不同有机基质诱发的水体黑臭及主要致臭物(VOSCs)产生机制研究

目前在研究湖泛发生方面还主要停留在视觉(黑色)水平,嗅觉(臭味)因为更加难以判断,有关致臭机制及致臭物质的研究仍停留在检测分析和理论假设方面,缺乏有效的证据证实.采用自制室内模拟装置研究不同有机基质作用下黑臭发生的情况,以确定挥发性有机硫化物(VOSCs)的前驱物并初步研究其降解机制.结果表明,有机物只要达到一定负荷水平(1.0 g.L-1)对水体均有致黑作用,但含硫有机物能使水体在7～13 d就变黑,而不含硫有机物需要13 d以上才能使水体变黑,且含硫有机物能使水体颜色变得更深(最高色度值达410度以上).只有含硫有机物才具有致臭作用,其中二甲基二硫醚(DMDS)、二甲基三硫醚(DMTS)和二甲基四硫醚(DMTeS)是黑臭水体主要的致臭物质.根据蛋氨酸降解产生的VOSCs情况,可确定蛋氨酸为VOSCs的主要前驱物.蛋氨酸以生物降解为主,硫酸还原菌(SRB)是水环境中重要的蛋氨酸降解菌之一,添加SRB使蛋氨酸快速分解为以DMDS、DMTS和DMTeS为主的VOSCs,降解率在第35 d高达95%,并使黑臭暴发的时间从13 d提前至8 d;产甲烷菌对蛋氨酸降解有抑制的趋势,其大量存在可能会抑制小分子硫化物的形成,因此添加甲烷菌抑制剂使黑臭暴发时间提前1 d.非生物降解是蛋氨酸降解的次要途径,仅能使蛋氨酸发生初步降解而水体始终未变黑.     

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...     

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 .     

Microcystis aeruginosa/Pseudomonas pseudoalcaligenes interaction effects on off-flavors in algae/bacteria co-culture system under different temperatures

We conducted an experiment to study the interaction effects of Microcystis aeruginosa and Pseudomonas pseudoalcaligenes on off-flavors in an algae/bacteria co-culture system at three temperatures (24, 28 and 32°C). Gas chromatography–mass spectrometry was applied to measure off-flavor compounds dimethyl sulfide (DMS), dimethyl trisulfide (DMTS), 2-methylisoborneol, geosmin (GEO) and β-cyclocitral. During the lag phase of co-cultured M. aeruginosa (first 15 days), P. pseudoalcaligenes significantly increased the production of DMS, DMTS and β-cyclocitral at all three temperatures. In the exponential phase of co-cultured M. aeruginosa (after 15 days), M. aeruginosa became the main factor on off-flavors in the co-culture system, and β-cyclocitral turned to the highest off-flavor compound. These results also indicated that DMS, DMTS and β-cyclocitral were the main off-flavor compounds in our M. aeruginosa/P. pseudoalcaligenes co-culture system. Univariate analysis was applied to investigate the effects of M. aeruginosa and P. pseudoalcaligenes on the production of off-flavors. The results demonstrated that both M. aeruginosa and P. pseudoalcaligenes could increase the production of DMS and DMTS, while β-cyclocitral was mainly determined by M. aeruginosa. Our results also provide some insights into understanding the relationship between cyanobacteria and heterotrophic bacteria.     

蒲河致嗅类VOSCs污染水平与空间分布及其影响因素

为研究蒲河中致嗅类VOSCs(挥发性有机硫化物)的污染水平、空间分布及其影响因素,采用吹扫捕集(P&T)与气相色谱(GC)/火焰光度检测器(FPD)联用方法,测定水样中14种致嗅类VOSCs的质量浓度,采用相关性分析确定水质因子〔ρ(DO)、ρ(NH₃-N)、ρ(COD_Cr)、ρ(BOD₅)〕对ρ(∑VOSCs)空间分布的影响. 结果表明:所调查的27个采样点中各目标化合物均有检出,ρ(∑VOSCs)的范围为85.82~1 766.04 ng/L;DMS(甲硫醚)为最主要的污染物,ρ(DMS)平均值为114.29 ng/L,检出率为96.30%,变异系数为0.42. ρ(DO)与ρ(∑VOSCs)显著相关,Pearson相关系数为-0.751,对ρ(∑VOSCs)的空间分布影响最大;其次是ρ(NH₃-N),Pearson相关系数为0.441;ρ(COD_Cr)和ρ(BOD₅)与ρ(∑VOSCs)不相关.      

Beyond hypoxia：Occurrence and characteristics of black blooms due to the decomposition of the submerged plant Potamogeton crispus in a shallow lake

Organic matter-induced black blooms(hypoxia and an offensive odor) are a serious ecosystem disasters that have occurred in some large eutrophic shallow lakes in China. In this study, we investigated two separate black blooms that were induced by Potamogeton crispus in Lake Taihu, China. The main physical and chemical characteristics, including color- and odor-related substances, of the black blooms were analyzed. The black blooms were characterized by low dissolved oxygen concentration(close to 0 mg/L), low oxidation-reduction potential, and relatively low pH of overlying water. Notably higher Fe2+and∑S2-were found in the black-bloom waters than in waters not affected by black blooms. The black color of the water may be attributable to the high concentration of these elements, as black FeS was considered to be the main substance causing the black color of blooms in freshwater lakes. Volatile organic sulfur compounds, including dimethyl sulfide, dimethyl disulfide, and dimethyl trisulfide, were very abundant in the black-bloom waters. The massive anoxic degradation of dead Potamogeton crispus plants released dimethyl sulfide, dimethyl disulfide, and dimethyl trisulfide, which were the main odor-causing compounds in the black blooms. The black blooms also induced an increase in ammonium nitrogen and soluble reactive phosphorus levels in the overlying waters. This extreme phenomenon not only heavily influenced the original lake ecosystem but also greatly changed the cycling of Fe, S, and nutrients in the water column.     

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.     

洞庭湖水体异味物质及其与藻类和水质的关系

以洞庭湖水体中异味物质为研究对象,开展异味物质调查,并结合藻类结构、水质及其营养状况等因素,深入分析洞庭湖异味物质的来源和变化情况. 结果表明,DMS(dimethylsulfide,甲硫醚)、DMTS(dimethyltrisulfide,二甲基三硫醚)、β-cyclocitral(β-环柠檬醛)、MIB(2-methylisoborneol,二甲基异冰片)和GSM(geosmin,土嗅素)在全湖广泛存在,其最高质量浓度分别达到500.80、28.80、21.84、14.50和22.40 ng/L. 结合与藻类生物量的相关分析发现,直链藻、冠盘藻等硅藻可能是洞庭湖中DMS、DMTS和β-cyclocitral的重要来源,湖区土壤、沉积物中的微生物和死亡分解的藻类是MIB和GSM主要来源. 洞庭湖水体绝大部分处于中营养水平,其中东洞庭湖TLI(综合营养状态指数,为48.3)最高,南洞庭湖(为47.3)其次,西洞庭湖(为42.7)最低. 异味物质含量和水质的相关分析发现,异味物质质量浓度与TLI、水温、pH、ρ(DO)、ρ(TN)和ρ(COD_Mn)显著相关,说明水质对异味物质含量有重要影响.      

南方泛黑水库Fe、Mn及硫化物的迁移规律研究:以南宁天雹水库为例

Fe和Mn是氧化还原敏感元素，厌氧与有氧均会造成Fe、Mn及硫化物沉积物释放和形态转化，导致水质恶化，目前鲜有研究将泛黑与Fe、Mn及硫化物迁移规律耦合。选取广西壮族自治区南宁天雹水库为研究对象，于2018年3-12月对水库不同深度进行采样，分析水库水质的季节性变化特征以及对Fe、Mn、硫化物迁移转化规律的影响。结果表明:热分层结构主要受气温变化影响，分层期温跃层形成导致垂向理化性质差异，形成底部低温厌氧环境。独特的红土壤结构使Fe和Mn具有更强的内源释放能力，在降雨冲刷及长期厌氧影响下Fe和Mn底层大量释放，浓度达到0.76，1.47 mg/L，高浓度Fe抑制了硫化物释放（0.005 mg/L）。泛黑期分层破坏引发垂向对流混合，复氧使Fe、Mn及硫化物形态转化，向上迁移同步产生FeS、MnS等致黑物质，触发表层产生泛黑现象，后续开展黑水触发机制与物质甄别研究是解决泛黑问题的关键。     

陶瓷膜组合工艺对自来水厂排泥水的处理效果

研究了陶瓷膜组合工艺对南方某自来水厂排泥水的净化处理效果,主要工艺单元包括混凝、臭氧氧化、超滤陶瓷膜与活性炭过滤,实现排泥水资源回收利用。采用规模为10 m3/d中试装置,陶瓷膜通量为100 L/（m2·h）,跨膜压差TMP<30 kPa。考察了组合工艺对浊度、色度、有机物（COD_Mn）、氨氮、土臭素（GSM）、二甲基三硫醚（DMTS）、2-甲基异莰醇（2-MIB）、药物和个人护理产品（PPCPs）和内分泌干扰物（EDCs）等污染物的去除效果。结果表明:经中试工艺处理后,出水指标均达到GB 5749—2006《生活饮用水卫生标准》。中试工艺对浊度、色度、COD_Mn和氨氮的平均去除率分别为99%、100%、75.9%和72.3%,对PPCPs、EDCs、DMTS和2-MIB的平均去除率分别为95.4%、78.3%、90.3%和100%,处理效果显著优于该自来水厂现有排泥水处理工艺。原位臭氧氧化还能够有效缓解膜污染。中试结果表明,臭氧/陶瓷膜和活性炭过滤组合工艺回收处理自来水厂排泥水在技术上稳定可行。     

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%。     

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     

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.     

HS-SPME-GC-MS法测定黑臭河流中二甲基三硫醚

该研究在优化分析条件的基础上,采用顶空固相微萃取(HS-SPME)和气相色谱/质谱(GC-MS)联用方法测定了黑臭河流水体中二甲基三硫醚的含量。通过研究萃取头涂层、萃取温度、萃取时间、水样体积和气相色谱进样口温度对二甲基三硫醚萃取效率的影响,得到了二甲基三硫醚最佳预处理和检测条件为:采用CAR-PDMS(75μm)萃取头,取20 mL待测水样在45℃恒温搅拌下顶空萃取30 min,进样口温度为250℃。采用优化后的方法对实际城市黑臭河流水样进行了检测,测得的二甲基三硫醚的浓度范围为5 853～8 939 ng/L。     

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.     

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.     

高铁酸钾对水中藻类及其次生嗅味污染物二甲基三硫醚同步去除研究

模拟高藻期碱性水源水,采用高铁酸钾对水中以颤藻和二甲基三硫醚为代表的藻类及微量嗅味污染物进行同步控制研究.在高铁酸钾与聚合氯化铁(PFC)单独混凝对藻类的控制效果对比的基础上,展开了高铁酸钾与高锰酸钾预氧化-PFC联用方法对藻类及嗅味污染物的控制效果对比,探讨了pH、预氧化时间和浊度等条件对控制效果的影响.结果表明,PFC单独混凝除藻率最高为90.6%,以Fe计的等量投加条件下,高铁酸钾控藻效果较PFC混凝好,除藻率可达92.4%.高锰酸钾对PFC具有强化混凝效果,可明显提高除藻率(94.5%).高铁酸钾较高锰酸钾预氧化对二甲基三硫醚的去除效果理想,且氧化时间大大缩短,高铁酸钾氧化时间1 min可去除92.5%二甲基三硫醚,高于高锰酸钾预氧化10 min后达到的去除率(74.6%).     

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.     

Release of volatile organic compounds during bio-drying of municipal solid waste

Three treatments were tested to investigate the release concentrations of volatile organic compounds (VOCs) during the bio-drying of municipal solid waste (MSW) by the aerobic and combined hydrolytic-aerobic processes. Results showed that VOCs were largely released in the first 4 days of bio-drying and the dominant components were: dimethyl disulfide, dimethyl sulfide, benzene, 2-butanone, limonene and methylene chloride. Thus, the combined hydrolytic-aerobic process was suggested for MSW bio-drying due to fewer aeration quantities in this phase when compared with the aerobic process, and the treatment strategies should base on the key properties of these prominent components. Malodorous sulfur compounds and terpenes were mainly released in the early phase of bio-drying, whereas, two peaks of release concentrations appeared for aromatics and ketones during bio-drying. Notably, for the combined hydrolytic-aerobic processes there were also high concentrations of released aromatics in the shift from hydrolytic to aerobic stages. High concentrations of released chlorinateds were observed in the later phase. For the VOCs produced during MSW bio-drying, i.e., malodorous sulfur compounds, terpenes and chlorinateds, their release concentrations were mainly determined by production rates; for the VOCs presented initially in MSW, such as aromatics, their transfer and transport in MSW mainly determined the release concentrations.     

藻源型湖泛发生过程水色变化规律

利用Y-型沉积物再悬浮发生模拟装置,模拟湖泛发生过程,分析水体吸收特性变化特征;同时,利用Hydrolight和CIE颜色匹配函数模拟水体颜色,分析湖泛水色变化规律.结果表明:在湖泛发生过程中,可溶性有色物质(CDOM)浓度(ag)不断增大,无机颗粒物浓度及吸收(ad)总体呈减小的趋势,而浮游植物色素浓度及吸收(aph)随时间变化不规律;基于Hydrolight模拟湖泛水体,离水辐亮度(Lw)和遥感反射比(Rrs)均随时间不断变小;3)另外,随SPIM或ag(443)的变大,水体颜色逐渐由绿色变为棕色.当SPIM增至40mg/L时,水体呈现棕色;当ag(443)达到10m-1时,水体呈现红棕色.通过研究湖泛发生过程水体光学特性和水色变化规律,有助于构建高精度的湖泛遥感监测模型.