Bioaccessibility and children health risk assessment of soil-laden heavy metals from school playground and public parks in Accra, Ghana.

Parks and playground soils constitute a critical matrix for children exposure to hazardous substances due to their high exposure rate. However, minimal investigation has been conducted in Ghana on the subject, thus the need for this research. One hundred and twenty (120) soil samples were collected between April 2015 and March 2016 and then analyzed for heavy metals using atomic absorption spectroscopy. The health risk posed to school children by the heavy metals laden in soil was assessed via oral bioaccessibility and hazard index. The oral bioaccessibility of the metals was estimated using the simple bioaccessibility extraction test (SBET) method. Iron (Fe) measured the highest range of total metal concentrations of 2785.0-15275.0 mg kg-1 followed by Pb of 2.1-284.0 mg kg-1. The oral bioaccessibility of the metals varied significantly with Pb and Cu exhibiting the highest mean values of 47.80% and 54.45%, respectively. The sequence for the mean bioaccessibility result does not correspond with the mean concentration of metals in the soil. The hazard index (HI) for most of the heavy metals indicated no potential non-carcinogenic health risk to children (HI < 1) except for Pb. The prolonged use of leaded fuel in Ghana prior to its outright ban on January 1 2004 and the persistence of Pb in soil media may account for its high risk. The deleterious health effects of Pb on children call for the adoption and implementation of appropriate environmental management of playgrounds so as to mitigate children's exposure to soil-laden heavy metals.

Inherent and external factors influencing the distribution of PAHs, hydroxy-PAHs, carbonyl-PAHs and nitro-PAHs in urban road dust.

The distribution and fate of hazardous polycyclic aromatic hydrocarbons (PAHs) and their associated transformed PAHs products (TPPs) notably carbonyl-PAHs (CPAHs), hydroxy-PAHs (HoPAHs), and nitro-PAHs (NPAHs) on urban road surfaces are influenced by diverse factors to varying extent. The pollutants are eventually transported to urban receiving waters via stormwater runoff posing risks to human and ecosystem health. In order to formulate an effective mitigation strategy, it is essential to comprehensively examine the role of both inherent and external factors in the distribution and fate of these hazardous pollutants, and thus, the need for this study. The research study showed that commercial land use has the highest cumulative concentration of PAHs and TPPs. Antecedent dry days (ADDs) has an inverse influence on the distribution of the total concentrations of low-molecular weight PAHs (LMW-PAHs), PAHs, and (PAHs + TPPs) irrespective of the type of land use, whilst there was no major influence on the total concentrations of high molecular weight PAHs (HMW-PAHs), and TPPs. The high volatility of LMW-PAHs compared to HMW-PAHs is considered to account for the decreasing concentration of LMW-PAH with increasing ADD. Particle size range has significant inverse influence on the cumulative concentration of pollutants across all land uses, since smaller particles are characteristically associated with larger surface area leading to the higher sorption of pollutants. Multivariate analysis of the influential factors indicated that two particle size ranges (0.45-150 µm and 150-425 µm) constitute the major influential factors on the distribution and fate of PAHs and TPPs in urban road dust. Greater quantum of pollutants are sorbed to the 0.45-150 µm particles due to the relatively higher specific surface area (SSA), concentration of total organic carbon (TOC) and total suspended solids (TSS) concentration. Therefore, it is critical to effectively remove finer particles from road surfaces in order to reduce exposure to hazardous pollutants.

Influence of photolysis on source characterization and health risk of polycyclic aromatic hydrocarbons (PAHs), and carbonyl-, nitro-, hydroxy- PAHs in urban road dust.

In this study, PAHs and their transformed PAH products (TPPs) in road dust were subjected to UV driven photolysis, and then extracted using simultaneous pressurized fluid extraction, and analysed using Shimadzu Triple Quadrupole GC/MS. The results of the analysis were used to investigate the robustness and reliability of 14 existing diagnostic ratios (DRs) and two newly proposed molecular DRs that are relevant for characterizing the sources of PAHs and TPPs. The influence of photolysis on the carcinogenic health risk posed to humans by these hazardous pollutants was then assessed. The findings indicated that the DRs segregated into stable, moderately stable and non-stable classes of source characteristics under the influence of photolysis. Only two of the existing DRs, namely, benzo(a)pyrene/benzo(ghi)perylene (BaP/BghiP) and total index exhibited consistent stability to photolysis, whilst fluoranthene/(fluoranthene + pyrene) (FRT/(FRT+PYR)) showed moderate stability. The two newly proposed DRs, naphthalene/1-nitronaphthalene (NAP/NNAP) and pyrene/(1-nitropyrene + 1-hydroxypyrene) (PYR/(1NPY+HPY)) were found to be highly reliable in post-emission source characterization. The cross-plots of the most stable DRs showed that traffic emissions is the primary source of PAHs, whilst post-emission photolysis is the secondary source of nitro-PAH (NPAH) TPPs. The percent resonance energy thermodynamic stability of the PAH pollutants does not exert any direct influence on the source characteristics of the DRs. Adults are more vulnerable to potential carcinogenic risks as a result of PAH and TPPs photolysis whereas negligible risk exist for children. This study contributes to a more reliable diagnosis of PAH and TPP sources and thus, to the regulatory mitigation of these hazardous pollutants thereby, promoting enhanced protection of human health and the environment.

Optimized simultaneous pressurized fluid extraction and in-cell clean-up, and analysis of polycyclic aromatic hydrocarbons (PAHs), and nitro-, carbonyl-, hydroxy -PAHs in solid particles.

The development, modification and optimization of analytical methods capable of simultaneous extraction and in-cell clean-up of extracts for subsequent determination of parent PAHs and their associated transformed nitro-PAHs (NPAH), carbonyl-PAHs (CPAH) and hydroxy-PAHs (HO-PAH) products (TPPs) is essential for reducing the time and cost of analysis. The aim of this study was to modify and optimize the pressurized fluid extraction (PFE) technique capable of simultaneous extraction and in-cell clean-up of PAHs and TPPs in urban dust standard reference material and road dust for GC-MS analyses. In this study, multivariate data analysis such as factor analysis (FA), and preference ranking organisation method for enrichment evaluation (PROMETHEE) and geometrical analysis for interactive aid (GAIA) were used to assess the performance of the methods. As the key outcome of the study, an optimized selective reaction monitoring (SRM) Triple Quadrupole (TQ) electron ionization (EI)-GC/MS for measuring PAHs and TPPs without derivatization of polar HO-PAHs was developed. The limits of detection (LOD) for parent PAHs, CPAHs, NPAHs and HO-PAHs using Shimadzu TQ were 1.0-5.0 pg, 1.0-5.0 pg, 1.0-50.0 pg, and 1.0-25.0 pg, respectively. The PROMETHEE-GAIA analysis of the results showed that a combination of 3% deactivated silica gel and activated alumina (2:1) as in-cell clean-up material, and sequential PFE extraction (200 °C ASE temperature, 9 min preheat time and 3 times extraction cycle) using 100% hexane followed by hexane/DCM (1:1) is the best condition for analytes extraction from road dust. An optimized, fast and reliable GC/MS method operated solely in electron ionization (EI) mode was developed for measuring all analytes. The outcomes of this study will contribute significantly to future research on PAHs and TPPs, thereby promoting a safe and sustainable environment.

Application of multivariate data techniques in photochemical study of polycyclic aromatic hydrocarbons (PAHs) and transformed PAH products in road dust.

Road dust is a key repository for PAHs and transformed PAH products (TPPs) generated from natural and anthropogenic sources in the urban environment. Eventhough PAHs and TPPs are prone to post-emission photochemical processes, very limited studies exist on the subject for road dust. This knowledge gap is of particular concern since some of the resultant TPPs are notably more carcinogenic than their precursor PAHs. This study evaluated the role of 254 nm ultraviolet (UV) photons on the photochemistry of PAHs and TPPs in road dust. The findings show that UV irradiation had varying effects on the fate of analytes, particularly naphthalene (NAP), phenanthrene (PHE), 7, 12-dimethylbenz(a)anthracene (DMBA), 1-hydroxypyrene (HPY), 1-nitropyrene (1NPY), pyrene (PYR) and 5-nitroacenaphthene (5NAC). Photochemical relationship was identified between PYR, 1NPY and HPY, and DMBA and benzo(a)anthracene. Unlike carbonyl-PAHs, parent PAHs, nitro-PAHs and hydroxy-PAHs can originate from photolysis. Photon irradiation durations of 3, 6 and 7.5 h had the most intense influence on the photolytic process with 7.5 h as optimum. The photochemical rate at optimum irradiation duration shows an increasing trend of NAP < PHE < 1NPY < DMBA < 5NAC < HPY with respective estimates of 0.08, 0.11, 0.21, 0.22, 0.43, and 0.59 mg kg-1 hr-1. Physicochemical properties of analytes such as index of refraction and vapour pressure (in logarithmic form) had an inverse effect on photolysis. The knowledge generated is significant for the in-depth understanding of the fate of PAHs and TPPs on urban road surfaces and contributes to the greater protection of human health and the environment.

Application of quantitative structure-activity relationship (QSAR) model in comprehensive human health risk assessment of PAHs, and alkyl-, nitro-, carbonyl-, and hydroxyl-PAHs laden in urban road dust.

The carcinogenic human health risks (CHHR) posed by the exposure to PAHs and transformed PAH products (TPPs) are currently inconclusive due to the lack of toxicity equivalency factors (TEFs) for most TPPs although some of these pollutants are more potent carcinogens. The applicability of quantitative structure-activity relationship (QSAR) model in predicting TEF of PAHs and TPPs to holistically evaluate the CHHR posed by the exposure to these pollutants in road dust from Gold Coast, Australia was examined. Statistical evaluation via ten metrics shows that partial least-squares regression (PLSR1) model has more statistical power in predicting TEF than multiple linear regression (MLR) within relevant applicability domain. For instance, the predicted residual sum of squares (PRESS) and standard deviation of error of prediction (SDEP) for PLSR is closer to zero than that of MLR. The total cancer risk estimated using the QSAR model derived TEFs and original TEFs for outliers gives a more holistic incremental lifetime cancer risk in relation to children and adults. Potential cancer risk exists for adults with this approach whereas reliance on only the originally available TEFs lead to a negligible risk diagnosis. The application of QSAR model in assessing CHHR due to PAHs and TPPs exposures is very viable.

Transformation and degradation of polycyclic aromatic hydrocarbons (PAHs) in urban road surfaces: Influential factors, implications and recommendations.

Polycyclic aromatic hydrocarbons (PAHs) are prone to post-emission transformation and degradation to yield transformed PAH products (TPPs) that are potentially more hazardous than parent PAHs. This review provides a comprehensive evaluation of the potential environmental processes of PAHs such as sorption, volatilisation, photo- and bio-transformation and degradation on road surfaces, a significant accumulation point of PAHs. The review primarily evaluates key influential factors, toxicity implications, PAHs and TPPs fate and viable options for mitigating environmental and human health impacts. Photolysis was identified as the most significant transformation and degradation process due to the light absorption capacity of most PAHs. Climate conditions, physicochemical properties of road dust (sorbent), PAHs and TPPs and the existence of heavy metals such as Fe (III) are notable underlying factors for photolysis. Available data points to the predominance of carbonyl TPPs than other products such as nitro and hydroxyl TPPs with decreasing concentration trend of 9-fluorenone > 9,10-anthraquinone > benzo[a]fluorenone on road surfaces. The review recommends conducting future investigations targeting the influential factors pertaining to the fate of road deposited PAHs and TPPs. Furthermore, development of cost and time effective modern analytical methods is needed to quantify PAHs and TPPs present in minute quantities of samples. The review also identified that the unavailability of toxicity equivalency factors (TEF) for the most critical TPPs can be addressed using quantitative structure-activity relationship (QSAR) models and bioassays simultaneously. The content of this review is significant to the future work of researchers across various fields including analytical and environmental chemistry, stormwater pollution and toxicology.

Dataset for the quantitative structure-activity relationship (QSAR) modeling of the toxicity equivalency factors (TEFs) of PAHs and transformed PAH products.

Sixteen significant physicochemical predictor variables for thirty PAHs and transformed PAH products (TPPs) were retrieved individually prior to collation from ChemSpider.com [1] whilst their corresponding toxicity equivalency factor (TEF) end-point was obtained from published articles by Bortey-Sam, Ikenaka [2] and Wei, Bandowe [3]. In order to achieve a 5:1 ratio of the number of observations to predictors which is vital for an effective quantitative structure-activity relationship (QSAR) modelling, factor analysis was used to reduce the data. Four fundamental predictors were obtained whilst the observations were found to cluster into two main groups of nitro-PAHs and other analytes. It is anticipated that the data presented here is highly relevant for future studies on the toxicity and health effects of the analytes in the environment. Secondly, the fate and distribution patterns of PAHs and TPPs are influenced by the parameters in the dataset. In this regard, studies on the behaviour patterns of these environmental pollutants require this information for a comprehensive evaluation and interpretation of results. Researchers across varied fields of environmental science and toxicology will find this dataset very useful. This data currently serves as supplementary information for the research article in the Journal of Hazardous Materials by Gbeddy, Egodawatta [4].

Spatial distribution, accumulation and human health risk assessment of heavy metals in soil and groundwater of the Tano Basin, Ghana.

Soil serves as a vast matrix for heavy metal accumulation and subsequent redistribution to critical aspects of the environment such as groundwater. Soil pollution study is essential for sustainable human health and ecosystem protection. This study provides vital insight into the fate, accumulation, interactions, and health risk posed by heavy metals in soil and groundwater by employing geochemical accumulation index (Igeo), risk assessment models and multivariate data analysis techniques such as principal component analysis (PCA), preference ranking organisation method for enrichment evaluation (PROMETHEE) and geometrical analysis for interactive aid (GAIA). The median Igeo estimates show moderate to strong Pb accumulation levels whilst all the other metals indicate uncontaminated to moderate levels. The PCA output point to anthropogenic origin of Pb and Cd in the Tano Basin and surrounding communities. PROMETHEE-GAIA results indicate that Pb, Cd, Zn and Fe accumulated in the soil matrix may potentially leach into the groundwater resources. The carcinogenic lifetime risks posed by Pb, Cd, and Ni metals to adults are within the tolerable acceptable risk and thus do not present an immediate danger in the study area. Due to the significant toxicity, bioaccumulation and biomagnification properties of Pb and Cd in the environment, areas associated with significant anthropogenic activities require regular monitoring and evaluation in order to ensure that these metals are consistently below the regulatory limits. This study has further elucidated the subject of heavy metal pollution and is therefore expected to enhance sustainable protection of the environment and human health.

Variability and uncertainty of particle build-up on urban road surfaces.

Particle build-up is a key stormwater pollutant process that is typically replicated using a power function with increasing antecedent dry days. Though the use of a power function is recommended by a range of researchers, its applicability is demonstrated primarily for residential roads. Particle build-up process is also subjected to significant variability due to catchment heterogeneity and variability associated with source characteristics such as traffic and land use. Variability in the build-up process and use of stereotypical coefficients can lead to significant model uncertainty. This study evaluates particle build-up characteristics on urban road surfaces using an extensive field investigation program, giving specific priority to industrial and commercial roads. Based on the outcomes, particle build-up process characteristics and respective uncertainties were evaluated and compared for road surfaces in residential, industrial and commercial areas. The study primarily found that both, industrial and commercial land uses generally manifested greater particle build-up loads compared to residential land uses. The study provides estimates for build-up coefficients for a range of land uses, including industrial and commercial with their potential uncertainties in build-up predictions. This provides new knowledge to improve stormwater quality modelling. Aside from land use, the proximity of sites to major road networks was also identified as a critical factor influencing the variability and uncertainty in particle build-up. Variability of the fraction of particles in the <75 µm size range with antecedent dry days exerts the most distinct influence on particle build-up variability across all land uses. The outcomes of this research study are expected to enhance stormwater quality monitoring, modelling and remediation, and thereby promoting greater protection of human and aquatic ecosystem health.

Rainfall erosivity index for the Ghana Atomic Energy Commission site.

Rainfall erosivity is the potential ability for rainfall to cause soil loss. The purpose of this study was to estimate the rainfall erosivity index for the Ghana Atomic Energy Commission site in order to compute the surface erosion rate. Monthly rainfall data, for the period 2003-2012 were used to compute annual rainfall erosivity indices for the site, using the Modified Fournier index. Values of the annual rainfall erosivity indices ranged from 73.5 mm for 2004 to 200.4 mm for the year 2003 with a mean annual erosivity index of 129.8 mm for the period. The Pearson's Coefficient of Correlation was used to establish the relationship between annual rainfall and annual rainfall erosivity. This showed a high degree of positive relationship (r = 0.7) for the study area. The computed mean annual erosivity index revealed that the site is in the high erosion risk zone. Therefore, it is necessary to develop soil protection and management strategies to protect the soil from erosion.