Distributions and sources of polycyclic aromatic hydrocarbons in surface sediments from the Cross River estuary,S.E. Niger Delta,Nigeria

Polycyclic aromatic hydrocarbon (PAH) analyses of surface sediments from the Cross River estuary by gas chromatography–mass spectrometry indicated natural diagenetically derived PAHs in the upper estuary, with minor and variable amounts of petrogenic and combustion-derived PAHs from human activities (lower estuary). The occurrence of significant amounts of perylene (average 23% of all PAHs) with the diagenetic natural PAHs in the middle estuary bordered by mangrove forests supports its origin from terrestrial organic matter. The natural PAHs represent the highest percentage (average 76%) of the total PAHs in this tropical environment. The traditional geochemical parameters, including the petrogenic PAHs, confirmed trace petroleum contamination in the estuary. Specific PAH ratios such as Fl/Py and Fl/(Fl+Py) also support this source contribution.     

PAH depositional history and sources in recent sediment core from Ukwa Ibom Lake, S. E. Nigeria

Analyses of recent sediment core from the Ukwa Ibom Lake show evidence of aquatic production, terrigenous, combustion and petroleum inputs. Total organic carbon/total nitrogen values (>10) for the sediments indicate greater wash-in of land-plant organic matter relative to algal production. The characteristic combustion ratios, fluoranthene/fluoranthene + pyrene (>0.50), anthracene/anthracene + phenanthrene (>0.10), benzo(a)anthracene/benzo(a)anthracene + chrysene (>0.35) as well as 1,7/1,7 + 2,6-dimethylphenanthrene (>0.70) were observed for the top section only. These results coincided with the most recent pave-road extension exercise involving tree logging and burning of bush. The highest total PAH concentration (91.13 ng/g dry weight (dw)) observed for the bottom section coincided with the period of inhabitation of the lake catchments (~5 decades ago) when discharge to the Lake water of domestic sewage and mill waste water were prevalent. The regular decline in total PAH concentrations upcore is a reflection of the ban placed on indiscriminate dumping of wastes following relocation of the inhabitants of the catchments. Besides the local depositional history, the irregular decrease in unresolved complex mixture (UCM) profiles suggests regional contaminant influx from the adjacent upper Cross River estuary, especially during intense rainfall event. The non-uniformity in methylphenanthrene indices (MPI-1 and MPI-2) shows evidence of importation and utilization of petroleum products of different thermal maturity histories into the Nigerian economy.     

Distribution of polycyclic aromatic hydrocarbons (PAHs) and sterols in termite nest, soil, and sediment from Great Kwa River, SE Nigeria

Costal sediment samples from Great Kwa River as well as adjoining termite nest and soil samples were analyzed for quantitative determination of polycyclic aromatic hydrocarbons (PAHs) and sterols using gas chromatography–mass spectrometry (GC–MS) in order to access the possibility of transport of biologically produced PAHs/sterols from termite nest to the sediments. The total PAH concentrations (sum of parent and alkyl) for the sediments ranged between 131.96 and 139.35 ng/g dry weight (dw) while those for the nest and soil samples were in the range 9.51–9.71 and 71.85–77.26 ng/g dw, respectively. These levels of PAHs in sediments were relatively low compared to other urban/industrial Asian and American countries. No evidence of the usual biologically produced PAHs was found, thus reducing the likelihood of transport of these compounds from the nest to the sediments. The absence of parent and alkyl PAHs in central compartment of the nest may reflect the selective fern leaves feeding pattern of the dominant termite species prevalent in the vicinity of the study site. Utilization of six selected PAH ratios such as Fla/(Fla + Pyr) (0.4–0.5), Ant/(Ant + Phe) (0.25–0.90), BaA/(BaA + Chrys) (0.45–0.61), MP/P (0.05–6.81), 1,7/(1,7?+?2,6)-DMP (0.61–0.95), and LPAH/HPAH ( 2.80–3.80) allows discrimination of PAH sources for the samples to be made with a mixed source dominance observed. Examination of sterol distributions in the samples shows relatively high abundance of cholest-5-en-3β-ol in central compartment of the nest, considered here as a consequence of metabolic conversion of phyto-/fungi sterols in the tissues of the termite species. The relatively reduced levels of stanol compounds in central compartment of the nest may be associated with their utilization by the termites for growth and development.     

Even-n-alkane/alkene predominances in surface sediments from the Calabar River, SE Niger Delta, Nigeria

We report the geochemical characterisation of hydrocarbons extracted from surface sediments of the Calabar River and coastal soils, SE Niger Delta, Nigeria using gas chromatography–mass spectrometry (GC–MS). As a result, a special group of organic compounds prevalent in the entire study area was identified. It consists of aliphatic hydrocarbons (7.3–22.2% of the total lipids) with several distinctive chemical features. These include a high abundance of even numbered n-alkanes (n-C₁₂–n-C₂₆, maximising at n-C₁₈, n-C₂₀ and n-C₂₂), n-alk-1-enes (n-C_14:1–n-C_26:1, maximising at n-C_18:1 and n-C_20:1), giving rise to Carbon Preference Indices (CPIs) between 0.15 and 0.82. An unresolved complex mixture (UCM) occurring in the range n-C₁₈–n-C₃₅, and the presence of hopanes indicate petroleum contamination. The predominance of even numbered n-alkanes in the Calabar River sediments are thought to be derived from inputs of different microorganisms inhabiting an oil-polluted environment and contributing to the organic matter (OM). This paper, for the first time, gives an account of the unusual predominance of even numbered n-alkanes/alkenes in surface sediments from the Niger Delta of Nigeria and thus contributes to the information on the rare occurrence of such distributions in the geosphere.     

Risk assessment of human exposure to polycyclic aromatic hydrocarbons via shrimp (<Emphasis Type="Italic">Macrobrachium felicinum</Emphasis>) consumption along the Imo River catchments,SE Nigeria

Shrimp species (Macrobrachium felicinum) collected from estuarine mangrove area of the Imo River is an important route of exposure to polycyclic aromatic hydrocarbons (PAHs). The estuarine associated sediment (EAS) composited sample showed higher TPAH, ΣAlkyl, ΣPAH_carc and ΣPAH_EPA concentrations (550.84, 172.36, 413.17 and 482.11 ng/g dry weight—dw) than their mean concentrations in shrimp samples (509.39 ± 354.21, 31.38 ± 18.49, 52.10 ± 1.35 and 460.06 ± 330.76 ng/g wet weight—ww), respectively. Among the individual PAHs congeners, phenanthrene was the dominant species detected in the EAS accounting for 21.02 % of the total PAH load and the decreasing order of 3- > 2- > 5- > 4- > 6-ring contamination was found. A different pattern predominated by naphthalene was observed for the shrimp species, suggesting that the organisms have different selectivity for a range of PAHs congeners. These variations may be attributed to different degree of bioavailability of these compounds, characteristic sandy lithology of the EAS and the protective capacity of soot particles associated with liquid fossil fuel combustion masking the uptake of high molecular weight PAHs by the organisms. Cancer risk associated with consumption of shrimps in the region was assessed using estimated daily intake (EDI) and compared with standards. The EDI values for naphthalene, benzo(a)pyrene and ∑PAH_carc were lower than the USEPA benchmarks and EFSA levels of concern values for adult and children population, suggesting low probability of developing cancer.