Egmont Richard Rohwer

Comprehensive two-dimensional gas chromatography time of flight mass spectrometry (GC × GC-TOFMS) for environmental forensic investigations in developing countries

The disposal and dumping of toxic waste is a matter of growing concern in developing countries, including South Africa. Frequently these countries do not possess access to gas chromatography-high resolution mass spectrometry (GC-HRMS) for the determination of persistent organic pollutants (POPs). This publication describes an alternative approach to the investigation of toxic waste using comprehensive gas chromatography coupled to time of flight mass spectrometry (GC×GC-TOFMS). The technology permits both comprehensive screening of toxic samples for numerous classes of organic pollutants and also quantitative analysis for the individual compounds. This paper describes the use of this technique by analysing samples obtained from a hazardous waste treatment facility in South Africa. After sampling and extraction the samples were analysed for polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and four dioxin-like non-ortho substituted polychlorinated biphenyls (PCBs). The quantitative values, as well as detection limits, obtained using the GC×GC-TOFMS methodology compares well with those obtained using GC-HRMS; the accepted benchmark technology for this analysis. Although GC×GC-TOFMS is not a target compound analytical technique (as is GC-HRMS), it is possible to obtain information on numerous other classes of organic pollutants present in the samples in one analytical run. This is not possible with GC-HRMS. Several different column combinations have been investigated for handling very complex waste samples and suggestions are presented for the most suitable combination.

Chemical characterization and screening of hydrocarbon pollution in industrial soils by headspace solid-phase microextraction

A headspace solid-phase microextraction method, followed by a gas chromatographic-mass spectrometric analysis, has been developed for the screening of soil samples polluted by coal tar or refined petroleum products. Vapor pressures of target analytes were determined using a capillary GC method to identify environmentally important components with a sufficiently high vapor pressure to be analyzed in the headspace mode. The method was optimized under non-equilibrium conditions with simplicity and automation in mind and does not require any extraction procedure or sample preparation, other than grinding, drying and homogenizing. The analytical performance and the significance of the results for the purpose of chemical characterization, source discrimination, determination of individual isomer distributions and to calculate source or weathering ratios, is discussed.

Analysis of odorous compounds in water by isolation by closed-loop stripping with a multichannel silicone rubber trap followed by gas chromatography-mass spectrometry

An alternative technique for the isolation and concentration of odorous compounds found in potable water is described. The method currently employed by water authorities is closed-loop stripping with the collection of these substances on a small activated carbon filter. The compounds of interest are then extracted from the carbon using a suitable solvent. The authors offer a multichannel silicone rubber trap as an alternative to the carbon filter. The absorbed compounds are thermally desorbed from the trap, directly on to the gas chromatographic column for analysis by GC-MS, thereby eliminating the solvent extraction step required by the carbon filter. The multichannel silicone rubber trap, producing equivalent results, offers a number of advantages over the carbon filter.

Detection of petrol (gasoline) in fire debris by Gas chromatography/mass spectrometry/mass spectrometry (GC/MS/MS)

Gas chromatography/mass spectrometry (GC/MS) is a well-known instrumental technique used for the analysis of fire debris for accelerant detection. However, matrix problems, such as pyrolysis product interference, are still encountered. These interferences often lead to inconclusive interpretation of the chromatographic results obtained. This paper describes a method of analyzing arson accelerants using gas chromatography coupled with ion trap mass spectrometry/mass spectrometry (GC/MS/MS). Petrol was investigated as an accelerant. Analysis incorporated an ion preparation method (IPM) that manipulates the ion population in the ion trap following ionization but prior to ion analysis. Parent ions of selected mass-to-charge (m/z) values, characteristic for petrol, are stored within the ion trap. All other unwanted ions are physically removed from the trap by sophisticated electrostatic waveforms. The parent ions fill the trap and are then fragmented by means of collision-induced dissociation (CID). The resultant daughter ion spectra are obtained, which can be used for identification purposes. In this manner, ions of pyrolysis origin are removed.

The use of multi-channel silicone rubber traps as denuders for polycyclic aromatic hydrocarbons

Atmospheric polycyclic aromatic hydrocarbons are ubiquitous environmental pollutants, which may be present both in the gaseous phase and adsorbed onto the surface of particles. Denuders are sampling devices which have been effectively employed in such partitioning applications. Here we describe and characterise a novel miniature denuder consisting of two multi-channel silicone rubber traps (each 178 mm long, 6 mm o.d. containing 22 silicone tubes), separated by a quartz fibre filter for particle phase collection. The denuder only requires a small portable personal sampling pump to provide sampling flow rates of ∼0.5 L min(-1). Theoretical considerations indicated that the air flow through the denuder was expected to be laminar, and the linear velocity arising from longitudinal diffusion was found to be negligible. The calculated particle transmission efficiency through the denuder was found to be essentially 100% for particles>50 nm, whilst the experimental overall efficiency, as determined by CPC and SMPS measurements, was 92 ± 4%. The size resolved transmission efficiency was <60% for particles below 20 nm and 100% for particles larger than 200 nm. Losses could have been due to diffusion and electrostatic effects. Semi-volatile gaseous analytes are pre-concentrated in the silicone of the trap and may be thermally desorbed using a commercially available desorber, allowing for total transfer and detection of the collected analytes by GC-MS. This enhances detection limits and allows for lower sampling flow rates and shorter sampling times, which are advantageous for studies requiring high temporal resolution.

Critical review of the analysis of brominated flame retardants and their environmental levels in Africa

World-wide, the prevalence of brominated flame retardants (BFRs) is well documented for routine analysis of environmental and biological matrices. There is, however, limited information on these compounds in the African environment and insufficient information on the analytical approaches used to obtain data. This paper presents a review on BFR levels in the African environment and the various analytical methodologies specifically applied in Africa for polybrominated diphenyl ethers (PBDEs), polybrominated biphenyls and alternative-BFRs. The analyses include liquid sample preparation using liquid-liquid and solid phase extraction and solid sample preparation involving Soxhlet extraction, with ultrasound-assisted extraction increasingly being applied. Instrumental detection techniques were limited to gas chromatography coupled with electron capture detector and electron impact ionisation with single quadrupole mass spectrometers. Information on congener profile prevalence in indoor dust, soil, aquatic environment (water, sediment, and aquatic organisms), eggs, wastewater treatment plant compartments, landfills (leachate and sediment) and breast milk are presented. Although PBDEs were inconsistently detected, contamination was reported for all investigated matrices in the African environment. The manifestation in remote regions indicates the ubiquitous prevalence and long-range transport of these compounds. Levels in sediment, and breast milk from some African countries were higher than reported for Asia and Europe. Due to limited data or non-detection of alternative-BFRs, it is unclear whether banned formulations were replaced in Africa. Most of the data reported for BFR levels in Africa were obtained in non-African laboratories or in South Africa and formed the basis for our discussion of reported contamination levels and related methodologies.

Establishing an alternative method for the quantitative analysis of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans by comprehensive two dimensional gas chromatography-time-of-flight mass spectrometry for developing countries

Comprehensive Gas Chromatography-Time-of-Flight Mass Spectrometry (GC×GC-TOFMS) methodology has been refined for the analysis of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in samples with different matrices. This is specifically for application in developing countries where access to gas chromatography-high resolution mass spectrometry (GC-HRMS) and highly skilled personnel is limited. The method, using an Rxi-5 Sil MS column in the first dimension ((1)D) coupled with an Rtx-200 column in the second dimension ((2)D), was used to quantify PCDDs and PCDFs in different environmental sample matrices. The results were compared with those obtained using GC-HRMS and good agreement was observed. The limit of detection (LOD) for the method (300fg on column for spiked soil samples) was determined using an Rxi-XLB ((1)D) column coupled with an Rtx-200 column ((2)D). Preliminary South African sample results are also discussed. Isomer specificity for different tetrachloro dibenzo-p-dioxins (TCDDs) and tetrachloro dibenzofurans (TCDFs) was investigated using a commercial standard. Adequate resolution was achieved. The method as described has great attraction for developing countries being both financially and operationally favourable.

Multi-channel open tubular traps for headspace sampling, gas chromatographic fraction collection and olfactory assessment of milk volatiles.

A headspace sampling method is described for concentrating milk volatiles onto a multi-channel open tubular silicone rubber trap (MCT) for thermal desorption into a GC-FID. Sections of the chromatographic profile, single peaks or combinations of compounds are recaptured with secondary MCTs during a subsequent run. The recaptured aroma is released in a controlled manner by heating the MCT in a portable heating device. An aroma release window of several minutes allows up to six people the opportunity to sniff each aroma fraction more than once. Olfactory results suggest that a synergistic combination of 2-heptanone and 2-nonanone could be responsible for a pungent cheese, sour milk-like aroma. MCTs containing single components or fractions can be desorbed into a GC-MS for compound identification.

Investigations into a novel method for atmospheric polycyclic aromatic hydrocarbon monitoring

A novel analytical method for atmospheric polycyclic aromatic hydrocarbons (PAHs) was developed based on laser induced fluorescence (LIF) of samples on quartz multi-channel polydimethylsiloxane traps. A tunable dye laser with a frequency doubling crystal provided the excitation radiation, and a double monochromator with a photomultiplier tube detected emitted fluorescence. The method allowed for the rapid (<5 min), cost effective analysis of samples. Those yielding interesting results could be further analysed by direct thermal desorption-gas chromatography-mass spectrometry (TD-GC-MS, with limits of detection of approximately 0.3 ng m(-3)), as photodegradation was minimal (<10% over 5 min irradiation). Small amounts of naphthalene photodegradation products identified by TD-GC-MS after >15 min irradiation, included phenol, benzyl alcohol and phthalic anhydride. Without any signal optimization, a LIF detection limit of approximately 1 microg m(-3) was established for naphthalene using a diffusion tube (diffusion rate of 2 ng s(-1)) and 292 nm excitation.

Volatile flavour components of marula juice

ZusammenfassungDie flüchtigen Aromastoffe von Marula-Saft, hergestellt aus in Südafrika gelesenen Früchten, wurden mit einer bewährten Flüssig-Flüssig-Extraktionsmethode angereichert. Mittels GC und GC-MS wurden 60 Verbindungen identifiziert, deren Kovats-Indices auf CW20M niedriger als 2000 lagen.Sesquiterpen Kohlenwasserstoffe bildeten die vorherrschende Gruppe von Verbindungen, wobei β-Caryophyllen Hauptbestandteil aller untersuchter Proben war. Insgesamt wurden 33 Sesquiterpenkohlenwasserstoffe detektiert, von denen 22 positiv identifiziert wurden, einschließlich aller Hauptkomponenten. Deutliche Unterschiede innerhalb der Aromafraktion der untersuchten Proben waren nur bei den Sesquiterpenen festzustellen.Geruchstests der gaschromatographisch getrennten Verbindungen ließen das Fehlen von Verbindungen mit „impact charakter” erkennen.SummaryThe volatile aromatics of marula fruit picked in the Republic of South Africa were enriched by means of an established liquid-liquid extraction technique. GC and GC-MS analyses were employed to identify 60 components with Kovats Indices lower than 2,000 (CW20M).Sesquiterpene hydrocarbons formed the most abundant group of compounds, with β-caryophyllene being the major constituent of all analyzed samples. 33 sesquiterpene hydrocarbons could be detected of which 22 were identified, including all major components. Significant differences between the analyzed samples were observed only within the sesquiterpene fraction. - Odour assesment indicated the absence of compounds with impact character.