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1.
基于气相色谱仪 (GC)和电子捕获检测器 (ECD) ,设计了一种连续测量大气中痕量氯氟烃的自动系统。系统色谱基线稳定 ,分离效果好 ,定性、定量准确可靠 ,系统高度自动化 ,长期运行无需人值守 ,自动校正数据 ,定时进行严格的质量控制 ;系统具有较高的现场测量频率 (6次 /h) ,改进的反吹 /外切设计使CFCs色谱峰不再受氧峰的干扰 ,大大延长了检测器的寿命 ,使长期连续观测成为可能。系统设计在分离效果方面优于世界气象组织 (WMO)全球大气监测网 (GAW )目前所使用的测量大气本底CFCs的方法 ,采用美国EPA认可的标气 ,外标工作曲线法测定大气CFCs的浓度 ,最低检测限可达1pL/L ,检测精密度小于 1 % ,准确度在± 3%之内 ,可用于我国本底大气观测站对CFCs的连续测定  相似文献   

2.
2015年8月23日—9月4日京津冀地区对部分污染源实行了临时性的减排管控措施,为保障9月3日北京大阅兵的空气质量起到了重要作用。天津作为协同减排的重要城市,阅兵期间空气质量变化一直备受关注。为评估这次减排管控措施对空气质量的改善效果,于2015年8月10日—9月15日,选择天津市气象局院内观测场,利用自动在线观测仪器对大气污染物NO_x、SO_2、CO、O_3及PM_(2.5)进行了连续观测,以天津所采取的临时减排措施为时间节点,对人为管控前后污染物的浓度水平、源贡献及日变化特征进行了比对分析,并结合气团输送特征讨论了气象条件在各时段的贡献。结果显示:在减排期间(2015年8月23日—9月4日),NO、NO_2、SO_2、CO、O_3及PM_(2.5)浓度较减排前(2015年8月10日—22日)分别降低了12.3%、34.1%、41.8%、21.1%、39.0%及63.1%,燃煤、工业及扬尘源控制效果显著;减排后(2015年9月5日—15日)较减排期,NO、NO_2、SO_2、CO及PM_(2.5)浓度分别升高了77.2%、46.1%、13.3%、12.5%和11.5%,空气质量主要受机动车源的影响。NO_2、SO_2、CO及PM_(2.5)在各时段的日变化基本呈早晚双峰型,NO呈早单峰型,O_3呈午后单峰型,减排措施有效降低了峰值和浓度水平,污染物排放至大气后,近地面气象要素也会有所影响。由气团的输送特征可知,有利的气象条件也是减排期间良好空气质量的重要因素,减排后CO、SO_2和PM_(2.5)无显著回升主要得益于清洁气团的频繁出现。  相似文献   

3.
采集天津市4个采样点的大气 PM_(10)与降尘样品,利用CH_2Cl_2和超声对样品中的邻苯二甲酸二甲酯(DMP)、邻苯二甲酸二乙酯(DEP)、邻苯二甲酸二丁酯(DBP)、邻苯二甲酸丁基苄基酯(BBP)、邻苯二甲酸(2-乙基己基)酯(DEHP)和邻苯二甲酸二辛酯(DOP)等6种邻苯二甲酸酯(PAEs)进行提取分离,采用气相色谱/质谱联用仪(GC/MS)定量分析。结果表明,4个采样点大气 PM_(10)样品中6种PAEs总质量浓度为2.371~24.201ng/m3,降尘样品中6种PAEs总质量浓度为222.310~1 184.503ng/g。对于6种PAEs,夏季浓度均高于冬季浓度,且DBP与DEHP是大气 PM_(10)与降尘样品中的主要污染物。6种PAEs总浓度、DBP浓度、DEHP浓度在大气 PM_(10)与降尘样品中存在相关关系,斯皮尔曼相关系数分别为0.929、0.881、0.905(双尾检验,在显著性水平0.01下)。回归分析表明,大气 PM_(10)与降尘样品中6种PAEs总浓度、DBP浓度、DEHP浓度具有一定的共变趋势。  相似文献   

4.
采集了武汉春季大气PM10样品,用超声萃取、衍生化、气相色谱/质谱(GC/MS)技术分析了其有机组成.结果表明,PM10质量浓度为160.3~296.7 μg/m3,其夜晚浓度大于白天.PM10中有机物浓度总体表现为正烷酸>左旋葡聚糖>正构烷烃>二元酸>甘油酸酯>多环芳烃>甾醇>藿烷和甾烷的特征,夜晚浓度大于白天,工作日(周一至周五)大于周末(周六、周日).武汉大气颗粒有机物(POM)既有来源于植物蜡等自然源的输入,也有交通和食物烹饪等人为源的影响.  相似文献   

5.
基于低温气相色谱分离技术、电子捕获检测技术和光化学合成技术,搭建了大气过氧乙酰硝酸酯(PAN)在线监测及校准装置,实现对大气中PAN的在线监测及自动校准。通过参数优化实验,确定了系统最佳运行条件为:柱箱温度12℃、柱前压18k Pa、电子捕获检测器温度50℃、尾吹气流量25 m L/min。测得该条件下基线平稳、噪声小,峰响应最佳;PAN保留时间为1.75 min,线性相关系数(R2)为0.999,检出限为0.026 nmol/mol,定量重复性为1.57%,24 h稳定性为0.74%。将该系统用于现场测试,结果表明系统能够自动运行,并实现定期自动校准。  相似文献   

6.
通过在线观测获得2012年杭州市华家池环境空气测点的两种主要温室气体(CH4和CO2)数据,以研究杭州市CO2、CH4的浓度变化规律及源与汇对其的影响。结果表明:(1)2012年,华家池环境空气测点CO2、CH4年日均值分别为835、1.47mg/m3。(2)CH4和CO2呈现较明显的日变化趋势,7:00左右达到最大值,15:00左右达到最小值。(3)CO2月均值较低的月份为7—9月,较高的月份为11—12月;CH4月均值较低的月份为7—8月,较高的月份为10月。CO2浓度在冬季最高,而CH4浓度在秋季最高,两者浓度在夏季均最低。CO2浓度变化主要受光合作用影响,而CH4浓度变化主要受·OH浓度影响,两者均受大气对流作用影响。(4)Spearman相关性分析表明,CO2和CH4浓度变化趋势较一致;CO2与气温具有显著负相关性,与SO2、NO2、PM10具有显著或极显著的相关性;CH4与风速具有负相关性,与PM10具有显著相关性。  相似文献   

7.
为了研究2008年北京奥运会前期污染物浓度变化特征,对北京气象塔3层高度上的大气污染物(NO2和O3)进行加强观测,分析其变化特征。观测结果表明,由于北京奥运会前期采取了严格的空气质量控制措施,NO2浓度相对车辆限行前下降了45.3%,且随着高度递增逐渐降低;O3浓度最大值和日均值有所降低,其最大值出现时间较10年前提前了1~2 h,且有4 h左右处于相对平稳状态。O3浓度峰值主要是受NO2的控制,O3浓度峰值出现时间提前反映出北京大气氧化效率不断提高。对于观测期间出现光化学污染事件,利用同期气象资料和大气污染监测数据分析,发现造成这次大气污染的主要原因是气象因子:地面多处于弱高压场控制中,大气层结稳定,风力较弱(小于2 m/s),并伴随着连续高温、强辐射和低湿。  相似文献   

8.
无锡市区大气污染物污染特征及影响因素研究   总被引:1,自引:0,他引:1  
利用2014年无锡市区的6种大气污染物浓度和气象因子等监测数据,研究了无锡市区各种大气污染物的污染特征及其影响因素。结果表明:(1)无锡市区PM_(2.5)、PM_(10)、SO_2、NO_2、CO浓度的季节变化特征为冬季最高,夏季最低;O_3浓度表现为夏季最高,冬季最低。就全年的综合情况而言,颗粒物污染,尤其是PM_(2.5)污染最严重。(2)PM_(2.5)、PM_(10)、SO_2、NO_2、CO浓度间两两呈正相关;PM_(2.5)、SO_2、NO_2、CO浓度均与O_3浓度呈负相关。(3)温度与PM_(2.5)、PM_(10)、SO_2、NO_2、CO浓度呈负相关,与O_3浓度呈正相关;相对湿度与PM_(2.5)、PM_(10)、SO_2、NO_2、O_3浓度呈负相关,与CO浓度无相关性;风级与PM_(2.5)、PM_(10)、SO_2、NO_2、CO浓度呈负相关,与O_3浓度无相关性。降水有利于PM_(2.5)、PM_(10)、SO_2、NO_2、O_3浓度的降低,但对CO浓度影响不大。(4)无锡市区空气质量周末比工作日差。NO_2、SO_2浓度周末低于工作日,O_3浓度周末高于工作日,呈现明显的"周末效应";PM_(2.5)、CO浓度周末高于工作日,未出现"周末效应"。  相似文献   

9.
在完全混合式产酸脱硫生物系统中,利用负压抽提法强化H2S的气液分离,以NaOH溶液吸收H2S气体。抽提装置实现对H2S自动、连续抽提与吸收,在60mmH2O柱负压力范围分离出H2S的量与抽提压力呈线性正相关。抽提作用可促进SRB对碳源底物的转化,显著提高硫化物的气/液比例,增加系统中硫化物的转化率。抽提后硫化物的气/液比例(摩尔比)由0044上升到061、分离出的H2S在硫化物总生成量中的比例由42%增加到356%,硫化物转化率由平均494%提高至610%。抽提作用可以提高系统的硫酸盐去除率和酸碱缓冲能力,同时可以纯化和浓缩H2S。  相似文献   

10.
北京与伦敦空气中气态污染物的比对研究   总被引:3,自引:0,他引:3  
城市空气质量问题已经引起广泛关注.通过对中英2个大城市北京与伦敦 2004 年 8 月~2005 年12 月空气中气态污染物 O3、NOx、SO2 和 CO 浓度变化的分析与对比发现:参照世界卫生组织空气质最准则、欧盟空气质量标准、美国国家空气质量标准或国家空气质量二级标准,北京O3、NO2、SO2和 CO 浓度的超标天数或时数明显高于伦敦.观测期内,北京 O3、NOx、SO2 和 CO 浓度明显高于伦敦,平均值分别是 17.9±22.1×10-9、72.4±76.1×10-9、19.5±21.8×10-9、2 004.6±1 509.8×10-9与10.8±9.9×10-9、54,6±38.9×10-9、1.8±2.2×10-9、372.3±235.0×10-9.两城市 O3 统计日变化形式均表现为白天高、夜晚低,峰值出现在午后 14:00 左右,日较差分别为 31.5±30.9×10-9与 11.1±7.7×10-9;NO、NO2、SO2 和 CO 呈双峰态日变化,峰值出现在交通的早高峰与晚高峰附近.北京 O3 最高值出现在夏季,而伦敦出现在春季;但两城市NOx、SO2 和 CO 最高值均出现在冬季.北京与伦敦的NO2与 NO 呈显著线性相关,且斜率与截距十分相似,分别是 1.25 和 1.28 与 28.1 和 23.2;同时两城市 CO/NOx 比率明显高于 SO2/NO 分别为 14.0、4.5 与 0.13、0.03.由此可以判断:对于两城市空气污染问题,交通源的贡献要远大于点源;但点源也对两城市空气质量造成影响.此外,连续逆温的天气是造成重污染事件的原因.  相似文献   

11.
Abstract

A semi-industrial scale test was conducted to thermally treat mixtures of spent oil and askarels at a concentration of 50,000 ppm and 100,000 ppm of polychlorinated biphenyls (PCBs) under a reductive atmosphere. In average, the dry-basis composition of the synthesis gas (syngas) obtained from the gasification process was: hydrogen 46%, CO 34%, CO2 18%, and CH4 0.8%. PCBs, polychlorinated dibenzo-p-dioxins, and polychlorinated dibenzofurans (PCDDs/PCDFs) in the gas stream were analyzed by high-resolution gas chromatography (GC)-mass spec-trometry. The coplanar PCBs congeners 77, 105, 118, 156/157, and 167 were detected in the syngas at concentrations <2 ×10?7 mg/m3 (at 298 K, 1 atm, dry basis, 7% O2). The chlorine released in the destruction of the PCBs was transformed to hydrogen chloride and separated from the gas by an alkaline wet scrubber. The concentration of PCBs in the water leaving the scrubber was below the detection limit of 0.002 mg/L, whereas the destruction and removal efficiency was >99.9999% for both tests conducted. The concentration of PCDDs/PCDFs in the syngas were 8.1 ×10?6 ng-toxic equivalent (TEQ)/m3 and 7.1 × 10?6 ng-TEQ/m3 (at 298 K, 1 atm, dry basis, 7% O2) for the tests at 50,000 ppm and 100,000 ppm PCBs, respectively. The only PCDD/F congener detected in the gas was the octachloro-dibenzo-p-dioxin, which has a toxic equivalent factor of 0.001. The results obtained for other pollutants (e.g., metals and particulate matter) meet the maximum allowed emission limits according to Mexican, U.S., and European regulations for the thermal treatment of hazardous waste (excluding CO, which is a major component of the syngas, and total hydrocarbons, which mainly represent the presence of CH4).  相似文献   

12.
An on-line supercritical fluid extraction–liquid chromatography–gas chromatography–mass spectrometry (SFE–LC–GC–MS) method was developed for the analysis of the particulate polycyclic aromatic hydrocarbons (PAHs). The limits of detection of the system for the quantification standards were in the range of 0.25–0.57 ng, while the limits of determinations for filter samples varied from 0.02 to 0.04 ng m−3 (24 h sampling). The linearity was excellent from 5 to 300 ng (R2>0.967). The analysis could be carried out in a closed system without tedious manual sample pretreatment and with no risk of errors by contamination or loss of the analytes. The results of the SFE–LC–GC–MS method were comparable with those for Soxhlet and shake-flask extractions with GC–MS. The new method was applied to the analysis of PAHs collected by high-volume filter in the Helsinki area to study the seasonal trend of the concentrations. The individual PAH concentrations varied from 0.015 to more than 1 ng m−3, while total PAH concentrations varied from 0.81 to 5.68 ng m−3. The concentrations were generally higher in winter than in summer. The mass percentage of the total PAHs in total suspended particulates ranged from 2.85×10−3% in July to 15.0×10−3% in December. Increased emissions in winter, meteorological conditions, and more serious artefacts during the sampling in summer season may explain the concentration profiles.  相似文献   

13.
The research team analyzed the emission characteristics of gaseous pollutants, including volatile organic compounds (VOCs), from biomass combustion in improved stoves in rural China. The research included measurements from five biofuels and two stove types in the months of January, April, and September. The measurements were conducted according to U.S. EPA Method 25 using a collection system with a cooling device and two-level filters. CO, CO2, NOx, CH4 and THC analyzers were used for in-field, real-time emission measurements. The emission data indicate that gaseous pollutants were emitted at higher concentrations in the early combustion stage and lower concentrations in the later stage. CH4 and THC, as well as CO and CO2, presented positive relationships during the whole entire combustion process for all tests. The chemical profiles of flue gas samples were analyzed by GC/MS and GC/FID/ECD. Aromatics, carbonyls, and alkenes & alkynes dominated the VOC emissions, respectively accounting for 37%, 33%, and 23% of total VOC emissions by volume. Benzene was the most abundant VOC species, consisting of 17.3 ± 8.1% of VOCs, followed by propylene (11.3 ± 3.5%), acetone (10.8 ± 8.2%), toluene (7.3 ± 5.7%) and acetaldehyde (6.5 ± 7.3%). Carbon mass balance approach was applied to calculate CO, CO2, CH4, NOx, and VOC species emission factors. This analysis includes a discussion of the differences among VOC emission factors of different biofuel-stove combinations.  相似文献   

14.
Three CO instruments, i.e., vacuum ultraviolet resonance fluorescence (VUV-RF), gas chromatography/reduction gas detection (GC/RGD), and non-dispersive infrared (NDIR) spectrometry, were inter-compared at a background site, i.e., Lulin Atmospheric Baseline Station (LABS) in central Taiwan. For a period of 18 days of continuous measurements, highly coherent results were observed between the three instruments. Calibration of the GC/RGD and VUV-RF was based on the same batch of CO standards, producing results that agreed within 4%. Nevertheless, NDIR displayed a significant bias with a large offset compared to the other two instruments (about ?63.1 ppb), due mainly to its over-simplified calibration procedure. The NDIR bias was then removed by aligning the NDIR data to those of GC/RGD in a process termed “post-run correction”. Through this practice, the NDIR was linked to the same calibration scale as that of GC/RGD. As a result, by simultaneously exploiting both GC/RGD and NDIR to measure background CO, both time-resolution and accuracy can be secured.  相似文献   

15.
The persistence and fate of chlorpyrifos and its two metabolites, chlorpyrifos-oxon and the 3, 5, 6-trichloro-2-pyridinol (TCP) break-down product were investigated on kale and collard leaves under field conditions. A simultaneous extraction and quantification procedure was developed for chrorpyrifos and its two main metabolites. Residues of chlorpyrifos, chlorpyrifos oxon, and TCP were determined using a gas chromatograph (GC) equipped with an electron capture detector (GC/ECD). Chlorpyrifos metabolites were detectable up to 23 days following application. Residues were confirmed using a GC equipped with a mass selective detector (GC/MSD) in total ion mode. Initial residues of chlorpyrifos were greater on collard (14.5 µg g?1) than kale (8.2 µg g?1) corresponding to half-lives (T1/2) values of 7.4 and 2.2 days, respectively. TCP, the hydrolysis product, was more persistent on collards with an estimated T1/2 of 6.5 days compared to kale (T1/2 of 1.9 days).  相似文献   

16.
Comprehensive field studies were initiated in 2002 to measure emissions of ammonia (NH3), hydrogen sulfide (H2S), carbon dioxide (CO2), methane (CH4), nonmethane hydrocarbons (NMHC), particulate matter <10 microm in diameter, and total suspended particulate from swine and poultry production buildings in the United States. This paper focuses on the quasicontinuous gas concentration measurement at multiple locations among paired barns in seven states. Documented principles, used in air pollution monitoring at industrial sources, were applied in developing quality assurance (QA) project plans for these studies. Air was sampled from multiple locations with each gas analyzed with one high quality commercial gas analyzer that was located in an environmentally controlled on-farm instrument shelter. A nominal 4 L/min gas sampling system was designed and constructed with Teflon wetted surfaces, bypass pumping, and sample line flow and pressure sensors. Three-way solenoids were used to automatically switch between multiple gas sampling lines with > or =10 min sampling intervals. Inside and outside gas sampling probes were between 10 and 115 m away from the analyzers. Analyzers used chemiluminescence, fluorescence, photoacoustic infrared, and photoionization detectors for NH3, H2S, CO2, CH4, and NMHC, respectively. Data were collected using personal computer-based data acquisition hardware and software. This paper discusses the methodology of gas concentration measurements and the unique challenges that livestock barns pose for achieving desired accuracy and precision, data representativeness, comparability and completeness, and instrument calibration and maintenance.  相似文献   

17.
A simultaneous method for quantifying eight metabolites of organophosphate pesticides and pyrethroid pesticides in urine samples has been established. The analytes were extracted using liquid–liquid extraction coupled with WCX solid phase extraction (SPE) cartridges. Eight metabolites were chemically derivatized before analysis using gas chromatography–tandem mass spectrometry (GC–MS–MS). The separation was performed on a HP-5MS capillary column (30 m × 0.25 mm × 0.25 µm) with temperature programming. The detection was performed under electro-spray ionization (ESI) in multiple reaction monitoring (MRM) mode. An internal standard method was used. The extraction solvent, types of SPE cartridges and eluents were optimized by comparing the sample recoveries under different conditions. The results showed that the calibration curves of the five organophosphorus pesticides metabolites were linear in the range of 0.2–200 μg/L (r2 ≥ 0.992) and that of the three pyrethroid pesticides metabolites were linear in the range of 0.025–250 μg/L (r2 ≥ 0.991). The limits of detection (LODs, S/N ≥ 3) and the limits of quantification (LOQs, S/N ≥ 10) of the eight metabolites were 0.008–0.833 μg/L and 0.25–2.5 μg/L, respectively. The recoveries of the eight metabolites ranged from 54.08% to 82.49%. This efficient, stable, and cost-effective method is adequate to handle the large number of samples required for surveying the exposure level of organophosphorus and pyrethroid pesticides in the general population.  相似文献   

18.
We investigated CO photoproduction from intact leaves of rice (Oryza sativa L.) and maize (Zea mays L.) by laboratory experiments. CO photoproduction showed positive correlation with light intensity and was positively dependent on oxygen concentration. The average CO photoproduction was 2.6±0.3×1010 molecules cm−2 s−1 from rice leaves and 2.2±0.1×1010 molecules cm−2 s−1 from maize leaves (n=5) at a radiation intensity of 49 mW cm−2. CO photoproduction from senescent rice leaves was 9 times greater (25.7±1.5×1010 molecules cm−2 s−1, n=2) at the same radiation intensity than from live leaves, and responded slowly to changes in oxygen concentration and light intensity. CO photoproduction showed no correlation with CO2 concentration or humidity. This indicates that CO photoproduction in leaves is not directly controlled by carbon metabolism or stomatal conductance. The lack of dependence on stomatal conductance leads to the conclusion that the diffusion of CO from inside the leaves to the atmosphere is not a controlling factor for CO photoproduction from rice and maize leaves.  相似文献   

19.
A simple multi-residue method based on modified QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) approach was established for the determination of 17 organochlorine (OC), 15 organophosphorous (OP) and 7 synthetic pyrethroid (SP) pesticides in an economically important medicinal plant of India, Senna (Cassia angustifolia), by gas chromatography coupled to electron capture and flame thermionic detectors (GC/ECD/FTD) and confirmation of residues was done on gas chromatograph coupled with mass spectrometry (GC-MS). The developed method was validated by testing the following parameters: linearity, limit of detection (LOD), limit of quantification (LOQ), matrix effect, accuracy–precision and measurement uncertainty; the validation study clearly demonstrated the suitability of the method for its intended application. All pesticides showed good linearity in the range 0.01–1.0 μg mL?1 for OCs and OPs and 0.05–2.5 μg mL?1 for SPs with correlation coefficients higher than 0.98. The method gave good recoveries for most of the pesticides (70–120%) with intra-day and inter-day precision < 20% in most of the cases. The limits of detection varied from 0.003 to 0.03 mg kg?1, and the LOQs were determined as 0.01-0.049 mg kg?1. The expanded uncertainties were <30%, which was distinctively less than a maximum default value of ±50%. The proposed method was successfully applied to determine pesticide residues in 12 commercial market samples obtained from different locations in India.  相似文献   

20.
A 96-microwell enzyme-linked immunosorbent assay (ELISA) method was evaluated to determine PCDDs/PCDFs in sediment and soil samples from an EPA Superfund site. Samples were prepared and analyzed by both the ELISA and a gas chromatography/high resolution mass spectrometry (GC/HRMS) method. Comparable method precision, accuracy, and detection level (8 ng kg(-1)) were achieved by the ELISA method with respect to GC/HRMS. However, the extraction and cleanup method developed for the ELISA requires refinement for the soil type that yielded a waxy residue after sample processing. Four types of statistical analyses (Pearson correlation coefficient, paired t-test, nonparametric tests, and McNemar's test of association) were performed to determine whether the two methods produced statistically different results. The log-transformed ELISA-derived 2,3,7,8-tetrachlorodibenzo-p-dioxin values and log-transformed GC/HRMS-derived TEQ values were significantly correlated (r=0.79) at the 0.05 level. The median difference in values between ELISA and GC/HRMS was not significant at the 0.05 level. Low false negative and false positive rates (<10%) were observed for the ELISA when compared to the GC/HRMS at 1,000 ng TEQ kg(-1). The findings suggest that immunochemical technology could be a complementary monitoring tool for determining concentrations at the 1,000 ng TEQ kg(-1) action level for contaminated sediment and soil. The ELISA could also be used in an analytical triage approach to screen and rank samples prior to instrumental analysis.  相似文献   

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