Monitoring the Physicochemical and Chemical Treatment of Textile Wastewater using GC/MS,LC/MS and ‐MS/MS Techniques

Abstract

Conventional biological wastewater treatment processes often fail in the elimination of finishing agents contained in textile wastewater such as dyes, surfactants, and softeners. Therefore, discharges from the textile industry are known as a major source of water pollution reaching groundwater and even drinking water treatment. Physicochemical treatment and advanced treatment processes (AOP) were applied to eliminate the pollutants prior to discharge. Ozone (O₃), O₃/UV, hydrogen peroxide/UV (H₂O₂/UV), Fenton's reagent (Fe²⁺/H₂O₂) were applied to eliminate by oxidation while ultrasonication (US) alone, US/UV or powdered activated carbon (PAC) were used for the physicochemical treatment. Elimination was monitored by a conventional sum parameter analyses (COD, BOD, DOC) while gas chromatography/mass spectrometry (GC/MS) and liquid chromatography coupled with MS and tandem mass spectrometry (LC/MS and ‐MS/MS) was applied for follow‐up of pollutants and their degradation products. The application of PAC, Fenton, and O₃/UV resulted in the highest dissolved organic carbon elimination. A complete or partial elimination and/or degradation of non‐polar or polar pollutants was observed by GC/MS or flow injection analysis/MS (FIA/MS) respectively. LC/MS and MS/MS analyses confirmed that ethoxylated surfactants (AEO) present in the original wastewater could be oxidized or destroyed resulting in carboxylated AEO and polyethylene glycol (PEG) or even carboxylated PEG.     

Determination of Unsaponifiable Constituents of Deodorizer Distillates by GC–MS

Deodorizer distillate is an important by-product obtained during deodorization in the edible oil industries. It is a complex mixture of many health beneficial constituents like phytosterols, tocopherols and squalene. In the present study a simple gas chromatographic method with mass spectrometry was used for the separation, detection and quantification of different components present in the deodorizer distillate in a very short analysis time of 18 min. A simple saponification procedure without derivatization was used for their analysis followed by GC–MS analysis. Phytosterols concentration (21.27–25.53%) was the most abundant in canola and palm distillate samples whereas, squalene and tocopherol were present in concentration ranges of 2.89–13.21% and 1.29–5.81%, respectively. The present study revealed that the unsaponifiable fraction of deodorizer distillate could be used in cosmetic preparations due to its appreciable amount of bioactive constituents.     

UPLC-ESI-Q-TOF/MS法测定化妆品中倍他米松及其8种类似物

建立了同时分析倍他米松及其8种类似物的超高效液相色谱-高分辨质谱联用仪(UPLC-ESI-Q-TOF/MS)的定性、定量检测方法。采用小颗粒色谱柱,梯度洗脱,电喷雾离子源正离子模式(ESI+),利用TOF采集的化合物母离子推测分子组成,子离子推测结构,并借助对照品加以确证,利用质谱一级准分子离子建立含量测定方法。对建立的检测方法进行方法学验证,发现考察范围内线性关系良好,检出浓度为0.05~0.34 mg/kg,回收率为93.1%~103.7%,相对标准偏差普遍小于6%。在对10批化妆品的分析中,有5批检出激素,并首次发现了2种新的激素添加物:倍他米松17-丙酸酯、倍他米松21-丙酸酯。     

LC–ESI–QTOF–MS, MS/MS Analysis of Glycerophospholipid Species in Three Tunisian Pistacia lentiscus Fruit Populations

Three populations of Pistacia lentiscus fruits were analyzed for their contents, classes and different molecular species of glycerophospholipids (PL) in order to promote their production and marketability. The LC–ESI–TOF–MS and MS/MS were used to accomplish this analysis. Only four classes of PL were detected at different retention times—phosphatidic acid (PA), phosphatidylethanolamine (PE), phosphatidylglycerol (PG) and phosphatidylinositol (PI). There was a significant difference in the relative observed abundance of various glycerophospholipid classes. PI was found to be the dominant class in the all provenances of lentisc fruit, followed by the PG class in the KO and RM populations. Within the TB population, the PA class is more abundant than PG and PE. The major molecular specie in the PA class is PA-C16:0/18:2 followed by PA-C18:1/18:2; and the minor species were determined to be PA-C16:0/18:3, and PA-C18:3/18:2. In the PE class of phospholipids PE-C18:1/18:1 and PE-C18:2/18:2 are the major species identified. The phospholipids PG-C18:2/18:2, PG-18:2/18:1, PI-C16:0/18:2 and PI-C16:0/18:1 are the most abundant species within the PG and PI classes. PG-C18:1/18:1, PI-C18:0/18:1 and PI-C16:0/18:3 are found to be only relatively minor chemical species. In conclusion, it is clear that the predominant molecular species of PL are those containing C16:0, C18;1, C18:2 fatty acids and the minor species are those containing C18:0 and C18:3.     

GC/MS/MS和LC/MS/MS联用技术的应用

气相色谱仪、液相色谱仪与质谱仪的联用对化合物的定性和定量分析提供了快捷简便的技术手段。串联质谱技术的出现进一步增强了上述联用技术在解决结构分析方面问题的能力。目前串联质谱技术在基础研究、生命科学、医药、材料科学等方面起着重要的作用，并取得了令人满意的结果。本报告对串联质谱的原理以及它们在基础研究、生命科学、医药、材料科学研究等方面的应用作一简要的综述。     

Quantitation of Multiple Sphingolipid Classes Using Normal and Reversed-Phase LC–ESI–MS/MS: Comparative Profiling of Two Cell Lines

Sphingolipids are an important class of compounds that regulate signal transduction and other vital cellular processes. Herein, we report sensitive normal and reversed phase LC–MS/MS methods for quantitation of multiple sphingolipid classes. In the normal-phase ESI/MS/MS method, a high content of organic solvents was utilized, which, although it included hexane, ethyl acetate, acetonitrile containing 2% methanol, 1–2% acetic acid, and 5 mM ammonium acetate, resulted in a very efficient electrospray ionization of the ceramides (Cers) and hexosylceramides (MHCers). Three normal-phase LC–MS/MS methods using segmented phases were developed to specifically target Cers, MHCers, or sphingomyelins (SMs). This segmentation scheme increases the number of data points acquired for a given analyte and enhances the sensitivity and specificity of the measurements. Nine separate reversed phase chromatography methods were developed for the three classes of compounds. These assays were used for comparing the levels of Cers, SMs, and MHCers from mouse embryonic fibroblast (pMEF) and human embryonic kidney (HEK293) cells. These findings were then compared with the reported data from RAW264.7 mouse macrophage cells, BHK21 hamster cells, and human plasma and serum samples. The analysis of cell lines, using both normal and reversed phase chromatography, revealed discrimination based on the type of chromatography chosen, while sphingolipid assays of samples containing different amounts of protein showed different results, even after normalizing for protein content. Also, LC/MS/MS profiles were provided for the classes and individual compounds so that they could be used as “molecular profiles” for class or individual sample analysis.     

LC-MS/MS法分析8%高氯·虱螨脲乳油

建立一种LC-MS/MS分析方法同时分离测定复配乳油中的高效氯氰菊酯和虱螨脲。方法以10 mmol/L乙酸铵水溶液+甲醇为流动相,使用Agilent Eclipse Plus-C_(18)色谱柱,对试样中高效氯氰菊酯和虱螨脲进行测定,外标法定量。高效氯氰菊酯和虱螨脲的线性相关系数分别为0.993和0.999,标准偏差分别为0.06和0.04,变异系数分别为2.45%和3.22%,平均回收率分别为110.28%和93.98%。该方法具有操作简便、快速,分离效果好,准确度和精确度高的特点。     

Quantification of Pentafluorobenzyl Oxime Derivatives of Long Chain Aldehydes by GC–MS Analysis

Negative ion mass spectrometric techniques, for compounds having good ionization properties, such as pentafluorobenzyl derivatives, are believed to be more sensitive than positive ion methods. Preparation of PFB oximes of fatty aldehydes from crude lipid extracts is problematic due to the release of free aldehydes from plasmalogens during derivatization. Accordingly, in these studies plasmalogens were removed by silicic acid column chromatography prior to pentafluorobenzyl derivatization. This simple purification step to remove plasmalogens is shown to facilitate the quantification of long-chain aldehydes by analysis of their pentafluorobenzyl oxime derivatives utilizing gas chromatography–mass spectrometry in the negative ion chemical ionization mode. The limit of detection for long chain fatty aldehydes using this method is 0.5 pmol and it is linear over two orders of magnitude. Silicic acid column chromatography followed by electrospray ionization mass spectrometry demonstrated that plasmalogens were removed (the detection limit for this analyses was ≤0.3 pmol). Furthermore, we have exploited the utility and sensitivity of this method to identify increases in hexadecanal and octadecanal in 3-amino-1,2,4-triazole treated human neutrophils. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

PLE萃取-GPC净化-LC-MS/MS法测定沉积物中8种性激素

建立了加压液体萃取(PLE)-凝胶渗透色谱(GPC)净化-液相色谱-串联质谱法(LC-MS/MS)测定沉积物中8种性激素含量的方法。结果表明,8种性激素在10~1 000μg/L范围内呈良好的线性关系,相关系数R~2≥0.999 6;检出限在10~100μg/kg之间;加标回收率为85.6%~101.4%,RSD为0.8%~2.7%。该方法自动化程度高,灵敏度高,回收率好。     

Development of an LC–MS/MS Method for the Analysis of Free Sphingoid Bases Using 4-Fluoro-7-nitrobenzofurazan (NBD-F)

The molecular species of sphingoid bases were tagged with the fluorescent amino group reagent, 4-fluoro-7-nitrobenzofurazan (NBD-F). The NBD-sphingoid bases were analyzed by a highly selective and sensitive liquid chromatography–electrospray ionization tandem mass spectrometry (LC–ESI–MS/MS) technique capable of reliable detection of several fmol of the derivatives. Lipid extracts from plant samples were derivatized with NBD-F, and all nine species of free sphingoid bases present in plant sphingolipids were separated and quantified for the first time; a complete baseline resolution was achieved for cis-8 and trans-8 isomers of sphingoid bases by reversed phase HPLC on a C₁₈ column. The extraction and derivatization procedures and LC–MS/MS method can facilitate the progress of the studies for seeking the active components of sphingoid bases species in response to biological challenges.     

Direct Determination of Glycidyl Esters of Fatty Acids in Vegetable Oils by LC–MS

An LC–MS method using a single quadrupole mass spectrometer was developed for direct analysis of glycidyl esters of fatty acids in vegetable oils. Without any sample clean-up, this method provided acceptable recovery of seven glycidyl esters, comparable results to a previously-published method utilizing two solid-phase extraction steps, and consistent detection parameters after greater than 200 injections without any cleaning operations performed. This method could readily be implemented as a screening assay for glycidyl esters in most oil laboratories.     

UPLC-MS/MS法同时测定化妆品中8种抗真菌药物的含量

以电喷雾离子源(ESI)为电离源,在正离子采集模式下建立了化妆品中8种抗真菌药物(氟康唑、酮康唑、萘替芬、联苯苄唑、克霉唑、益康唑、咪康唑、灰黄霉素)含量测定的超高效液相色谱-串联质谱(UPLC-MS/MS)方法,得到了8种抗真菌药物在0.02～0.60μg/mL范围内线性关系良好;平均回收率为91.71％ ～101....     

LC-MS/MS同时分析血液中8种苯二氮卓类药物

建立LC-MS/MS同时对血液中8种苯二氮卓类药物进行定性定量分析的方法。采用岛津LC-20AD高效液相色谱仪与AB Sciex 3200 Q TRAP质谱仪联用法,Phenomenex C18色谱柱,高纯水-乙腈作为流动相进行梯度洗脱。8种化合物的线性范围0.5~200ng·mL~(-1),相关系数均高于0.998;8种化合物的检测限(S/N≥3)均低于0.3ng·mL~(-1)。方法重现性好,准确度高,可用于强奸、抢劫、杀人等案件的血液检材中苯二氮卓类药物的定性定量分析。     

Mild Method for Preparation of 4,4-Dimethyloxazoline Derivatives of Polyunsaturated Fatty Acids for GC–MS

A mild and convenient method has been developed for preparing 4,4-dimethyloxazoline (DMOX) derivatives of fatty acids for GC–MS analysis. First, fatty acid methyl esters are converted to corresponding amides by incubation overnight at room temperature with 2-amino-2-methyl-1-propanol and a catalytic amount of sodium methoxide. The resulting 2-(methylpropanol) amides were isolated by partition between hexane–diethyl ether and water, and then converted to 4,4-dimethyloxazoline derivatives by treatment with trifluoroacetic anhydride under mild conditions (50 °C for 45 min). Structures of 2-methylpropanol amide and a DMOX derivative of oleic acid were confirmed by GC–MS. This method was applied to different FAME prepared from animal, plant or microbial lipids. The suggested method is most suitable for structure analysis of polyunsaturated fatty acids (PUFA) and for acids with double bonds in close to terminal positions. Application of the method is illustrated with spectra of the DMOX derivatives of 16:1(n-13), 24:5(n-6) and 24:6(n-3) acids.     

防晒乳液中8种紫外线吸收剂的UPLC-Q-TOF/MS定性及稳定性研究

基于45℃、75%RH的恒温恒湿加速试验,采用UPLC-Q-TOF/MS对不同类型的加速防晒乳液中的8种紫外线吸收剂进行了定性及稳定性研究。结果表明,在防晒乳液体系中,8种紫外线吸收剂的化学稳定性较差,与加速时间呈正相关降解,且采用UPLC-Q-TOF/MS分析时计算所得降解率明显高于HPLC分析。对紫外线吸收剂进行降解产物分析时发现,其某些降解产物可能与原型化合物具有相同的母核结构,故具有类似的紫外吸收特性和色谱保留行为,从而造成UPLC-Q-TOF/MS和HPLC分析时的结果差异。因此,相较于HPLC而言,UPLC-Q-TOF/MS灵敏度更高、专属性更强,可利用化合物特有的精确分子量,对结构和性质类似的不同降解程度的紫外线吸收剂降解产物实现更好地区分,更适用于紫外线吸收剂的稳定性研究。     

SPE-LC/MS/MS检测全血中溴敌隆

建立全血中溴敌隆的固相萃取-液相色谱串联质谱联用检测方法。血液中加入pH=6缓冲溶液,用HLB固相小柱萃取浓缩后吹干,采用ZORBAX SB-C_(18)(2.1 mm×100 mm,1.8μm)色谱柱,流动相为0.1%甲酸和20 m M乙酸铵-乙腈,流速为0.3 m L/min;进样量:1μL,电喷雾离子源(ESI),负离子模式,采用多反应监测(MRM)监测。在50~800 ng/m L范围内线性良好,全血中溴敌隆在高中低三个浓度条件下的回收率为69.4%~72.2%,相对标准偏差为2.3%~5.0%;溴敌隆的仪器检出限为6.6 ng/m L。该固相萃取方法自动化高、溶剂用量少,可用于全血中的溴敌隆检测。     

Research on the Application of Melamine Sulphonate（MS） in Monolithic Refractories

Through research on the application of MS in monolicthic refractiories,the authors found that the absorptive style of MS is Lang-muir constant temperature absorption,the maxmium absorption is 20 mg/g in the mono-lithic refractories with pure calcium aluminte cement as binder,When the additive quantity is between 0.5% to 1.0%,the cold crushing strength of castable refractoies is 100% to 230% more than ordinary sample ,the modulus of rupture is 80% to 200% more,the bulk den-sity is 6% to 9.5% more and the porosity decrease by 15% to 36% than ordinary sampl,The authors consider tha MS is a kind of excellent high molecular compound in monolithic refractories.     

Detection of Hydrocarbons in Irradiated Chilled Beef by HS-SPME–GC–MS and Optimization of the Method

The hydrocarbons 1,7-hexadecadiene (1,7-C16:2) and 8-heptadecene (8-C17:1), which are used as markers for identifying irradiated chilled beef, were easily detectable in chilled beef irradiated at 0.5 kGy or higher by using a new method of headspace solid-phase microextraction, gas chromatography and mass spectrometry (HS-SPME–GC–MS). The conditions for using SPME were optimized in this study for qualitative and quantitative determination of 1,7-C16:2 and 8-C17:1 produced by γ-radiation in chilled beef. The relationship between irradiation dose and production of hydrocarbons was also studied, which showed good linear correlation with the coefficients of 0.9942 and 0.9943 for 1,7-C16:2 and 8-C17:1, respectively. HS-SPME–GC–MS is a simple and sensitive method for the analysis of hydrocarbons in irradiated chilled beef.     

Thermal Oxidation Rate of Oleic Acid Increased Dramatically at 140 °C Studied using Electron Spin Resonance and GC–MS/MS

Thermal oxidation of oleic acid at high temperatures was studied using combination of electron spin resonance (ESR) spin-trapping technique and solid phase microextraction (SPME)-Gas chromatography-mass spectrometry-mass spectrometry (GC–MS/MS). Dimethyl pyridine N-oxide (DMPO) was applied as the spin trap. Alkyl, alkoxyl, and oxidized DMPO adducts were identified in the experimental spectra. At 140 °C, the alkyl radical adduct was the major component, accounting for 63.89% of the total radical adducts. However, the alkoxyl radical adduct was the main radical adduct in the temperature range of 120 to 135 °C. The total amount of spins, a parameter to indicate radical concentrations, detected at 140 °C was nearly three times higher than that at 135 °C. And, the total amount of alkyl radical adducts was higher than that of alkoxyl radical adducts at 140 °C, which indicated a higher alkyl radical formation rate. Besides, a larger amount (10.30%) of oleic acid degraded at 140 °C than that at 135 °C with the detection of GC. More (E)-2-Decenal (plastic) and (E)-2-undecenal (herbaceous) formed affect the flavor of frying.     

GC/MS/MS法测定油菜籽中异丙甲草胺残留量

采用甲醇和水提取,正己烷萃取,经SPE柱净化,GC/MS/MS测定,建立了油菜籽中异丙甲草胺残留量的GC/MS/MS测定方法.添加质量分数为0.05、0.001 mg/kg,方法平均回收率分别为88.5%和101.7%,相对标准偏差分别为3.0%、6.2%,最低检出质量分数为0.001 mg/kg.