蔬菜废弃物与畜禽粪便联合好氧发酵挥发性有机物排放特征

为研究蔬菜废弃物与畜禽粪便联合好氧发酵过程产生的挥发性有机物(volatile organic compound,VOCs)及主要致臭物质,开展了蔬菜废弃物与畜禽粪便联合好氧发酵试验,采用气相色谱-质谱法和三点比较式臭袋法分析了好氧发酵升温、高温和降温阶段产生的VOCs种类和浓度及臭气浓度。结果表明,蔬菜废弃物与畜禽粪便联合好氧发酵过程共检出34种VOCs,其中芳香烃类化合物11种、烷烃7种、含硫化合物4种、酮类4种、卤烃类化合物3种、醇类2种、酯类2种、醛类1种;发酵升温期臭气浓度最大,达72 443,而在降温期产生的VOCs种类最多为29;在联合好氧发酵过程中主要致臭物质为甲硫醚、二甲二硫醚、二硫化碳、NH3和H2S,羰基硫、乙醛和苯乙烯仅在高温期产生且浓度较高;根据嗅阈值比值大小与最大浓度,需重点监测和控制恶臭物质的顺序是二甲二硫醚H2SNH3甲硫醚。该研究结果为蔬菜废弃物与畜禽粪便联合好氧发酵过程中恶臭物质的监测和控制策略研究提供理论依据。     

牛粪好氧发酵挥发性物质排放特征及恶臭物质分析

不同原料好氧发酵产生的臭气物质组分和浓度存在差异。以牛粪和玉米秸秆为原料研究好氧发酵过程挥发性有机物（Volatile Organic Compound,VOCs）的产排特征及主要致臭物质,开展牛粪好氧发酵试验,采用气相色谱-质谱法分析测定发酵升温期、高温期、降温期及腐熟期等不同发酵阶段的VOCs组分和浓度,硼酸溶液吸收,盐酸滴定法测定NH3,便携式检测器（Tion NH3-H2S 300 G）测定H2S,3点比较式臭袋法测定不同发酵阶段臭气浓度。结果表明,牛粪好氧发酵过程中共检出31种VOCs,其中含硫化合物4种,醇类1种,酯类1种,酮类1种,卤代烃4种,苯系物9种,烷烃类8种,烯烃3种;在好氧发酵高温期臭气浓度最高为724（无量纲）,VOCs产生与排放主要在高温期。基于恶臭污染排放标准和恶臭物质气味活度值,并结合各物质检出率、GS-MS图谱及相关性分析,发现NH3、H2S、甲硫醚是牛粪好氧发酵过程的主要致臭物质;其次芳香族化合物对臭气浓度贡献也相对较大,应进行重点监测与控制。该研究可为牛粪好氧发酵过程臭气物质减控提供理论支撑。     

猪粪堆肥挥发性有机物的产生规律与影响因素

堆肥是畜禽粪便处理及资源化利用的有效途径,然而堆肥过程中极易产生挥发性有机物(VOCs,volatile organic compounds),引发恶臭问题,并对人体健康带来危害。该研究以猪粪和秸秆为原料,通过堆肥试验,研究了含水率、碳氮比和通风速率等工艺参数对猪粪堆肥过程中主要VOCs产生的影响。研究结果表明:堆肥过程中TVOCs的最高体积分数可达2 000×10~(-6)以上,主要在堆肥升温期产生。二甲二硫、二甲三硫是主要的致臭VOCs,其中,影响二甲二硫排放的主要因素为物料初始含水率,影响二甲三硫排放的主要因素为通风速率。极差及方差分析结果表明,堆肥过程中采用含水率65%,碳氮比30,通风速率0.1 m~3/(min·m~3)可以有效控制VOCs的排放。     

病死猪辅热好氧发酵尾气中的恶臭物质分析

为了明确病死猪辅热好氧发酵过程中产生的恶臭气体种类及其排放规律,为控制恶臭气体排放浓度、降低病死猪无害化处理过程对环境的污染提供基础依据,该研究以病死猪为发酵原料,以玉米秸秆为辅料,开展病死猪辅热好氧发酵试验,发酵过程中,采集处理槽排放的尾气,分析尾气中的有机恶臭物质组分并测定其排放浓度,同时测定其中的氨气浓度,并对不同发酵阶段尾气中气味活度值大于1的恶臭物质进行相关性分析和主成分分析。结果表明：在病死猪辅热好氧发酵过程中共检出36种恶臭物质,其中能准确定性与定量检测的有3种含硫化合物,1种烷烃化合物,12种芳香烃化合物,1种酚类化合物,1种胺类化合物和1种无机气体;发酵全程或部分时间点超过其嗅阈值的有3-乙基甲苯、4-乙基甲苯、二甲基二硫醚、二甲基硫醚、氨气、对甲酚、甲硫醇、三甲胺8种,达到的最高浓度依次为0.241、0.350、0.247、0.280、69.06、0.041、0.314、0.033 mg/m3,与其嗅阈值的比值依次为2.746、8.635、29.326、36.982、66.669、173.315、374.770、432.471;各发酵阶段的主要致臭物质成分存在差异：在0～12 h的发酵阶段,三甲胺、甲硫醇、二甲基硫醚、二甲基二硫醚、氨气、对甲酚、3-乙基甲苯、4-乙基甲苯为主要致臭物质,在12～36 h的发酵阶段,三甲胺、甲硫醇、二甲基硫醚、二甲基二硫醚、氨气、对甲酚为主要致臭物质,在36～72 h的发酵阶段,三甲胺、甲硫醇、二甲基硫醚、二甲基二硫醚、氨气为主要致臭物质;不同发酵阶段的臭气强度存在较大波动：在0～72 h内的发酵过程中,0～3 h内臭气强度缓慢增强,但第6小时臭气强度有明显下降,在6～18 h时再次增强,第18小时臭气强度达到峰值,18～72 h内持续下降直至平稳。该研究可为病死猪辅热好氧发酵过程中恶臭物质的减控策略提供理论参考。     

生活垃圾堆肥过程中恶臭物质分析

恶臭污染已成为生活垃圾堆肥过程中的主要环境问题.以15~80 mm粒径段的生活垃圾作为研究对象,利用嗅觉测定法和GC-MS分析了不同阶段堆肥尾气的臭气浓度和恶臭化合物的种类及其排放浓度,并对不同堆肥阶段臭气浓度和恶臭物质排放浓度的相关性进行分析.结果表明,垃圾堆肥过程中共检测到50种挥发性有机物,其中含硫恶臭物质5种,烃类化合物25种,芳香烃类化合物14种,其他物质6种.通过相关性分析,发现硫化氢、甲硫醚、二硫化碳、二甲二硫、1,3二甲基苯和邻二甲苯均与臭气浓度呈极显著相关(p<0.01),结合各恶臭物质的嗅阈值,15~80 mm粒径段垃圾堆肥过程中恶臭物质优先控制的顺序为硫化氢>甲硫醚>二甲二硫>二硫化碳>1,3二甲基苯>邻二甲苯.甲硫醇的嗅阈值非常低,即使其排放浓度很低,也会带来严重的臭气污染;NH3虽然对臭气浓度的贡献相对较小,但是其排放量很大,因此也应该对这2种恶臭物质进行重点监测和控制.该研究结果为生活垃圾堆肥过程中恶臭物质的监测、制定控制策略提供参考.     

生物过滤法去除死猪堆肥排放臭气效果的中试

为研究生物过滤法去除死猪堆肥发酵处理过程产生臭气以及挥发性有机物(volatile organic compounds,VOCs)的可行性,开展了死猪和猪粪混合堆肥试验,分析了死猪堆肥过程臭气浓度特性和VOCs组分特征,对生物过滤法去除臭气中VOCs的工艺关键参数-停留时间进行优化试验。死猪堆肥过程中排放VOCs种类达37种,其中主要致臭组分为三甲胺、二甲基硫、二甲基二硫、二甲基三硫;以腐熟猪粪堆肥作为滤料(添加3%活性污泥),在停留时间为30~100 s的条件下,生物过滤法对死猪堆肥排放臭气去除率达90%以上;停留时间60~100 s的条件下对VOCs中主要致臭组分的去除效率达82.2%~100%,生物过滤法去除死猪堆肥过程臭气浓度和VOCs的优化停留时间为60 s。研究结果能为死猪堆肥发酵过程排放臭气的处理和控制技术进一步研发提供科学依据。     

中试规模猪粪堆肥挥发性有机物排放特征

为监测堆肥过程挥发性有机物(volatile organic compounds,VOCs)排放情况,该文开展了猪粪堆肥现场试验,采用苏玛罐采样,气相色谱-质谱法分析了猪粪好氧堆肥过程中VOCs浓度。结果表明:猪粪好氧堆肥过程中可以检测出的VOCs有81种,包括烷烃类34种,芳香烃类21种,卤烃类19种,胺类1种,含硫化合物3种,氟利昂类3种;其中检出率高且浓度远远超过其嗅阈值的VOCs包括三甲胺、二甲基硫、二甲基二硫和二甲基三硫,VOCs排放主要发生在堆肥的前2周。该研究将为控制猪粪堆肥过程中VOCs气体排放提供科学数据支持。     

风干预处理对堆肥腐熟度及臭气排放量的影响

该研究以风干猪粪堆肥为处理,以新鲜猪粪堆肥为对照,在秸秆调理相同C/N基础上,对两个处理腐熟度和臭气排放进行比较分析。从温度、p H值、电导率和发芽率来看,利用新鲜猪粪和风干猪粪堆肥所得的产品均能达到腐熟和无害化标准;在硫化氢、羰基硫、二硫化碳、甲硫醚、乙硫醚、二甲二硫、甲硫醇和乙硫醇几种含硫臭气中,甲硫醚和二甲二硫占96%以上;风干猪粪堆肥比新鲜猪粪堆肥少排放71.09%的氨气,66.11%的甲硫醚和9.66%的二甲二硫。在不考虑风干环节存在的问题条件下,与新鲜猪粪堆肥相比,风干猪粪堆肥堆肥时间短,在堆肥品质提高的基础上,堆肥产品产量增加60%。通过降低水分和体积风干猪粪运输成本降低1/3,且对环境影响小,是远距离资源化处理畜禽粪便的较好途径。     

通风方式对猪粪堆肥主要臭气物质控制的影响研究

为控制堆肥过程中产生的臭气,开展了3种不同通风方式下的猪粪和秸秆堆肥试验,通过连续监测堆肥过程中氨气、硫化氢、总挥发性有机物(total volatile organic compounds,TVOCs)和二甲二硫、二甲三硫排放浓度的变化,优化堆肥通风方式。研究表明,在鼓风5 min间隔30 min、鼓风5 min间隔15 min和连续通风下,硫化氢和TVOCs的最大排放质量浓度和体积分数分别为29.4、18.9和10.3 mg/m~3以及420.3×10~(-6)、382.7×10~(-6)和326.5×10~(-6),每千克干物料硫化氢和TVOCs累积排放量分别为14.3、13.5、31.5 mg/kg以及1.26、2.00和6.08 L/kg;二甲二硫和二甲三硫的最大排放质量浓度分别为1 730.1、3 646.2和3 971.8 ng/L以及991.4、6 678.8和1 883.4 ng/L,每千克干物料中二甲二硫和二甲三硫的累积排放量分别为1.5、4.3和10.6 mg/kg以及0.37、4.37和4.94 mg/kg,增加通风频次有助于降低硫化氢和TVOCs的最高排放浓度,但会增加堆肥过程中硫化氢、TVOCs以及二甲二硫和二甲三硫的累积排放量,增加环境危害程度。该试验以降低臭气累积排放量为工艺优化目标,发现通风5min,间隔30min是最佳通风方式。研究结果可为有机肥生产过程中臭气的控制提供参考依据。     

调理剂在猪粪处理中的除臭及保氮作用

通过室内培养与室外堆肥试验，研究了添加调理剂对猪粪发酵过程中臭味及氮素损失的影响。结果表明，添加调理剂可以减少猪粪发酵中氨与硫化氢的挥发，减轻氮素损失与猪粪的恶臭。使用本研究中所采用的发酵剂与发酵工艺，75％含水量的猪粪经过15d的发酵，可达基本腐熟程度。     

Evolution of volatile sulfur compounds from soils treated with sulfur-containing organic materials

Release of volatile S compounds from soils treated with S-containing organic materials was studied by sensitive gas chromatographic techniques. Methyl mercaptan, dimethyl sulfide, dimethyl disulfide, carbonyl sulfide and carbon disulfide were identified as gaseous products of decomposition of animal manures, sewage sludges and plant materials in soils under aerobic or waterlogged conditions. No release of hydrogen sulfide was detected. Most of the S volatilized from soils treated with sludges was in the form of dimethyl sulfide and dimethyl disulfide. whereas most of the S volatilized from soils treated with manures and plant materials was in the form of methyl mercaptan and dimethyl sulfide. More S compounds were released, and more S was volatilized, by decomposition of manures, sludges or plant materials in soils under waterlogged conditions than by decomposition under aerobic conditions. When calculated as a percentage of the S added as organic material, the average amount of S volatilized under aerobic or waterlogged conditions was < 0.2% < 0.5% and < 3.4% for the sludges, manures and plant materials, respectively. The five volatile S compounds produced by decomposition of manures, sludges and plant materials in soils under aerobic and waterlogged conditions also were produced by decomposition of plant proteins (zein, gluten and gliadin). It is concluded that the volatile S compounds released by decomposition of the above organic materials in soils are largely, if not entirely, produced by microbial degradation of methionine and cystine in these materials.     

Comparison of three lychee cultivar odor profiles using gas chromatography-olfactometry and gas chromatography-sulfur detection

Odor volatiles in three major lychee cultivars (Mauritius, Brewster, and Hak Ip) were examined using gas chromatography-olfactometry, gas chromatography-mass spectrometry, and gas chromatography-pulsed flame photometric detection. Fifty-nine odor-active compounds were observed including 11 peaks, which were associated with sulfur detector responses. Eight sulfur volatiles were identified as follows: hydrogen sulfide, dimethyl sulfide, diethyl disulfide, 2-acetyl-2-thiazoline, 2-methyl thiazole, 2,4-dithiopentane, dimethyl trisulfide, and methional. Mauritius contained 25% and Brewster contained 81% as much total sulfur volatiles as Hak Ip. Cultivars were evaluated using eight odor attributes: floral, honey, green/woody, tropical fruit, peach/apricot, citrus, cabbage, and garlic. Major odor differences in cabbage and garlic attributes correlated with cultivar sulfur volatile composition. The 24 odor volatiles common to all three cultivars were acetaldehyde, ethanol, ethyl-3-methylbutanoate, diethyl disulfide, 2-methyl thiazole, 1-octen-3-one, cis-rose oxide, hexanol, dimethyl trisulfide, alpha-thujone, methional, 2-ethyl hexanol, citronellal, (E)-2-nonenal, linalool, octanol, (E,Z)-2,6-nonadienal, menthol, 2-acetyl-2-thiazoline, (E,E)-2,4-nonadienal, beta-damascenone, 2-phenylethanol, beta-ionone, and 4-vinyl-guaiacol.     

Gas chromatographic identification of sulfur gases in soil atmospheres

Simple gas Chromatographic methods for identification of sulfur gases in soil atmospheres are described. They involve the use of a flame photometric detector fitted with a sulfur filter and of Teflon columns packed with Chromosorb T and Deactigel. The methods permit identification of 13 volatile sulfur compounds (sulfur dioxide, hydrogen Sulfide, carbon disulfide, carbonyl sulfide, sulfur hexafluoride, methyl mercaptan, ethyl mercaptan, n-butyl mercaptan, dimethyl sulfide, ethyl methyl sulfide, diethyl sulfide, dimethyl disulfide, and diethyl disulfide) in air containing trace (nanogram) amounts of these compounds, and they are not subject to interference by various gases known to be evolved from soils under aerobic or anaerobic conditions. The Deactigel column is not required if the gas mixture analyzed does not contain hydrogen sulfide or carbonyl sulfide.     

Volatilization of sulfur from unamended and sulfate-treated soils

Volatilization of sulfur from unamended and sulfate-treated soils was studied by sensitive gas chromatographic techniques using a flame photometric detector fitted with a sulfur filter. The soils employed were surface samples of 25 Iowa soils selected to obtain a wide range in properties. No release of volatile sulfur compounds was detected when 11 of these soils were incubated under aerobic or waterlogged conditions before or after treatment with sulfate (400 μg sulfate S/g soil). Fourteen soils released volatile sulfur compounds when incubated under waterlogged conditions before and after addition of sulfate, but only 4 of these soils released volatile sulfur compounds when incubated under aerobic conditions. Where volatilization of sulfur was observed, the volatile sulfur detected was identified as dimethyl sulfide or as dimethyl sulfide associated with smaller amounts of carbonyl sulfide, carbon disulfide, methyl mercaptan, and (or) dimethyl disulfide. No trace of hydrogen sulfide was detected. Where release of volatile sulfur was observed, the amount of sulfur volatilized at 30°C in 60 days under aerobic or waterlogged conditions was very small and did not account for more than 0–05% of the sulfur in the unamended or sulfate-treated soils studied. It is concluded that gaseous loss of sulfur from unamended or sulfate-treated soils is insignificant under conditions likely to be encountered in the field.