Atomic/molecular layer deposition strategies for enhanced CO2 capture, utilisation and storage materials.

Elevated levels of carbon dioxide (CO2) in the atmosphere and the diminishing reserves of fossil fuels have raised profound concerns regarding the resulting consequences of global climate change and the future supply of energy. Hence, the reduction and transformation of CO2 not only mitigates environmental pollution but also generates value-added chemicals, providing a dual remedy to address both energy and environmental challenges. Despite notable advancements, the low conversion efficiency of CO2 remains a major obstacle, largely attributed to its inert chemical nature. It is imperative to engineer catalysts/materials that exhibit high conversion efficiency, selectivity, and stability for CO2 transformation. With unparalleled precision at the atomic level, atomic layer deposition (ALD) and molecular layer deposition (MLD) methods utilize various strategies, including ultrathin modification, overcoating, interlayer coating, area-selective deposition, template-assisted deposition, and sacrificial-layer-assisted deposition, to synthesize numerous novel metal-based materials with diverse structures. These materials, functioning as active materials, passive materials or modifiers, have contributed to the enhancement of catalytic activity, selectivity, and stability, effectively addressing the challenges linked to CO2 transformation. Herein, this review focuses on ALD and MLD's role in fabricating materials for electro-, photo-, photoelectro-, and thermal catalytic CO2 reduction, CO2 capture and separation, and electrochemical CO2 sensing. Significant emphasis is dedicated to the ALD and MLD designed materials, their crucial role in enhancing performance, and exploring the relationship between their structures and catalytic activities for CO2 transformation. Finally, this comprehensive review presents the summary, challenges and prospects for ALD and MLD-designed materials for CO2 transformation.

Recent Progress on Bimetallic-Based Spinels as Electrocatalysts for the Oxygen Evolution Reaction.

Electrocatalytic water splitting is a promising and viable technology to produce clean, sustainable, and storable hydrogen as an energy carrier. However, to meet the ever-increasing global energy demand, it is imperative to develop high-performance non-precious metal-based electrocatalysts for the oxygen evolution reaction (OER), as the OER is considered the bottleneck for electrocatalytic water splitting. Spinels, in particular, are considered promising OER electrocatalysts due to their unique properties, precise structures, and compositions. Herein, the recent progress on the application of bimetallic-based spinels (AFe2 O4 , ACo2 O4 , and AMn2 O4 ; where A = Ni, Co, Cu, Mn, and Zn) as electrocatalysts for the OER is presented. The fundamental concepts of the OER are highlighted after which the family of spinels, their general formula, and classifications are introduced. This is followed by an overview of the various classifications of bimetallic-based spinels and their recent developments and applications as OER electrocatalysts, with special emphasis on enhancing strategies that have been formulated to improve the OER performance of these spinels. In conclusion, this review summarizes all studies mentioned therein and provides the challenges and future perspectives for bimetallic-based spinel OER electrocatalysts.

Concentrations of Pb and Other Associated Elements in Soil Dust 15 Years after the Introduction of Unleaded Fuel and the Human Health Implications in Pretoria, South Africa.

Leaded fuel has been reported to contain certain amounts of toxic trace metals such as Pb and Cadmium (Cd), which may have negative impacts on humans and the environment. Unleaded fuel was introduced to South Africa in 2006 with the aim of reducing and eventually eliminating the negative impact of leaded fuel on the environment. However, trace metals are usually nonbiodegradable, and it may therefore be necessary to monitor their presence in the environment so as to evaluate their possible impact on human health. The present study evaluated the levels of Pb and other heavy metals in soil samples collected from petrol (gas) filling stations and from busy roads just around the filling stations in Pretoria, South Africa, fifteen years after the introduction of unleaded fuel. A total of twenty-four (24) soil samples were analysed for lead (Pb), chromium (Cr), copper (Cu), zinc (Zn), arsenic (As), iron (Fe), manganese (Mn), nickel (Ni), titanium (Ti), and cadmium (Cd) using Inductively Coupled Plasma Mass Spectrometry (ICP-MS). The results showed that the concentrations of the trace metals were in the following ranges: Pb, 0.08 ± 0.02−188.36 ± 15.32 ug/g; Mn, 5.35 ± 0.34−6842.43 ± 1.35 ug/g; Zn, 1.82 ± 0.22−9814.89 ± 22.32 ug/g; As, 0.21 ± 0.00−8.42 ± 2.44 ug/g; Cu, 10.51 ± 3.41−859 ± 0.09 ug/g; Cr, 5.80 ± 2.21−417.70 ± 9.08 ug/g; Ti, 19.94 ± 4.99−1036.12 ± 1.49 ug/g; and Fe, 3.06 ± 7.87−674.07 ± 12.22 mg/g. The highest concentrations from all the elements were recorded for Fe in all the collected soil samples. The concentrations of Pb in the soils collected from sites associated with high traffic and industrial areas were higher than for those from all other sites, and the differences were significant (p < 0.05). The pollution index (PI), which is the anthropogenic influence of the trace metals, and the geoaccumulation (Igeo), which allows for the removal of possible variations as regards the studied element in the soil due to the possible differences in the background value, showed that some samples were enriched anthropogenically. The PI for Ni, Pb, Cu, and Cr indicated highly anthropogenically contaminated soils, especially at sites associated with high traffic volumes and in industrial areas. The Igeo showed moderately polluted areas for Pb and Cu in high-traffic areas. The exposure routes for the toxic trace metals that were of concern in the study were either through ingestion or dermal contact. The calculated hazard quotient showed both noncarcinogenic and carcinogenic risks for Fe and Mn via ingestion and through dermal contact for both children and adults, respectively. The concentrations of Pb were high and similar to those that were previously reported in the study and pointed to vehicular emission as one of the contributors. The study also noticed an increase in the presence of Mn and Fe in all soil samples.

Occurrence and infant exposure assessment of per and polyfluoroalkyl substances in breast milk from South Africa.

The exposure of infants to per and polyfluoroalkyl substances (PFAS) through breast-feeding is of global concern owing to their numerous detrimental health effects. This study investigated the occurrence of eleven perfluorocarboxylic acids (PFCAs) and four perfluorosulfonates (PFSAs) in breast milk of nursing mothers from South Africa. The concentrations of PFAS in these samples were measured by using a validated UHPLC - MS/MS method. The median concentrations of Σ15 PFAS ranged from

Health Risk Assessments of Selected Trace Elements and Factors Associated with Their Levels in Human Breast Milk from Pretoria, South Africa.

While breast milk is the recommended food for infants up to at least six months, exogenously derived compounds such as trace elements have been widely reported in human milk which may make it become toxic or a source of pollutants to the infants. Numerous short- and long-term health effects have been associated with high body-burdens of trace elements, which are amplified in infants. The current study determined the levels and possible contributing factors of six trace elements in breast milk of nursing mothers from a local hospital in Pretoria. Extraction of trace elements employed a digestion technique using perchloric and nitric acid in a ratio of 1:3, while Inductively Coupled Plasma-Membrane Spectrophotometry was used to identify and quantify their levels in breast milk. Concentrations of Cr and Mn were the highest in breast milk, with values ranging from 0.30 to 5.72 µg/L and 0.23 to 5.13 µg/L, respectively. Levels of Co, As, Pb and Cd ranged from

Confirmatory Analysis of Per and Polyfluoroalkyl Substances in Milk and Infant Formula Using UHPLC-MS/MS.

An ultra-high performance liquid chromatography tandem mass spectrometry method was developed and validated for the sensitive determination and unambiguous confirmation of residues of per and polyfluorinated alkyl substances (PFAS) in breastmilk, retail milk and infant formulas following two sample preparation methods. Sample pre-treatment was carried out by a simplified QuEChERS method without requiring dSPE or any further clean-up. The method was validated in accordance with the requirements of Commission Decision 657/2002/EC with slight modifications. The method displayed good linearity with R2 ranging from 0.9843-0.9998 for all target PFAS. The recovery and within-laboratory reproducibility of the method (n = 63) were in the range 60-121% and 5-28%, respectively. The decision limit, detection capability and limit of quantitation ranged from 30-60 ng kg-1 to 40-100 ng kg-1 and 5-50 ng kg-1, respectively. Acceptable matrix effect values in the range -45-29% were obtained with uncertainty of measurement lower than 25% for all target PFAS. The method displays its suitability for the sensitive and high-throughput confirmatory analysis of C4-C14 PFAS in breastmilk, dairy milk and infant formulas.

An ethnobotanical survey of medicinal plants used by traditional healers for the treatment of cancer in Hammanskraal and Winterveld, Tshwane Metropolitan Municipality, South Africa.

Background: Knowledge of medicinal plants used by the traditional healers are mostly confined among the locals and the adherents, hence, proper enquiry and documentation can help the ever dynamic scientific world to find permanent cure to the menace of such deadly diseases such as cancer. This study aimed at (1) specifically recording medicinal plants traditionally used for the treatment of cancer in Hammanskraal and Winterveld, South Africa, and (2) documenting the different methods of preparation and administration of those medicinal plants as recorded during the study. Method: An open-ended semi-structured questionnaire was administered to 90 willing traditional healers in Hammanskraal and Winterveld area, Tshwane Municipality, South Africa to document plants used for cancer treatments. The study was conducted over a period of six months (July - December, 2018). Descriptive statistics was used to present the obtained data. Results: The study recorded twenty-eight plant species belonging to 18 families for the treatment of different types of cancer. Plant species in the Fabaceae family particularly Lessertia frutescens (L.) Goldblatt and J.C. Manning, Senna italica Mill and Trifolium pratense L. were the most prominently mentioned (highest citation frequency) by the traditional healers for lung, and skin cancer treatment. Based on the citation frequency, the most treated cancer by the traditional healers is in the order: skin cancer > lung cancer > breast cancer > prostate cancer > cervical cancer. The method of preparation included decoction (32.3%), infusion (29%), paste (16.1%) and maceration (22.6%). Conclusion: In addition to the documentation of indigenous knowledge related to the use of medicinal plants in the traditional management of cancer in South Africa, this study opens a vista for investigations into the phytochemical and pharmacological properties of the documented plants.

Determination and assessment of human dietary intake of per and polyfluoroalkyl substances in retail dairy milk and infant formula from South Africa.

Dairy milk and infant formula play important roles in the diet of adolescents, adults and infants, respectively, in the South African population. However, data on the occurrence of legacy and emerging contaminants such as PFAS in these important food sources is lacking. In this study, the concentration of fifteen PFAS were measured in 23 pooled retail dairy milk and 7 pooled infant formulas by means of an ultrahigh performance liquid chromatography tandem mass spectrometric method. The concentrations of Σ15PFAS ranged from 0.08-15.51 ng mL-1 and 0.42-5.74 ng mL-1 in dairy milk and infant formulas, respectively. PFBA, PFPeA, PFuDA, PFTrDA and PFDoA were the most prevalent PFAS in both matrices with detection frequency > 96%. Highest PFAS concentrations of 2.02 ng ml-1 and 2.76 ng ml-1 were recorded for PFDoA in infant formulas and dairy milk, respectively. The concentrations of legacy PFAS -PFOA and PFOS, shows resemblance with global data, however, elevated concentrations of long chain C9 - C14 PFAS were observed in this study. Though, higher concentrations of PFAS were measured in full cream dairy milk, no statistical significant difference (P = 0.546) was observed for the various classes of dairy milk. The EDI of Σ15PFAS through infant formulas were 184.92, 329.47 and 166 ngkg-1BWday-1 for partially breastfed, exclusively formula fed and older infants, respectively. Similarly, the EDI of PFAS through dairy milk for toddlers, adolescents, female and male adults for the rural population were 14.17, 1.09, 2.59 and 3.16 ngkg-1BWday-1 respectively while they were 20.41, 3.84, 4.13 and 4.26 ngkg-1BWday-1 respectively in the urban population. Although, the EDI of PFAS through the consumption of infant formulas and dairy milk are lower than the daily tolerable limits, the relative importance of long-term exposure and the cumulative effects of multiple exposure pathways cannot be overemphasized.

Dinuclear uranium(VI) salen coordination compound: an efficient visible-light-active catalyst for selective reduction of CO2 to methanol.

A new dinuclear uranyl salen coordination compound, [(UO2)2(L)2]·2MeCN [L = 6,6'-((1E,1'E)-((2,2-dimethylpropane-1,3-diyl)bis(azaneylylidene))-bis(methaneylylidene))bis(2-methoxyphenol)], was synthesized using a multifunctional salen ligand to harvest visible light for the selective photocatalytic reduction of CO2 to MeOH. The assembling of the two U centers into one coordination moiety via a chelating-bridging doubly deprotonated tetradentate ligand allowed the formation of U centers with distorted pentagonal bipyramid geometry. Such construction of compounds leads to excellent activity for the photocatalytic reduction of CO2, permitting a production rate of 1.29 mmol g-1 h-1 of MeOH with an apparent quantum yield of 18%. Triethanolamine (TEOA) was used as a sacrificial electron donor to carry out the photocatalytic reduction of CO2. The selective methanol formation was purely a photocatalytic phenomenon and confirmed using isotopically labeled 13CO2 and product analysis by 13C-NMR spectroscopy. The spectroscopic studies also confirmed the interaction of CO2 with the molecule of the title complex. The results of these efforts made it possible to understand the reaction mechanism using ESI-mass spectrometry.

Efficient Micropropagation Protocol for the Conservation of the Endangered Aloe peglerae, an Ornamental and Medicinal Species.

A number of Aloe species are facing an extremely high risk of extinction due to habitat loss and over-exploitation for medicinal and ornamental trade. The last global assessment of Aloe peglerae Schönland (in 2003) ranked its global conservation status as 'endangered' with a decreasing population trend. In the National Red List of South African Plants, the extremely rapid decline of this species has resulted in its conservation status being elevated from 'endangered' to 'critically endangered' based on recent or new field information. This dramatic decline necessitates the development of a simple, rapid and efficient micropropagation protocol as a conservation measure. An in vitro propagation protocol was therefore established with the regeneration of 12 shoots per shoot-tip explant within 8 weeks using Murashige and Skoog (MS) medium supplemented with 2.5 µM meta-topolin riboside (an aromatic cytokinin). The rooting of the shoots with a 100% frequency on half-strength MS medium without any plant growth resulted in additional six shoots produced per cultured shoot. The resultant plantlets were successfully acclimatized with a 100% survival frequency after 6 weeks. Overall, the developed protocol can result in the production of 3906 transplantable shoots that are ready for rooting per annum from a single shoot-tip explant. It is simple and efficient for seedling production in the ex situ cultivation and conservation of the endangered A. peglerae.

Per- and polyfluoroalkyl substances in human breast milk and current analytical methods.

Per- and polyfluoroalkyl substances (PFASs) have since become a major health concern as they have been reportedly found in human tissues, blood and breast milk. The main aim of the study was to review the current data on PFASs in human breast milk, including the challenges of analysis as well as the possible modes of transfer from maternal blood. In this paper, previously published data on the concentrations of PFASs in human breast milk from around the world were reviewed and summarised. Eligible studies with reference lists published before 1 June 2017 were included by searching several databases (including Scopus, ScienceOpen and SciFinder). From this search, studies with the number of participants in each study ranging from 2 to 1237 were identified. The review indicated that based on the structural profiles and concentration levels, there was variation in the geographical distribution of these compounds in breast milk. Although there are no recorded investigations on the modes of transfer from maternal blood to breast milk, literature suggests that the PFASs tend to be transferred through binding to various proteins. The review also examined the different sample preparation and analytical methods employed to measure the concentrations of PFASs in human breast milk. This showed that solid phase extraction was the most common extraction method. After extraction, liquid chromatography coupled with tandem mass spectrometry was the most common analysis method. Since several of these methods were initially dedicated to monitoring PFASs in food and water, they demonstrate some limitations with regard to specificity and sensitivity to human fluids. Additionally, there are currently no published records of certified reference materials and/or proficiency scheme devoted to standardising PFAS concentrations in breast milk.

Perception of Scavengers and Occupational Health Hazards Associated with Scavenging from a Waste Dumpsite in Pretoria, South Africa.

Objective: Scavenging is a source of income for most unskilled people in the developing countries. The present study investigated the perception of scavengers on scavenging and related health hazards from the Onderstepoort waste dumpsite in Pretoria, South Africa. Methods: Primary data were obtained through observation and implementation of a questionnaire to a total number of 53 scavengers (27 females and 26 males). The questionnaire was structured to extract information that included perceptions of scavengers about their activities, health implications of scavenging, monthly income, and behavioural norms. Results: Educated scavengers had high school education. The period of scavenging ranged from 10 to 15 years. The majority of scavengers did not use protective clothing. However, few used gloves and boots picked from the dumpsite. Common health issues reported included back pain, headache, diarrhoea, and shortness of breath. Some sustained injuries from sharp objects. Scavengers stored food among the waste; food could be either brought from home or bought from the vendors who cook at the dumpsite. Some drank bottled water picked from the waste. Eighty-five percent of females cleaned themselves immediately after work in temporary shacks at the dumpsite, while all males bathed at home. The average monthly income from scavenging was approximately R1372 (approximately $91 (US)). Women scavengers liked their job despite associated health risks. Conclusion: Scavengers would benefit if government and nongovernmental organisations educate them on the significance of protective clothing and good hygiene. Policymakers should assist the scavengers by providing necessary workshops on-site that will assist them to change their behaviour.

Assessment of trace metals using lichen transplant from automobile mechanic workshop in Ile-Ife metropolis, Nigeria.

The level of air pollution around the automobile mechanic workshops has been generally overlooked. This study, examined the level of trace metals in automobile mechanic workshops and the suitability of using transplanted lichen thalli of Lepraria incana for measuring air pollution in such areas. Samples of the lichen thalli were transplanted into seven different sites and were attached to the bark of trees at each site. The samples were harvested from the sites after 3-month exposure. Concentrations of Pb, Cu, Cd, Fe, Zn, and S content were determined using an atomic absorption spectrophotometer. Results showed that there was a significant difference in the trace metals concentrations across the sites (p < 0.05). The analyzed lichen samples showed a range of 91.26-119.35 ppm for Fe, 30.23-61.32 ppm for Zn, 1.25-2.45 ppm for Cu, 0.017-0.043 ppm for Cd, 0.018-0.051 ppm, and 0.37-0.42 ppm for S. From the study, sites 6 and 7 presented higher concentrations of Cd, Pb, and Zn than other sites. The enrichment factor calculated showed that Zn, Cd, and Pb were greatly enriched from the workshops. The trend in the concentration of these heavy metals suggests that activities in these workshops might become a major source of certain heavy metals in the environment and if the pollution activities persist, it might become worrisome over time.