². day) for Mn and 0.08 mg/(m². day) for As, which indicated a daily increase of 0.93 μg/L for Mn and 0.02 μg/L for As in surface water. The increasing concentration of metals in the sediment and the flux of metals from pore water to overlying water by diffusion and other physical processes should not be ignored for drinking-water sources.     

Characterization of dissolved organic matter as N-nitrosamine precursors based on hydrophobicity, molecular weight and fluorescence

It is very important to identify the dominant precursors for N-nitrosamine formation from bulk organic matter, to enhance the understanding of N-nitrosamine formation pathways in water treatment plants and allow the development of practical treatment technologies. In this study, dissolved organic matter (DOM) from two source waters was fractionated with XAD resins and ultra- filtration membranes. The N-nitrosamine formation potential (FP) (ng of N-nitrosamines formed per mg of dissolved organic carbon (DOC)) from raw water and each fraction were measured and correlated with the fluorescence excitation-emission matrix (EEM), molecular weight (MW) and other assays. The results showed that the hydrophilic fraction had N-nitrosamine FP 1.3 to 3.5 times higher than the hydrophobic fraction from both source waters. The DOM fraction with low MW was the dominant fraction in these two source waters and contributed more precursors for N-nitrosamine formation than the larger MW fraction. The EEM spectra indicated there were notable amounts of soluble microbial products (SMPs) and aromatic proteins in the two studied rivers, which probably originated from wastewater discharge. The SMPs tended to be more closely correlated with N-nitrosodimethylamine formation potential than the other DOM components. Higher N-nitrosamine FP were also related to fractions with lower DOC/DON ratios and lower SUVA 254 values.     

Full-scale study of removal effect on Cyclops of zooplankton with chlorine dioxide

Cyclops of zooplankton propagated excessively in eutrophic water body and could not be effectively inactivated by the conventional disinfections process like chlorination due to its stronger resistance to oxidation. In this paper, a full-scale study of chlorine dioxide preoxidation cooperating with routine clarification process for Cyclops removal was conducted in a waterworks. The experimental results were compared with that of the existing prechlorination process in several aspects: including the Cyclops removal efficiencies of water samples taken from the outlets of sedimentation tank and sand filter and the security of drinking water and so on. The results showed that chlorine dioxide might be more effective to inactivate Cyclops than chlorine and Cyclops could be thoroughly removed from water by pre-dosing chlorine dioxide process. The GC-MS examination and Ames test further showed that the sort and amount of organic substance in the treated water by chlorine dioxide preoxidation were evidently less than that of prechlorination and the mutagenicity of drinking water treated by pre-dosing chlorine dioxide was substantially reduced compared with prechlorination.     

Growth characteristics of algae during early stages of phytoplankton bloom in Lake Taihu, China

Three treatments, sediment plus lake water (S+W), sterilized sediment plus lake water (SS+W), and sediment plus filtered lake water (S+FW), were recruited to investigate the growth characteristics of algae during pre-bloom and the importance of algal inocula in the water column and sediment. The results showed that in the water column, biomass of all algae increased in all treatments when recruitment was initiated, whereas this tendency differed among treatments with further increment of temperature. The process of algal growth consisted of two stages: Stage I, the onset of recruitment and Stage II, the subsequent growth of algae. Compared with S+W, in Stage I, SS+W significantly increased the biomass of cyanophytes by 178.70%, and decreased the biomass of non-cyanophytes by 43.40%; In Stage II, SS+W notably stimulated the growth of all algae, thus incurring the occurrence of phytoplankton bloom. Further analyses revealed that both metabolic activity and photochemical activity of algae were enhanced in SS+W, which resulted from the releasing of nutrients from sediment. These results suggest that algal growth in Stage II and algal inocula in the water column can be important factors for the formation of phytoplankton bloom. In addition, possible mechanisms promoting algal recruitment and subsequent growth of algae were explored.     

Identification of causative compounds and microorganisms for musty odor occurrence in the Huangpu River, China

There are regular problems of musty odor in the Huangpu River,a major source of drinking water for Shanghai,China.In this study,the musty odor and its main causative compounds in the Huangpu River source water were confirmed through a yearly investigation using flavor profile analysis combined with HSPME-GC-MS analysis.The investigation showed that 2-methylisoborneol (2-MIB) with a concentration level between 28.6 and 71.0 ng/L was responsible for the musty odor in summer from July to September.Microscopic observation confirmed with the cloning results showed that Phormidium spp.,which accounted for 80%-95% of the algal cell density,was the microorganisms responsible for the production of 2-MIB and the estimated 2-MIB yield was 0.022 pg/cell.Results from a wide-area sampling campaign in the Huangpu River watershed showed that,other than the large tributaries receiving water from Tai Lake,several small creeks close to the intake may have contributed most of the 2-MIB and the Phormidium spp.to the Huangpu River source water.This study provides methodology for the investigation of odor causing compounds and microorganisms in river-type source water,and the result will be useful for water quality control in both source water and drinking water.     

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.     

Reduction of DOM fractions and their trihalomethane formation potential in surface river water by in-line coagulation with ceramic membrane filtration

This research was aimed at investigating the reduction of DOM fractions and their trihalomethane formation potential （THMFP） by in-line coagulation with 0.1 μm ceramic membrane filtration. The combination of ceramic membrane filtration with a coagulation process is an alternative technology which can be applied to enhance conventional coagulation processes in the field of water treatment and drinking water production. The Ping River water （high turbidity water） was selected as the raw surface water because it is currently the main raw water source for water supply production in the urban and rural areas of Chiang Mai Province. From the investigation, the results showed that the highest percent reductions of DOC, UV-254, and THMFP （47.6%, 71.0%, and 67.4%, respectively） were achieved from in-line coagulation with ceramic membrane filtration at polyaluminum chloride dosage 40 mg/L. Resin adsorption techniques were employed to characterize the DOM in raw surface water and filtered water. The results showed that the use of a ceramic membrane with in-line coagulation was able to most efficiently reduce the hydrophobic fraction （HPOA） （68.5%）, which was then followed by the hydrophilic fraction （HPIA） （49.3%）. The greater mass DOC reduction of these two fractions provided the highest THMFP reductions （55.1% and 37.2%, respectively）. Furthermore, the in-line coagulation with ceramic membrane filtration was able to reduce the hydrophobic （HPOB） fraction which is characterized by high reactivity toward THM formation. The percent reduction of mass DOC and THMFP of HPOB by in-line coagulation with ceramic membrane filtration was 45.9% and 48.0%, respectively.     

Influential factors of formation kinetics of flocs produced by water treatment coagulants

The growth rate and size of floc formation is of great importance in water treatment especially in coagulation process.The floc formation kinetics and the coagulation efficiency of synthetic water were investigated by using an on-line continuous optical photometric dispersion analyze and the analysis of water quality.Experimental conditions such as alum dosage,pH value for coagulation,stirring intensity and initial turbidity were extensively examined.The photometric dispersion analyze results showed that coagulation of kaolin suspensions with two coagulants(alum and polyaluminium chloride) could be taken as a two-phase process:slow and rapid growth periods.Operating conditions with higher coagulant doses,appropriate pH and average shear rate might be particularly advantageous.The rate of overall floc growth was mainly determined by a combination of hydraulic and water quality conditions such as pH and turbidity.The measurement of zeta potential indicates that polyaluminium chloride exhibited higher charge-neutralizing ability than alum and achieved lower turbidities than alum for equivalent Al dosages.Under the same operating conditions,the alum showed a higher grow rate,but with smaller floc size.     

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.     

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.