Assessing transformation processes of organic contaminants by compound-specific stable isotope analysis

The analysis of variations in stable isotope composition is becoming an essential approach for evaluating enzymatic and abiotic reactions of organic contaminants in soils and aquatic systems. Different, sometimes complementary analytical techniques are currently used and developed to determine stable isotope ratios in individual organic compounds. Anticipating an increasing demand for compound-specific isotope analysis, this survey compiles information for choosing the most promising analytical approach to an isotope-related problem. To this end, we review the principles of instrumentation for compound-specific isotope analysis and show how they can be exploited to assess contaminant transformation processes. Using chlorinated solvents and triazine herbicides as illustrative examples, we discuss how the isotope-sensitive techniques impact the investigation of stable isotope fractionation in environmental chemistry and microbiology.     

Precise and accurate compound-specific carbon and nitrogen isotope analysis of RDX by GC-IRMS

A new analytical method is presented for the compound-specific carbon and nitrogen isotope ratio analysis of a thermo-labile nitramine explosive hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) by gas chromatograph coupled to an isotope ratio mass spectrometer (GC-IRMS). Two main approaches were used to minimise thermal decomposition of the compound during gas chromatographic separation: programmed temperature vaporisation (PTV) as an injection technique and a high-temperature ramp rate during the GC run. δ¹⁵N and δ¹³C values of RDX measured by GC-IRMS and elemental analyser (EA)-IRMS were in good agreement within a standard deviation of 0.3‰ and 0.4‰ for nitrogen and carbon, respectively. Application of the method for the isotope analysis of RDX during alkaline hydrolysis at 50°C revealed isotope fractionation factors ε _carbon?=??7.8‰ and ε _nitrogen?=??5.3‰.     

Application of Compound-Specific Isotope Analysis in Environmental Forensic and Strategic Management Avenue for Pesticide Residues

Unintended pesticide pollution in soil, crops, and adjacent environments has caused several issues for both pesticide users and consumers. For users, pesticides utilized should provide higher yield and lower persistence while considering both the environment and agricultural products. Most people are concerned that agricultural products expose humans to pesticides accumulating in vegetation. Thus, many countries have guidelines for assessing and managing pesticide pollution, for farming in diverse environments, as all life forms in soil are untargeted to these pesticides. The stable isotope approach has been a useful technique to find the source of organic matter in studies relating to aquatic ecology and environmental sciences since the 1980s. In this study, we discuss commonly used analytical methods using liquid and gas chromatography coupled with isotopic ratio mass spectrometry, as well as the advanced compound-specific isotope analysis (CSIA). CSIA applications are discussed for tracing organic pollutants and understanding chemical reactions (mechanisms) in natural environments. It shows great applicability for the issues on unintended pesticide pollution in several environments with the progress history of isotope application in agricultural and environmental studies. We also suggest future study directions based on the forensic applications of stable isotope analysis to trace pesticides in the environment and crops.     

Compound-specific stable isotope analysis of organic contaminants in natural environments: a critical review of the state of the art,prospects, and future challenges

Compound-specific stable isotope analysis (CSIA) using gas chromatography-isotope ratio mass spectrometry (GC/IRMS) has developed into a mature analytical method in many application areas over the last decade. This is in particular true for carbon isotope analysis, whereas measurements of the other elements amenable to CSIA (hydrogen, nitrogen, oxygen) are much less routine. In environmental sciences, successful applications to date include (i) the allocation of contaminant sources on a local, regional, and global scale, (ii) the identification and quantification of (bio)transformation reactions on scales ranging from batch experiments to contaminated field sites, and (iii) the characterization of elementary reaction mechanisms that govern product formation. These three application areas are discussed in detail. The investigated spectrum of compounds comprises mainly n-alkanes, monoaromatics such as benzene and toluene, methyl tert-butyl ether (MTBE), polycyclic aromatic hydrocarbons (PAHs), and chlorinated hydrocarbons such as tetrachloromethane, trichloroethylene, and polychlorinated biphenyls (PCBs). Future research directions are primarily set by the state of the art in analytical instrumentation and method development. Approaches to utilize HPLC separation in CSIA, the enhancement of sensitivity of CSIA to allow field investigations in the µg L^–1 range, and the development of methods for CSIA of other elements are reviewed. Furthermore, an alternative scheme to evaluate isotope data is outlined that would enable estimates of position-specific kinetic isotope effects and, thus, allow one to extract mechanistic chemical and biochemical information.Abbreviations BTEX benzene, toluene, ethylbenzene, xylenes - MTBE methyl tert-butyl ether - PAHs polycyclic aromatic hydrocarbons - VOCs volatile compounds - PCBs polychlorinated biphenyls - CSIA compound-specific (stable) isotope (ratio) analysis - GC-IRMS, GC/IRMS or GCIRMS gas chromatography-isotope ratio mass spectrometry - GC-C-IRMS, GC/C/IRMS or GCC-IRMS gas chromatography-combustion-isotope ratio mass spectrometry - irmGC/MS isotope ratio monitoring gas chromatograph-mass spectrometry - GC/P/IRMS gas chromatography-pyrolysis-isotope ratio mass spectrometry (used for D/H) - KIE kinetic isotope effect - PSIA position-specific isotope analysis (for intramolecular isotope distribution) - SNIF-NMR site-specific natural isotopic fractionation by nuclear magnetic resonance spectroscopy     

Stable Carbon Isotope Analysis of Hexachlorocyclohexanes by Liquid–Liquid Extraction Gas Chromatography Isotope Ratio Mass Spectrometry: Method Evaluation and Applications

Compound specific isotope analysis (CSIA) and enantiomer specific isotope analysis (ESIA) are powerful tools for assessing the fate of hexachlorocyclohexanes (HCHs) in the environment. However, there is no systematic study on the CSIA and ESIA analysis test methods of the carbon isotopes of HCHs in water and soil environments, in particular the isotope fractionation in the pre-concentration process. We endeavored to test the compatibility of CSIA and ESIA with the liquid–liquid extraction method of HCHs in water. The results showed that there were negligible changes in the δ¹³C of HCHs after extraction, indicating that liquid–liquid extraction can be used as a pre-concentration method for the determination of δ¹³C of HCHs in water. The optimized method was validated and then applied to differentiate three HCHs from different manufacturers, to identify in situ degradation of HCHs of groundwater from a contaminated site and to resolve the carbon isotope fractionation occurring in the α-HCH oxidation by CaO₂/Fe(II) Fenton system. The results showed that the same reagents from different manufacturers have different carbon isotope compositions, and different isomers from the same manufacturer also have different isotope compositions, showing useful evidence in identifying the source of HCHs. The more enriched δ¹³C in the down-gradient wells indicated that HCHs have undergone biodegradation or/and chemical reactions in the groundwater system of the site. Carbon isotopic enrichment factors (ε_C) of −1.90 ± 0.10‰ were obtained in the oxidation process. Hence, the method validated in this study has great potential as a method for identifying the degradation of HCHs in a water environment.