我国饮用水中嗅味问题及其研究进展

综述了我国饮用水中的嗅味问题及其国内外研究进展,着重讨论了我国面临的饮用水中嗅味问题的现状、水中嗅味来源及饮用水中嗅味的定性定量分析技术、致嗅物质组成特性、典型致嗅物质的去除技术及工艺.旨在阐明除了土嗅素(geosmin)和2-甲基异莰醇(2-MIB)等微生物代谢产物外,硫醇硫醚类厌氧分解产物也是我国饮用水中重要的致嗅物质.硫醇硫醚类致嗅物质于2006年首次在东莞饮用水中发现,后被证明也是2007年太湖饮用水危机中的主要致嗅物质.Geosmin和2-MIB的吸附效果好于氧化,而硫醇硫醚类致嗅物质易于被氧化去除,不易被吸附去除.需要尽快开展我国饮用水中致嗅物质组成特性及典型致嗅物质去除技术和工艺的研究,形成应对不同水源、不同季节、不同致嗅物质嗅味的饮用水处理工艺.     

东江水中典型致嗅物质的调查

为去除由于运河排洪造成的东江饮用水中的嗅味,利用臭氧氧化-活性炭吸附中试装置,分别对东江水、运河水、装置进水和出水取样,进行吹扫捕集–GC-MS谱图分析,通过水样的臭阈值和吹扫捕集-GC-MS谱图对比,确定了东江夏季排洪时的致嗅物质,并分析了该江水中致嗅物质的组成特点.结果表明,东江水中致嗅物质来源于市内运河,其组成随季节不同变化较大,除了土嗅素和2-甲基异莰醇微生物代谢产物类致嗅物质外,以1-丙烯基-1-硫醇为主的硫醇、硫醚类厌氧分解产物是其夏季饮用水中主要的致嗅物质.     

我国饮用水嗅味问题的发生、主要嗅味物质及来源

嗅味是影响饮用水品质的重要指标之一.水中致嗅物质种类繁多、来源复杂,掌握并研判其发生机制及分布规律,对于提高我国饮用水嗅味管控能力、提升饮用水品质具有重要意义.本文重点阐释了我国饮用水水源水体中典型致嗅物质的发生与来源,剖析了主要嗅味问题的发生机理,旨在为应对不同水源水体嗅味发生提供科学与技术参考.     

生物粉末活性炭-超滤组合工艺对微污染水源水中嗅味物质的去除效能及其微生物特性

采用生物粉末活性炭-超滤(BPAC-UF)组合工艺对模拟微污染水源水中的嗅味物质进行了去除试验,并对组合工艺中微生物量的分布和变化进行了测定.结果表明,相比混凝沉淀常规工艺,BPAC-UF组合工艺对微污染水源水中的嗅味物质有较好的控制效果,对二甲基三硫醚、2-甲基异莰醇和β-紫罗兰酮的平均去除率分别可达77.51%、65.86%和98.43%,并且对原水冲击负荷有更好的适应性;炭池是组合工艺中去除嗅味物质的主要单元,其微生物量远高于其它区域;炭池生物量变化平稳,组合工艺对原水中嗅味物质的去除具有稳定性.     

饮用水中典型致嗅物质去除技术研究

为去除某市饮用水中的嗅味,根据该市饮用水水源中致嗅物质的组成特点,采用氧化、吸附和臭氧活性炭对其中典型致嗅物质的去除效果及工艺选择进行了研究.结果表明,硫醇硫醚类物质可以用氧化法有效去除,对土嗅素(geosmin)和2-甲基异莰醇(2-MIB)采用氧化法和活性炭吸附法均有效,但吸附法的效果更好;当原水中硫醇、硫醚类致嗅物质浓度<20 μg/L,不含有其他类型致嗅物质时,可以采用强化混凝＋高锰酸钾氧化工艺去除;当原水中geosmin、 2-MIB等微生物代谢产物类致嗅物质浓度<30 ng/L,不含有硫醇硫醚类致嗅物质时,可以采用强化混凝+粉末活性炭吸附工艺去除;当原水中硫醇、硫醚类致嗅物质浓度>20 μg/L,geosmin、 2-MIB浓度>30 ng/L时,需要增加臭氧活性炭深度处理工艺;当原水中硫醇、硫醚类致嗅物质浓度>150 μg/L,或者土嗅素、 2-MIB的浓度>100 ng/L时,需要根据致嗅物质组成特点,选择预KMnO₄氧化或者粉末活性炭吸附＋臭氧活性炭深度处理的组合工艺去除.     

黑臭水体中主要致嗅组分特征分析

黑臭水体中致嗅挥发性物质是造成水体产生异味的主要原因。通过气相色谱/质谱法对黑臭水体中的挥发性组分进行连续监测,同时利用气味活性值(OAV)识别了其中的主要致嗅组分,并讨论了其在不同河道和不同时间的变化特征。结果显示:黑臭水体中检出频率和浓度最高的16种组分中,包括5种醛类、5种氯代烃、5种苯酚类物质及二甲基二硫醚。二甲基二硫醚、壬醛、辛醛、柠檬醛及苯酚的OAV1,是研究选取河道中的主要致嗅组分。其中,辛醛与壬醛天然存在于自然水体中;二甲基二硫醚主要来源于黑臭水体中厌氧微生物代谢;而苯酚与柠檬醛可能是由于外源污染的排放。     

高锰酸钾与粉末活性炭联用解决水厂致嗅物污染问题研究

饮用水中的嗅味问题一直是大众关注的焦点,会直接影响人们的生活质量,通常会产生土霉味的土臭素和二甲基异莰醇,常规工艺对其去除能力有限。本文以根本性去除水中异嗅味为目标,尝试采用高锰酸钾和粉末活性炭联用手段,有效解决原水致嗅物超标问题,是值得一用的解决饮用水嗅味问题的应急处理方案。     

饮用水处理中嗅和味的去除研究进展

在水处理过程中,常规工艺难以去除污染原水中的土腥味和霉烂味,产生这些嗅味的化合物主要是二甲基异冰片（2-MIB）和土臭素（Geosmin）等。本文介绍了国内外给水处理中嗅和味的现状,水源水中嗅味物质去除方法及影响因素等。     

超声活化过硫酸盐降解水中典型嗅味

为有效解决饮用水嗅味污染问题,选取水中典型致嗅物质二甲基异莰醇（2-MIB）和土臭素（GSM）作为目标污染物,系统研究了超声（US）活化过硫酸盐（PS）高级氧化技术对两种致嗅物质的降解规律及其影响因素.结果表明,在15 min内超声/过硫酸盐联用工艺能有效去除水中典型嗅味,与单独超声处理相比,2-MIB和GSM的去除率分别可提高57.0%和63.6%;2-MIB与GSM浓度在100~800 ng·L^-1范围内US/PS联用工艺均有较高的去除率,且在100 ng·L^-1时降解效果最佳,去除率分别可达88.7%和93.3%;典型致嗅物质的降解速率随PS浓度（0.25~2mmol·L^-1）和US声强（0.33~0.53 W·cm^-2）的增加而加快;水体中腐殖酸存在会竞争消耗自由基使嗅味降解受到抑制但影响效果不显著;在反应体系中分别加入甲醇与叔丁醇（自由基清除剂）后,2-MIB与GSM去除率明显下降,且甲醇对嗅味降解抑制程度强于叔丁醇,表明US/PS高级氧化技术对嗅味快速的降解主要是硫酸根自由基与羟基自由基共同作用的结果.     

饮用水中致嗅和味原因研究进展

介绍了国内外给水处理中嗅和味的现状,水源水中嗅味物质的来源及致嗅和味物质的分类及测定方法等。     

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.     

Characterization of typical taste and odor compounds formed by Microcystis aeruginosa

Production and characteristics of typical taste and odor (T&O) compounds by Microcystis aeruginosa were investigated. A few terpenoid chemicals, including 2-MIB, β-cyclocitral, and β-ionone, and a few sulfur compounds, such as dimethyl sulfide and dimethyl trisulfide, were detected. β-Cyclocitral and β-carotene concentrations were observed to be relevant to the growth phases of Microcystis. During the stable growth phase, 41-865 fg/cell of β-cyclocitral were found in the laboratory culture. β-Cyclocitral concentrations correlated closely with β-carotene concentrations, with the correlation coefficient R2 = 0.96, as it is formed from the cleavage reaction of β-carotene. For dead cell cases, a high concentration of dimethyl trisulfide was detected at 3.48-6.37 fg/cell. Four T&O compounds, including β-cyclocitral, β-ionone, heptanal and dimethyl trisulfide, were tested and found to be able to inhibit and damage Microcystis cells to varying degrees. Among these chemicals, β-cyclocitral has the strongest ability to quickly rupture cells.     

北京市安定生活垃圾填埋场VOCs恶臭物质及其臭气强度

挥发性有机物(VOCs)是填埋场重要的恶臭源之一.为了深入了解造成填埋场恶臭的VOCs及其臭气强度情况,在2014年7—8月采用固相微萃取(SPME)-气相色谱(GC)-质谱(MS)联用法测定了北京市安定生活垃圾卫生填埋场内各代表性地点的VOCs.共确认了48种化合物,包括烷烃、烯烃、芳香烃、环烷烃、萜类、酯类、醛酮类、卤代烃、醇类及含硫化合物和含氮化合物.烷烃的种类最多,达到13种,其次是芳香烃,为9种.以内标法和外标法相结合测定了其中35种物质的含量,发现浓度在0.05~40 mg·m~(-3)之间.在厂区入口和作业面浓度最高的VOC是2,2,4,6,6-五甲基庚烷,在沼气干管是甲苯.从实际经验和臭气强度出发,建立了一种恶臭物质筛选方法,即首先以检出频次和各地点浓度比值筛选出可能的恶臭物质,然后由臭气强度确定最终的恶臭物质.筛选结果表明,填埋场内的恶臭VOCs是对伞花烃、对二甲苯、乙苯、甲苯和邻二甲苯,其中对伞花烃和对二甲苯对恶臭贡献尤为显著.这些恶臭VOCs浓度之间呈现出显著的相关关系,表明这些物质均来源于填埋场内生活垃圾的降解过程.     

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.      

Determination of urine-derived odorous compounds in a source separation sanitation system

Source separation sanitation systems have attracted more and more attention recently.However, separate urine collection and treatment could induce odor issues, especially in large scale application. In order to avoid such issues, it is necessary to monitor the odor related compounds that might be generated during urine storage. This study investigated the odorous compounds that emitted from source-separated human urine under different hydrolysis conditions. Batch experiments were conducted to investigate the effect of temperature, stale/fresh urine ratio and urine dilution on odor emissions. It was found that ammonia, dimethyl disulfide, allyl methyl sulfide and 4-heptanone were the main odorous compounds generated from human urine, with headspace concentrations hundreds of times higher than their respective odor thresholds. Furthermore, the high temperature accelerated urine hydrolysis and liquid–gas mass transfer, resulting a remarkable increase of odor emissions from the urine solution. The addition of stale urine enhanced urine hydrolysis and expedited odor emissions. On the contrary, diluted urine emitted less odorous compounds ascribed to reduced concentrations of odorant precursors. In addition,this study quantified the odor emissions and revealed the constraints of urine source separation in real-world applications. To address the odor issue, several control strategies are recommended for odor mitigation or elimination from an engineering perspective.     

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.     

夏季有机生活垃圾堆肥过程恶臭排放特征及健康风险评估

为研究有机生活垃圾在夏季堆肥过程的恶臭污染物分布特征及对堆肥厂职业暴露人员的非致癌和致癌风险水平,以北方某有机生活垃圾堆肥厂为研究对象,利用冷阱富集-气质联用（GC/MS）技术对恶臭气体进行分析.结果表明:①堆肥过程中的恶臭物质以含氧有机物为主,其次是芳香烃,这两类物质分别占总恶臭污染物质量浓度的63.46%±2.65%和15.56%±0.67%.②各单元的主要恶臭贡献物质种类存在差异,卸料单元和粉碎单元主要为乙酸和甲硫醚,占这两个单元总异味活度值的83.07%和85.44%;发酵单元和腐熟单元恶臭贡献的主要物质是乙酸、乙醛、甲硫醚、α-蒎烯、二甲二硫醚、柠檬烯、b-蒎烯和乙醇,占两个单元总异味活度值的96.60%和92.51%.③从人群健康风险来看,腐熟单元HI（非致癌健康风险指数）最高（13.54）,其次是发酵单元（7.95）和粉碎单元（5.36）,卸料单元最低（4.94）,而苯是主要的致癌风险物[LCR（终生致癌风险）>10-4].研究显示,有机生活垃圾堆肥厂在夏季产生的恶臭污染物对人群可能产生较大影响,应加强堆肥过程中恶臭污染物的控制,另外加强对职业暴露人群的健康防护以及对恶臭物质的有效处理以减少对人群健康的不利影响.      

基于监测统计的垃圾收运车恶臭污染释放特征

为了明确生活垃圾初期收运过程中恶臭物质的释放特征,对典型垃圾收运压缩车和非压缩车展开了为期一年的监测.共检出了6大类别75种恶臭物质,其中以乙醇为主的含氧化合物浓度最高,平均检出浓度超过360μg/m³.垃圾初期收运车辆释放的恶臭物质在秋季污染水平最高,而冬季污染水平较低.通过对全部样品进行统计分析发现,压缩车与非压缩车释放恶臭物质的种类与浓度之间并无明显差异.根据阈稀释倍数法,乙醇、萘、二氯甲烷、二甲二硫醚和丙烯醛被筛选为典型恶臭物质.其中含硫化合物嗅阈值低,即使浓度很低也容易被感受到,在检测过程需要格外关注.本研究可为固体废物收运与管理过程的二次污染控制提供科学依据.     

典型工业恶臭源恶臭排放特征研究

恶臭污染具有主观性和复杂性特点,结合使用仪器分析和嗅觉方法,可以从成分和感官两方面充分反映恶臭污染特征.本文参考USEPA TO14A和GB/T 14675-93方法,选择天津滨海新区内的6个不同类型的工业恶臭源,包括制药、喷漆、炼油、石化、树脂合成和橡胶,采集了各类源工艺流程中通过有组织方式排放的恶臭废气,测定了废气的感官臭气浓度并定量分析了其中的恶臭VOCs物质.使用臭气浓度、恶臭指数及统计学方法进行研究,结果发现,炼油源和制胶源的废气具有非常严重的感官刺激性.甲硫醇等硫化物是炼油源和制胶源的主要特征恶臭物质;苯乙烯和甲苯分别是合成树脂源和喷涂源的特征恶臭组分;对苯二甲酸(PTA)源和制药源属于混合型恶臭源.甲苯是喷漆源和制药源的标识组分;二硫化碳是制胶源的标识组分;间,对-二甲苯可以用来标识石化PTA污染源;炼油源的标识组分为三氯乙烯、氯乙烷和1,2-二溴乙烷;苯乙烯是合成树脂源的标识组分.     

Desorption of odor substances from water bodies to the atmosphere

A method is described for evaluation of odor pollution caused by waste-water. Two standard analytical procedures were applied to the determination of odor substances in water: head space analysis and purge-trap method. Henry's constants for five odor substances: hydrogen sulfide, methylmercaptan, dimethyl sulfide, ammonia and trimethylamine were measured at several conditions of pH and equilibrium temperature and were used for the estimation of odor emission from waste-water.