Olalekan S. Fatoki

A review on sources of brominated flame retardants and routes of human exposure with emphasis on polybrominated diphenyl ethers

The presence of brominated flame retardants (BFRs) in various environmental matrices, including humans, has been well documented. Increasing levels of these emerging contaminants in various environmental compartments suggest the wide application of these chemicals in products of everyday use. The release of BFRs from treated products is generally believed to be the major source of these contaminants into the environment, particularly in indoor environments. The sources and pathways through which BFRs enter the human system are evaluated in this paper. Human exposure via consumption of contaminated food and water, inhalation and ingestion of dust, as well as dermal absorption, are important pathways for these contaminants. Consumption of fatty foods especially fish, meat, dairy products as well as human milk constitute important routes for human exposure to these contaminants. Although brominated diphenyl ether (BDE) 209 has been found to be less bioaccumulative due to its high molecular weight, its domina...

Adsorption of Cr (VI) on synthetic hematite (α-Fe2O3) nanoparticles of different morphologies

The adsorption of Cr (VI) from aqueous solution onto nanoparticles hematite (α-Fe2O3) of different morphologies synthesized by acid hydrolysis, transformation of ferrihydrite, sol gel methods has been investigated. The hematite particle sizes were in the range 15.69-85.84 nm and exhibiting different morphologies such as hexagonal, plate-like, nano-cubes, sub-rounded and spherical. The maximum adsorption capacity of Cr (VI) was found to be in the range 6.33–200 mgg−1 for all hematite samples. The kinetics of sorption was rapid, reaching equilibrium at 45–240 minutes. Sorption kinetics and equilibria followed pseudo-second order and Langmuir adsorption isotherm models. The rate constants were in the range 0.996–2.37×10−2 g/mg/min for all samples. The maximum adsorption was attained at pH 3.0, while adsorption decreased as the pH increased from pH 3.0 to 10.0. The study revealed that the hematite with plate-like morphology has the highest adsorption capacity. The sorption process has been found to be feasible following a chemisorption process, and adsorption of Cr (VI) onto hematite nanoparticles was by inner sphere surface complexation due to low desorption efficiency in the range 9.54–53.4%. However, the result of ionic strength revealed that the reaction was by outer sphere complexation. This study showed that morphologies play a vital role in the adsorption capacities of samples of hematite in the removal of Cr (VI) from aqueous solution.

Human Exposure, Biomarkers, and Fate of Organotins in the Environment

Organotin compounds result from the addition of organic moieties to inorganic tin.Thus, one or more tin-carbon bonds exist in each organotin molecule. The organo-tin compounds are ubiquitous in the environment. Organotin compounds have many uses, including those as fungicides and stabilizers in plastics, among others in industry. The widespread use of organotins as antifouling agents in boat paints has resulted in pollution of freshwater and marine ecosystems. The presence of organotin compounds in freshwater and marine ecosystems is now understood to be a threat, because of the amounts found in water and the toxicity of some organotin compounds to aquatic organisms, and perhaps to humans as well. Organotin com-pounds are regarded by many to be global pollutants of a stature similar to biphenyl,mercury, and the polychlorinated dibenzodioxins. This stature results from the high toxicity, persistence, bioaccumulation, and endocrine disruptive features of even very low levels of selected organotin compounds.Efforts by selected governmental agencies and others have been undertaken to find a global solution to organotin pollution. France was the first country to ban the use of the organotins in 1980. This occurred before the international maritime organization (IMO) called for a global treaty to ban the application of tributyltin (TBT)-based paints. In this chapter, we review the organotin compounds with emphasis on the human exposure, fate, and distribution of them in the environment. The widespread use of the organotins and their high stability have led to contamination of some aquatic ecosystems. As a result, residues of the organotins may reach humans via food consumption. Notwithstanding the risk of human exposure, only limited data are available on the levels at which the organotins exist in foodstuffs consumed by humans. Moreover, the response of marine species to the organotins, such as TBT, has not been thoroughly investigated. Therefore, more data on the organotins and the consequences of exposure to them are needed. In particular, we believe the following areas need attention: expanded toxicity testing in aquatic species, human exposure, human body burdens, and the research to identify biomarkers for testing the toxicity of the organotins to marine invertebrates.

Determination of polycyclic aromatic hydrocarbons [PAHs] in processed meat products using gas chromatography – Flame ionization detector

The concentrations of polycyclic aromatic hydrocarbons (PAHs) in smoked, grilled and boiled meats were determined using gas chromatography - flame ionization detector (GC-FID). PAHs in the processed meats were extracted in n-hexane after hydrolysis with methanolic KOH. Clean-up was achieved using solid phase extraction in neutral-Si/basic-Si/acidic-Si/neutral-Si frits. The fractions, benzo[k]fluoranthene (BkP), benzo[a]pyrene (BaP), indeno[123-cd]pyrene (IP) and benzo[ghi]perylene (BghiP) were separated and quantified using GC-FID. The method and instrument limits of detections were 0.1, 0.1, 0.2, 0.3μg/kg and 0.5, 0.5, 1.0, 1.5μg/kg, respectively, for BkP, BaP, IP and BghiP. The methods recovery and precision generally varied between 83.69% and 94.25% with relative standard deviation (RSD) of 3.18-15.60%; and 90.38-96.71% with relative standard deviation (RSD) of 1.82-12.87% respectively. The concentration of BkP, BaP, IP and BghiP in smoked, grilled and boiled meat samples were ranged 0.64-31.54μg/kg, 0.07-7.04μg/kg, 0.09-15.03, 0.51-46.67μg/kg and 0.01-5.11μg/kg, respectively.

Isolation and Determination of Polycyclic Aromatic Hydrocarbons in Surface Runoff and Sediments

The distribution of Polycyclic Aromatic Hydrocarbons (PAHs) was investigated in surface runoff and sediments of Lagos, Osogbo and Ile-Ife Western areas of Nigeria. Method for the analysis of PAHs was based on Liquid-Liquid extraction of the runoff and a soxhlet extraction of the sediments followed by a clean up adsorption procedure. The PAHs were separated and quantified by Gas Chromatography-Mass spectrometry (GC-MS) technique. A blank experiment was done using triply distilled water and following the same procedure for the samples to establish blank levels. In both street runoff and sediments 13 PAHs were identified and quantified. At Osogbo and Ile-Ife areas, the mean levels of PAHs in surface runoff ranged between 0.10–15.81 mg L-1 while in the Lagos area the levels were between 0.1–73.72 mg L-1. Generally, the PAH levels in surface runoff of Lagos constitute 53.03 mg L-1 average ∑ PAH detected in the study area compared to 31.96 mg L-1 average ∑ PAH contribution made by samples from Osogbo and Ile-Ife. The levels of PAHs in sediments are relatively higher compared to those of the street runoff in the study area. PAHs in sediment of Lagos contribute an average of 228.57 mg kg-1 ∑ PAH to the total sediment PAH burden compared to Osogbo and Ile-Ife areas that contribute only 91.13 mg kg-1 average ∑ PAH to the total PAH burden of the study area. The relatively higher average ∑ PAHs reported for Lagos area compared with those of Osogbo and Ile-Ife, is consistent with higher industrial activities and traffic density of the former (1000–10000 vehicles/hr) than the later (450–1500 vehicles/hr).

Kinetics and equilibrium models for the sorption of tributyltin to nZnO activated carbon and nZnO / activated carbon composite in artificial seawater

The removal of tributyltin (TBT) from artificial seawater using nZnO, activated carbon and nZnO/activated carbon composite was systematically studied. The equilibrium and kinetics of adsorption were investigated in a batch adsorption system. Equilibrium adsorption data were analyzed using Langmuir, Freundlich, Temkin and Dubinin-Radushkevich (D-R) isotherm models. Pseudo first- and second-order, Elovich, fractional power and intraparticle diffusion models were applied to test the kinetic data. Thermodynamic parameters such as ΔG°, ΔS° and ΔH° were also calculated to understand the mechanisms of adsorption. Optimal conditions for the adsorption of TBT from artificial seawater were then applied to TBT removal from natural seawater. A higher removal efficiency of TBT (>99%) was obtained for the nZnO/activated carbon composite material and for activated carbon but not for nZnO.

Characterization of Fly Ash Generated from Matla Power Station in Mpumalanga, South Africa

In this study, fly ash was obtained from Matla power station and the physicochemical properties investigated. The fly ash was characterized by x-ray fluorescence, x-ray diffraction, scanning electron microscopy, and inductively coupled plasma mass spectrometry. Surface area, particle size, ash and carbon contents, pH, and point of zero charge were also measured. The results showed that the fly ash is alkaline and consists mainly of mullite (Al6Si2O13) and quartz (SiO2). Highly toxic metals As, Sb, Cd, Cr, and Pb as well as metals that are essential to health in trace amounts were also present. The storage and disposal of coal fly ash can thus lead to the release of leached metals into soils, surface and ground waters, find way into the ecological systems and then cause harmful effect to man and its environments.

Heavy Metals Speciation and Human Health Risk Assessment at an Illegal Gold Mining Site in Igun, Osun State, Nigeria

Background There is increasing global concern over the health effects of heavy metals arising from various anthropogenic activities, especially mining. Mining activities in developing countries are often carried out at an artisanal level using a variety of extraction methods with human health and environmental consequences. Objectives The broad objective of this study is to assess the chemical forms, distribution pattern, and health risks due to mining and processing techniques at a gold mining site in Igun, Osun State, Nigeria. Methods Samples were collected from 28 active mine pits and sequentially extracted using standard methods. Extracts were analyzed for metals using inductively coupled plasma optical emission spectrometer (ICP/OES), while health risk was assessed using United States Environmental Protection Agency (USEPA) and Dutch methods. Chemical speciation of heavy metals and health risk assessment was calculated using mobile phase fraction summation. Results Metals were exclusively present in the residual fractions, indicating that these metals are strongly bound to the resistant components of the soil matrix. The percentage in the residual fraction ranged from 9.41% (tin) to 99.42% (aluminium). The heavy metals geoaccumulation index for the site ranged from 0 (no contamination) to 6 (extremely contaminated). The cancer risk ranged from 6.17E-13 to 7.77E-05 and 2.73E-12 to 4.64E-04 for adults and children, respectively. Discussion Cancer risk and non-cancer risk (hazard index) assessment showed that arsenic poses a higher risk in adults and children compared to other metals through the dermal exposure route.

Catalytic activities of ultra-small β-FeOOH nanorods in ozonation of 4-chlorophenol

We report the catalytic properties of ultra-small β-FeOOH nanorods in ozonation of 4-chlorophenol (4-CP). XRD, TEM, EDS, SAED, FTIR and BET were used to characterize the prepared material. Interaction between O3 and β-FeOOH was evident from the FTIR spectra. The removal efficiency of 4-CP was significantly enhanced in the presence of β-FeOOH compared to ozone alone. Removal efficiency of 99% and 67% was achieved after 40min in the presence of combined ozone and catalyst and ozone only, respectively. Increasing catalyst load increased COD removal efficiency. Maximum COD removal of 97% was achieved using a catalyst load of 0.1g/100mL of 4-CP solution. Initial 4-CP concentration was not found to be rate limiting below 2×10(-3)mol/L. The catalytic properties of the material during ozonation process were found to be pronounced at lower initial pH of 3.5. Two stage first order kinetics was applied to describe the kinetic behavior of the nanorods at low pH. The first stage of catalytic ozonation was attributed to the heterogeneous surface breakdown of O3 by β-FeOOH, while the second stage was attributed to homogeneous catalysis initiated by reductive dissolution of β-FeOOH at low pH.

Application of Cyanex® extractant in cobalt/nickel separation process by solvent extraction

This study presents a detailed review on the advanced hydrometallurgical treatment involving the extraction and separation of Cobalt (Co) and Nickel (Ni) by Cyanex® extractants. The structures, properties and applications of various Cyanex® extractants such as Cyanex®272, Cyanex®301, Cyanex®921, Cyanex®923 and Cyanex®421X were discussed and compared. Cyanex®272 thus proved to be the most appropriate solvent extractant for the separation of Co and Nickel from sulphate and chloride media due to its stability to common oxidant, better physicochemical properties and its ability to avoid gypsum crystallization in stripping-electrowinning circuit. Finally, various solvent extraction (SX) techniques for the extraction and separation of Co and Ni using Cyanex® extractants were discussed as well as newer processes of extraction and separation.