Preserving Cultural Diversity in Rural Africa Using Renewable Energy.

Ninety percent of the large interior, rural part of Africa is not an abundant user of fossil fuels and is not connected to an electricity grid. This limits habitability and leads to significant migration to larger cities in attempts to improve economic and social welfare, which happens at the cost of its rich cultural diversity by inevitable adaption and mixing of societies. A direct transition from a firewood to an off-grid renewable electricity age can mitigate this detrimental development. This perspective discusses the interdisciplinary requirements linking cultural, sociological, economic, and technical aspects for a transition to modern life without loss of valuable traditions. Photovoltaic power and wind energy can provide local affordable electricity in off-grid locations. Intermediate storage for day-night cycles is catered for by novel types of batteries. Purifying and recycling water, refrigerating food and medicine, and benefitting from contact with the world via electronic media permit a tremendous increase in living conditions and significantly lower the pressure of migration into cities. Access to energy is a fundamental requirement for the preservation of the rich cultural diversity with family and tribal bindings, local languages, traditions, and religions, and allows for a more moderate transition to a modern society.

Advancing the analytical toolkit in the investigation of vector mosquito host biting site selection.

High-resolution mass spectrometry and ion mobility spectrometry provide additional confidence in biological marker discovery and elucidation by adding additional peak capacity through physiochemical separation orthogonal to chromatography. Sophisticated analytical techniques have proved valuable in the identification of human skin surface chemicals used by vector mosquitoes to find their human host. Polydimethylsiloxane (PDMS) was used as a non-invasive passive wearable sampler to concentrate skin surface non-volatile and semi-volatile compounds prior to solvent desorption directly in an LC vial, thereby simplifying the link between extraction and analysis. Ultra-performance liquid chromatography with ion mobility spectrometry coupled with high-resolution mass spectrometry (UPLC-IMS-HRMS) was used for compound separation and detection. A comparison of the skin chemical profiles between the ankle and wrist skin surface region sampled over a 5-day period for a human volunteer was done. Twenty-three biomarkers were tentatively identified with the aid of a collision cross-section (CCS) prediction tool, seven associated with the ankle skin surface region and 16 closely associated with the wrist skin surface. Ten amino acids were detected and unequivocally identified on the human skin surface for the first time. Furthermore, 22 previously unreported skin surface compounds were tentatively identified on the human skin surface using accurate mass, CCS values and fragmentation patterns. Method limits of detection for the passive skin sampling method ranged from 8.7 (sulfadimethoxine) to 95 ng (taurine). This approach enabled the detection and identification of as-yet unknown human skin surface compounds and provided corresponding CCS values.

Detection of tuberculosis-associated compounds from human skin by GCxGC-TOFMS.

Tuberculosis (TB) remains a global health concern. This study aimed to investigate the potential of human skin volatile organic compounds (VOCs) as prospective biomarkers for TB diagnosis. It employed a non-invasive approach using a wearable silicone rubber band for VOC sampling, comprehensive gas chromatography - time of flight mass spectrometry (GCxGC-TOFMS), and chemometric techniques. Both targeted and untargeted biochemical screening was utilized to explore biochemical differences between healthy individuals and those with TB infection. Results confirmed a correlation between compounds found in this study, and those reported for TB from other biofluids. In a comparison to known TB-associated compounds from other biofluids our analysis established the presence of 27 of these compounds emanating from human skin. Additionally, 16 previously unreported compounds were found as potential biomarkers. The diagnostic ability of the VOCs selected by statistical methods was investigated using predictive modelling techniques. Artificial neural network multi-layered perceptron (ANN) yielded two compounds, 1H-indene, 2,3 dihydro-1,1,3-trimethyl-3-phenyl; and heptane-3-ethyl-2-methyl, as the most discriminatory, and could differentiate between TB-positive (n = 15) and TB-negative (n = 23) individuals with an area under the receiver operating characteristic curve (AUROC) of 92 %, a sensitivity of 100 % and a specificity of 94 % for six targeted features. For untargeted analysis, ANN assigned 3-methylhexane as the most discriminatory between TB-positive and TB- negative individuals. An AUROC of 98.5 %, a sensitivity of 83 %, and a specificity of 88 % were obtained for 16 untargeted features as chosen by high performance variable selection. The obtained values compare highly favourable to alternative diagnostic methods such as breath analysis and GeneXpert. Consequently, human skin VOCs hold considerable potential as a TB diagnostic screening test.

Mass spectral studies on the human skin surface for mosquito vector control applications.

Human skin surface chemical cues comprise a complex mixture of compounds that mosquitoes use to locate and select their human host, based on inter- and intra-human variation in chemical profiles. The complexity of the skin surface matrix calls for advanced analytical techniques to enable separation and identification of biomarkers, which may be used as topical attractants and repellants in future mosquito vector control programmes. The perceived mosquito attractiveness between 20 volunteers and the preference of mosquitoes to bite certain regions, namely, ankle versus wrist, of the human host were investigated in this study, by comparing skin surface chemical profiles. Ion mobility was combined with high resolution mass spectrometry to provide additional confidence in biological marker discovery and identification of human skin surface compounds. This study employed a non-intrusive sampling scheme using a polydimethylsiloxane (PDMS) sampler and solvent desorption analysed with ultra-performance liquid chromatography with ion mobility high-resolution mass spectrometry (UPLC-IMS-HRMS). Statistical approaches guided the identification of 14 biological markers discerning difference in perceived mosquito attractiveness and 20 biomarkers associated with the different skin regions sampled. A broad range (m/z 96.0437 to 788.6095) of chemical compounds was detected from a variety of classes (including sugars, steroids, fatty acids, peptides and peptide derivatives, and compounds of food origin). Ten compounds were unequivocally identified on the human skin surface, and caffeine was reported on the human skin surface for the first time. Furthermore, 77 compounds, of which 64 to the authors' knowledge have not previously been reported, were detected on the human skin surface using accurate mass, collision cross section (CCS) values and fragmentation patterns. This approach enabled comprehensive human skin surface chemical profiling and provides an extensive list of tentatively identified skin surface compounds together with accurate mass values and adducts with their corresponding CCS values.

Non-invasive sorptive extraction for the separation of human skin surface chemicals using comprehensive gas chromatography coupled to time-of-flight mass spectrometry: A mosquito-host biting site investigation.

Variation in inter-human attractiveness to mosquitoes, and the preference of mosquitoes to bite certain regions on the human host, are possible avenues for identifying lead compounds as potential mosquito attractants or repellents. We report a practical, non-invasive method for the separation and detection of skin surface chemical compounds and comparison of skin chemical profiles between the ankle and wrist skin surface area sampled over a 5-day period of a human volunteer using comprehensive gas chromatography coupled to time-of-flight mass spectrometry. An in-house made polydimethylsiloxane passive mini-sampler, worn as an anklet or a bracelet, was used to concentrate skin volatiles and semi-volatiles prior to thermal desorption directly in the gas chromatography. A novel method for the addition of an internal standard to sorptive samplers was introduced through solvent modification. This approach enabled a more reliable comparison of human skin surface chemical profiles. Compounds that were closely associated with the wrist included 6-methyl-1-heptanol, 3-(4-isopropylphenyl)-2-methylpropionaldehyde, 2-phenoxyethyl isobutyrate, and 2,4,6-trimethyl-pyridine. Conversely, compounds only detected on the ankle region included 2-butoxyethanol phosphate, 2-heptanone, and p-menthan-8-ol. In addition to known human skin compounds we report two compounds, carvone and (E)-2-decenal, not previously reported. Limits of detection ranged from 1 pg (carvone) to 362 pg (indole).

Chemical profiling of the human skin surface for malaria vector control via a non-invasive sorptive sampler with GC×GC-TOFMS.

Volatile organic compounds (VOCs) and semi-VOCs detected on the human skin surface are of great interest to researchers in the fields of metabolomics, diagnostics, and skin microbiota and in the study of anthropophilic vector mosquitoes. Mosquitoes use chemical cues to find their host, and humans can be ranked for attractiveness to mosquitoes based on their skin chemical profile. Additionally, mosquitoes show a preference to bite certain regions on the human host. In this study, the chemical differences in the skin surface profiles of 20 human volunteers were compared based on inter-human attractiveness to mosquitoes, as well as inter- and intra-human mosquito biting site preference. A passive, non-invasive approach was followed to sample the wrist and ankle skin surface region. An in-house developed polydimethylsiloxane (PDMS) passive sampler was used to concentrate skin VOCs and semi-VOCs prior to thermal desorption directly in the GC inlet with comprehensive gas chromatography coupled to time-of-flight mass spectrometry (GC×GC-TOFMS). Compounds from a broad range of chemical classes were detected and identified as contributing to the differences in the surface skin chemical profiles. 5-Ethyl-1,2,3,4-tetrahydronaphthalene, 1,1'-oxybisoctane, 2-(dodecyloxy)ethanol, α,α-dimethylbenzene methanol, methyl salicylate, 2,6,10,14-tetramethylhexadecane, 1,2-benzenedicarboxylic acid, bis(2-methylpropyl) ester, 4-methylbenzaldehyde, 2,6-diisopropylnaphthalene, n-hexadecanoic acid, and γ-oxobenzenebutanoic acid ethyl ester were closely associated with individuals who perceived themselves as attractive for mosquitoes. Additionally, biological lead compounds as potential attractants or repellants in vector control strategies were tentatively identified. Results augment current knowledge on human skin chemical profiles and show the potential of using a non-invasive sampling approach to investigate anthropophilic mosquito-host interactions. Graphical abstract.

Short-, medium-, and long-chain chlorinated paraffins in South African indoor dust and cat hair.

Polychlorinated n-alkanes or chlorinated paraffins (CPs) contain a magnitude of structural isomers and are categorized as short-chain (SCCPs), medium-chain (MCCPs), and long-chain (LCCPs) CPs, according to the carbon chain lengths. In this study the Æ©SCCPs, Æ©MCCPs, and Æ©LCCP concentrations are reported for South African indoor dust and pet cat hair. The median concentrations of the Æ©CPs (C9-C37) ranged from 33 to 663 µg/g for freshly collected dust (FD), 36-488 µg/g for dust collected from household vacuum cleaner bags (VD), and 1.2-15 µg/g for cat hair (CH) samples. MCCPs were the dominant CP group, followed by SCCPs and LCCPs. The Æ©MCCP concentration ranged from 13 to 498 µg/g in dust and 0.6-6.5 µg/g in cat hair. SCCPs with shorter carbon chains and lower chlorine substitution were observed in cat hair. LCCPs with carbon chains > C20 were detected in dust and hair samples, possibly indicating the use of wax grade LCCP formulations. Non-traditional Kendrick mass defect plots were used to obtain information on the magnitude of CPs and provide evidence of possible interfering compounds. This is the first report on the occurrence of SCCPs, MCCPs, and LCCPs in the South African indoor environment.

Brominated and organophosphorus flame retardants in South African indoor dust and cat hair.

Flame retardants (FRs), such as brominated flame retardants (BFRs) and organophosphorus flame retardants (OPFRs), are diverse groups of compounds used in various products related to the indoor environment. In this study concentrations of eight polybrominated diphenyl ethers (PBDEs), two alternative BFRs and ten OPFRs were determined in indoor dust (n = 20) and pet cat hair (n = 11) from South Africa. The OPFRs were the major FRs, contributing to more than 97% of the total FR concentration. The median Ʃ10OPFRs concentrations were 44,800 ng/g in freshly collected dust (F-dust), 19,800 ng/g in the dust collected from vacuum cleaner bags (V-dust), and 865 ng/g in cat hair (C-hair). Tris(1-chloro-2-propyl) phosphate (TCIPP) was the dominant OPFR in the dust samples with median concentrations of 7,010 ng/g in F-dust and 3,590 ng/g in V-dust. Tris(2-butoxyethyl) phosphate (TBOEP) was the dominant OPFR in C-hair, with a median concentration of 387 ng/g. The concentrations of Ʃ8PBDEs were higher in F-dust than in V-dust. BDE209 was the dominant BFR in all three matrices. Bis(2-ethylhexyl)-3,4,5,6-tetrabromo-phthalate (BEH-TEBP) and 2-ethylhexyl-2,3,4,5- tetrabromobenzoate (EH-TBB) showed notable contributions to the BFR profile in cat hair. A worst-case dust exposure estimation was performed for all analytes. The estimated TCIPP daily intake through dust ingestion was up to 1,240 ng/kg bw for toddlers. The results indicate that OPFRs are ubiquitous in South African indoor environment. Indoor dust is a major source of human exposure to environmental contaminants. This can for example occur through hand-to-mouth contact of toddlers, and is an important route of exposure to currently used FRs accumulated on dust particles. The presence of FRs, in particular high concentrations of OPFRs, suggests that children and indoor pet cats may have greater exposure to FRs than adults.

Development and optimization of a plunger assisted solvent extraction method for polycyclic aromatic hydrocarbons sampled onto multi-channel silicone rubber traps.

A plunger assisted solvent extraction (PASE) method for multi-channel silicone rubber trap samplers was developed and evaluated as an alternative to direct thermal desorption for the monitoring of polycyclic aromatic hydrocarbons (PAHs). The proposed extraction method was simple, fast (a total of 2 min for extraction), and used a small volume of solvent (a total of 2 mL from two sequential 1 mL extractions). The PASE method presented an advantage over thermal desorption in that samples could be re-analyzed, as only a portion of the extract was injected. Additionally, this approach is cost effective and can be applied in laboratories which do not have thermal desorption systems, hence allowing for the more widespread use of the polydimethylsiloxane samplers which can be employed as denuders in the monitoring of gas and particle partitioning of air pollutants. The method was validated over a wide concentration range (0.005-10 ng µL-1) and the limits of detection ranged from 13.6 ng m-3 for naphthalene to 227.1 ng m-3 for indeno[1,2,3-cd]pyrene. Overall extraction efficiencies of the target PAHs were good (from 76% for naphthalene to 99% for phenanthrene) with relative standard deviations below 6%. The PASE method was successfully applied to the analysis of domestic fire air emission samples taken at 10 and 20 min after ignition, using a sampling flow rate of 500 mL min-1 for 10 min in each case. The samples were found to contain primarily naphthalene (maximum concentration of 9.5 µg m-3, 10 min after ignition), as well as fluorene, anthracene, phenanthrene, fluoranthene and pyrene.

Comprehensive two-dimensional gas chromatography coupled to high resolution time-of-flight mass spectrometry for screening of organohalogenated compounds in cat hair.

The coupling of comprehensive two-dimensional gas chromatography with high-resolution time-of-flight mass spectrometry offers the best separation efficiency combined with accurate mass measurements over a wide mass range. The tremendous power of this screening tool is illustrated by trace qualitative screening analysis of organohalogenated compounds (OHCs) in pet cat hair. Tentative identification was supported by mass spectral database searches and elemental formula prediction from the experimentally determined accurate mass data. This screening approach resulted in the first tentative identification of pentabromoethylbenzene, decabromodiphenyl ethane, hexabromocyclododecane, trisbromoneopentyl alcohol, tris(2-chloroethyl) phosphate and tris(2-chloroisopropyl)phosphate in the South African indoor environment. A total of seventy-two OHCs were identified in the samples and include known flame retardants, such as polybrominated diphenyl ethers, and legacy contaminants such as polychlorinated biphenyls and organochlorine, organophosphorous and pyrethroid pesticides. The results obtained from cat hair indicate that these pets are exposed to complex mixtures of OHCs and the detection of these compounds suggests that non-invasive cat hair samples can be used to model indoor exposure with reference to external deposition of OHCs present in the air and dust surrounding people. Toddlers share the same environment as pet cats and therefore also the same health risks.

Comparison of a disposable sorptive sampler with thermal desorption in a gas chromatographic inlet, or in a dedicated thermal desorber, to conventional stir bar sorptive extraction-thermal desorption for the determination of micropollutants in water.

The presence of micropollutants in the aquatic environment is a worldwide environmental concern. The diversity of micropollutants and the low concentration levels at which they may occur in the aquatic environment have greatly complicated the analysis and detection of these chemicals. Two sorptive extraction samplers and two thermal desorption methods for the detection of micropollutants in water were compared. A low-cost, disposable, in-house made sorptive extraction sampler was compared to SBSE using a commercial Twister sorptive sampler. Both samplers consisted of polydimethylsiloxane (PDMS) as a sorptive medium to concentrate micropollutants. Direct thermal desorption of the disposable samplers in the inlet of a GC was compared to conventional thermal desorption using a commercial thermal desorber system (TDS). Comprehensive gas chromatography coupled to time-of-flight mass spectrometry (GC × GC-TOFMS) was used for compound separation and identification. Ten micropollutants, representing a range of heterogeneous compounds, were selected to evaluate the performance of the methods. The in-house constructed sampler, with its associated benefits of low-cost and disposability, gave results comparable to commercial SBSE. Direct thermal desorption of the disposable sampler in the inlet of a GC eliminated the need for expensive consumable cryogenics and total analysis time was greatly reduced as a lengthy desorption temperature programme was not required. Limits of detection for the methods ranged from 0.0010 ng L-1 to 0.19 ng L-1. For most compounds, the mean (n = 3) recoveries ranged from 85% to 129% and the % relative standard deviation (% RSD) ranged from 1% to 58% with the majority of the analytes having a %RSD of less than 30%.

Preliminary screening of polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCDD) and tetrabromobisphenol A (TBBPA) flame retardants in landfill leachate.

The occurrence of selected brominated flame retardants, including nine polybrominated diphenyl ether (PBDE) congeners, hexabromocyclododecane (HBCDD) and tetrabromobisphenol A (TBBPA) in leachate samples from eight landfill sites in South Africa, were investigated. In addition, the possible influences of dissolved organic carbon on their levels were also evaluated. Filtered leachate samples were subjected to solid-phase extraction to isolate the various target compounds. PBDEs with six bromine substituents and above, as well as α-HBCDD, ß-HBCDD and TBBPA, were generally found below the detection limit. However, the mean value of the total lower PBDE congeners ranged between 0.04 and 0.48 µg L-1, and the concentrations of γ-HBCDD ranged from not detectable (ND) to 0.05 µg L-1. No significant correlation was observed between the target compounds and dissolved organic carbon, although weak to moderate correlations were mostly observed for the lower PBDEs.

Database-driven screening of South African surface water and the targeted detection of pharmaceuticals using liquid chromatography - High resolution mass spectrometry.

Pharmaceuticals and personal care products are released into aquatic environments, largely as a result of ineffectual removal during wastewater treatment. Here we present a screening strategy based on the use of three commercially available mass spectral databases, combined into a single searchable entity and parallelized by cluster computing. In addition to this, a targeted solid phase extraction method with Ultra High Pressure Liquid Chromatography coupled to quadrupole time of flight mass spectrometry (UHPLC-QTOF) was used to quantify 99 pharmaceuticals in South African surface water on a national level. Limits of quantification were in the low ng/L range for the majority of the compounds and it was found that nationally both Lamotrigine and Nevirapine occurred most often. Prednisolone and Ritonavir were present at the highest average concentration; 623 and 489 ng/L respectively. It is however shown that more than 50% of the targets chosen for analysis are not detectable in any of the samples, which highlights the utility of untargeted, database driven screening; prior to the use of costly analytical standards. Untargeted screening detected 45% of the compounds detected in targeted mode, and furthermore tentatively identified a total of 4273 unique compounds across the samples. Automatically triggered MS/MS analyses yielded 92 unique hits with greater than 95% confidence. It is therefore suggested that untargeted screening should precede the targeted approach as a matter of economy and to guide the selection of targets for quantification. There is however great room for improvement in current commercial database search methodologies as a large bottleneck exists due to processing time.

Multi-channel silicone rubber traps as denuders for gas-particle partitioning of aerosols from semi-volatile organic compounds.

During many measurements it is important to account for possible changes in the gas-particle distribution of aerosols containing semi-volatile organic compounds (SVOCs). If denuders are combined with currently used personal air samplers, a simultaneous differential sampling of the gas and particle phase is possible. Here we analysed the transmission efficiency of denuders based on multi-channel silicone rubber traps (setup: 9 cm long glass liner (ID 4 mm), containing 22 parallel silicone rubber tubes (55 mm long, ID 0.3 mm, OD 0.5 mm)) with polystyrene latex (PSL) particles for different scenarios. n-Hexadecane, dimethyl phthalate and diethylene glycol gases were used to measure the time-dependent gas phase collection efficiency of a denuder. Additionally, the evaporation of n-hexadecane aerosol particles passing through the denuders was investigated. Our results showed high transmission efficiencies from 91 to 100% (variation coefficients 3.69-9.65%) for the denuders operated vertically at a flow rate of 0.5 l min-1. With regard to the gas phase collection efficiency, nonpolar n-hexadecane gas was trapped with higher efficiency (87% after 22 h) than dimethyl phthalate gas (27% after 22 h), while for highly polar diethylene glycol the gas phase collection efficiency was 50% after 2 h. Regarding the evaporation of aerosol particles, smaller particles and lower flow rates led to higher particle volume reduction inside the denuders. In conclusion, the tested denuders are suitable for determining the gas-particle partitioning of SVOC aerosols of nonpolar substances and show above 90% transmission for all tested particle sizes.

Determination of endocrine disrupting chemicals and antiretroviral compounds in surface water: A disposable sorptive sampler with comprehensive gas chromatography - Time-of-flight mass spectrometry and large volume injection with ultra-high performance liquid chromatography-tandem mass spectrometry.

Many rural dwellers and inhabitants of informal settlements in South Africa are without access to treated water and collect untreated water from rivers and dams for personal use. Endocrine disrupting chemicals (EDCs) have been detected in surface water and wildlife of South Africa. EDCs are often present in complex environmental matrices at ultra-trace levels complicating detection thereof. We report a simplified multi-residue approach for the detection and quantification of EDCs, emerging EDCs, and antiretroviral drugs in surface water. A low cost (less than one US dollar), disposable, sorptive extraction sampler was prepared in-house. The disposable samplers consisted of polydimethylsiloxane (PDMS) tubing fashioned into a loop which was then placed in water samples to concentrate EDCs and emerging pollutants. The PDMS samplers were thermally desorbed directly in the inlet of a GC, thereby eliminating the need for expensive consumable cryogenics. Comprehensive gas chromatography coupled to time-of-flight mass spectrometry (GC×GC-TOFMS) was used for compound separation and identification. Linear retention indices of EDCs and emerging pollutants were determined on a proprietary Crossbond® phase Rtx®-CLPesticides II GC capillary column. In addition, large volume injection of surface water into an ultra-performance liquid chromatograph tandem mass spectrometer (UPLC-MS/MS) was used as complementary methodology for the detection of less volatile compounds. Large volume injection reduced tedious and costly sample preparation steps. Limits of detection for the GC method ranged from 1 to 98pg/l and for the LC method from 2 to 135ng/l. Known and emerging EDCs such as pharmaceuticals, personal care products and pesticides, as well as the antiretroviral compounds, efavirenz and nevirapine, were detected in surface water from South Africa at concentration levels ranging from 0.16ng/l to 227ng/l.

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.

Polybrominated diphenyl ethers (PBDEs) in eggshells of the Southern Ground-Hornbill (Bucorvus leadbeateri) and Wattled Crane (Bugeranus carunculatus) in South Africa.

This study was undertaken to assess the levels of eight PBDE congeners, namely: PBDE-17, 47, 100, 99, 154, 153, 183 and 209 in eggshells of Southern Ground-Hornbill (SGH) Bucorvus leadbeateri and Wattled Crane (WC) Bugeranus carunculatus obtained from different nesting sites within the eastern savanna of Limpopo Province and the midlands of KwaZulu-Natal, respectively. Analyses were performed using gas chromatography­mass spectrometry employing the electron impact ionization technique. The results obtained indicated that the lower brominated congeners were predominant in both species. The total PBDEs ranged between not detected (ND) to 264 µg g−1 lipid weight and 5.98­7146 µg g−1 lipid weight in the SGH and WC samples, respectively. More so, the mean recoveries of the 13C-labelled surrogate standards ranged between 40% (PBDE-100) and 136% (PBDE-99). The potential hazards to these birds via PBDEs exposure were evaluated by determining the hazard quotients (HQs) by employing the established Lowest Observed Effect Level (LOEL) values associated with impaired pipping and hatching success as well as that associated with impaired reproduction. HQs values varying from 0.58 to 0.94 and 27.71 to 45.27, respectively were obtained for SGH and WC species. This implies that the SGH populations are exposed to low to moderate hazards, while the WC populations are susceptible to high hazards. Considering the potential threats posed by PBDEs, particularly to the WC species, it is likely that exposure to the current environmental levels of PBDEs by these birds may contribute to their reduced breeding success and declining population trends.

Investigating the coffee flavour in South African Pinotage wine using novel offline olfactometry and comprehensive gas chromatography with time of flight mass spectrometry.

Pinotage wine from several South African wine cellars has been produced with a novel coffee flavour. We have investigated this innovative coffee effect using in house developed solventless sampling and fractionating olfactometric techniques, which are unique in their ability to study synergistic aroma effects as opposed to traditional gas chromatography olfactometry (GC-O) which is designed to, ideally, evaluate single eluting compounds in a chromatographic sequence. Sections of the chromatogram, multiple or single peaks, were recaptured on multichannel open tubular silicone rubber (polydimethylsiloxane (PDMS)) traps at the end of a GC column. The recaptured fractions were released in a controlled manner for offline olfactory evaluation, and for qualitative analysis using comprehensive gas chromatography coupled to time of flight mass spectrometry (GC×GC-TOFMS) for compound separation and identification, thus permitting correlation of odour with specific compounds. A combination of furfural and 2-furanmethanol was responsible for a roast coffee bean-like odour in coffee style Pinotage wines. This coffee perception is the result of a synergistic effect in which no individual compound was responsible for the characteristic aroma.

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.

Novel method for determining DDT in vapour and particulate phases within contaminated indoor air in a malaria area of South Africa.

The organochlorine insecticide DDT (1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane) is still used for malaria vector control in certain areas of South Africa. The strict Stockholm Convention on Persistent Organic Pollutants (POPs) allows spraying on the inside of traditional dwellings with DDT. In rural villages contaminated dust presents an additional pathway for exposure to DDT. We present a new method for the determination of DDT in indoor air where separate vapour and particulate samples are collected in a single step with a denuder configuration of a multi-channel open tubular silicone rubber (polydimethylsiloxane (PDMS)) trap combined with a micro quartz fibre filter. The multi-channel PDMS trap section of the denuder concentrates vapour phase insecticide whereas particle associated insecticide is transferred downstream where it is collected on a micro-fibre filter followed by a second multi-channel PDMS trap to capture the blow-off from the filter. The multi-channel PDMS trap and filter combination are designed to fit a commercial thermal desorber for direct introduction of samples into a GC-MS. The technique is solvent-free. Analyte extraction and sample clean-up is not required. Two fractions, vapour phase and particulate phase p,p'-DDT, o,p'-DDT; p,p'-DDD, o,p'-DDD; p,p'-DDE and o,p'-DDE in 4 L contaminated indoor air, were each quantitatively analysed by GC-MS using isotopically labelled ring substituted (13)C(12) -p,p'-DDT as an internal standard. Limits of detection were 0.07-0.35 ng m(-3) for p,p'-DDT, o,p'-DDT, p,p'-DDD, o,p'-DDD, p,p'-DDE and o,p'-DDE. Ratios of airborne p,p'-DDD/p,p'-DDT and of o,p'-DDT/p,p'-DDT are unusual and do not match the ideal certified ingredient composition required of commercial DDT. Results suggest that the DDT products used for indoor residual spraying (IRS) prior to, and during 2007, may have been compromised with regards to insecticidal efficacy, demonstrating the power of this new environmental forensics tool.