车间空气中酚浓度测定方法改进

对于车间空气中酚浓度的测定,目前采用DB14/35-41-1999《工业劳动卫生监测监护规范》的方法,此方法采用串联吸收管采样,操作繁琐,且在分析过程中对样品溶液的pH值控制不严,溶液的pH值对测定影响很大,当pH<7.4时,两个分子的4-氨基安替比林缩合成红色安替比林染料,使空白值增加,在pH 9~10.7时,酚与4-氨基安替比林生成物的颜色最深,所以测定时应严格控制pH 10±0.2,本文对原方法进行了改进,经过多次试验证明,改进后的方法准确度、精密度及线性均较好。1试验部分[1]1.1主要仪器与试剂KC-6D型大气采样器721型分光光度计气泡吸收管吸收液:pH …     

ReO-4、IO-4、MnO-4在水/硝基苯界面上转移过程的伏安法研究

本文用循环伏安法研究了Re0_4~-L、102、MnO_4~-等过氧酸根阴离子在水/硝基苯界面上的转移过程, 详细研究了各种条件对转移离子行为的影响. 三种离子均表现为可逆离子转移过程。转移过程CV峰电流与水相中阴离子的浓度成线性关系, 据此可进行ReO_4~-、TO_4~-、MnO_4~-的测定, 并且有用液/液界面电化学方法监测IO_4~-的氧化还原反应的意义。     

被动采样-离子色谱法测定博物馆环境空气中二氧化硫和二氧化氮的含量

将清洗干净并烘干的采样器的吸收膜上加入20%三乙醇胺-10%甘油-1%次亚磷酸钠混合吸收液100μL,按规定将采样器置于博物馆环境的空气中,对其中二氧化硫和二氧化氮作被动采样3~5d。采样结束时,将采样器的底膜及吸收膜取出,分别用水5.00 mL进行超声提取10min,用离子色谱法测定提取液中NO_2~-、NO_3~-、SO3_~(2-)和SO_4~(2-)等含量。以IonPac AS18色谱柱为分离柱,25mmol·L~(-1)氢氧化钾溶液为流动相,采用抑制型电导检测器测定。4种阴离子的检出限(3S/N)依次为0.007 8,0.008 9,0.009 0,0.008 0 mg·L~(-1),加标回收率为91.0%~103%,测定值的相对标准偏差(n=6)依次为2.5%,22%,21%,29%。     

24小时连续采样—分光光度法监测空气中SO2的不确定度评定

本文基于HJ194-2005和HJ482-2009,建立了分光光度法监测空气中SO2不确定度的数学模型,分析了在24 h连续采样、手工分析方法监测空气中SO2过程中,影响监测结果不确定度的因素(如温度、大气压、仪器流量、容量器皿刻度精度等),并对其影响进行了量化评估,得出了环境空气中SO2监测过程中的不确定度。     

大气环境降水监测的质量控制方法

根据《环境监测质量管理规定》、《江苏省环境监测质量管理实施细则》及环境监测技术规范的要求,探讨了降水监测采样、样品保存技术、实验室分析的质量控制方法。采用不同采样方法、不同采样器同时采集15场降水,其降雨量、电导率、pH值的比对监测结果合格率均大于90%。经试验,降水各组分有效保存时间不同,其中NO_3~-,NH_4~+为3 d;F~-,Cl~-,SO_4~(2-)为14d;K~+,Na~+,Ca~(2+),Mg~(2+)为30 d。选择2家实验室对降水样品、空白样品、标准样品同时测试,结果显示,空白测定结果均低于方法检出限,标准曲线相关性系数r≥0.999 0,测定结果的相对标准偏差为1.4%~5.9%(n=6),加标回收率为89.8%~106%,标准样品的分析结果均合格。该方法能保证降水监测结果准确、可靠,满足HJ/T 165-2004《酸沉降监测技术规范》的要求。     

复合催化剂上CO2加氢合成C2+烃类

介绍了由CO2＋H2合成C2^ 烃的几种复合催化剂体系的研究进展，比较和评价了复合催化剂体系的活性和选择性及对C2^ 烃类生成的影响。着重于复合催化剂体系对C4^ 烃的生成及产物分布的影响并简述反应机理。     

被动采样法测定室内空气环境中的二氧化氮

用基于气体分子扩散理论研制的被动采样器 (Passivesampler) ,结合Saltzman法 ,离子色谱法 (IC)分析、测定室内空气环境中的NO2 ,利用风洞实验装置进行模拟曝露实验 ,着重研究捕集液的种类、浓度和风洞内NO2 初始浓度、湿度对捕集NO2 能力的影响以及采样器的材料、结构与采样性能的关系。结果表明 ,本文研制的采样器在空气中曝露数个小时后 ,测定空气中NO2 浓度可达n×1 0 μg/L ,与用NOx 分析仪直接测定结果比较误差在 2 0 %以内。本采样器体积小、质量小、结构简单 ,不仅适用于生活环境中NO2 的测定 ,也适用于NO2 个人曝露量的测定     

催化光度法测定痕量钴的研究

研究了钴 (Ⅱ )离子在碱性介质中催化H2 O2 氧化 2 ,2′ 二甲基 4 ,4′ 二氨基联苯 (o Tolidine)的显色反应 ,发现当Co2 +浓度在 0 8～ 3 6ng mL时具有强烈的催化显色作用 ,而当Co2 +浓度在 0 0 4～0 2 4 μg mL时则对显色作用具有抑制效应。基于此研究了测定痕量Co(Ⅱ )离子的影响因素 ,建立了测定痕量Co2 +离子的催化光度法。测定的线性范围Co(Ⅱ )的浓度在 0 0 4～ 0 2 4 μg mL时 ,灵敏度为 3 1 6× 1 0 -6g L ;Co(Ⅱ ) 0 8～ 3 6ng mL时 ,灵敏度为 1 78× 1 0 -6g L。实验操作简便 ,应用于工业污水中痕量Co2 +离子的监测 ,结果满意。     

复合型固体超强酸SO4^2-／SnO2-TiO2催化合成乙酸松油酯的研究

采用溶胶-凝胶法制备了新型复合固体超强酸SO4^2-／SnO2-TiO2，通过XRD和IR对其结构进行了表征。以该固体酸为催化剂、松油醇和乙酸酐为原料合成乙酸松油酯，考察了影响反应的因素。结果表明：反应温度40-50℃、催化剂用量1．8-—2．2％、醇酐摩尔比1：1．6、反应时间4-5h是最适宜的反应条件，其松油醇转化率达到98％以上，产物中乙酸松油酯含量为88％。与普通单氧化物固体酸比较，该复合型固体酸有更高的催化活性和选择性。     

镀金石英砂富集-冷原子吸收光谱法测定环境空气中的汞

建立镀金石英砂富集–冷原子吸收光谱法测定环境空气中的汞。利用大气采样器采集空气样品,优化镀金石英砂工艺,使其与空气中的汞发生金汞齐反应,将大气中的汞进行富集,通过电热蒸发–直接进样,采用冷原子吸收光谱法测定。环境空气中汞含量在0~20 ng范围内与吸光度有良好的线性关系,相关系数大于0.999。采样量为60 L时,方法的检出限为0.001 3 ng/L,测量下限为0.005 2 ng/L。测定结果的相对标准偏差为1.7%~4.5%(n=7),样品的加标回收率为94.7%~102.8%。该方法操作简单,干扰小,检测效率高,适用于空气中汞的测定。     

ICP-AES测定铀污染土壤植物中铀的研究

采用电感耦合等离子体发射光谱(ICP-AES)对铀污染土壤植物中铀的测定方法进行了研究.在λU385.958 nm处,选择了仪器的最佳工作条件,考察了酸度和常见共存元素对测定的干扰情况,并且对比了干灰化消解和湿式消解对测定的影响.研究发现2%硝酸溶液为最佳介质,干扰离子对测定没有显著影响,干灰化消解比湿式消解得彻底.在选定条件下,方法检出限为0.18 mg·L-1,测定下限为0.61 mg·L-1,5.0000 mg·L-1的铀标准溶液的相对标准偏差RSD(n=10)为0.81%,方法回收率为96.2%～106.2%.该方法操作简单,快速.结果表明,用ICP-AES测定铀污染土壤植物样品中的铀是可行的.     

测定血清中Na 含量不确定度的评定

对血清中Na离子含量的测量不确定度进行评定。不确定度的来源主要包括Na离子标准工作液的配制过程、血清样品的定容消化制备、标准曲线拟合、钠离子各分量不确定度的合成等引入的不确定度计算出各分量的不确定度,通过合成得到测量结果的合成不确定度、扩展不确定度及测试结果的报告形式。     

茶叶中高氯酸盐检测方法研究进展

茶叶中新型污染物高氯酸盐在近年来受到越来越多的关注,相应的检测技术也在不断加强.参考国内外文献,综述了茶叶中高氯酸盐的检测方法.目前,茶叶中高氯酸盐的检测方法主要有离子色谱法（IC）、离子色谱-质谱法（IC-MS）和高效液相色谱-串联质谱法（LC-MS-MS）.比较了不同检测方法的局限性和优越性,重点比较了高效液相色谱-串联质谱法不同前处理方法、净化小柱和检测条件的优劣,对茶叶高氯酸盐检测技术的发展和研究进行了展望,为检测茶叶中高氯酸盐的新材料研发和检测新标准的建立提供理论依据.     

Assessment of performance of laboratories in determining acrylamide in crispbread

A proficiency testing round was undertaken to assess the performance of laboratories to measure acrylamide in a sample of crispbread. Retail samples of crispbread were ground to a fine powder and after thorough mixing were packed in 40 g units for distribution. Ten samples were selected at random and analyzed in duplicate for acrylamide by liquid chromatography/mass spectrometry (LC/MS). Standard statistical tests showed that the material was homogeneous for the purposes of proficiency testing. Test samples were distributed to 55 laboratories in 16 countries in Europe, North America, Australia, and the Middle East. The results were analyzed by standard proficiency testing statistical procedures, and laboratories were awarded z-scores on the basis of their reported results. Based on a target standard deviation (sigmap value) taken from the Horwitz equation, for a robust mean value of 1.2 mg/kg acrylamide, satisfactory results (z-score within +/- 2 for those between 0.8 and 1.6 mg/kg) were obtained by 86% of the 37 laboratories that returned results. Only 1 laboratory was unsatisfactory and 4 had questionable results. About equal numbers of laboratories used gas chromatography (GC)/MS and LC/MS procedures with about 25% using MS/MS and one using GC with electron capture detection. There was no evident trend in performance or bias in results. GC/MS and LC/MS data were evenly distributed across the population of laboratories reporting results.     

超临界流体萃取技术在提取中药挥发油中的应用

用超监介CO2流体萃取技术对多种中药挥发油的提取进行了综述,并将其与传统的水蒸馏法进行比较。结果表明,用超临界流体法不仅挥发油的收率高,而且提取时间也大大缩短。     

Interpretation of inorganic arsenic metabolism in humans in the light of observations made in vitro and in vivo in the rat

The toxicity of inorganic trivalent arsenic for living organisms is reduced by in vivo methylation of the element. In man, this biotransformation leads to the synthesis of monomethylarsonic (MMA) and dimethylarsinic (DMA) acids, which are efficiently eliminated in urine along with the unchanged form (As_i). In order to document the methylation process in humans, the kinetics of As_i, MMA and DMA elimination were studied in volunteers given a single dose of one of these three arsenicals or repeated doses of As_i. The arsenic methylation efficiency was also assessed in subjects acutely intoxicated with arsenic trioxide (As₂O₃) and in patients with liver diseases. Several observations in humans can be explained by the properties of the enzymic systems involved in the methylation process which we have characterized in vitro and in vivo in rats as follows: (1) production of As_i metabolites is catalyzed by an enzymic system whose activity is highest in liver cytosol; (2) different enzymic activities, using the same methyl group donor (S-adenosylmethionine), lead to the production of mono- and di-methylated derivatives which are excreted in urine as MMA and DMA; (3) dimethylating activity is highly sensitive to inhibition by excess of inorganic arsenic; (4) reduced glutathione concentration in liver moderates the arsenic methylation process through several mechanisms, e.g. stimulation of the first methylation reaction leading to MMA, facilitation of As_i uptake by hepatocytes, stimulation of the biliary excretion of the element, reduction of pentavalent forms before methylation, and protection of a reducing environment in the cells necessary to maintain the activity of the enzymic systems.     

Kinetics of dehydration in chelates of quinones involved in photosystem-II

The solid-state deaquation of thetrans- andcis-oximates of lawsone (I) and phthiocol (II) with cobalt(II) was investigated by means of non-isothermal thermogravimetry. The modes of deaquation during the thermolyses of hydrated oximates of (I) and (II) with compositions CoL₂·2H₂O were compared. The weight lossvs. temperature data were treated by using the Coats and Redfern relations. The kinetic data support a rearrangement-type mechanism for the deaquation of the oximate of phthiocol. TheE _a values for both the ligands and water molecules were found to be 23 kJ/mol.

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Zusammenfassung Mittels nichtisothermer Thermogravimetrie wurde die Dehydratation der trans- und cis-Kobalt(II)-oximate von Lawson (I) und Phthiokol (II) untersucht. Die Arten der Dehydratation während der Thermolyse der hydratierten Oximate von (I) und (II) mit der Zusammensetzung CoL₂·2H₂O wurden verglichen. Bei der Auswertung der Massenverlust-Temperatur-Daten wurden Coats-Redfern Beziehungen angewendet. Die kinetischen Daten bekräftigen einen Umlagerungsmechanismus für die Dehydratation des Oximates von Phthiokol. DieE _a Werte betragen sowohl für die Liganden als auch für Wasser etwa 23 kJ/mol.

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- - (I) (II) . I II CoL₂ · 2₂ . -. . _a , 23 · ^–1

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Production of radicals in the ozonolysis of propene in air

Radical production in the ozonolysis of propene in air was monitored directly by a peroxy radical chemical amplification (PERCA) instrument at room temperature (298±2 K) and atmospheric pressure (1×105 Pa). The ozonolysis reactions were conducted in a flow tube under pseudo-first-order conditions for ozone. The decay in ozone was calculated based on reaction time tr and effective rate constant keff (keff = k1[C3H6]0)) for the ozone-propene reaction. The total radical yields relative to consumed ozone were d...