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Biomass burning is a significant anthropogenic source of air pollution, including the preharvest burning of sugar cane. These burn events result in atmospheric emissions, including semivolatile organic compounds, that may have adverse impacts on air quality and human health on a local, regional, and even a global scale. Gaseous and particulate polycyclic aromatic hydrocarbon (PAH) emissions from various sugar cane burn events in the province of Kwa‐Zulu Natal in South Africa were simultaneously sampled using a portable denuder sampling technology, consisting of a quartz fiber filter sandwiched between two polydimethylsiloxane multichannel traps. Total gas and particle phase PAH concentrations ranged from 0.05 to 9.85 µg m–3 per individual burn event, and nine PAHs were quantified. Over 85% of all PAHs were found to exist in the gas phase, with smaller two‐ and three‐ring PAHs, primarily naphthalene, 1‐methyl naphthalene, and acenaphthylene, being the most dominant and causing the majority of variance between the burn sites. The PAH profiles differed between the different burn events at different sites, emphasizing the significant influence that the crop variety, prevailing weather conditions, and geographical location has on the type and number of pollutants emitted. The potential carcinogenicity of the PAH exposure was estimated based on toxic equivalency factors that showed varying risk potentials per burn event, with the highest value of 5.97 ng m–3. Environ Toxicol Chem 2023;42:778–792. © 2023 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC. [ABSTRACT FROM AUTHOR]

The development of amine‐functionalized graphene quantum dots (GQDs) linked to mycolic acids (MAs) as a potential fluorescent biosensor to detect tuberculosis (TB) biomarkers is described. GQDs have attractive properties: high fluorescence, excellent biocompatibility, good water solubility, and low toxicity. MAs are lipids that are found in the cell wall of Mycobacterium tuberculosis that are antigenic, however, they are soluble only in chloroform and hexane. Chloroform‐soluble MAs were covalently linked to synthesized water‐soluble GQDs using an amide connection to create a potential fluorescent water‐soluble TB biosensor: MA‐GQDs. Fluorescence results showed that GQDs had a narrow emission spectrum with the highest emission at 440 nm, while MA‐GQDs had a broader spectrum with the highest emission at 470 nm, after exciting at 360 nm. The appearance of the peptide bond (amide linkage) in the Fourier‐transform infrared spectrum of MA‐GQDs confirmed the successful linking of MAs to GQDs. Powder X‐ray diffraction exhibited an increase in the number of peaks for MA‐GQDs relative to GQDs, suggesting that linking MAs to GQDs changed the crystal structure thereof. The linked MA‐GQDs showed good solubility in water, high fluorescence, and visual flow through a nitrocellulose membrane. These properties are promising for biomedical fluorescence sensing applications. [ABSTRACT FROM AUTHOR]

This work explores the potential use of cadmium‐based quantum dots (QDs) coupled to mycolic acids (MAs) as a fluorescent probe to detect anti‐MA antibodies which are biomarkers for tuberculosis (TB). The use of free MAs as antigens for the serodiagnosis of TB is known but has not been developed into a point of care test. This study focuses on the synthesis, solubility, and lateral flow of QDs coupled to MAs. Water‐soluble CdSe/ZnS QDs capped with l‐cysteine were synthesised and covalently coupled to MAs via amide linkages to form a water‐soluble fluorescent probe: MA‐CdSe/ZnS QDs. The MA‐CdSe/ZnS QDs showed broad absorption bands and coupling, confirmed by the presence of amide bonds in the Fourier‐transform infrared (FTIR) spectrum, resulting in a blue shift in fluorescence. Powder X‐ray diffraction (XRD) revealed a shift and increase in the number of peaks for MA‐CdSe/ZnS QDs relative to the L‐cys‐CdSe/ZnS QDs, suggesting that coupling changed the crystal structure. The average particle size of MA‐CdSe/ZnS QDs was ~3.0 nm. Visual paper‐based lateral flow of MA‐CdSe/ZnS QDs was achieved on strips of nitrocellulose membrane with both water and membrane blocking solution eluents. The highly fluorescent MA‐CdSe/ZnS QDs showed good water solubility and lateral flow, which are important properties for fluorescence sensing applications. [ABSTRACT FROM AUTHOR]

In the last two decades, environmental experts have focused on the development of several biological, chemical, physical, and thermal methods/technologies for remediation of PAH‐polluted water. Some of the findings have been applied to field‐scale treatment, while others have remained as prototypes and semi‐pilot studies. Existing treatment options include extraction, chemical oxidation, bioremediation, photocatalytic degradation, and adsorption (employing adsorbents such as biomass derivatives, geosorbents, zeolites, mesoporous silica, polymers, nanocomposites, and graphene‐based materials). Electrokinetic remediation, advanced phytoremediation, green nanoremediation, enhanced remediation using biocatalysts, and integrated approaches are still at the developmental stage and hold great potential. Water is an essential component of the ecosystem and highly susceptible to PAH contamination due to crude oil exploration and spillage, and improper municipal and industrial waste management, yet comprehensive reviews on PAH remediation are only available for contaminated soils, despite the several treatment methods developed for the remediation of PAH‐polluted water. This review seeks to provide a comprehensive overview of existing and emerging methods/technologies, in order to bridge information gaps toward ensuring a green and sustainable remedial approach for PAH‐contaminated aqueous systems. Practitioner points: Comprehensive review of existing and emerging technologies for remediation of PAH‐polluted water.Factors influencing efficiency of various methods, challenges and merits were discussed.Green nano‐adsorbents, nano‐oxidants and bio/phytoremediation are desirous for ecofriendly and economical PAH remediation.Adoption of an integrated approach for the efficient and sustainable remediation of PAH‐contaminated water is recommended. [ABSTRACT FROM AUTHOR]

Semi-volatile organic compounds (SVOCs), partitioned between particulates and vapours of an aerosol, require special attention. The toxicological effects caused by the inhalation of such aerosols may depend on the concentration and in which phase the organic compounds are found. A personal denuder-gas–particle separation aerosol sampler was developed to provide information about the partitioning of aerosols from organic compounds. The sampler was tested in a series of controlled laboratory experiments, which confirmed the capability and accuracy of the sampler to measure gas–particle mixtures. An average difference of 14.8 ± 4.8% was found between sampler and reference laboratory instruments. The obtained results showed that our sampler enables a more accurate measurement of the SVOC aerosols' gas–particle fractionation, compared with that of conventional samplers. [ABSTRACT FROM AUTHOR]

Unbanded crocodilian eggs do not form an opaque band around their lesser circumference, indicating fertilization failure or early embryonic death. Assuming they represent fertile eggs prior to the onset of embryonic metabolism, the concentration and content of calcium (Ca) and phosphorus (P) in each component (shell, shell membrane, yolk and albumen) of unbanded farm‐laid Nile crocodile (Crocodylus niloticus) eggs were described. The grouping effect of clutch (clutch effect) on each component's Ca and P concentration and content were assessed. Using regression models, the clutch size, clutch laying date, pond of origin, component mass and component Ca and P concentration were evaluated for an effect on each component's Ca and P content. Eggshell made by far the greatest contribution to total egg Ca whilst contributing no measurable P. Yolk contributed by far the greatest quantity of P and a significant quantity of Ca. Albumen contributed variable, but generally very low quantities of Ca and P to the egg. A strong clutch effect existed for shell Ca content and yolk Ca and P concentration and content. A very weak clutch effect existed for shell Ca concentration, and albumen Ca and P concentration. Shell membrane was an unreliable sample type in this study, likely reflecting issues with processing. Shell Ca and yolk Ca and P content were influenced primarily by component mass, and secondarily by element concentration. Albumen Ca and P content was principally influenced by element concentration. These descriptive findings will guide sample selection for future research. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

In this work, we synthesized water-soluble L-cysteine-capped alloyed CdSeTe core quantum dots (QDs) and investigated the structural and optical properties of deposition of each of CdS, CdS/ZnSe and CdS/ZnSe/ZnS shell layers. Photophysical results showed that the overcoating of a CdS shell around the alloyed CdSeTe core [quantum yield (QY) = 8.4%] resulted in effective confinement of the radiative exciton with an improved QY value of 93.5%. Subsequent deposition of a ZnSe shell around the CdSeTe/CdS surface decreased the QY value to 24.7%, but an increase in the QY value of up to 49.5% was observed when a ZnS shell was overcoated around the CdSeTe/CdS/ZnSe surface. QDs with shell layers showed improved stability relative to the core. Data obtained from time-resolved fluorescence measurements provided useful insight into variations in the photophysical properties of the QDs upon the formation of each shell layer. Our study suggests that the formation of CdSeTe/CdS core/shell QDs meets the requirements of quality QDs in terms of high photoluminescence QY and stability, hence further deposition of additional shells are not necessary in improving the optical properties of the core/shell QDs. Copyright © 2015 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

Despite extensive electrification of low-income residential areas on the South African Highveld, extensive use is still made of wood and coal as domestic fuels, particularly for winter space heating. In informal settlements characterised by poverty and lacking electrification, coal is combusted in non-standardised, inefficient and polluting metal braziers, colloquially known as imbaulas. Copious emissions from domestic coal fires result in elevated household and ambient air pollution levels well above national air quality limits. Despite the severity of this pollution as a public health issue, emissions data from residential coal-burning braziers are still scarce. Consequently, there is a need to evaluate the emission characteristics of these devices. In this paper, we report on controlled combustion experiments carried out to investigate systematically influences of fire-ignition methods and stove ventilation rates on gaseous and condensed matter (smoke) emissions from informal residential coal combustion braziers. Two methods of stove ignition--conventional bottom-lit updraft (BLUD) and the top-lit updraft (TLUD) (colloquially known as the Basa njengo Magogo) were investigated. Emission factors (EFs) were found to be dependent on fire ignition method and stove ventilation rates. The top-lit ignition method reduces PM10/PM2.5 by 76% to 80% compared to the BLUD method. Carbon monoxide emissions do not change significantly with the ignition method. Pollutant emissions from normal combustion in high ventilation conditions were low compared to pollutants emitted when an oxygen deficient atmosphere was created under low ventilation conditions. High stove ventilation rates resulted in a 50% reduction in PM10/PM2.5 emissions compared to the low ventilation rates. Emissions of gaseous and particulate matter from incomplete combustion can be minimised by design optimisation of the braziers. Ideally, the emissions of condensed matter particles (which form the bulk of emitted particles in residential coal fires) can be reduced through good mixing of emitted gases and air, and by ensuring a long residence time in the high temperature oxygen rich post combustion zone, to allow for complete oxidation. This study is significant in that it presents the first systematic and comprehensive study of factors affecting emissions from coal braziers. [ABSTRACT FROM AUTHOR]

Students often regard laboratory instruments as 'black boxes' which generate results, without understanding their principles of operation. This lack of understanding is a concern because the correct interpretation of analytical results and the limitations thereof is invariably based on an understanding of the mechanism of measurement. Moreover, a number of tertiary institutions in Africa have very limited resources and access to laboratory equipment, including that related to the field of photonics, which prevents students from acquiring hands-on practical experience. We address both of these challenges by describing how students can assemble a novel, low-cost spectrophotometer, called the SpecUP, which can then be used in a range of experiments. The same kind of information can be generated as that obtained with costly commercial spectrophotometers (albeit of a lower quality). With the SpecUP, students also have the opportunity to vary instrumental parameters and to observe the effects these changes have on their experimental results, allowing for enquiry-based learning of spectroscopic principles. The results obtained for some chemistry-related spectrophotometric experiments are described for each of the two operational modes of the SpecUP, although the instrument can be applied in fields ranging from physics to biochemistry. [ABSTRACT FROM AUTHOR]

Parmotrema austrosinense (Zahlbr.) Hale lichens were collected from the Pretoria central business district (CBD), as well as three sites to the east of Pretoria; the National Botanical Gardens, the CSIR campus and the suburb of Lynnwood, with the aim of utilising these lichens as biomonitors of air quality to determine the effects of the phasing out of leaded petrol and the simultaneous introduction of manganese anti-knock additives to fuel in South Africa. In addition to lichens, roadside dust and soil samples were collected from the CBD and CSIR campus, and all samples were analysed by flame atomic absorption spectrometry after acid digestion. There was no significant difference (95 % confidence) between the Mn content of lichens from all sampling sites (overall average of 97.1 ± 39.1 μg·g-1, n= 28), which was most likely due to an even suspension of Mn-containing particles arising from soil dust. Additional contributions to Mn loading as a result of vehicle emissions were currently not evident. For all non-CBD sites, higher Pb levels were found in lichens which were nearer to busy roads, suggesting an historical impact by vehicular emissions of Pb arising from leaded petrol usage. The Pb concentrations in lichens found in the CBD (average of 181.1 ± 98.0 μg·g-1, n=10) were significantly higher (95 % confidence limits) than those of lichens growing outside of the CBD area (average of 41.5 ± 36.4 μg·g-1, n=118), and the Pb levels were higher than those of Mn, which was contrary to that found in sites outside the CBD. [ABSTRACT FROM AUTHOR]

We present experimental results of emission factors from a suite of domestic coal-burning braziers (lab fabricated and field collected) that span the possible range of real-world uses in the Highveld region of South Africa. The conventional bottom-lit updraft (BLUD) method and the top-lit updraft (TLUD) method were evaluated using coal particle sizes between 20 mm and 40 mm. Emission factors of CO2, CO and NOx were in the range of 98-102 g/MJ, 4.1-6.4 g/MJ and 75-195 mg/MJ, respectively. Particulate matter (PM2.5 and PM10) emissions were in the range 1.3-3.3 g/MJ for the BLUD method and 0.2-0.7 g/MJ for the TLUD method, for both field and lab-designed stoves. When employing the TLUD method, emission factors of PM2.5/PM10 reduced by up to 80% compared with those when using the BLUD method. Results showed the influence of ventilation rates on emission factors, which reduced by ~50% from low to high ventilation rates. For energy-specific emission rates, the combined (3-h) PM10 emission rates were in the range of 0.0028-0.0120 g/s, while the combined average CO emission rates were in the range of 0.20-0.26 g/s, with CO2 emission rates in the range of 0.54-0.64 g/s. The reported emission factors from coal braziers provide the first comprehensive, systematic set of emission factors for this source category, and fill a major gap in previous efforts to conduct dispersion modelling of South African Highveld air quality. [ABSTRACT FROM AUTHOR]

Multi-channel polydimethylsiloxane rubber traps were used to sample the headspace of rosemary samples (two essential oils from different sources, one oleoresin and one dried herb) followed by comprehensive two-dimensional gas chromatography - time of flight mass spectrometry (GCxGC-TOFMS) orGC-MS analyses.The aroma of different headspace samples was characterized using a custom-built olfactory apparatus. The differences between the aroma profileswere evident from bubble plots of the perceived aroma at different temperatures. The samples were heat-treated to simulate cooking of food products, and were then reassessed to determine any changes in the aroma profile. It was found that the intense menthol and cooling aromas subsided in all the samples with heating. GCxGC-TOFMS allowed for separation of the numerous components in the headspace samples. Many terpenes and aliphatics were thus tentatively identified and the relative peak areas were compared to better understand the mixture that contributes to the rosemary aroma. [ABSTRACT FROM AUTHOR]

Polycyclic aromatic hydrocarbons (PAHs) are a group of emerging chemical pollutants that pose severe health challenges and toxicity to people and aquatic organisms exposed to these pollutants. This study sought to assess the types and levels of PAHs and their eco-toxicity indices in surface waters of Narok and Bomet counties of Kenya, which have witnessed an increase in charcoal-burning activities and vehicular emissions near water bodies. Sampling was done in eight regions of the two counties based on their proximity to PAH sources. Extraction of the water samples was done via a solid-phase mmethod. Seven US Environmental Protection Agency (US EPA) priority PAHs were detected. The concentrations of these PAHs varied from below the limits of detection up to 31.42 µg l -1 for dibenzo[ a,h ]anthracene. The majority of the PAHs from Narok County were pyrogenic, while those from Bomet were petrogenic based on PAH diagnostic ratios. The surface waters were significantly polluted with dibenzo[ a,h ]anthracene, with risk quotients above 1.0 in the surface waters, and were found to be hazardous, with hazard quotients above 10.0, thus indicating potential environmental risks. The findings indicate the need for stringent measures to be put in place to mitigate the risks posed by these PAHs., Competing Interests: We declare we have no competing interests., (© 2024 The Author(s).)

The development of amine-functionalized graphene quantum dots (GQDs) linked to mycolic acids (MAs) as a potential fluorescent biosensor to detect tuberculosis (TB) biomarkers is described. GQDs have attractive properties: high fluorescence, excellent biocompatibility, good water solubility, and low toxicity. MAs are lipids that are found in the cell wall of Mycobacterium tuberculosis that are antigenic, however, they are soluble only in chloroform and hexane. Chloroform-soluble MAs were covalently linked to synthesized water-soluble GQDs using an amide connection to create a potential fluorescent water-soluble TB biosensor: MA-GQDs. Fluorescence results showed that GQDs had a narrow emission spectrum with the highest emission at 440 nm, while MA-GQDs had a broader spectrum with the highest emission at 470 nm, after exciting at 360 nm. The appearance of the peptide bond (amide linkage) in the Fourier-transform infrared spectrum of MA-GQDs confirmed the successful linking of MAs to GQDs. Powder X-ray diffraction exhibited an increase in the number of peaks for MA-GQDs relative to GQDs, suggesting that linking MAs to GQDs changed the crystal structure thereof. The linked MA-GQDs showed good solubility in water, high fluorescence, and visual flow through a nitrocellulose membrane. These properties are promising for biomedical fluorescence sensing applications., (© 2022 John Wiley & Sons Ltd.)

The United States Environmental Protection Agency categorized polycyclic aromatic hydrocarbons (PAHs) as hazardous to humans upon acute and/or chronic exposure. This study investigated the simultaneous adsorption of several PAHs onto graphene wool (GW), thereby providing holistic insights into the competitive adsorption of PAHs onto graphene-based materials. SEM, TEM and FTIR provided evidence for the adsorption of PAHs and successful regeneration of the adsorbent accompanied by distinct morphological changes. Isotherm experiments revealed that adsorption of PAHs was significantly influenced by hydrophobic interactions between the sorbate and hydrophobic surface of GW. The Freundlich multilayer isotherm model best fit the experimental data obtained for both multi-component PAH and single-solute experiments as indicated by the Error Sum of Squares (SSE) obtained from nonlinear regression analysis. Experiments revealed that competitive adsorption had a limiting effect on the overall adsorption capacity as q max and K d were higher in single-solute than multi-component PAH experiments. The results suggest that partition distribution coefficients ( K d ) between the solid-liquid interphase played a significant role in the overall adsorption and a positive correlation between K d and Log K ow of PAHs was established in single-solute experiments. Sorption-desorption experiments revealed that PAHs were adsorbed with a maximum removal efficiency of 100% at an optimum GW dosage of 2 g/L. Adsorption thermodynamics revealed that PAH adsorption onto GW is spontaneous and endothermic. The adsorbent was regenerated and reused for up to six times and its efficiency remained fairly constant.

The sources, ecotoxicological impact, and potential remediation strategies of antiretroviral drugs (ARVDs) as emerging contaminants in surface waters are reviewed based on recent literature. The occurrence of ARVDs in water bodies raises concern because many communities in Africa depend on rivers for water resources. Southern Africa is a potential hotspot regarding ARVD contamination due to relatively high therapeutic application and detection thereof in water bodies. Efavirenz and nevirapine are the most persistent in effluents and are prevalent in surface water based on environmental concentrations. Whereas the highest concentration of efavirenz reported in Kenya was 12.4 µg L -1 , concentrations as high as 119 and 140 µg L -1 have been reported in Zambia and South Africa, respectively. Concentrations of ARVDs ranging from 670 to 34 000 ng L -1 (influents) and 540 to 34 000 ng L -1 (effluents) were determined in wastewater treatment plants in South Africa, compared with Europe, where reported concentrations range from less than limit of detection (LOD) to 32 ng L -1 (influents) and less than LOD to 22 ng L -1 (effluents). The present African-based review suggests the need for comprehensive toxicological and risk assessment of these emerging pollutants in Africa, with the intent of averting environmental hazards and the development of sustainable remediation strategies. Environ Toxicol Chem 2022;41:247-262. © 2021 SETAC., (© 2021 SETAC.)

This work explores the potential use of cadmium-based quantum dots (QDs) coupled to mycolic acids (MAs) as a fluorescent probe to detect anti-MA antibodies which are biomarkers for tuberculosis (TB). The use of free MAs as antigens for the serodiagnosis of TB is known but has not been developed into a point of care test. This study focuses on the synthesis, solubility, and lateral flow of QDs coupled to MAs. Water-soluble CdSe/ZnS QDs capped with l-cysteine were synthesised and covalently coupled to MAs via amide linkages to form a water-soluble fluorescent probe: MA-CdSe/ZnS QDs. The MA-CdSe/ZnS QDs showed broad absorption bands and coupling, confirmed by the presence of amide bonds in the Fourier-transform infrared (FTIR) spectrum, resulting in a blue shift in fluorescence. Powder X-ray diffraction (XRD) revealed a shift and increase in the number of peaks for MA-CdSe/ZnS QDs relative to the L-cys-CdSe/ZnS QDs, suggesting that coupling changed the crystal structure. The average particle size of MA-CdSe/ZnS QDs was ~3.0 nm. Visual paper-based lateral flow of MA-CdSe/ZnS QDs was achieved on strips of nitrocellulose membrane with both water and membrane blocking solution eluents. The highly fluorescent MA-CdSe/ZnS QDs showed good water solubility and lateral flow, which are important properties for fluorescence sensing applications., (© 2021 John Wiley & Sons Ltd.)

Procedures for the design of a fluorescence sensor based on molecularly imprinted polymer-capped quantum dots (MIP@QDs) together with the synthesis of quantum dots and MIP@QDS are described. Spherical and monodispersed nanoparticles are suitable for fluorescence sensing of an analyte such as pharmaceuticals and polycyclic aromatic hydrocarbons (PAHs). In addition, excellent optical properties, higher quantum yield, and photoluminescence efficiency as well as easy detection of emission spectra are distinctive advantages of quantum dots as fluorescence sensors. Optimization of different variables and analytical applications of the sensor are also presented, which are of value for fluorescence sensing., (© 2021. The Author(s), under exclusive license to Springer Science+Business Media, LLC, part of Springer Nature.)

In developing countries, household energy use is highly variable and complex, yet emissions arising from fuel combustion indoors are typically poorly quantified. Polycyclic aromatic hydrocarbons (PAHs) are emitted during the combustion of organic fuels such as charcoal and biomass. In the present study, multichannel polydimethylsiloxane rubber traps were used for gas-phase PAH sampling and extracted using a low-solvent volume plunger-assisted solvent extraction method. Sixteen US Environmental Protection Agency priority PAHs, primarily in the gas phase, were investigated in indoor air of rural and urban residential homes in coastal Kenya (Mombasa and Taita Taveta Counties) using typical combustion devices of each area. Average gaseous PAH concentrations per household were higher in rural (ranging 0.81-6.09 µg m -3 ) compared to urban (ranging 0-2.59 µg m -3 ) homes, although ambient PAH concentrations were higher in urban environments, likely attributable to traffic contributions. The impact of fuel choice and thereby combustion device on PAH emissions was very clear, with the highest concentrations of PAHs quantified from wood-burning emissions from 3-stone stoves (total PAH averages 46.23 ± 3.24 µg m -3 [n = 6]). Average benzo[a]pyrene equivalent total concentrations were evaluated for the priority PAHs and ranged from not detected to 43.31, 88.38, 309.61, and 453.88 ng m -3 for gas, kerosene, jiko, 3-stone, and improved 3-stone stoves, respectively. Environ Toxicol Chem 2020;39:538-547. © 2019 SETAC., (© 2019 SETAC.)

A novel graphene wool (GW) material was used as adsorbent for the removal of phenanthrene (PHEN) and pyrene (PYR) from aqueous solution. Adsorption kinetics, adsorption isotherms, thermodynamics of adsorption and effect of pH, ionic strength, and temperature on the adsorption of PHEN and PYR onto GW were comprehensively investigated. Isothermal and kinetic experimental data were fitted to Langmuir, Freundlich, Temkin, Sips and Dubinin-Radushkevich models, as well as pseudo-first-order and pseudo-second-order kinetic models. The adsorption kinetic data best fit the pseudo-second-order kinetic model for PHEN and PYR sorption with R 2 value >0.999, whilst the Sips model best fit isotherm data. Kinetic data revealed that 24 hr of contact between adsorbent and polycyclic aromatic hydrocarbons (PAHs) was sufficient for maximum adsorption, where the Langmuir maximum adsorption capacity of GW for PHEN and PYR was 5 and 20 mg g -1 and the optimum removal efficiency was 99.9% and 99.1%, respectively. Thermodynamic experiments revealed that adsorption processes were endothermic and spontaneous. Desorption experiments indicated that irreversible sorption occurred with a hysteresis index greater that zero for both PAHs. The high adsorption capacity and potential reusability of GW makes it a very attractive material for removal of hydrophobic organic micro-pollutants from water.

Atrazine is a common agricultural pesticide which has been reported to occur widely in surface drinking water, making it an environmental pollutant of concern. In the quest for developing sensitive detection methods for pesticides, the use of quantum dots (QDs) as sensitive fluorescence probes has gained momentum in recent years. QDs have attractive and unique optical properties whilst coupling of QDs to molecularly imprinted polymers (MIPs) has been shown to offer excellent selectivity. Thus, the development of QD@MIPs based fluorescence sensors could provide an alternative for monitoring herbicides like atrazine in water. In this work, highly fluorescent CdSeTe/ZnS QDs were fabricated using the conventional organometallic synthesis approach and were then encapsulated with MIPs. The CdSeTe/ZnS@MIP sensor was characterized and applied for selective detection of atrazine. The sensor showed a fast response time (5 min) upon interaction with atrazine and the fluorescence intensity was linearly quenched within the 2-20 mol L -1 atrazine range. The detection limit of 0.80 × 10 -7  mol L -1 is comparable to reported environmental levels. Lastly, the sensor was applied in real water samples and showed satisfactory recoveries (92-118%) in spiked samples, hence it is a promising candidate for use in water monitoring., (© 2019 John Wiley & Sons, Ltd.)

Triclosan (TCS) is a common antimicrobial found in many personal care products. A large amount of TCS thus enters the wastewater system leading to the accumulation thereof in water sources. In this work, core-shell structured GSH-CdSe/ZnS fluorescent quantum dots (QDs) were synthesized based on organometallic synthesis with a thiol ligand capping agent. The GSH-CdSe/ZnS QDs showed excellent photostability and a photoluminescence quantum yield of 89%. The fluorescence of the GSH-CdSe/ZnS QDs was enhanced by the introduction of TCS, likely owing to fluorescence resonance energy transfer from TCS to the QDs, allowing for its use as a "turn on" fluorescence probe for the detection and determination of TCS. A linear response was observed in the range of 10-300 nmol L -1 with limits of detection and quantification of 3.7 and 12.4 nmol L -1 respectively. The probe displayed good recoveries (94%-117.5%) for the determination of TCS in tap and river water samples which demonstrated the suitability of this novel sensor for a monitoring application of environmental relevance., (Copyright © 2018 Elsevier B.V. All rights reserved.)

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., (Copyright © 2018 Elsevier B.V. All rights reserved.)

In this work, we synthesized water-soluble L-cysteine-capped alloyed CdSeTe core quantum dots (QDs) and investigated the structural and optical properties of deposition of each of CdS, CdS/ZnSe and CdS/ZnSe/ZnS shell layers. Photophysical results showed that the overcoating of a CdS shell around the alloyed CdSeTe core [quantum yield (QY) = 8.4%] resulted in effective confinement of the radiative exciton with an improved QY value of 93.5%. Subsequent deposition of a ZnSe shell around the CdSeTe/CdS surface decreased the QY value to 24.7%, but an increase in the QY value of up to 49.5% was observed when a ZnS shell was overcoated around the CdSeTe/CdS/ZnSe surface. QDs with shell layers showed improved stability relative to the core. Data obtained from time-resolved fluorescence measurements provided useful insight into variations in the photophysical properties of the QDs upon the formation of each shell layer. Our study suggests that the formation of CdSeTe/CdS core/shell QDs meets the requirements of quality QDs in terms of high photoluminescence QY and stability, hence further deposition of additional shells are not necessary in improving the optical properties of the core/shell QDs., (Copyright © 2015 John Wiley & Sons, Ltd.)

Environmental pollutants, such as the polycyclic aromatic hydrocarbons (PAHs), become widely distributed in the environment after emission from a range of sources, and they have potential biological effects, including toxicity and carcinogenity. In this work, we have demonstrated the analytical potential of a covalently linked L-cysteine-capped CdSeTe/ZnSe/ZnS core/shell/shell quantum dot (QD)-graphene oxide (GO) nanocomposite fluorescence probe to detect PAH compounds in aqueous solution. Water-soluble L-cysteine-capped CdSeTe/ZnSe/ZnS QDs were synthesized for the first time and were covalently bonded to GO. The fluorescence of the QD-GO nanocomposite was enhanced relative to the unconjugated QDs. Various techniques including TEM, SEM, HRSEM, XRD, Raman, FT-IR, UV/vis and fluorescence spectrophotometry were employed to characterize both the QDs and the QD-GO nanocomposite. Four commonly found priority PAH analytes namely; phenanthrene (Phe), anthracene (Ant), pyrene (Py) and naphthalene (Naph), were tested and it was found that each of the PAH analytes enhanced the fluorescence of the QD-GO probe. Phe was selected for further studies as the PL enhancement was significantly greater for this PAH. A limit of detection (LOD) of 0.19 µg/L was obtained for Phe under optimum conditions, whilst the LOD of Ant, Py and Naph were estimated to be ~0.26 µg/L. The fluorescence detection mechanism is proposed., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Air dispersion software models for evaluating pesticide spray drift during application have been developed that can potentially serve as a cheaper convenient alternative to field monitoring campaigns. Such models require validation against field monitoring data in order for them to be employed with confidence, especially when they are used to implement regulatory measures or to evaluate potential human exposure levels. In this case study, off-target pesticide drift was monitored during ground application of a pesticide mixture to a sorghum field in South Africa. Atrazine was used as a drift tracer. High volume air sampling onto polyurethane foam (PUF) was conducted at six downwind locations and at four heights at each sampling point. Additional data, including meteorological information, required to simulate the spray drift with the AGDISP® air dispersion model was collected. The PUF plugs were extracted by a plunger method utilizing a hexane:acetone mixture with analysis by GC-NPD (94.5% recovery, 3.3% RSD, and LOD 8.7 pg). Atrazine concentrations ranged from 4.55 ng L(-1) adjacent to the field to 186 pg L(-1) at 400 m downwind. These results compared favourably with modeled output data, resulting in the validation of the model up to 400 m from the application site for the first time. Sensitivity studies showed the importance of droplet size distribution on spray drift, which highlighted the need for good nozzle maintenance. Results of this case study indicate that the model may provide meaningful input into environmental and human health risk assessment studies in South Africa and other developing countries., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

The pathological and physiological effects of reactive oxygen and nitrogen species (ROS/RNS) have instigated increasing awareness in the scientific field with respect to the development of suitable probes for their detection. Among the various probes developed to date, semiconductor quantum dots (QDs) fluorescent probes have attracted significant attention. The unfavourable properties of ROS/RNS with respect to their detection, such as their short lifetimes and the competitive presence of various endogenous reactive species, capable of interfering with the probe in biological matrices, have hindered the effective performance of most probes as well as complicating the design of suitable probes. The development of novel QD fluorescent probes capable of circumventing these problems is thus, of scientific interest. In this review, we highlight the challenges faced, pros and cons and published developments to date, with respect to QD fluorescent probes for ROS/RNS such as H2O2, O2(·-), ·OH, HOCl, NO and ONOO(-)., (Copyright © 2014 Elsevier B.V. All rights reserved.)

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 chromatography–mass 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 5.98–7146 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.

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., (Copyright © 2011 Elsevier B.V. All rights reserved.)

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.