甲醇气体标准样品的研制

介绍了甲醇气体标准样品的制备和定值方法,考察采用重量法制备氮气中甲醇标准气体样品的重现性、标准气体的均匀性和稳定性.试验表明,甲醇气体标准样品在气瓶内均匀性良好,在12个月研制期间没有不稳定趋势.摩尔分数为149.2×10-6甲醇气体标准样品,扩展不确定度为3%,能够满足环境污染源废气中甲醇气体监测的要求.     

环境气体标准样品量值的计算及不确定度分析

依据《气体分析校准气体混合物的制备重量法》（1SO6142—2001）和《气体分析气体标准样品组成的测定和校验比较法》（ISO6143—2001），阐述了环境气体标准样品不同定值方法的量值计算及不确定度来源，并比较了同一气体标准样品采用不同定值方法得到的不同量值结果及不确定度：     

二氧化硫(高压)气体标准样品的研制

文章对高压气瓶中二氧化硫气体标准样品的制备方法进行了研究 ,对各种可能影响二氧化硫气体标准样品量值准确性的因素进行了分析。所制备的 2 0 .2 μmol/ mol二氧化硫气体标准样品的不确定度仅为 1 .4 % ,且具有良好的压力稳定性并能稳定保存 2 0个月     

甲烷气体标准样品的研制

对称量制备甲烷气体标准样品的制备方法进行了详细研究 ,对可能引起甲烷量值不确定度的各种误差来源进行了分析。文中提出的甲烷气体标准样品制备方法具有很好的重现性 ,所制备的甲烷气体标准样品具有良好的压力稳定性并已能在三种气瓶中稳定保存 1 8个月 ,其量值准确、可比 ,并已在全国环境监测网试用。     

气体分析仪测量不确定度的分析

参照国际标准化组织颁布的"1S0 6143:2001(E)"标准方法,利用相对法求出回归方程,对环境气体分析仪进行了不确定度评定。分析了校准曲线图上每个校准点处的标准物质的不确定度和仪器响应值对回归直线参数的不确定度贡献,并将这些不确定度合成,给出参数的不确定度以及气体分析仪测定气体样品的不确定度。     

室内空气污染监测用氨标准样品研究

根据中国对室内空气污染监测的实际需要,介绍了室内空气污染监测用氨标准样品的研制方法,包括试剂的验证、均匀性和稳定性检验、分析定值和测定数据的统计检验等方面。氨标准样品采用重量法制备,用纳氏试剂分光光度法对样品进行均匀性和稳定性研究,并进行不确定度评估。研究结果表明,氨标准样品的均匀性良好,室温条件下可稳定18个月以上;在全面分析不确定度来源的基础上,定值结果为0.494 mg/L,不确定度小于3%。与美国同类标准物质进行比对分析,结果具有可比性。可用于氨测定的质量控制、分析方法评价以及实验室能力验证等方面。     

便携式GC-MS测定气体样品中6种典型VOCs的不确定度评定

以便携式GC-MS测定气体样品中6种典型挥发性有机物(VOCs)组分(苯、1,1,2-三氯乙烷、四氯乙烯、乙苯、间二甲苯和1,3,5-三甲基苯)为例,应用不确定度理论,从检测过程和计算方法的角度分析了影响测量不确定度的各种因素:标准气体定值、标准气体稀释、工作曲线的非线性及重复性测定。对各测量不确定度分量进行计算和评定,同时采用稳健统计方法对测定结果进行准确度评价。结果表明:采用便携式GC-MS测定气体样品中VOCs不确定度的主要影响因素是标准气体定值和工作曲线的非线性,其次是重复性测定,标准气体稀释引入的不确定度较小。当VOCs组分含量为200 nmol/mol浓度水平时,测量扩展不确定度为14～17 nmol/mol,测量相对扩展不确定度为7.1%～9.2%(k=2,置信水平为95%),相对误差为1.5%～4.0%。     

固定污染源废气监测用挥发性卤代烃标准气体制备不确定度研究

针对固定污染源挥发性卤代烃污染物的排放监测需求,采用称量法制备固定污染源废气监测用挥发性卤代烃标准气体(各组分具有浓度差异),并开展制备不确定度评定研究。通过分析原料试剂纯度、液态/气态组分称量、混合液配比、摩尔质量、气体残留等因素和环节引入的不确定度,确立标准气体制备不确定度评定流程。最终,确定固定污染源废气监测用挥发性卤代烃标准气体制备过程引入的相对扩展不确定度(k=2)小于1%。液态/气态组分称量和上一级中间气浓度引入的不确定度对特性量值不确定度的贡献较大,原料试剂纯度对不确定度的影响较小,摩尔质量和气体残留对不确定度的影响可忽略。     

环境监测用5种氯代烯烃混合气体标准样品研制

介绍了1μmol/mol氮气中5种氯代烯气体标准样品的研制方法。这5种氯代烯包括氯乙烯、1,1-二氯乙烯、顺1,2-二氯乙烯、三氯乙烯、四氯乙烯,其中氯乙烯常温下为气态,其他4种为液态,并且沸点低,将这几种氯代烯制备成气体标准样品存在制备精度低、气液转换不完全等困难。经研究,采用2步称量法制备5种氯代烯气体标准样品,重复制备的相对标准偏差小于1.6%。建立了5种氯代烯标准气体瓶内均匀性的实验方法,并通过考察样品量值伴随样品压力的变化来评价样品的均匀性。结果显示,5种氯代烯标准气体是均匀的,最低使用压力为1 MPa。依照ISO 15000.3来考察样品的时间稳定性,样品有效期为12个月。相对扩展不确定度为3%(置信度为95%)。     

异辛烷中2,2',4,4',5,5'-六溴联苯标准样品的研制

介绍了异辛烷中2,2',4,4',5,5'-六溴联苯(PBB-153)标准样品的研制方法。分别采用气相色谱法、差示扫描量热法对PBB-153原料进行纯度分析,测定了原料中水分、杂质的含量,利用质量平衡法计算得到纯品纯度为99.0%,相对扩展不确定度为1.2%(k=2)。异辛烷中PBB-153标准样品采用称量-容量法制备,配制浓度为50.00μg/m L,利用气相色谱法对其进行均匀性检验和稳定性监测,结果显示均匀性良好,稳定性可达18个月以上。对不确定度进行评估,结果显示相对扩展不确定度为4%(k=2)。该标准样品与国外同类样品具有量值一致性,能有效支撑中国六溴联苯的履约监测与环境管理等工作。     

运用线性拟合法评定水中总磷的测量不确定度

采用Top—Down不确定度评定理念，利用实验室日常质控数据，结合标准样品的线性校准方法（线性拟合法），评定水中总磷的测量不确定度，并将评定结果与GUM评定法相比较，相对偏差≤20％。指出线性拟合法适用于测量系统校准函数成线性，且实验总残差符合常数剩余标准差假定情况下的不确定度评定。     

Can NO(2) be used to indicate ambient and personal levels of benzene and 1,3-butadiene in air?

The aim of this study was to investigate the relation between two toxic volatile organic compounds, 1,3-butadiene and benzene, and a commonly used indicator of vehicle exhaust fumes, NO(2). This was to see if NO(2) can be used to indicate personal exposure to carcinogenic substances or at least estimate ambient levels measured at a stationary point. During the winter of 2001, 40 randomly selected persons living in the City of Umea (in the north of Sweden) were recruited to the study. Personal measurements of 1,3-butadiene, benzene and NO(2) were performed for one week, and were repeated for 20 of the 40 participants. Additional information was gathered using a diary kept by each participant. During the same time period weekly stationary measurements were performed at one urban background station and one street station in the city centre. The results from the personal measurements showed a negligible association of NO(2) with 1,3-butadiene (r= 0.06) as well as with benzene (r= 0.10), while the correlation coefficient between 1,3-butadiene and benzene was high and significant (r= 0.67). In contrast to the personal measurements, the stationary measurements showed strong relations between 1,3-butadiene, benzene and NO(2) both within and in-between the street and urban background station. This study supports NO(2) as a potential indicator for 1,3-butadiene and benzene levels in streets or urban background air, while the weak relations found for the personal measurements do not support the use of NO(2) as an indicator for personal 1,3-butadiene and benzene exposure.     

The impact of domestic wood burning on personal, indoor and outdoor levels of 1,3-butadiene, benzene, formaldehyde and acetaldehyde

The aim of this study was to quantify personal exposure and indoor levels of the suspected or known carcinogenic compounds 1,3-butadiene, benzene, formaldehyde and acetaldehyde in a small Swedish town where wood burning for space heating is common. Subjects (wood burners, n = 14), living in homes with daily use of wood-burning appliances were compared with referents (n = 10) living in the same residential area. Personal exposure and stationary measurements indoors and at an ambient site were performed with diffusive samplers for 24 h. In addition, 7 day measurements of 1,3-butadiene and benzene were performed inside and outside the homes. Wood burners had significantly higher median personal exposure to 1,3-butadiene (0.18 microg m(-3)) compared with referents (0.12 microg m(-3)), which was also reflected in the indoor levels. Significantly higher indoor levels of benzene were found in the wood-burning homes (3.0 microg m(-3)) compared with the reference homes (1.5 microg m(-3)). With regard to aldehydes, median levels obtained from personal and indoor measurements were similar although the four most extreme acetaldehyde levels were all found in wood burners. High correlations were found between personal and indoor levels for all substances (r(s) > 0.8). In a linear regression model, type of wood-burning appliance, burning time and number of wood replenishments were significant factors for indoor levels of 1,3-butadiene. Domestic wood burning seems to increase personal exposure to 1,3-butadiene as well as indoor levels of 1,3-butadiene and benzene and possibly also acetaldehyde. The cancer risk from these compounds at exposure to wood smoke is, however, estimated to be low in developed countries.     

定电位电解法测定烟气中氮氧化物的不确定度评定——以湿法脱硫除尘电厂为例

以某湿法脱硫除尘电厂为例,对定电位电解法测定烟气中氮氧化物的不确定度进行评定。分析认为,测量结果的不确定度可能来自于仪器的校准过程、重复性测量过程和其他气体或杂质的干扰,通过将定电位电解法和紫外分光光度法进行对比分析,确定其他气体或杂质的干扰在本分析过程中造成的不确定度可以忽略。最终计算得出,此次使用3012H型自动烟尘测试仪测量氮氧化物的相对扩展不确定度为±6.57%,其中B类不确定度分量的贡献较大,在分析过程中应加强仪器的维护与保养。     

环境监测质量控制中水质标准物质应用问题的研究

对环境监测质量控制中水质标准物质的应用问题进行了分析和论述。分别从实验室分析测试标准、质量控制标准的不确定度、质量控制方式的选择以及实验分析的准确度和分析方法研究等方面,讨论了实验室质量控制过程中水质标准物质应用出现的误区和问题。对如何做好实验室分析的质量控制,从多个不同的方面介绍了在使用分析校准用标准物质及水质质量控制用标准物质过程中,如何避免或减少分析误差的方法和措施。同时对计量、质量控制的重要工具水质标准物质的正确使用以及标准物质的规范应用方面提出了相关建议。