Patricia B.C. Forbes

Challenges and advances in quantum dot fluorescent probes to detect reactive oxygen and nitrogen species: a review.

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(-).

Fluorescence detection of pesticides using quantum dot materials – A review

High pesticide use, especially in agriculture, can lead to environmental pollution and potentially adverse health effects. As result, pesticide residues end up in different media, including water and food products, which may serve as direct routes for human exposure. There is thus a continuous drive to develop analytical methods for screening and quantification of these compounds in the different environmental media in which they may occur. Development of quantum dot (QD) based sensors for monitoring pesticides has gained momentum in recent years. QD materials have excellent and unique optical properties and have high fluorescence quantum yields compared to other fluorophores. They have thus been used in numerous studies for the development of probes for organic pollutants. In this paper we specifically review their application as fluorescence probes for pesticide detection in different media including water and in fruits and vegetables. The low detection limits reported demonstrate the potential use of these methods as alternatives to expensive and time-consuming conventional techniques. We also highlight potential limitations that these probes may present when it comes to routine application. Finally we discuss possible future improvements to enhance the selectivity and robustness of these sensors. We note that there is still a need for researchers to develop standardized QD based sensors which could lead to their commercialization and routine application.

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.

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.

l-Cysteine-capped core/shell/shell quantum dot–graphene oxide nanocomposite fluorescence probe for polycyclic aromatic hydrocarbon detection

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.

Monitoring of atmospheric gaseous and particulate polycyclic aromatic hydrocarbons in South African platinum mines utilising portable denuder sampling with analysis by thermal desorption-comprehensive gas chromatography-mass spectrometry

Concentrations of diesel particulate matter and polycyclic aromatic hydrocarbons (PAHs) in platinum mine environments are likely to be higher than in ambient air due to the use of diesel machinery in confined environments. Airborne PAHs may be present in gaseous or particle phases each of which has different human health impacts due to their ultimate fate in the body. Here we report on the simultaneous sampling of both phases of airborne PAHs for the first time in underground platinum mines in South Africa, which was made possible by employing small, portable denuder sampling devices consisting of two polydimethylsiloxane (PDMS) multi-channel traps connected in series separated by a quartz fibre filter, which only require small, battery operated portable personal sampling pumps for air sampling. Thermal desorption coupled with comprehensive gas chromatography-mass spectrometry (TD-GC×GC-TofMS) was used to analyse denuder samples taken in three different platinum mines. The samples from a range of underground environments revealed that PAHs were predominantly found in the gas phase with naphthalene and mono-methylated naphthalene derivatives being detected at the highest concentrations ranging from 0.01 to 18 μg m(-3). The particle bound PAHs were found in the highest concentrations at the idling load haul dump vehicle exhausts with a dominance of fluoranthene and pyrene. Particle associated PAH concentrations ranged from 0.47 to 260 ng m(-3) and included benzo[k]fluoranthene, benzo[a]pyrene, indeno[1,2,3-cd]pyrene and benzo[ghi]perylene. This work highlights the need to characterise both phases in order to assess occupational exposure to PAHs in this challenging sampling environment.

Validation of the AGDISP model for predicting airborne atrazine spray drift: A South African ground application case study

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.

Status of PAHs in Environmental Compartments of South Africa: A Country Report

This article covers the status of PAH concentrations and composition patterns in surface water, air, sediment, and soil samples from South Africa. Despite South Africa being one of the largest economies in Africa, it is only recently that researchers have reported the presence and possible sources of these compounds in various environmental compartments. This article discusses the potential hotspots and possible sources of these compounds. It also compares the total PAH concentrations and percentage composition patterns of the individual PAHs. So far, total concentrations of five PAHs determined in sediment samples from the Johannesburg area, Gauteng Province, gave the highest concentrations ranging from 1233–136,276 μg kg−1. The total concentration of six PAHs found in runoff water from the Venda region of the Limpopo Province, gave the highest concentration with a range of 28.7–3192.6 μg L−1. The decreasing order of percentage composition of PAHs in water samples tended to follow 3-ring > 4-ring > 2-ring PAHs. In soil samples the decreasing order of percentage composition followed 4-ring > 3-ring > 5-ring > 2-ring > 6-ring PAHs. The total freely dissolved PAHs followed solubility of the compounds with 2-ring > 3-ring > 4-ring > 5-ring > 6-ring PAHs. Some of the identified sources of PAHs using molecular ratios include petrogenic emissions such as from petroleum combustion from vehicles and pyrolytic sources such as coal combustion by coal powered power stations, as well as iron and steel production industries. Oil spills were also identified as major PAH contributor in runoff water from the Venda region of the Limpopo Province.

Deposition of CdS, CdS/ZnSe and CdS/ZnSe/ZnS shells around CdSeTe alloyed core quantum dots: effects on optical properties

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.

Particle emissions from household fires in South Africa

The effects of airborne particles on the atmosphere, climate and public health are among the central topics in current environmental research. South Africa is a developing country, therefore not all households have access to electricity. In municipalities in the province of the Eastern Cape, for example, electricity usage for cooking ranges from 95.5% of households to only 8.1%. The households which do not utilise electricity make use of other resources to meet their needs in terms of energy provision for lighting, cooking and heating, including charcoal and wood burning in braziers. This paper investigates the particle emissions from household fires prepared using two methods, with reference to potential human health effects. Particles were sampled onto quartz fibre filters, which were analysed by scanning electron microscopy and GCxGC-MS. Particulate matter collected near the traditional fire contained higher concentrations of adsorbed organic compounds, including polycyclic aromatic hydrocarbons, which are of concern due to their potential human health effects. Changes in combustion conditions had a marked effect on the organic and particulate emissions. An integrated approach to reduce potential exposure from household fires should be explored, including energy efficient housing design; the provision of cost effective, energy efficient combustion appliances; as well as appropriate community education campaigns.