Maik A. Jochmann

Current challenges in compound-specific stable isotope analysis of environmental organic contaminants

AbstractCompound-specific stable-isotope analysis (CSIA) has greatly facilitated assessment of sources and transformation processes of organic pollutants. Multielement isotope analysis is one of the most promising applications of CSIA because it even enables distinction of different transformation pathways. This review introduces the essential features of continuous-flow isotope-ratio mass spectrometry (IRMS) and highlights current challenges in environmental analysis as exemplified for the isotopes of nitrogen, hydrogen, chlorine, and oxygen. Strategies and recent advances to enable isotopic measurements of polar contaminants, for example pesticides or pharmaceuticals, are discussed with special emphasis on possible solutions for analysis of low concentrations of contaminants in environmental matrices. Finally, we discuss different levels of calibration and referencing and point out the urgent need for compound-specific isotope standards for gas chromatography–isotope-ratio mass spectrometry (GC–IRMS) of organic pollutants. FigureCompound-specific isotope analysis of environmental contaminants: chromatographic separation is followed by online conversion to a suitable measurement gas (M) and subsequent isotope ratio mass spectrometry. Current challenges in the field concern the analysis of multiple elements (C, H, N, O, Cl) in polar compounds, at low concentrations and in the presence of matrix interferences. An urgent need exists for contaminant-specific reference materials.

Compound-specific chlorine isotope analysis: a comparison of gas chromatography/isotope ratio mass spectrometry and gas chromatography/quadrupole mass spectrometry methods in an interlaboratory study.

Chlorine isotope analysis of chlorinated hydrocarbons like trichloroethylene (TCE) is of emerging demand because these species are important environmental pollutants. Continuous flow analysis of noncombusted TCE molecules, either by gas chromatography/isotope ratio mass spectrometry (GC/IRMS) or by GC/quadrupole mass spectrometry (GC/qMS), was recently brought forward as innovative analytical solution. Despite early implementations, a benchmark for routine applications has been missing. This study systematically compared the performance of GC/qMS versus GC/IRMS in six laboratories involving eight different instruments (GC/IRMS, Isoprime and Thermo MAT-253; GC/qMS, Agilent 5973N, two Agilent 5975C, two Thermo DSQII, and one Thermo DSQI). Calibrations of (37)Cl/(35)Cl instrument data against the international SMOC scale (Standard Mean Ocean Chloride) deviated between instruments and over time. Therefore, at least two calibration standards are required to obtain true differences between samples. Amount dependency of δ(37)Cl was pronounced for some instruments, but could be eliminated by corrections, or by adjusting amplitudes of standards and samples. Precision decreased in the order GC/IRMS (1σ ≈ 0.1‰), to GC/qMS (1σ ≈ 0.2-0.5‰ for Agilent GC/qMS and 1σ ≈ 0.2-0.9‰ for Thermo GC/qMS). Nonetheless, δ(37)Cl values between laboratories showed good agreement when the same external standards were used. These results lend confidence to the methods and may serve as a benchmark for future applications.

In-Tube Extraction of Volatile Organic Compounds from Aqueous Samples: An Economical Alternative to Purge and Trap Enrichment

A novel in-tube extraction device (ITEX 2) for headspace sampling was evaluated for GC/MS analysis of aqueous samples. Twenty compounds of regulatory and drinking water quality importance were analyzed, including halogenated hydrocarbons, BTEX compounds (benzene, toluene, ethylbenzene, xylenes), fuel oxygenates, geosmin, and 2-methylisoborneol. Five commercially available sorbent traps were compared for their compound specific extraction yield. On the basis of the results, a mixed bed trap was prepared and evaluated. The extraction parameters were optimized to yield maximum sensitivity within the time of a GC run, to avoid unnecessary downtime of the system. Method detection limits of 1-10 ng L(-1) were achieved for volatile organic compounds (VOCs), which is much lower than demands by regulatory limit values. The performance of the ITEX system is similar to that of purge and trap systems, but it requires lower sample volumes and is less prone to contamination, much simpler, more flexible, and affordable. Average relative standard deviations below 10% were achieved for all analytes, and recoveries from spiked tap water samples were between 90% and 103%, mostly. The extraction is nonexhaustive, removing a fraction of 7% to 55% of the target compounds, depending on the air-water partitioning coefficients. The method was also tested with nonsynthetic samples, including tap, pond, and reservoir water and different soft drinks.

Caffeine in your drink: natural or synthetic?

Owing to possible adulteration and health concerns, it is important to discriminate between natural and synthetic food ingredients. A new method for compound-specific isotope analysis (CSIA) by coupling high-temperature reversed-phase liquid chromatography to isotope ratio mass spectrometry (HT-RPLC/IRMS) was developed for discrimination of natural and synthetic caffeine contained in all types of drinks. The analytical parameters such as stationary phase, column inner diameter, and column temperature were optimized for the separation of caffeine directly from drinks (without extraction). On the basis of the carbon isotope analysis of 42 natural caffeine samples including coffee beans, tea leaves, guaraná powder, and maté leaves, and 20 synthetic caffeine samples from different sources by high-temperature reversed-phase liquid chromatography coupled to isotope ratio mass spectrometry, it is concluded that there are two distinguishable groups of caffeine δ(13)C-values: one between -25 and -32‰ for natural caffeine, and the other between -33 and -38‰ for synthetic caffeine. Isotope analysis by HT-RPLC/IRMS has been applied to identify the caffeine source in 38 drinks. Four mislabeled products were detected due to added but nonlabeled synthetic caffeine with δ(13)C-values lower than -33‰. This work is the first application of HT-RPLC/IRMS to real-world food samples, which showed several advantages: simple sample preparation (only dilution), high throughput, long-term column stability, and high precision of δ(13)C-value. Thus, HT-RPLC/IRMS can be a very promising tool in stable isotope analysis of nonvolatile compounds.

High‐temperature reversed‐phase liquid chromatography coupled to isotope ratio mass spectrometry

Compound-specific isotope analysis (CSIA) by liquid chromatography coupled to isotope ratio mass spectrometry (LC/IRMS) has until now been based on ion-exchange separation. In this work, high-temperature reversed-phase liquid chromatography was coupled to, and for the first time carefully evaluated for, isotope ratio mass spectrometry (HT-LC/IRMS) with four different stationary phases. Under isothermal and temperature gradient conditions, the column bleed of XBridge C(18) (up to 180 °C), Acquity C(18) (up to 200 °C), Triart C(18) (up to 150 °C), and Zirchrom PBD (up to 150 °C) had no influence on the precision and accuracy of δ(13) C measurements, demonstrating the suitability of these columns for HT-LC/IRMS analysis. Increasing the temperature during the LC/IRMS analysis of caffeine on two C(18) columns was observed to result in shortened analysis time. The detection limit of HT-RPLC/IRMS obtained for caffeine was 30 mg L(-1) (corresponding to 12.4 nmol carbon on-column). Temperature-programmed LC/IRMS (i) accomplished complete separation of a mixture of caffeine derivatives and a mixture of phenols and (ii) did not affect the precision and accuracy of δ(13)C measurements compared with flow injection analysis without a column. With temperature-programmed LC/IRMS, some compounds that coelute at room temperature could be baseline resolved and analyzed for their individual δ(13)C values, leading to an important extension of the application range of CSIA.

Origin and Fate of Organic Compounds in Water: Characterization by Compound-Specific Stable Isotope Analysis

Within the past 15 years, compound-specific stable isotope analysis has continued to increase in popularity in the area of contaminant hydrology of organic molecules. In particular, in cases where concentration data alone are insufficient to elucidate environmental processes unequivocally, the isotope signature can provide additional unique information. Specifically, it can help answer questions about contaminant source apportionment, quantification of biotic and abiotic processes, and identification of transformation reactions on a mechanistic level. We review advances in laboratory and field investigations and exemplary applications in contaminant hydrology via stable isotope analysis. We also highlight future directions in the field.

Solvent-free microextraction techniques in gas chromatography

Microextraction techniques represent a major part of modern sample preparation in the analysis of organic micropollutants. This article provides a short overview of recent developments in solvent-free microextraction techniques. From the first open-tubular trap techniques in the mid-1980s to recent packed-needle devices, different implementations of in-needle packings for microextraction are discussed with their characteristic benefits, shortcomings and possible sampling modes. Special emphasis is placed on methods providing full automation and solvent exclusion. In this context, in-tube extraction and the needle trap are discussed, with an overview of current research on new sorbent materials, together with the requirements for more efficient method development.

When Other Separation Techniques Fail: Compound-Specific Carbon Isotope Ratio Analysis of Sulfonamide Containing Pharmaceuticals by High-Temperature-Liquid Chromatography-Isotope Ratio Mass Spectrometry

Compound-specific isotope analysis (CISA) of nonvolatile analytes has been enabled by the introduction of the first commercial interface to hyphenate liquid chromatography with an isotope ratio mass spectrometer (LC-IRMS) in 2004, yet carbon isotope analysis of unpolar and moderately polar compounds is still a challenging task since only water as the eluent and no organic modifiers can be used to drive the separation in LC. The only way to increase the elution strength of aqueous eluents in reversed phase LC is the application of high temperatures to the mobile and stationary phases (HT-LC-IRMS). In this context we present the first method to determine carbon isotope ratios of pharmaceuticals that cannot be separated by already existing separation techniques for LC-IRMS, such as reversed phase chromatography at normal temperatures, ion-chromatography, and mixed mode chomatography. The pharmaceutical group of sulfonamides, which is generally mixed with trimethoprim in pharmaceutical products, has been chosen as probe compounds. Substance amounts as low as 0.3 μg are sufficient to perform a precise analysis. The successful applicability and reproducibility of this method is shown by the analysis of real pharmaceutical samples. The method provides the first tool to study the pharmaceutical authenticity as well as degradation and mobility of such substances in the environment by using the stable isotopic signature of these compounds.

Microwave-assisted nonionic surfactant extraction of aliphatic hydrocarbons from petroleum source rock.

The extraction of aliphatic hydrocarbons from petroleum source rock using nonionic surfactants with the assistance of microwave was investigated and the conditions for maximum yield were determined. The results showed that the extraction temperatures and kinetic rates have significant effects on extraction yields of aliphatic hydrocarbons. The optimum temperature for microwave-assisted nonionic surfactant extraction of aliphatic hydrocarbons from petroleum source rock was 105°C. The optimum extraction time for the aliphatic hydrocarbons was at 50 min. Concentration of the nonionic surfactant solution and irradiation power had significant effect on the yields of aliphatic hydrocarbons. The yields of the analytes were much higher using microwave assisted nonionic surfactant extraction than with Soxhlet extraction. The recoveries of the n-alkanes and acyclic isoprenoid hydrocarbons for GC-MS analysis from the extractant nonionic surfactant solution by in-tube extraction (ITEX 2) with a TENAX TA adsorbent were found to be efficient. The results show that microwave-assisted nonionic surfactant extraction (MANSE) is a good and efficient green analytical preparatory technique for geochemical evaluation of petroleum source rock.

River restoration and the trophic structure of benthic invertebrate communities across 16 European restoration projects

River restoration enhances not only habitat diversity in the stream channel and riparian zone, but also retention of organic matter, which together are expected to enhance aquatic-terrestrial linkages, and the range of autochthonous and allochthonous resources. Consequently, alterations of food-web structure and trophic relationships can be expected. We applied stable isotope analysis (δ13C, δ15N) to characterize changes in the trophic structure of benthic invertebrate communities between paired restored and unrestored river reaches across 16 European catchments. We sampled dominant taxa of invertebrate assemblages belonging to different functional feeding groups and calculated δ13C range to estimate the diversity of basal resources assimilated, δ15N range as an indicator of the trophic length and standard ellipse area corrected for small samples as a measure of isotopic niche width. We analysed (1) if restoration influences the trophic structure of invertebrates, (2) if effects of restoration depend on the extent of restoration effort, and (3) if effects of restoration depend on restoration measures applied. Our European-scale comparison indicates that river habitat restoration effects trophic structure, primarily by increasing the breadth of resources assimilated by consumers; this effect increases with restoration effort and it depends on restoration measure type.