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Sediment traps were deployed in the Tema Harbour to estimate the settling fluxes of silt-clay particles and associated metals (Fe, Mn, Pb, Cr, Cu, Zn, Ni, Hg, Sn and As) and characterise their potential ecotoxicological risks. The mean daily settling fluxes of the silt-clay particles and associated metals ranged from 42.7 to 85.0gm -2 d -1 and 1.3×10 -2 to 49.4mgm -2 d -1 , respectively, and were characterised by large fluctuations at each station. The silt-clay and metal fluxes strongly correlated, indicating the important role of the silt-clay particles in metal transport and distribution in the harbour. Geochemical indices indicated anthropogenic influences on the harbour as the Pb, Cr, Zn, Hg, Sn and As content in the settling silt-clay particles exceeded their average crustal concentrations. Sediment quality guidelines indicated these metals pose appreciable ecotoxicological risks, particularly As. Increasing temporal trends in As necessitates increased pollution control efforts at the harbour., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Settling fluxes and sediment accumulation rates in coastal Tema Harbour (Ghana) were investigated by the combined analyses of results in sediment traps and sediment cores. Sediment traps were deployed at 5 stations within the Tema Harbour at two sampling depths and were retrieved every two weeks till the end of 12weeks to estimate the Settling Fluxes (SFs). Four sediment cores from the harbour were analysed for their radioactivity ( 7 Be, 234 Th, 210 Pb, 212 Pb, 226 Ra, 40 K and 137 Cs) profiles to quantify Sediment Accumulation Rates (SARs). The sediment cores exhibited variable bulk density profiles, indicating highly dynamic and non-steady sedimentation conditions. 7 Be-derived gross-estimates of very recent SARs using the constant flux-constant sedimentation (CF-CS) model were in the range of 2.5-9.0g·cm -2 ·y -1 . These values were much lower than the estimated average SFs (15.2-53.8g·cm -2 ·y -1 ), indicating sediment resuspension plays an important role. On a decadal time scale, conventional 210 Pb sediment dating models did not allow any estimation of SARs in the Tema Harbour. Thus, the 210 Pb-based TERESA model was applied to depict a reliable scenario for sedimentation with time-averaged SARs in the range of 1.4-3.0g·cm -2 ·y -1 and fluxes of matter contributed by the marine inflow and local sources. Sediment accretion rates of 1.7-3cm·y -1 were also inferred, which may pose a moderate problem of sustainability for the Tema Harbour. This study reveals how the geochemical behaviour of different radionuclides with Gamma spectrometry in the marine environment can be used to obtain reliable information on the complex dynamics of Suspended Particulate Matter (SPM), even in a very disturbed and anthropic environment as a coastal harbour area where (1) conventional 210 Pb-based dating methods fail and (2) the use of sediment traps and 234 Th and 7 Be profiles in sediment cores show serious constraints., (Copyright © 2017 Elsevier B.V. All rights reserved.)

This study assessed DDTs, HCHs and PAHs contamination in sediments from the Tema Harbour (Ghana) and the associated ecotoxicological risks. The results showed widespread DDTs, HCHs and PAHs contamination in the harbour sediments with mean concentrations ranging from 6.0-12.8, 2.8-12.7 and 2750-5130μg·kg -1 d·w, respectively. The silt-clay and total organic carbon contents of the sediments poorly correlated with the pollutant concentrations. DDTs and HCHs contamination relate to past use of DDT and lindane, which under the anoxic harbour conditions resulted in disproportionately higher concentrations of p,p'-DDD and γ-HCH in the sediments. No conclusion could be drawn on the sources of PAHs as either petrogenic or pyrogenic. The pollutant concentrations in the harbour sediments, particularly γ-HCH, may pose high ecotoxicological risks. In comparison to a previous study, this study indicates there has been a considerable reduction in PAH contamination in the Tema Harbour since the last major oil spill in 2007., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

We present results of a preliminary geochemical assessment of Cd, Pb, V, As, Ni, Cu, Zn, Mg, Al, K, Ca, and Fe in marine sediments from the Eastern Equatorial Atlantic, off the Coast of Ghana. Samples were taken along 4 regions G1, G2, G3 and G4 at approximately 25m, 100m, and 250m, 500m and 1000m depths. Elemental compositions were assessed through the estimation of Al-normalized enrichment factors and geochemical accumulation indices, and the concentrations determined to produce any potential toxic effects to biota. Significant enrichment of the bottom sediments with Cd, Ni and As were observed at some locations with sediments showing signs of heavy pollution with As at region G4. Apart from Ni, V and As which were beyond threshold effects levels at most regions, all other metals were below probable effect levels. Both natural and anthropogenic processes controlled trace metal accumulation and distribution in the Ghanaian coastal environment., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

In the present study, the concentrations of persistent organochlorine (OC) pesticides such as dichlorodiphenyltrichloroethane and its metabolites (DDTs), hexachlorocyclohexane isomers (HCHs), hexachlorobenzene (HCB) and dieldrin in pooled samples of human breast milk (n=109), and serum (n=115) from vegetable farmers in Ghana, during 2005, were determined. Gas chromatography with mass spectrometry was used to quantify residue levels on a lipid basis of the OCs. The pattern of OCs in human fluid showed that DDTs was consistently the prevalent OC in milk and blood. The levels of DDTs, HCHs, and dieldrin in the breast milk samples were found to correlate positively with age of the milk sample donors (r(s)=0.606, 0.770, and 0.540, respectively). When blood serum levels of the OCs were compared between male and female farmers, no pronounced relationship for HCHs and HCB (p>0.05) was observed. However, DDTs and dieldrin residues were significantly higher (p<0.05) in males than in females. There was association between breast milk and serum residues. When daily intakes of DDTs and HCHs to infants through human breast milk were estimated, some individual farmers (in the case of DDTs) and all farmers (in the case of HCHs) accumulated OCs in breast milk above the threshold (tolerable daily intake, TDI, guidelines proposed by Health Canada) for adverse effects, which may raise concern on children health.

The trypanocidal effects of aqueous gold(III) and palladium(II) and their metalloporphyrin derivatives on Trypanosoma brucei brucei growth in culture have been studied using an Alamar Blue indicator assay. All the experiments were conducted in the dark. As previously described for mercury(II), cadmium(II) and lead(II) porphyrins [Chem.-Biol. Interact. 139 (2002) 177], the toxicity of the metalloporphyrin complex of palladium(II) to T. b. brucei parasites was much higher compared to the aqueous free palladium(II) and free base porphyrin. Palladium(II) porphyrin, free palladium(II), and the free base porphyrin were trypanocidal to T. b. brucei at concentrations >1.5 x 10(-6), >6.1 x 10(-6) and >1.9 x 10(-5) M, respectively. While gold(III) porphyrin was effective against the parasites at concentrations >4.8 x 10(-6) M, its aqueous gold(III) was toxic at concentrations as low as 2.0 x 10(-7) M due to the generation of free radicals in the presence of this metal ion which enhanced its toxicity to the T. b. brucei parasites. Although some cell division was observed in some of the cells treated with palladium(II) porphyrin, some dividing cells had no nucleus due to unequal division and delivery of the nuclei into the daughter cells. As a result, the rate of cell division decreased with time and cell death occurred within 24 h. Interestingly, trypanosomes treated with metalloporphyrin complexes displayed different morphological features from those cells treated with free base porphyrin or metal ions. Of all the porphyrins and free metal ions tested, only mercury(II) porphyrin and aqueous gold(III) ion were toxic to the trypanosomes in the 10(-7) M range. The chemotherapeutic potential of these observations is discussed.

The interactions of the metalloporphyrins of tetrakis (1-methylpyridinium-4yl)porphyrin ([M(TMPyP)](4+)) where M=Hg(II), Cd(II) and Pb(II)) with pBluescript II plasmid DNA have been studied by the measurement of circular dichroism (CD), UV-visible and fluorescence spectra at 0.1 M NaNO(3), pH 7.5 and 25 degrees C. The CD spectra of the DNA changed quite significantly, with the conformational changes in the presence of the metalloporphyrins being much more enhanced compared to that of their free metal ion counterparts. The conformational changes in DNA upon binding to the Hg(II) porphyrin and Hg(II) were, however, different from those of the Cd(II) porphyrin, Pb(II) porphyrin, Pb(II), Cd(II) and H(2)(TMPyP)(4+). In the concentration range of 0-2.30 x 10(-5) M of DNA, the absorption spectra of H(2)(TMPyP)(4+) showed substantial hypochromicity at 423 nm and a red shift of Deltalambda=16 nm in the presence of DNA whereas the Hg(II)-, Pb(II)- and Cd(II) porphyrins showed blue shifts of absorption maximum wavelengths of Deltalambda=-17 nm, Deltalambda=-35 nm and Deltalambda=-4.5 nm, respectively. Furthermore, the shifted absorption maximum wavelengths/nm of the porphyrins in excess amount of DNA were comparable; 438, 439, 440 and 440 for H(2)(TMPyP)(4+), Hg(II)-, Pb(II)- and Cd(II) porphyrins, respectively. The changes in absorption spectra for Hg(II)-, Pb(II)- and Cd(II) porphyrins revealed that these metalloporphyrins dissociated upon binding to DNA which was confirmed by CD as well as fluorescence spectra. The CD results, UV-Vis and fluorescence data indicate that the metalloporphyrins interact differently with DNA based on their binding modes. And the enhanced changes in conformation of DNA in the presence of the metalloporphyrins are due to the synergistic effects of the simultaneous binding of the metal ions and the free base porphyrin to DNA compared to their free metal ion counterparts: [M(TMPyP)](4+)+DNA+2H(+) right harpoon over left harpoon [M(II)(DNA)H(2)(TMPyP)(4+)]. The detailed equilibrium reactions have been described along with suggestions of possible applications in the medical and biological fields.

The effects of free mercury(II), cadmium(II) and lead(II) ions and their metalloporphyrin-derivatives on Trypanosoma brucei brucei growth in culture were studied. All experiments were conducted in the dark. IC(50) values on growth obtained in 24-h time-course experiments were 1.5 x 10(-7), 2.4 x 10(-6), 4.4 x 10(-6) and 2.6 x 10(-5) M for mercury(II) porphyrin, cadmium(II) porphyrin, lead(II) porphyrin and free base porphyrin, respectively. While the IC50 values for Hg2+, Cd2+ and Pb2+ were 3.6 x 10(-6), 1.5 x 10(-5) and 1.6 x 10(-5) M, respectively. These results clearly indicate that the toxicity of the metalloporphyrin complexes of mercury(II), cadmium(II) and lead(II) to T. b. brucei parasites was much higher compared to their free metal ions and free base porphyrin at low concentrations. It was also observed after 8 h incubation that the metalloporphyrins were effective in inhibiting the division of the parasites at concentrations >1.25 x 10(-7) M for mercury(II) porphyrin, concentrations >1.2 x 10(-6) M for cadmium(II) and lead(II) porphyrins and at concentrations >3.6 x 10(-6) M for Hg2+ ion. These observations were not detected in samples treated with the free metal ions and the free base porphyrin at the same concentrations. Interestingly, trypanosomes treated with metalloporphyrin complexes displayed different morphological features from those cells treated with free base porphyrin or metal ions. The chemotherapeutic potential of the metalloporphyrins of H2TMPyP for treatment of African trypanosomiasis is discussed.