Electrospray Ionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (ESI FT-ICR MS): Characterization of Complex Environmental Mixtures

Structural and chemical characterization of compounds within complex environmental mixtures provides unique insights into the roles of these compounds in different environmental processes. Here, an emerging technique in environmental chemistry, electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS), is described and its applications to the molecular characterization of humic acids and petroleum products are reviewed and examined. ESI is a low-fragmentation ionization technique that preferentially ionizes polar functional groups prior to mass spectrometric analysis. This technique allows the characterization of intact polar macromolecules that are inaccessible to standard chromatographic techniques. ICR MS is an ultrahigh resolution and mass accuracy MS technique based on the detection of ion cyclotron motion within a magnetic field. The combination of ESI FT-ICR MS with other structural techniques such as nuclear magnetic resonance (NMR) allows the unprecedented identification and characterization of polar macromolecules in environmental mixtures and will find numerous applications within environmental chemistry and forensics.     

Detailed characterization of polar compounds of residual oil in contaminated soil revealed by Fourier transform ion cyclotron resonance mass spectrometry

Effects of remediation technologies on polar compounds of crude oil in contaminated soils have not been well understood when compared to hydrocarbons. In this study, ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) was used to characterize the changes in NSO polar compounds of crude oil and residual oil after long-term natural attenuation, biostimulation and subsequent ozonation following biostimulation of contaminated soils. N₁ and O₁ species, which were abundant in the crude oil, were selectively biodegraded, and species with higher double bond equivalent values and smaller carbon numbers appeared to be more resistant to microbial alteration. O₂-O₆ species were enriched by biodegradation and contained a large number of compounds with a high degree of unsaturation. Ozone could react with a variety of polar compounds in residual oil after biodegradation and showed high reactivity with polar species containing aromatic or multi-aliphatic rings, including the residual N₁ and O₁ species, naphthenic acids and unsaturated O₃-O₆ compounds. Fatty acids and O₃-O₈ species dominated by saturated alkyl compounds were resistant to ozonation or the primarily incomplete ozonation products. Principal component analysis of identified peaks in the FT-ICR MS spectra provided a comprehensive overview of the complex samples at the molecular level and the results were consistent with the detailed analysis. Taken together, these results showed the high complexity of polar compounds in residual oils after biodegradation or ozonation in contaminated soil and would contribute to a better understanding of bioremediation and ozonation processes.     

Comprehensive characterization of oil refinery effluent-derived humic substances using various spectroscopic approaches

Refinery effluent-derived humic substances (HS) are important for developing refinery effluent reclamation techniques and studying the environmental chemistry of wastewater effluents. In this study, dissolved organic matter (DOM) from refinery effluent was concentrated using a portable reverse osmosis (RO) system. HS were isolated from RO retentates with XAD-8 resin. A variety of approaches such as specific UV absorbance at 254nm (SUV(254)), elemental analysis, size exclusion chromatography (SEC), solid-state cross polarization magic angle spinning (13)C nuclear magnetic resonance spectrometry ((13)C CPMAS NMR), Fourier transform infrared spectrometry (FTIR), and electrospray ionization/ion trap/mass spectrometry (ESI/ion trap/MS) were employed for characterization of HS. The portable RO system exhibited high yield and recovery of DOM for concentrating refinery effluent. The concentration of dissolved organic carbon (DOC) in the refinery effluent was 9.9mg/l, in which humic acids (HA) and fulvic acids (FA) accounted for 2.3% and 34.6%, respectively. Elemental and SUV(254) analyses indicated relative high amounts of aliphatic structures and low amounts of aromatic structures in refinery effluent-derived HS. Refinery effluent-derived HS displayed lower molecular weight than natural HS. The number-average molecular weight (M(n)) and the weight-average molecular weight (M(w)) of HA were 1069 and 2934, and those of FA were 679 and 1212 by SEC, respectively. By ESI/ion trap/MS, the M(n) and the M(w) of FA were 330 and 383. Four kinds of carbon structures (aliphatic, aromatic, heteroaliphatic, and carboxylic carbons) were found in refinery effluent-derived HS by (13)C NMR analysis. The quantitative results support the interpretation that these HS are rich in aliphatic carbons and poor in aromatic carbons. Proteinaceous materials were identified by FTIR analysis in refinery effluent-derived HS.     

Evaluation of reverse phase liquid chromatography/mass spectrometry for estimation of n-octanol/water partition coefficients for organic chemicals

A reverse-phase high pressure liquid chromatography/mass spectrometry (HPLC/MS method was developed for estimating n-octanol/water partition coefficients (K_ow) of anthropogenic molecules in complex chemical mixtures (e.g., complex effluents and solid waste leachates). The average error for an estimated log K_ow was ca. 0.5 and this error was similar for both aliphatic and aromatic compounds. The minimum level of detection using the total ion current profile generally decreased with increasing molecular weight between 100 and 600 daltons. Results obtained demonstrate that the HPLC/MS method is a viable technique for estimating log K_ow's of anthropogenic chemicals in complex environmental samples.     

Selected ion chromatograms and tandem mass spectrometry for detection of trace polycyclic aromatic hydrocarbons in diesel exhaust

Polycyclic aromatic hydrocarbon (PAH) measurements are essential for scientists and engineers who investigate these anthropogenic compounds. Diesel engines contribute to the problem, so analysts are measuring PAHs from these sources. However, diesel exhaust presents special problems for precise analytical measurements. The exhaust matrix is very complex; consequently, PAH detection sensitivity deteriorates, especially for trace PAHs in the exhaust. Yet, these are conditions and amounts that exist in real samples. Nonetheless, selected ion chromatogram (SIC) and tandem mass spectrometry (MS/MS) techniques improve trace PAH detection; ion trap technology makes both mass techniques possible. The purpose of this investigation was to evaluate SIC and MS/MS for applications to measure PAHs in diesel exhaust samples. The signal-to-noise ratio for accurate quantitation improves, relative to traditional mass techniques, because these techniques ignore or eliminate interfering components. On a VF-5MS chromatographic column, these techniques improve sensitivity and reproducibility. They produce a superior limit of detection in the useful range for PAH samples extracted from actual engine exhaust, 10-30 pg for the smaller PAHs and 1-6 ng for the larger PAHs. The results with SIC and MS/MS are reproducible, so analysts can report PAH amounts with defined statistical confidence intervals. SIC and MS/MS improve detection for trace PAHs in convoluted diesel exhaust samples.     

Selected Ion Chromatograms and Tandem Mass Spectrometry for Detection of Trace Polycyclic Aromatic Hydrocarbons in Diesel Exhaust

Abstract

Polycyclic aromatic hydrocarbon (PAH) measurements are essential for scientists and engineers who investigate these anthropogenic compounds. Diesel engines contribute to the problem, so analysts are measuring PAHs from these sources. However, diesel exhaust presents special problems for precise analytical measurements. The exhaust matrix is very complex; consequently, PAH detection sensitivity deteriorates, especially for trace PAHs in the exhaust. Yet, these are conditions and amounts that exist in real samples. Nonetheless, selected ion chromatogram (SIC) and tandem mass spectrometry (MS/MS) techniques improve trace PAH detection; ion trap technology makes both mass techniques possible. The purpose of this investigation was to evaluate SIC and MS/MS for applications to measure PAHs in diesel exhaust samples. The signal-to-noise ratio for accurate quantitation improves, relative to traditional mass techniques, because these techniques ignore or eliminate interfering components. On a VF-5MS chromatographic column, these techniques improve sensitivity and reproducibility. They produce a superior limit of detection in the useful range for PAH samples extracted from actual engine exhaust, 10–30 pg for the smaller PAHs and 1–6 ng for the larger PAHs. The results with SIC and MS/MS are reproducible, so analysts can report PAH amounts with defined statistical confidence intervals. SIC and MS/MS improve detection for trace PAHs in convoluted diesel exhaust samples.     

Photolytic degradation of fluoroquinolone carboxylic acids in aqueous solution

Subsequent to irradiation with a xenon lamp simulating sunlight, fluoroquinolone carboxylic acids in aqueous solution form polar pyridone dicarboxylic and tricarboxylic acids. After liquid/liquid partition with chloroform/water these substances can be isolated by ion exchange chromatography of the aqueous phase. They can be regarded as intermediate compounds on the route to a complete photomineralization. The structural elucidation is performed by such mass spectroscopic methods as MS, GC/MS and HPLC/MS, whereby HPLC/MS shows the highest reliability. Additionally¹H- and¹³C-NMR measurements confirm the structure of the main polar degradation product.     

Computer-based QSARs for predicting mixture toxicity of benzene and its derivatives

During the past decades, the Quantitative structure-activity relationships (QSARs) have been proven to be reliable tools when little or no empirical data are available in medicinal chemistry, biochemistry, toxicology, and environmental sciences. However, only few studies that quantitatively predict mixtures toxicity have been reported. In this study, the QASR models for the binary mixtures toxicity of 12 benzene and its derivatives, including eight non-polar-narcotic compounds and four polar narcotic compounds were developed, without reference to exact toxicity mechanisms of single compounds. All parameters for the QSAR studies were defined on the basis of quantum mechanical calculations and these parameters were selected by the stepwise procedure. The results of this study provided a simple means of predicting the binary mixtures toxicity from the chemical structure.     

High-molecular weight sulfur-containing aromatics refractory to weathering as determined by Fourier transform ion cyclotron resonance mass spectrometry

Biomarkers and low-molecular weight polyaromatic compounds have been extensively studied for their fate in the environment. They are used for oil spill source identification and monitoring of weathering and degradation processes. However, in some cases, the absence or presence of very low concentration of such components restricts the access of information to spill source. Here we followed the resistance of high-molecular weight sulfur-containing aromatics to the simulated weathering condition of North Sea crude oil by ultra high-resolution Fourier transform ion cyclotron resonance mass spectrometry. The sulfur aromatics in North Sea crude having double bond equivalents (DBE) from 6 to 14 with a mass range 188-674 Da were less influenced even after 6 months artificial weathering. Moreover, the ratio of dibenzothiophenes (DBE 9)/naphthenodibenzothiophenes (DBE 10) was 1.30 and 1.36 in crude oil and 6 months weathered sample, respectively reflecting its weathering stability. It also showed some differences within other oils. Hence, this ratio can be used as a marker of the studied crude and accordingly may be applied for spilled oil source identification in such instances where the light components have already been lost due to environmental influences.     

Comparison of dioxin and furan TEQ determination in contaminated soil using chemical,micro-EROD,and immunoassay analysis

High resolution mass spectrometry gas chromatography (GC/MS) is the standard method for dioxin and furan analysis in environmental matrices. Considered as very accurate, this method is however time consuming and expensive. Methods based on biological interactions have the necessary sensitivity but began only recently to be investigated in the context of environmental applications. We have compared dioxin and furan toxicity levels (expressed as toxic equivalent quantities (TEQs)) in soil samples by three analytical approaches: the micro-ethoxyresorufin-o-deethylase (EROD) bioassay (a receptor-based method), an immunoassay (antibody-based method) and GC/MS analysis (used as a reference) using a shortened extraction-purification method. Both biological methods were sensitive to interferences from compounds co-extracted from samples. Most samples were underestimated by the immunoassay and, at a greater extent, overestimated by the EROD bioassay. The average accuracy of TEQ estimation (86 +/- 45% of values established by GC/MS) and the absence of false-negatives showed by the immunoassay suggest the usefulness of this method for semi-quantitative, preliminary characterization of potentially contaminated sites.     

PM2.5 source apportionment with organic markers in the Southeastern Aerosol Research and Characterization (SEARCH) study

Positive matrix factorization (PMF) and effective variance (EV) solutions to the chemical mass balance (CMB) were applied to PM_2.5 (particulate matter with an aerodynamic diameter <2.5 μm) mass and chemically speciated measurements for samples taken from 2008 to 2010 at the Atlanta, Georgia, and Birmingham, Alabama, sites. Commonly measured PM_2.5 mass, elemental, ionic, and thermal carbon fraction concentrations were supplemented with detailed nonpolar organic speciation by thermal desorption-gas chromatography/mass spectrometry (TD-GC/MS). Source contribution estimates were calculated for motor vehicle exhaust, biomass burning, cooking, coal-fired power plants, road dust, vegetative detritus, and secondary sulfates and nitrates for Atlanta. Similar sources were found for Birmingham, with the addition of an industrial source and the separation of biomass burning into open burning and residential wood combustion. EV-CMB results based on conventional species were qualitatively similar to those estimated by PMF-CMB. Secondary ammonium sulfate was the largest contributor, accounting for 27–38% of PM_2.5, followed by biomass burning (21–24%) and motor vehicle exhaust (9–24%) at both sites, with 4–6% of PM_2.5 attributed to coal-fired power plants by EV-CMB. Including organic compounds in the EV-CMB reduced the motor vehicle exhaust and biomass burning contributions at both sites, with a 13–23% deficit for PM_2.5 mass. The PMF-CMB solution showed mixing of sources within the derived factors, both with and without the addition of speciated organics, as is often the case with complex source mixtures such as those at these urban-scale sites. The nonpolar TD-GC/MS compounds can be obtained from existing filter samples and are a useful complement to the elements, ions, and carbon fractions. However, they should be supplemented with other methods, such as TD-GC/MS on derivitized samples, to obtain a wider range of polar compounds such as sterols, sugars, and organic acids. The PMF and EV solutions to the CMB equations are complementary to, rather than replacements for, each other, as comparisons of their results reveal uncertainties that are not otherwise evident.

Implications:?Organic markers can be measured on currently acquired PM_2.5 filter samples by thermal methods. These markers can complement element, ion, and carbon fraction measurements from long-term speciation networks. Applying the positive matrix factorization and effective variance solutions for the chemical mass balance equations provides useful information on the accuracy of the source contribution estimates. Nonpolar compounds need to be complemented with polar compounds to better apportion cooking and secondary organic aerosol contributors.     

Identification and removal of polycyclic aromatic hydrocarbons in wastewater treatment processes from coke production plants

Identification and removal of polycyclic aromatic hydrocarbons (PAHs) were investigated at two coke plants located in Shaoguan, Guangdong Province of China. Samples of raw coking wastewaters and wastewaters from subunits of a coke production plant were analyzed using gas chromatography–mass spectrometry (GC/MS) to provide a detailed chemical characterization of PAHs. The identification and characterization of PAH isomers was based on a positive match of mass spectral data of sample peaks with those for PAH isomers in mass spectra databases with electron impact ionization mass spectra and retention times of internal reference compounds. In total, 270 PAH compounds including numerous nitrogen, oxygen, and sulfur heteroatomic derivatives were positively identified for the first time. Quantitative analysis of target PAHs revealed that total PAH concentrations in coking wastewaters were in the range of 98.5?±?8.9 to 216?±?20.2 μg/L, with 3-4-ring PAHs as dominant compounds. Calculation of daily PAH output from four plant subunits indicated that PAHs in the coking wastewater came mainly from ammonia stripping wastewater. Coking wastewater treatment processes played an important role in removing PAHs in coking wastewater, successfully removing 92 % of the target compounds. However, 69 weakly polar compounds, including PAH isomers, were still discharged in the final effluent, producing 8.8?±?2.7 to 31.9?±?6.8 g/day of PAHs with potential toxicity to environmental waters. The study of coking wastewater herein proposed can be used to better predict improvement of coke production facilities and treatment conditions according to the identification and removal of PAHs in the coke plant as well as to assess risks associated with continuous discharge of these contaminants to receiving waters.     

Determination of estrogenic compounds in wastewater using liquid chromatography-tandem mass spectrometry with electrospray and atmospheric pressure photoionization following desalting extraction

Two complementary LC-MS ionization methods, electrospray (ESI) and atmospheric pressure photoionization (APPI), have been optimized to determine three natural estrogenic compounds (estrone, 17beta-estradiol and estriol) and two synthetic estrogenic compounds (17alpha-ethynylestradiol and diethylstilbestrol) in the influent and effluent of wastewater treatment plants (WWTPs). The wastewater samples were first subjected to solid-phase extraction coupled with desalting extraction to remove matrix interference. The analytes were then detected using liquid chromatography-tandem mass spectrometry (LC-MS-MS) with ESI and dopant-assisted (DA) APPI to evaluate the ion suppression effect and to complement the detection and quantification of estrogenic compounds in complex wastewater samples. The average ion suppression factors for the extracts of the WWTP influent analyzed using ESI and APPI were 52+/-5% and 27+/-7%, respectively. The sensitivity and ionization efficiency of the LC-ESI-MS-MS system decreased dramatically when a complex matrix was present in the WWTP influent sample. Estrogenic compounds could be detected in the WWTP influent and effluent samples at concentrations below the parts-per-billion level. The lower detection limits obtained when using ESI and the higher matrix tolerance of the APPI method allowed the complete quantification of estrogenic compounds in very complex samples in a complementary manner.     

微囊藻毒素-RR的提取和臭氧氧化降解

在对采自云南滇池水华蓝藻细胞中的微囊藻毒素-RR(microcystin-RR,MC-RR)提取并发现其含量达到0.19mg/g(干重)的基础上,重点研究了臭氧氧化降解所提取的MC-RR。结果表明,当反应体系中臭氧浓度为5.7 mg/L时,初始浓度1.9 mg/L的MC-RR在15 min内被完全降解。利用HPLC/ESI/MS对提取的MC-RR及其氧化降解产物质荷比测定发现,降解前MC-RR的质谱图中出现特征离子m/z=1 038.7、m/z=519.8以及m/z=135.0。而降解后的产物质谱图中只有Adda基团中带苯环结构化合物(C9H10O)的特征离子峰m/z=135.0存在,其他2个离子峰完全消失。由此推断反应体系中MC-RR(m/z=1 038.2)在大量臭氧及其.OH自由基全面攻击下,分子结构中Adda基团以及单环结构中的不饱和双键直接被氧化而发生断链,最终形成小分子的有机物。     

Negative ion chemical ionization mass spectrometry - a useful technique for the selective detection of polar substituted polycyclic aromatic hydrocarbons with mutagenic properties

Earlier studies have shown that many compounds with toxic properties are able to form stable negative ions. The negative ion mass spectrometric response of polar substances found in indoor air extracts from aluminium smelters was determined and compared with available mutagenicity data. The results indicate that the relationship mentioned above also is valid for polar compounds.     

植物-微生物联合修复石油污染土壤的实验研究

筛选高效石油降解菌并考察菌株的石油降解能力,通过植物-微生物联合修复石油污染土壤室内实验,在修复过程中测定了土壤中细菌和固氮菌,碱解氮、速效磷和速效钾的含量变化,同时采用傅立叶变换离子回旋共振质谱(ESI FT-ICR MS)考察了植物-微生物联合修复效果。结果表明,菌株3#、4#的生长适应性较强,其混合菌的降解效果最好,将其混合菌液与植物进行植物-微生物联合修复不同浓度的石油污染土壤,经过150 d的温室降解,最高降解率达到73.47%。ESI FT-ICR MS分析结果表明,与空白组相比,植物组的O1、O2和N1类等化合物相对丰度都发生了显著变化,石油污染物得到一定程度的生物降解。     

Relevance of enantiomeric separations in environmental science

A significant number of all organic chemicals that are released into the environment are racemic mixtures. Most environmental regulations and scientific environmental studies treat racemic mixtures as though they were single, pure compounds. This can lead to incorrect toxicological, distribution, degradation and other data. A series of new enantioselective chromatographic techniques have been developed that allow the facile separation and quantitation of chiral compounds of environmental importance. Nineteen racemic compounds that have been or currently are being released to the environment are resolved. These include: rodenticides--Warfarin, Coumachlor and Coumafuryl; insecticides--Crufomate, Bulan, Fonofos, Mitotane; insect repellent--Ethohexadiol; herbicides and fungicides--Ancymidol, Silvex, Napropamide, phenyl mercuric lactate, 2-[3-chlorophenoxy]propionamide, and 2-chloropropionic acid; and halocarbons-1,2-dichloropropane, 2-bromo-1-chloropropane, 1,2-dibromo-3-chloropropane, 2,3-dichlorobutane and alpha-1,2,3,4,5,6-hexachlorocyclohexane. Several examples are given to illustrate the importance of enantioselective measurements of these and other compounds. Choosing the proper chromatographic technique and chiral stationary phase based on analyte structure is also discussed.     

An overview of the methods used in the characterisation of natural organic matter (NOM) in relation to drinking water treatment

Natural organic matter (NOM) is found in all surface, ground and soil waters. During recent decades, reports worldwide show a continuing increase in the color and NOM of the surface water, which has an adverse affect on drinking water purification. For several practical and hygienic reasons, the presence of NOM is undesirable in drinking water. Various technologies have been proposed for NOM removal with varying degrees of success. The properties and amount of NOM, however, can significantly affect the process efficiency. In order to improve and optimise these processes, the characterisation and quantification of NOM at different purification and treatment processes stages is important. It is also important to be able to understand and predict the reactivity of NOM or its fractions in different steps of the treatment. Methods used in the characterisation of NOM include resin adsorption, size exclusion chromatography (SEC), nuclear magnetic resonance (NMR) spectroscopy, and fluorescence spectroscopy. The amount of NOM in water has been predicted with parameters including UV-Vis, total organic carbon (TOC), and specific UV-absorbance (SUVA). Recently, methods by which NOM structures can be more precisely determined have been developed; pyrolysis gas chromatography-mass spectrometry (Py-GC-MS), multidimensional NMR techniques, and Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS). The present review focuses on the methods used for characterisation and quantification of NOM in relation to drinking water treatment.     

Gas chromatography/mass spectrometry applied for the analysis of triazine herbicides in environmental waters

The excess use of triazine herbicides in agriculture causes severe contamination to the environment especially for ground water. Gas chromatography coupled with mass spectrometry (GC/MS) was used to analyze simazine, atrazine (ATR), cyanazine, as well as the degradation products of ATR such as deethylatrazine and deisopropylatrazine in environmental water samples. These compounds were baseline separated by the established GC method. The water samples were pre-concentrated by solid-phase-extraction (SPE) and analyzed by ion trap MS at sub- to low-ppt levels. Recovery of ATR by the SPE pre-concentration using a C18 cartridge was determined as 90.5 +/- 3.5%. Detection limit of the method using selected ion monitoring technique for ATR was 1.7 ppt when one liter water was analyzed. The relative analytical error for ATR fortified water samples at 200 ppt was -12.5% (n=12) with triple analysis and the relative standard deviation was 3.2%. Trace levels of ATR at 3.9 and 9.7 ppt were determined in water samples collected from a reservoir and a river in Hong Kong.     

Analysis of dioxins and furans in environmental samples by GC-ion-trap MS/MS

The work aims to characterise PCDDs/Fs in environmental matrices by high resolution gas chromatography coupled to low resolution quadrupole ion-trap mass spectrometry (GC-QITMS/MS). In particular, the study was mainly focused in different environmental samples such as sewage sludge, soils, and sediments and in combustion residues as fly ashes. Previous experiences have already detected and quantified PCDDs/PCDFs in all matrices studied. Moreover, isomer-specific analysis of 2,3,7,8-PCDDs/Fs compounds corroborated good correlation between GC-QITMS/MS and a well-established technique such as high resolution mass spectrometry (HRMS). Finally, QC measures included the participation in intercalibration exercises. Successful results were achieved using GC-QITMS/MS in the analysis of fly ashes, soils and sediment materials. In general, GC-QITMS/MS constitutes an interesting alternative for routine analysis of dioxins in such as matrices.