紫外光度法测定海水石油类质控指标研究

采取问卷调查的形式对76家"近海网"成员单位海水石油类测定情况进行调查,根据调查问卷获得的数据信息,结合实验室数据,采用控制图法确定了紫外光度法测定海水石油类质控指标限值,包括萃取剂透光率、检出限、校准曲线斜率、平行样偏差等。     

红外分光光度法测定石油类萃取方法的改进

红外分光光度法作为国家标准方法，具有灵敏度高、适用范围广等优点，目前得到普遍应用。但在测定过程中，还存在萃取过程烦琐、萃取剂毒性大、有时准确度偏低等问题．结合工作经验，对红外分光光度法测定石油类中的萃取剂的替代、萃取次数、脱水操作进行了改进试验，结果表明，采用四氯乙烯替代四氯化碳作为萃取剂，能够满足环境监测中油类测试的精度要求．一次萃取在样品浓度为100mg／L以下时能满足测定要求，萃取液放在瓶中以无水硫酸钠脱水后再在普通漏斗中经脱脂棉过滤后定量也可满足测试要求．     

石油类测定方法的改进

使用F2000型红外光度测油仪,以四氯化碳作为参比溶液测定水体中石油类,由于是以未经过与水样相同的步骤萃取的四氯化碳作为参比溶液以及F2000型红外光度测油仪是直接显示水样中石油类的浓度,所得的水样浓度并未扣除水样萃取过程中可能存在的干扰,因此,笔者认为用经活性炭吸附处理过的超纯水,通过与水样相同的操作步骤所得的萃取液作为测定水样时的参比溶液,测定的结果更加贴近实际,能够更好的反映水体受石油类污染的情况。     

液液萃取-气相色谱法测定水质可萃取性石油烃C10~C40

建立了以环己烷为萃取剂、气相色谱法(氢火焰离子化检测器,FID)测定水质样品中可萃取性石油烃(C_(10)～C_(40))的分析方法。以正构烷烃混合标准溶液为定性和定量校准标准,以色谱峰面积总和与混合标准溶液总浓度建立校准曲线进行外标法定量。方法检出限为0.01 mg/L,经验证方法精密度和准确度良好。同时,分别以气相色谱法和红外光度法测定了地表水、污水处理厂出水、海水和化工废水等实际样品,对比实验结果表明,在可萃取性石油烃C_(10)～C_(40)的碳数范围内,气相色谱法的测试结果与红外光度法无明显差异,有较好的可比性。     

水中石油类和动植物油类测定标准的探讨

对水中油类测定的新旧标准---《水质石油类和动植物油类的测定红外分光光度法》（ HJ 637-2012）和《水质石油类和动植物油类的测定红外分光光度法》（ GB/T 16488-1996）作比较，前者的内容中增加了总油的定义，修改了干燥剂的处理条件、样品体积的测量方法及萃取条件和萃取液脱水方式，删除了絮凝富集萃取的内容。试验证明，改进后的方法降低了检出限和空白干扰，样品体积测量更加准确。     

深圳市政污水排海工程排污混合区范围的确定

应用全场数学模型模拟了深圳排海的市政污水中悬浮物、化学需氧量、无机氮、活性磷酸盐及大肠菌群5个污染因子在海域大潮和小潮时对海域面积的影响。指出在不同水文条件和23m^3/d排放量下，不同质量浓度的活性磷酸盐和大肠菌群超过Ⅲ类海水水质标准的影响面积在大潮时分别为0.04km^2和7.72km^2，小潮时分别大于0.08km^2和6.16km^2；无机氮由于海水本底值较高，使得这一指标在全海域内超过Ⅲ类海水水质标准；而化学需氧量和总悬浮物质量浓度符合Ⅲ类海水水质标准。通过将现场监测资料用数模计算，提出排海污水混合区面积为1.5km^2。同时还引用部分国外的计算公式，对几种混合区允许范围进行了估算。     

快速溶剂萃取红外分光光度法测定土壤中石油类

研究快速溶剂萃取红外分光法对土壤中石油类的提取效果,并与超声波萃取红外分光法比较.结果表明,快速溶剂萃取对土壤中的石油类的回收率高,精密度好,方法快速简便.     

石油类样品测定中萃取方法的改进

在非分散红外分光光度法测定石油类中，本文将对样品的2次萃取改为1次萃取，并对两种方法的准确性和精密性进行了比较验证，结果表明，1次萃取法准确、可靠，且减轻了工作量，提高了分析速度，在日常的样品监测中可行．     

环境监测中质控样品存在的问题

某些标准样品与自然样品在监测过程中前处理步骤的不一致性。例如在目前红外分光光度法测油的项目中 ,质控样采用了直接稀释、测量的方法 ,而自然样品却有前处理步骤——酸化、萃取、去水。这样 ,质控样主要起到的是检定测油仪的作用 ,对操作人员在前处理步骤中的操作水平没有给予检验。但在环境监测中 ,质控样检验的是样品分析的整个过程 ,它不仅包括仪器的正常使用情况 ,还包括操作人员在任一阶段的操作水平。在石油类的监测中 ,前处理是该项目测定的重要部分 ,很多影响测定结果的因素产生在这里 ,因此 ,目前石油类的标准样品不能对测定石…     

水和废水中黄磷的测定

试验了黄磷在紫外光区的吸收光谱,建立了紫外分光光度法测定水和废水中黄磷的方法.该方法不需酸化、氧化,可在萃取后直接比色测定.当样品中含有石油类干扰物质时,可用含氧化剂的酸性水溶液对萃取液进行反萃取即能将其排除.该方法灵敏,具有测定范围宽、准确度高、精密度好、操作简便等特点.     

In situ laser-induced fluorescence (LIF) analysis of petroleum product-contaminated soil samples

General considerations of the calibrations of in situ measurements are presented and the concept of using an "average oil" with average analysability for calibration purposes is introduced. The in situ analysis of 30 petroleum product-contaminated soil samples with laser-induced fluorescence (LIF) spectroscopy was performed. Compared to an uncontaminated laboratory reference (LR) soil, 23 soil samples exhibited significantly higher LIF signals, so that these soil samples were classified as contaminated. The repeatability and reproducibility of the in situ LIF analysis were investigated. For the calibration of the LIF data, two LR oils (a fuel oil and a crude oil) were employed. The degree of soil contamination with petroleum products ranged from the limit of detection (LOD) for LIF analysis (ca. 100 ppm), or below, to more than 10,000 ppm. The petroleum product concentrations determined with in situ LIF analysis reveal a reasonable correlation with the results of standard IR analysis after extraction of the contaminated soils.     

气相色谱-质谱法测定废酸油渣中的16种多环芳烃

建立了废酸油渣中16种多环芳烃超声萃取、Florisil萃取柱净化、气相色谱-质谱测定的方法。笔者对提取方式、提取剂类型和体积、提取时间和次数、净化方式等进行研究,采用无水硫酸钠分散,二氯甲烷作为提取剂超声40 min,提取液经纯水清洗、离心后取适量有机相经过3 g Florisil萃取柱净化,采用气相色谱-质谱选择离子模式(SIM),加入内标进行定量分析。结果表明:二氯甲烷提取效率比正己烷好,丙酮可能引起酸性样品中多环芳烃的降解,丙酮超声萃取时加入无水硫酸钠能在一定程度上防止目标物降解,但萃取效率不可控制,宜采用二氯甲烷作为萃取剂。分散提取能有效减少提取时间,超声清洗仪超声40 min提取效率为86.2%～104%。3g Florisil萃取柱净化比1 g Florisil萃取柱净化和GPC净化效果略好。方法检出限为0.4～1.3 mg/kg,6次空白加标的相对标准偏差为2.3%～15.3%,6个实际样品测定结果的相对标准偏差为1.2%～27.3%,基体加标回收率为51.3%～126%,连续校准稳定。该方法适用于废酸油渣样品中16种多环芳烃的检测,比直接溶解有效,比加速溶剂萃取、索氏提取、微波萃取和超声探头萃取简单、快捷,能有效减少设备污染和腐蚀,净化方法有效,测定结果准确可靠,是实现大批量样品检测的可行方法。     

新标准方法实施后水中石油类检测实验室能力验证结果比对研究

为推进国际履约进程,我国自2019年1月1日起停止实验室用途使用四氯化碳,原针对水中石油类的分析方法《水质石油类和动植物油类的测定红外分光光度法》(HJ 637—2012)随之失效,新分析方法则在2018年10月正式发布。随着新分析方法的发布实施,有必要考察实验室采用新方法分析水中石油类的能力。通过汇总两次能力验证计划的统计结果,分析了实验室采用两种新方法分析水中石油类的能力。结果显示:采用紫外分光光度法(HJ 970—2018)和红外分光光度法(HJ 637—2018)测定水中石油类能力验证参加实验室的满意率分别为79.1%和86.6%,分别低于和高于新方法发布之前水中石油类检测能力验证参加实验室的满意率。实验室在操作时的样品空白、正己烷透光率以及器皿污染控制等因素对检测结果的影响较大。目前市场上用于水质检测的石油类标准样品的来源较广泛,原料来源的不同可能导致标准量值存在差异,从而导致不同实验室的分析结果偏差较大。     

Assessment of cyclodextrin-enhanced extraction of crude oil from contaminated porous media

The purpose of this study was to evaluate the effects of cyclodextrin (CD) on the extraction of Macondo well oil from contaminated porous media over a range of hydroxypropyl-β-CD (HPβCD) concentrations. To our knowledge, this is the first dataset on this type of CD yet assembled for an actual crude oil. The results showed that HPβCD can significantly increase oil extraction efficiency, demonstrated by increasing concentrations of all tested normal alkanes (nC(15)-nC(35)) and polyaromatic hydrocarbons (PAHs) in the aqueous phase with increasing CD concentration. A linear relationship between the extraction enhancement effect and CD concentration were verified experimentally and high correlation coefficients for total PAHs (R(2) = 0.82) and alkanes (R(2) = 0.99) were determined. For a 20% CD solution, 3.13 wt% of alkanes and 32.12 wt% of total PAHs were extracted to the aqueous phase, which was significantly more than what was extracted with water only (0.04% and 0.21% for alkanes and PAHs, respectively). This result shows that the remediation of oil contaminated media can be significantly enhanced through the use of HPβCD solutions in flushing or pump and treat operations to remove sorbed oil. The CD extraction enhancement effect decreases with increasing n-alkane chain length for the carbon number range tested. CD significantly enhanced PAH extraction from sand and the enhancement effect increased in the order of parent compounds < C-1 substituted < C-2 substituted < C-3 substituted for most PAHs tested. This study provides important information to assess the feasibility of using CD as a near-shore agent to enhance the cleanup of oil contaminated porous media.     

对城市污水厂污泥中矿物油和动植物油测定方法的改进

研究了用超声波萃取城市污水处理厂污泥中动植物油和矿物油的方法,并与索氏提取法进行比较.结果表明,超声波萃取法对污泥中矿物油和动植物油测定操作简单快速,标样回收率高,精密度好.     

河口水中矿物油分析的研究

紫外分光光度法在河口水中矿物油测定中，存在着标准油品的选择、水样萃取的乳化处理及河口水样测定方法选择等问题。提出了解决存在问题的可行方法，进一步完善测定方法。     

Comparison of response of six different luminescent bacterial bioassays to bioremediation of five contrasting oils

The performance of six different bioluminescent bacteria for the assessment of oil bioremediation was compared. Three contained lux genes linked to promoters from hydrocarbon degradation pathways: Pseudomonas fluorescens HK44 (pUTK21), Escherichia coli HMS174 (pOS25) and E. coli DH5 alpha (pGEc74, pJAMA7), responding to naphthalene, isopropylbenzene and octane, respectively. The other three expressed lux constitutively: E. coli HB101 (pUCD607) and P. putida F1 (pUCD607) are genetically engineered, while Vibrio fischeri is naturally bioluminescent and was included to facilitate comparison with previous work. Five different oils (four crude oils plus diesel) were spiked into soil, and the progress of remediation was followed over a period of 119 d by monitoring both hydrocarbon disappearance and changes in the microbial response to soil extracts. The octane bioassay was the only one of the hydrocarbon-responsive bacterial assays to show any appreciable response, with up to 20-fold induction by light crude oils. Heavy crude oil and diesel elicited a much weaker response. The metabolic (lux constitutively expressed) bioassays showed that there was a general increase in toxicity over the course of the experiment, although toxicity to E. coli HB101 (pUCD607) appeared to be decreasing by the final sampling point. The metabolic bioassay response was much less variable between the different oils than for the first three, catabolic, strains.     

A New Method for Determination of Chlorophylls in Freshwater Algae

A new method (NMM, using acetic acid fiber filter and 90% ethanol) was established to determine chlorophyll in freshwater algae, and it was compared with US standard method (USM, using glass fiber filter and 90% acetone) and the method recommend by EPA of China (CHM, using acetic acid fiber filter and 90% acetone). The precision and repeatability of NMM is equivalent to that of USM, but NMM is safer to laboratory workers than USM and CHM because ethanol was used as solvent in NMM instead of acetone used in USM and CHM, and time and money were also greatly saved by the new method. The precision and repeatability of CHM was much less than USM and NMM, and the advice improving the method was proposed that the extraction time must be prolonged.     

2-Nitroso-1-naphthol as a selective reagent for preconcentration of cobalt by vortex assisted combined with solidification of organic droplet and its determination by flame atomic absorption spectrometry

Highly rapid and selective vortex-assisted liquid–liquid microextraction based on solidification of organic drop has been used for determination of cobalt ion. 2-Nitroso-1-naphthol (2N1N) was used as a selective complexing agent to form stable cobalt–2N1N complex which can be extracted with 1-undecanol at a short time by the assistance of vortex agitator system followed by its determination using flame atomic absorption spectrometry. In vortex assisted, vigorous vortex stream as well as the vibrant effect of vortex system cause very fine droplets of extraction solvent to be produced and extraction occurred at a short time. Some parameters influencing the extraction process such as pH of samples, concentration of 2-nitroso-1-naphthol, extraction solvent volume, extraction time, ionic strength and surfactant addition, as well as interferences were evaluated in detail and optimum conditions were selected. At the optimum conditions, the calibration curve was linear in the range of 15 to 400 μg L^?1 of cobalt ions. The relative standard deviation based on ten replicate analysis of sample solution containing 50 μg L^?1 of cobalt was 3.4 %. The detection limit (calculated as the concentration equivalent to three times of the standard deviation of the blank divided by the slope of the calibration curve after preconcentration) was 5.4 μg L^?1. The accuracy of the proposed method was successfully evaluated by the analysis of certified reference materials. This selective and highly rapid method was used for determination of cobalt ions in different water samples.