Some applications of Freon-22 in supercritical fluid chromatographic analysis of environmental pollutants

The applications of Freon-22 (R22) as a mobile phase and as a modifier in supercritical fluid chromatography were investigated. For the purpose of this investigation, the separation of eleven phenols listed by the United States Environmental Protection Agency as priority pollutants was studied. It was found that the use of neat R22 greatly reduced the retention times of the phenols compared with the use of neat carbon dioxide as mobile phase. Satisfactory separation of all the eleven phenols could be achieved using 5% R22 as modifier in carbon dioxide. The promising results obtained in this preliminary investigation indicate the potential for the use of R22 in supercritical fluid separation processes.     

Supercritical fluid extraction of polycyclic aromatic hydrocarbons from white pine (Pinus strobus) needles and its implications

A supercritical fluid extraction (SFE) method was developed for the extraction of polycyclic aromatic hydrocarbons (PAHs) from fresh and fallen pine needles. Toluene-modified CO2 was used as the extracting fluid, and the extracted PAHs were analyzed by GC-MS. Using a two-stage extraction procedure, a static extraction at 180 degrees C and a dynamic extraction at 60 degrees C, and an in-cell silica gel plug plus a post-oven silica gel column, the extraction and fractionation of PAHs can be accomplished in one step. Over a seven month period, a significant variation was observed for PAHs in urban samples, while PAHs in mountain samples were at much lower levels (by a factor of approximately 8) and showed little seasonal change. Although dry fallen needles and fresh needles contained similar amounts of PAHs, in the fallen needles the lower molecular weight PAHs were partially lost while the higher molecular weight PAHs were slightly enriched. Pollution in urban areas was found to be highly localized, and buildings and trees are believed to be important factors in the restriction of atmospheric PAHs.     

Effects of exposure of aquatic snails to sublethal concentrations of waste drilling fluid

Static bioassays were carried out using two aquatic snails (Pilia sp. and Lanistes sp.) as test organisms in soft natural dilution water, with waste drilling fluid as the test material, at 28±2°C. Comparison of results for the control and different concentrations of the waste drilling fluid were made by means of the F-statistic method. The waste drilling fluid was practically non-toxic to the two aquatic snails.     

Effects of exposure of crocodiles to sublethal concentrations of Petroleum waste drilling fluid in the Niger Delta basin of Midwestern Nigeria

Static bioassay were carried out using two aquatic crocodiles (the short nosed crocodile, Osteolemus tetraspis and the Nile crocodile, Crocodilus niloticus) as test organisms in soft natural dilution water, with Petroleum waste drilling fluid as the test material, at 28 ± 2 °C. Comparison of results for the control and different concentrations of the waste drilling fluid were made by means of the F-statistic method. Both crocodile species exhibited a high insensitivity to the undiluted waste drilling fluid and the different dilutions. Differences in concentration of waste drilling fluid did not influence the response of crocodiles to the potential toxicant. Percentage of deaths which was never greater than 0.2% in control tanks was not significantly different from that in test tanks where mortality values of organisms was typically 1.6% or less in most cases. There was a delay toxicant – induced mortality effect.     

Comparison of pressurized fluid extraction, Soxhlet extraction and sonication for the determination of polycyclic aromatic hydrocarbons in urban air and diesel exhaust particulate matter

In order to characterize and compare the chemical composition of diesel particulate matter and ambient air samples collected on filters, different extraction procedures were tested and their extraction efficiencies and recoveries determined. This study is an evaluation of extraction methods using the standard 16 EPA PAHs with HPLC fluorescence analysis. Including LC analysis also GC and MS methods for the determination of PAHs can be used. Soxhlet extraction was compared with ultrasonic agitation and pressurized fluid extraction (PFE) using three solvents to extract PAHs from diesel exhaust and urban air particulates. The selected PAH compounds of soluble organic fractions were analyzed by HPLC with a multiple wavelength shift fluorescence detector. The EPA standard mixture of 16 PAH compounds was used as a standard to identify and quantify diesel exhaust-derived PAHs. The most effective extraction method of those tested was pressurized fluid extraction using dichloromethane as a solvent.     

Comparison of SFE with Soxhlet in the analyses of PCDD/PCDFs and PCBs in sediment

The efficiency of supercritical fluid extraction (SFE) for the isolation of polychlorinated biphenyls (PCBs), dibenzo-p-dioxins (PCDD) and dibenzofurans (PCDF) from sediments was investigated by comparing SFE with Soxhlet. Five sediments obtained from an international interlaboratory study were used as a test material. SFE was performed with an automatic system where extracted analytes were collected by solid-phase trapping using carbon mixed with Celite as an adsorbent. For the first time, SFE of the most toxic PCBs, coplanar PCBs, was studied with real sediment samples. The majority of PCBs investigated, a total of 38 congeners from tri- to decachlorinated, were quantitatively extracted from sediment by SFE with pure CO2 at pressure 400 atm and temperature 100 degrees C. Under these conditions a successful extraction was obtained also for PCDD/PCDFs except for hepta- and octachlorinated congeners. Copper powder added to the sediment efficiently prevented the transfer of sulfur from the sample during SFE. The TEQs of both PCDD/PCDFs and PCBs obtained by SFE corresponded well with those obtained by the Soxhlet-based method. The reproducibility of SFE was high for both groups.     

气相色谱法测定苯酚生产废水中芳香族化合物

建立了用气相色谱法同时测定苯酚生产废水中异丙苯、α-甲基苯乙烯、α-甲基苯甲醇、2-苯基-2-丙醇、苯酚、苯乙酮、2-苯基丙醛等7种芳香族有毒有机污染物的定量分析方法。采用二氯甲烷对水样进行萃取后进行分析测定,气相色谱条件:DB-WAX型色谱柱,FID检测器,程序升温,进样量1μL。方法的检出限、精密度、回收率实验表明,该方法对苯酚生产废水中各污染物组分具有较好的分离效果,对7种物质的检测限均低于0.05 mg/L,5次测定的相对标准偏差小于5%,实际水样的加标回收率大于97%。     

Investigation of sequential and enzymatic extraction of arsenic from drinking water distribution solids using ICP-MS

A sequential extraction approach was utilized to estimate the distribution of arsenite [As(iii)] and arsenate [As(v)] on iron oxide/hydroxide solids obtained from drinking water distribution systems. The arsenic (As) associated with these solids can be segregated into three operationally defined categories (exchangeable, amorphous and crystalline) according to the sequential extraction literature. The exchangeable As, for the six drinking water solids evaluated, was estimated using 10 mM MgCl(2) and 10 mM NaH(2)PO(4) and represented between 5-34% of the total As available from the solid. The amorphously bound As was estimated using 10 mM (NH(4))(2)C(2)O(4) and represented between 57-124% of the As available from the respective solid. Finally, the crystalline bound As was estimated using titanium citrate and this represented less than 1.5% of the As associated with the solids. A synthetic stomach/intestine extraction approach was also applied to the distribution solids. The stomach fluid was found to extract between 0.5-33.3 microg g(-1) As and 120-2,360 microg g(-1) iron (Fe). The As concentrations in the intestine fluid were between 0.02-0.04 microg g(-1) while the Fe concentration ranged from 0.06-0.7 microg g(-1) for the first six drinking water distribution solids. The elevated Fe levels associated with the stomach fluid were found to produce Fe based precipitates when the intestinal treatment was applied. Preliminary observations indicate that most of the aqueous Fe in the stomach fluid is ferric ion and the observed precipitate produced in the intestine fluid is consistent with the decreased solubility of ferric ion at the pH associated with the intestine.     

乙腈盐析萃取HPLC-PDA同时测定水中11种苯胺类化合物

通过对色谱分析和样品萃取条件的选择和优化,建立了同时分析水中11种苯胺类化合物的HPLC方法。样品经乙腈盐析萃取后直接进样分析,采用 ODS色谱柱,以乙腈-水为流动相进行梯度洗脱,用PDA检测。结果表明,11种苯胺类化合物在0.20~100mg/L范围内其浓度和检测信号呈良好的线性关系,方法检出限为0.002~0.007mg/L,地表水和废水样品加标回收率为81.6%~97.4%,相对标准偏差为1.5%~5.5%。     

Determination of synthetic musk compounds in sewage biosolids by gas chromatography/mass spectrometry

A review of sewage sludge regulations and land application practices by the United States National Research Council (2002) recommended development of improved analytical techniques to adequately identify and quantify new chemical contaminants, such as synthetic musk compounds in Class A sewage sludge (i.e., biosolids). This prompted the development of a rugged analytical method using gas chromatography coupled to mass spectrometry to detect this group of organic pollutants in biosolids. In this paper, the term "biosolids" is used interchangeably with "sewage sludge", which is defined in the regulations and used in the statue (Clean Water Act). Samples of Class A biosolids obtained from sewage treatment plants in Los Angeles, California, the City of Las Vegas, Nevada, and also in the form of a commercial fertilizer, were extracted using pressurized liquid extraction technique, subjected to gel permeation chromatography clean-up, and analyzed by GC/MS using the selected ion monitoring mode. The method developed has the potential to detect synthetic musk compounds in complex matrices, may provide accurate data useful in human health and environmental risk assessment, and may be useful in determining the efficacy of municipal sewage treatment plants for removing synthetic musk compounds.     

便携式GC法测定石油污染地地下水中苯、乙苯和二甲苯

采用便携式气相色谱法测定石油污染地地下水中苯、乙苯和二甲苯,通过试验选择出测定的最佳色谱条件和适宜内标物,并对样品平衡时间、NaCl用量、取样后 VOA瓶中液-气体积比等条件进行优化。试验表明,该方法在0 mg/L～2．00 mg/L范围内线性良好,相关系数均＞0．98;方法检出限为0．05 mg/L ～0．15 mg/L。用该方法和吹扫捕集-气相色谱/质谱联用法同时测定实际水样,两种方法测定结果具有良好的一致性。     

Determination of ethanolamine,ethylene glycol and triethylene glycol by ion chromatography for laboratory and field biodegradation studies

The determination of alkanolamines and glycols in groundwater and subsurface environments is essential for environmental assessment, remediation and monitoring for selected industrial sites. Monoethanolamine (MEA), ammonium, sodium, magnesium and calcium detection was performed using cation exchange chromatography (IC) with suppressed conductivity detection. Acetate, chloride, nitrite, nitrate, phosphate, sulfate and oxalate were monitored employing anion exchange chromatography with suppressed conductivity. Detection of ethylene glycol (MEG) and triethylene glycol (TEG) and ethanol was carried out using ion exclusion chromatography with pulsed amperometric detection. Effective determination of MEA, MEG and TEG in complex groundwater matrices without compound transformation offered improved monitoring capabilities. This study presents robust analytical tools for MEA, MEG and TEG determination in biodegradation studies. Using ion chromatography offered significant advantages for the analyses of groundwater samples and laboratory bioreactor monitoring.     

The Influence of Temperature on Chemical Fluid-Rock Reactions in Geological CO2 Sequestration

For a Bunter formation in the German Federal State of North Rhine Westphalia, we use numerical models to consider reactions between the supercritical, aqueous, and solid phases. These reactions may occur in a CO₂-water system representing a saline aquifer CO₂ storage scenario. Thus, the models are used for determining the extent of fluid–rock reactions during mineral dissolution or precipitation. In particular, we study the effect of temperature by comparing results for our system set at 100 °C and at 58 °C. Results show that the abundance of dissolved ions changes as a result of elevated temperature. For the entire 10,000-year simulation period, the overall geochemical behavior of the Bunter reservoir rock at the Minden site is explained in terms of different mineral transformations, although some of them are not changed significantly. This mainly comprises the alteration of carbonate minerals such as calcite, and aluminium silicates such as oligoclase, chlorite, illite, albite, kaolinite, and Na-smectite. Another chemical behavior derives from the generation and consumption of new secondary minerals such as dawsonite, pyrite, and Ca-smectite. In contrast to a system temperature of 58 °C, the mineralogical transformations of other minerals such as siderite, ankerite, dolomite, and magnesite are not observed at 100 °C. Also, the numerical simulation results show that at elevated temperature, the dominant role played by hydrodynamic mechanism dwarfs the role of other trapping mechanisms including dissolution and mineralization. Results also demonstrate how geological, petrophysical, and geochemical data can be integrated to estimate quantitatively the magnitude of the fluid–rock reactions. These reactions may entail new geotechnical problems, such as rock self-fracturing which ultimately decreases the CO₂ sequestration projects security.     

衍生气相色谱法在环境监测中的应用

衍生化气相色谱法就是利用化学反应改变目标化合物分子中的原子或官能团,通过检测新生产物对目标化合物进行气相色谱定性和定量分析,具有高灵敏度、良好的分离效果和绿色环保等优点。通过对衍生化与气相色谱联用在环境监测中特别是有机污染物的应用,具体介绍了该技术在醛酮类、酚类、酸类化合物及其他有机污染物分析中的应用及反应原理,并提出了该技术的注意事项及应用展望。     

离子色谱技术在环境监测中的应用

详细介绍了离子色谱仪的构造，功能，以及离子色谱技术的发展状况，离子色谱作为一种新的分析方法以其独特的优点可广泛应用于水，气，土壤，生物等环境监测领域。     

超声提取-离子色谱法测定常见土壤中的高氯酸盐

建立了测定土壤中高氯酸盐的离子色谱法,通过前处理条件优化和色谱条件优化形成准确高效的测定方法,并采集实际土壤样品进行实验验证。称取 1.00 g土壤样品,用20 mL超纯水混合均匀,超声提取40 min,离心后采用水系微孔滤膜过滤的前处理方式,土壤中高氯酸盐的加标回收率最稳定;在淋洗液浓度和流速都满足测定条件的前提下,为了缩短高氯酸盐的保留时间,避免复杂基质干扰,延长淋洗液发生器的使用寿命以及保护色谱柱,选择淋洗液浓度为40 mmol/L,流速为1.0 mL/min。在优化条件下,高氯酸盐的方法检出限为0.04 mg/kg。实际样品加标中高氯酸盐的相对标准偏差为1.9%~8.8%,加标回收率为91.0%~106%,结果表明离子色谱法测定土壤中高氯酸盐简单、灵敏、快速。     

液液萃取/气相色谱法测定环境水样中邻苯二甲酸酯类化合物

建立了液液萃取-气相色谱法测定环境水样中邻苯二甲酸酯类化合物的方法。该方法能有效分离8种邻苯二甲酸酯类化合物。标准曲线线性回归相关系数均大于0．9999，最小检测量可达10^-11g，相对标准偏差为0．47％～1．83％。加标回收率为73．5％～114．6％。     

Determination of isocyanic acid in air

A method is presented for the determination of isocyanic acid (ICA), HNCO, in air samples as a di-n-butylamine (DBA) derivative. The method is based on sampling in midget impinger flasks containing 10 ml of 0.01 mol l-1 DBA in toluene. Quantification was made using liquid chromatography (LC) and electrospray mass spectrometry (MS) monitoring positive ions. The instrumental detection limit for the LC-MS was 10 fmol of ICA-DBA. ICA was generated by thermal decomposition of urea. A standard solution containing the DBA derivatives of ICA was prepared by collecting the emitted ICA in an impinger flask containing DBA. ICA in the reference solution was characterised by LC and time-of-flight (TOF) MS and quantified by LC chemiluminescent nitrogen detection (LC-CLND). The instrumental detection limit for the LC-CLND was 1 ng of nitrogen. ICA was emitted during thermal degradation of PFU resins and polyurethane (PUR) lacquers, from car metal sheets. ICA was the most dominant isocyanate and in PUR coating up to 8% of the total weight was emitted as ICA and for PFU resins up to 14% was emitted as ICA. When air samples were collected in an iron foundry during casting in sand moulds with furan resins, concentrations of ICA in the range 50-700 micrograms m-3 were found in the working atmosphere.     

LLE-GC-MS法测定水中27种有机农药

建立了同时测定水中27种有机农药的LLE-GC-MS法。该法前处理前需调节水样pH值2,不加甲醇作为改性剂,以1:1(V/V)正己烷-石油醚为萃取溶剂进行液液萃取,GC-MS法进行检测。方法在各目标化合物质量浓度0.010~0.500 mg/L范围内线性良好,相关系数R2均0.995,检出限为0.021~0.250μg/L,加标回收率为73.6%~113.6%,相对标准偏差RSD为4.0%~14.1%,适用于水中27种有机农药的检测。