畜禽场空气污染物检测技术综述

doi:10.3864/j.issn.0578-1752.2019.08.015

摘要/Abstract

摘要：

随着畜禽养殖集约化程度的提高,高密度、集约化的畜禽养殖引起的畜禽养殖场空气污染问题日益突出,畜牧业已成为我国空气污染的重要来源之一。畜禽场排放的氨气（NH₃）、硫化物（H₂S）、颗粒物（particulate matters,PM）和挥发性有机物（volatile organic compounds,VOCs）等空气污染物不仅对畜禽场人畜健康造威胁,还会扩散到周围环境中形成大气污染。科学适用的空气污染物检测方法和技术是研究和控制畜禽场空气污染的前提。文章对国内外畜禽场的NH₃、H₂S、温室气体、PM以及恶臭等主要空气污染物的检测方法与技术进行了介绍与分析。以NH₃、H₂S为代表的畜禽场有害气体检测方法主要有化学分析法、半导体气体传感器检测法、光谱法、质谱法与气相色谱法,其中,湿化学法灵敏度高,成本低,可以准确获取气体浓度,但检测费时费力,且无法实时在线检测;气体检测管法成本较低,操作简单,但误差相对较大;电化学传感器法灵敏度较高,成本适中,可以连续检测气体浓度,但存在装置易老化、使用寿命较短等缺陷;光谱法、质谱法以及气相色谱法可快速准确检测气体,但检测仪器昂贵,使用成本较高,不适合生产性畜禽场的常规检测。文章主要介绍与分析了反刍动物肠道发酵、畜禽舍、粪污贮存与处理过程中温室气体CH₄、CO₂、N₂O的检测方法和技术。畜牧业温室气体排放随时间、季节和采样点等不同而不断变化,实现畜牧业温室气体的精确监测较为困难,目前仍未有国际通用的检测方法与测量标准,畜牧业温室气体检测方法与技术及其标准研究亟待开展。文章从物理特征、化学特征及生物特征三个方面对畜禽场排放的颗粒物检测方法与技术进行了综述。畜禽场PM成分复杂,其吸附的NH₃、恶臭化合物、微生物的影响有待评估,因此亟待完善PM的物理、化学和生物成分的检测方法与技术,以获取畜禽场PM的全面特征信息。文章对畜禽场的主要恶臭物质成分和恶臭感官的检测方法与技术进行了综述。相比气相色谱-质谱联用法,采用专业嗅辨人员对恶臭浓度进行嗅辨分析的方法成本更高,且主观性较强。但气相色谱-质谱联用技术无法仅凭借气体样品确定所有气态有机化合物,同时难以确定引起恶臭的化合物种类。因此结合气相色谱与动态嗅觉仪可更全面的分析恶臭样品指标。文章还对国内外畜禽场空气污染物（包含有害气体、温室气体、颗粒物以及恶臭物质）的主要检测方法与技术进行综述,以期为我国畜禽养殖业的空气污染物检测技术的研发与应用提供参考。

关键词: 畜禽场, 空气污染, 检测, 有害气体, 颗粒物, 恶臭物质

Abstract:

With the intensification of livestock breeding, the air quality problem of livestock farms caused by high density breeding is becoming more and more serious. Animal husbandry has become one of the important sources of air pollutants in China. Air emitted from most intensive livestock houses contains a large amount of pollutants, including ammonia, sulfides, particulate matters (PM), volatile organic compounds (VOCs), which not only poses a big threat to animals and workers in livestock farms, but also spreads to the surrounding environment resulting in air pollution. Scientific and applicable air pollutants measuring methods are the basis of monitoring and controlling air pollution in livestock and poultry farms. In this article, the detection methods of livestock farming related hazardous gases (e.g., NH₃, H₂S), greenhouse gases, particulate matters and odor were summarized. The detection methods of hazardous gases in livestock houses mainly include chemical analysis, semiconductor gas sensor detection, spectroscopic methodology and mass spectrometry. The wet-chemical method is cheap and can detect gases sensitively and accurately, while it cannot detect gases in real time, and the process is time-consuming and labor-intensive. The gas tube is cheap and easy to operate, but the deviation is great. Electrochemical sensor is of high sensitivity, moderate cost and can be used to detect gas concentration continuously, however, the devices are easy to age. Spectrum method and mass spectrometry can detect gas quickly and accurately, but it is not suitable for conventional air detection of productive livestock farming due to its high costs. In this paper, the detection methods of greenhouse gases (e.g., CH₄, CO₂) generated from animal intestinal fermentation and livestock environment were also summarized. It is hard to conclude an accurate detection of greenhouse gases in animal husbandry, because the concentrations of greenhouse gases in animal husbandry changes all the time (diurnal and seasonal) and are related to other factors including sampling points. No international common testing method and measurement standard are concluded till now, therefore, the research of greenhouse gases detection method and standard in animal husbandry should be carried out as soon as possible. The detection methods of particulate matters (PM) in livestock farms were reviewed from three aspects: physical, chemical and biological characteristics. PM contains complex components in livestock farms, therefore, it is highly needed to improve PM detection technology. Besides, the component analysis and sensory analysis of odorous substances in livestock farms were overviewed. The odor analysis of professional olfactory discernment personnel owns stronger subjectivity and costs higher than gas chromatography- mass spectrometry. While, using gas chromatography-mass spectrometry is unable to determine all gaseous organic compounds with one sample. Combining gas chromatography and dynamic olfactometer can be more efficient for comprehensive analysis of odor samples. In this article, detection methods and techniques of air pollutants in animal husbandry were comprehensively reviewed to provide a reference for the development of air pollutants detection technologies in livestock and poultry breeding in China.

Key words: livestock and poultry farm, air pollution, measurement, harmful gases, particulate matter, odor

汪开英,吴捷刚,赵晓洋. 畜禽场空气污染物检测技术综述[J]. 中国农业科学, 2019, 52(8): 1458-1474.

WANG KaiYing,WU JieGang,ZHAO Xiaoyang. Review of Measurement Technologies for Air Pollutants at Livestock and Poultry Farms[J]. Scientia Agricultura Sinica, 2019, 52(8): 1458-1474.

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图/表 6

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表6

畜禽场恶臭成分分析方法"

成分分析方法 Component analysis method	原理 Theory	检测物质 Substance detected	优点 Advantages	缺点 Disadvantages	参考文献 References
湿化学法 Wet-chemical method	利用被测气体成分与示剂的化学反应来测定气体浓度 Determination of gas concentration by chemical reaction between measured gases and indicators	NH₃、H₂S、SO₂、硫醇类物质等 NH₃, H₂S, SO₂, thiols, etc.	方法成熟,检测精度较高 mature method and high precision	检测时间较长 Longer detection time	[107]
气体探测管 Gas tubes	利用被测气体成分附着在固体指示剂表面的显色反应来测定气体浓度 Determination of gas concentration by color reaction of the gas components attached to the surface of the solid indicators	NH₃、H₂S、二甲基硫醚等 NH₃, H₂S, dimethyl sulfide, etc.	使用方便 Convenience of usage	检测精度较低 Low detection accuracy	[108, 109]
气相色谱分析法 Gas chromatography	利用不同组分在流动相（载气）和固定相间的分配差异进行分离 Separation of different components between mobile phase (carrier gas) and stationary phase	H₂S、CS₂、甲苯、二甲苯、吲哚类物质等 H₂S, CS₂, toluene, xylene, indole, etc.	分析速度快,灵敏度高 Fast analysis and high sensitivity	无法反映恶臭的气味特征,采样容器易造成样品污染和损失 Unable to reflect the smell characteristics of odors; samples easy to get polluted	[110-112]
质谱分析法 Mass spectrometry	将样品离子化,变为气态离子混合物,并按质荷比（m/z）分离,从而测定物质的质量与含量及其结构 Ionized into a gaseous ion mixture and separated according to the mass charge ratio (m/z), so as to determine the mass, content and structure of the substance.	甲苯、二甲苯、等 Toluene, xylene, etc.	分析对象范围广泛、检测灵敏度高 Wide range and high sensitivity	仪器使用、维护成本高 High cost	[113-116]
色谱-质谱联用法 Chromatography-mass spectrometry	结合气相色谱法对混合物的高效分离能力与质谱法对纯化合物的准确定性能力对恶臭进行分析 Analysis of odor by high efficientseparation of mixtures by gas chromatography and accurate qualitative analysis of pure compounds by mass spectrometry	SO₂、甲苯、二甲苯、等多种恶臭物质 SO₂, toluene, xylene, etc.	结合色谱法与质谱法优点 Combined advantages of chromatography and mass spectrometry	仪器使用、维护成本高 High cost	[117-120]

表6

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气体检测管种类 Gas sampling tube type	准确性 Accuracy	检测限 Detection limit	反应时间 Reaction time	采样成本 Cost
主动式 Active	较差 Worse	较高 Higher	s	较低 Lower
被动式 Passive	较好 Better	较低 Lower	h	较高 Higher

	灵敏度 Sensitivity	检测方法 Testing method	数据表达 Readout	采样方式 Active or passive	反应时间 Response time	仪器成本 Cost
湿化学法 Wet-chemical method	0.1-1mg·L^-1	点 Point	间接 Indirect	主动 Active	h	低 Low
pH试纸法 pH test paper method	mL·L^-1	点 Point	直接 Direct	被动 Passive	s	非常低 Very low
主动采样管 Active dosimeter tubes	0.5 mL·L^-1	点 Point	直接 Direct	主动 Active	s	低 Low
被动采样管 Passive dosimeter tubes	mL·L^-1	点 Point	直接 Direct	被动 Passive	h	低 Low
电化学传感器法 Electrochemical sensor method	μL·L^-1	点 Point	直接 Direct	主动/被动 Active/Passive	h	高 High
半导体传感器法 Semiconductor sensor method	mL·L^-1	点 Point	直接 Direct	主动 Active	s	低 Low
FTIR光谱法 FTIR spectral method	μL·L^-1	开路 Point	直接 Direct	被动 Passive	min	非常高 Very high
UV-DOAS探测仪 UV-DOAS detector	μL·L^-1	开路 Open path	直接 Direct	被动 Passive	s	高 High
光声红外探测器法 Photoacoustic infrared detector method	mL·L^-1	点 Point	直接 Direct	主动 Active	s	高-非常高 High-very high
质谱法 Mass spectrometry method	μL·L^-1	开路 Open path	直接 Direct	主动 Active	s	高 High

	灵敏度 Sensitivity	检测方法 Testing method	数据表达 Readout	采样方式 Active or passive	反应时间 Response time	仪器成本 Cost
湿化学法 Wet-chemical method	0.1-1 mg·L^-1	点 Point	间接 Indirect	主动 Active	h	低 Low
主动采样管 Active dosimeter tubes	mL·L^-1	点 Point	直接 Direct	被动 Passive	h	低 Low
被动采样管 Passive dosimeter tubes	mL·L^-1	点 Point	直接 Direct	主动 Active	s	低 Low
半导体传感器法 Semiconductor sensor method	mL·L^-1	点 Point	直接 Direct	主动 Active	s	低 Low
FTIR光谱法 FTIR spectral method	μL·L^-1	开路 Open path	直接 Direct	被动 Passive	min	高 High
气相色谱法 Gas chromatography method	mL·L^-1	开路 Open path	直接 Direct	主动 Active	s	高 High

检测方法 Testing method	优点 Advantages	缺点 Disadvantages
呼吸代谢箱法 Respiratory metabolism box method	发展较为成熟,应用广泛;可精确的测量肠道发酵产生的甲烷 Mature development and wide application; Accurate measurement of methane produced by intestinal fermentation	不能真实反映家畜体外的自然环境;构造和维修费用昂贵 Unable to reflect the external natural environment of livestock; High cost
六氟化硫示踪法 sulfur hexafluoride tracer method	投资和运行费用低;可进行群体检测 Low investment and operating costs; Group detection	发展不够成熟,仪器设备有待改进 Instruments and equipment need to be improved
头罩法和面罩法 Headcover and mask method	成本低 Low cost	低估甲烷产量;准确度不高;使用具有局限性 Understating methane production; Low accuracy; Limitations of usage

分析内容 Analysis content	采样器 Sampler	分析方法 Analytic method
离子 Ions	带尼龙滤膜的颗粒物采样器 Particle sampler with nylon filter membrane	离子色谱法 Chromatography of ions
元素 Elements	带特氟龙滤膜的颗粒物采样器 Particle sampler with Teflon filter membrane	能量色散X射线光谱分析法 Energy dispersive x-ray spectroscopy
有机碳、元素碳 OC、EC	带石英滤膜的颗粒物采样器 Particle sampler with quartz filter membrane	热光学分析法 Thermal optical analysis