总氮测定中空白吸光值的控制方法

分析了总氮测定过程中影响空白值的一些因素及控制方法。总氮测定过程中,消解温度和时间、蒸馏水纯度、试剂选用和存放时间、器皿洁净度等等均会影响到试验空白吸光值。笔者提出采用消解温度控制在120～124℃、消解时间在45 min、空白样消解后加入蒸馏水、选用分析纯试剂、试剂存放时间小于7 d等措施可以有效地控制试验空白吸光值。     

测定总氮时影响空白吸光值的因素

针对测定水质中总氮时遇到实验空白值偏高的情况，分析了实验用水、试验及环境因素对空白值的影响。     

空白平行测定批内标准差及检测限的计算

计算检测限公式L=2 2~(1/2)t_fS_(wb)中,S_(wb)是空白平行测定浓度值的批内标准差,用空白浓度值求算S_(wb),有时会人为降低S_(wb)值。建议先直接用空白试验值求算试验值S_(wb),然后换算成空白浓度值S_(wb)。     

降低水质氨氮测定中试剂空白值的方法

氨氮的测定通常采用纳氏试剂比色法,该法具有操作简便、灵敏等特点。但我们在日常分析水样中普遍发现,有时所购买的抗金属干扰掩蔽剂酒石酸钾钠试剂含氨较高,造成该方法试剂空白值增高,试剂空白值吸光度大于0.06。由于试剂空白值较高,因此给分析结果带来误差。本文采用纳氏试剂对50％的酒石酸钾钠溶液进行提纯,方法简便易行,解决了以上问题,使试剂空白吸光度降至小于0.025,取得满意效果。     

PM 2.5中铂族元素及微量元素采样滤膜的选择

为准确分析大气PM_(2.5)中的铂族元素及微量元素,得到更低的检出限,对3种石英滤膜(Whatman石英滤膜(WH)、Pall石英滤膜(PA)、国产石英滤膜(CC))的空白值进行检测,并用王水处理WH,以检验其空白值的降低效果。结果表明:PA中铂族元素及微量元素含量最低。王水处理WH(WH’)中铂族及微量元素的空白值得到有效降低。WH’和PA可用于PM_(2.5)中铂族元素及微量元素的采集和分析。     

接种稀释水的空白对BOD_5测定的影响

从接种液种类、空白 BOD5大小、接种液最佳添加范围等方面对 BOD5测定进行探讨 ,提出以接纳工业废水的河水作为最佳接种液 ,雨季时以土壤浸取液更适合。探讨了接种液空白值对 BOD5标液和工业废水的影响。结果表明 ,河水空白应控制在 0 .1～0 .8mg/ L,土壤浸取液空白控制在 0 .0 1～ 0 .1 0 mg/ L为宜。     

接种稀释水的空白对BOD5测定的影响

从接种液种类、空白ＢＯＤ５大小、接种液最佳添加范围等方面对ＢＯＤ５测定进行探讨，提出以接纳工业废水的河水作为最佳接种液，雨季时以土壤浸取液更适合。探讨了接种液空白值对ＢＯＤ５标液和工业废水的影响，结果表明，河水空白应控制在０．１－０．８ｍｇ／Ｌ土壤浸取液空白控制在０．０１－０．１０ｍｇ／Ｌ为宜。     

总氮测定中的注意事项

碱性过硫酸钾消解紫外分光光度法测定总氮中，对空白值偏高的影响因素进行了实验和分析，提出了几点建议及改进措施。     

次溴酸盐氧化法测定海水氨氮影响因素的探讨

测定海水中氨氮时,经常会出现曲线线性不好、空白值高等情况。文中通过对实验室环境、实验用水、器皿、试剂、操作过程等因素进行分析探讨,找出了实验出现问题的原因,并进行了校正。     

测定高锰酸盐指数考核样品时的计算方法修正

针对测定高锰酸盐指数考核样品时的结果偏高现象，经过查找，其原因是由于按公式计算没有考虑稀释用纯水的空白值响应。经修正公式后计算，其考核样品的结果则均为正确。     

Sources of polychlorinated biphenyl blank contamination and their impact on fingerprinting

Abstract

The development of high-resolution mass spectrometry methods for the measurement of polychlorinated biphenyls (PCBs) in environmental samples has dramatically reduced detection limits, leading to problems obtaining clean blanks. When PCBs are detected in samples at concentrations similar to the blanks, blank contamination must be addressed before fingerprinting and source apportionment through positive matrix factorization (PMF) can be successful. We tested a variety of blank correction methods using data from a study of water column concentrations of PCBs in the Spokane River, where concentrations of Σ₂₀₉PCBs in whole water samples averaged 171?pg/L without blank correction and Σ₂₀₉PCBs in the blanks averaged 88?pg/L. The results suggest that subtracting blank masses from sample masses can lead to erroneous results. Instead, censoring at one times the batch-specific blank level is a better approach. The sources of PCBs in field and method blanks were investigated by examining their congener profiles via PMF. The results suggest that commercial PCB formulations (in the US, Aroclors) continue to be the primary source of PCBs in blanks forty years after PCB production and use were banned in the United States. Other sources of PCBs to blanks include PCB 11 from pigments; PCBs 44?+?47?+?65, 45?+?51, and 68 arising from polymers cured using bis(2,4-dichlorobenzoyl) peroxide; and PCBs 1, 2, 3, 4, 8, 15 and others arising from silicone products derived from phenylsiloxanes, such as silicone-based adhesives.     

Quantitative analysis of environmental factors in differential weighing of blank Teflon filters

Mass differences less than 100 microg must be correctly measured in gravimetric analysis of particles collected on filters. Even small variations in mass measurement may contribute significant errors to calculated concentrations. In addition to the collected particles, a number of other factors affect the observed mass difference between the measurements before and after sampling. The most often controlled of these factors are static charge, temperature, and humidity. Using 951 laboratory blank filter weights, we have statistically analyzed these and other factors that affect the observed filter weight. Some of these are controllable or correctable; others are not and enter into the final results as errors. The standard deviation of differential blank filter weighing after applying all corrections was 2.7 microg. The most important correctable factors are air buoyancy variation and filter storage time. When weighing blank Teflon filters at relative humidity < 50%, these are an order of magnitude more important than weighing-room humidity. Using field blank filters in each weighing batch could control these three factors but also doubles the errors caused by balance random variation and filter handling contamination, because four weighing measurements and the handling of two filters are needed to obtain one corrected differential mass result.     

Adjusted blank correction method for UV–vis spectroscopic analysis of PTIO-coated filters used in nitrogen oxide passive samplers

Passive sampling devices are popular in applications which do not require the monitoring of hourly concentrations. Nitrogen oxides are often collected using filters coated with 2-phenyl-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide (PTIO). The filter extract can then be analyzed using flow injection analysis ion chromatography fitted with a copper/cadmium reduction column or UV–vis spectroscopy. When the latter is used to measure low concentrations of nitrogen oxides, absorbance by PTIO at the analytical wavelength of 545 nm contributes significantly. PTIO concentration on the filter also shows variation with filter storage and exposure time not accounted for in a single point blank subtraction at the analytical wavelength. A method is presented that uses a scaling factor to account for variations in concentration of PTIO on the field blank and provides a more accurate method for determining and correcting for the PTIO contribution to absorption when measuring ambient nitrogen oxide concentrations.     

火焰原子吸收分光光度法测定土壤中锌消解方法的改进

对火焰原子吸收分光光度法测定土壤中的锌消解方法进行了改进,通过器皿的精心清洗、加盖防止尘埃污染以及选择优级纯的消解试剂等措施,降低了空白试验的测定值,从而提高了样品测定的精密度和准确度.     

Estimation of organic carbon blank values and error structures of the speciation trends network data for source apportionment

Because the particulate organic carbon (OC) concentrations reported in U.S. Environment Protection Agency Speciation Trends Network (STN) data were not blank corrected, the OC blank concentrations were estimated using the intercept in particulate matter < or = 2.5 microm in aerodynamic diameter (PM2.5) regression against OC concentrations. The estimated OC blank concentrations ranged from 1 to 2.4 microg/m3 showing higher values in urban areas for the 13 monitoring sites in the northeastern United States. In the STN data, several different samplers and analyzers are used, and various instruments show different method detection limit (MDL) values, as well as errors. A comprehensive set of error structures that would be used for numerous source apportionment studies of STN data was estimated by comparing a limited set of measured concentrations and their associated uncertainties. To examine the estimated error structures and investigate the appropriate MDL values, PM2.5 samples collected at a STN site in Burlington, VT, were analyzed through the application of the positive matrix factorization. A total of 323 samples that were collected between December 2000 and December 2003 and 49 species based on several variable selection criteria were used, and eight sources were successfully identified in this study with the estimated error structures and min values among different MDL values from the five instruments: secondary sulfate aerosol (41%), secondary nitrate aerosol (20%), airborne soil (15%), gasoline vehicle emissions (7%), diesel emissions (7%), aged sea salt (4%), copper smelting (3%), and ferrous smelting (2%). Time series plots of contributions from airborne soil indicate that the highly elevated impacts from this source were likely caused primarily by dust storms.     

EDTA滴定法测定硫酸盐的检出限确定

在美国环保总署方法检出限程序的基础上，设计了一个能考虑样品空白和总硬度的可变性对样品测量值贡献的方法检出限程序，并按照此程序对EDTA滴定法测定硫酸盐的检出限进行了确定。对确定结果进行了信噪比和加标回收率检查，证明确定结果能客观地反映实验室对该方法的测试能力。