Heavy metals speciation in surface sediments of the Cross River Estuary, Gulf of Guinea, South East Nigeria.

The speciation of heavy metals (Ni, Cr, Cu, Zn, Pb, and Cd) was studied in surface sediments of the Cross River Estuary (CRE), Gulf of Guinea, South East Nigeria. Pb (~56 %), Cd (~71 %), Zn (~67 %), and Cr (~76 %) were mainly available in non-residual phases, suggesting potential bioavailability. High contents of Ni and Cu in residual phase indicated immobilization of these metals in aluminosilicate minerals. Cd was the most polluted heavy metal with the highest bioavailability risk. Bayesian Network model results revealed that sedimentary organic carbon (OC) from terrestrial C3 plants controlled the contents and variability of Pb and Zn, while the input of terrestrial soil OC strongly influenced Cu and Ni. However, Cd and Cr were dominantly influenced by sediment pH, while Ni was mainly influenced by sediment salinity. Strong interdependency between Cd and total nitrogen (TN) suggested that nitrogen might increase Cd bioavailability upon release from sediments.

Contamination and ecological risk assessment of heavy metals, and relationship with organic matter sources in surface sediments of the Cross River Estuary and nearshore areas.

Chemical speciation of heavy metals (Zn, Pb, Cu, and Cd) was studied to evaluate the contamination status and associated risks and to constrain the sources of heavy metals in relation to sedimentary organic matter (OM) sources in surface sediments of the Cross River Estuary (CRE) and nearshore areas surrounded by a degrading mangrove ecosystem (typical C3 plants). The contamination factor (CF) and geo-accumulation (Igeo) indicated that Cd and Zn were the most polluted heavy metals. High percentages of Zn (63.78%), Pb (64.48%), Cd (76.72%) and the considerable amount of Cu (48.57%) in non-residual fractions indicated that these heavy metals are bioavailable. Cd showed moderate to high ecological and bioavailability risk based on the ecological risk (Er) and risk assessment code (RAC). Significant positive correlations occurred among the heavy metals, fine-grained sediments, and sedimentary OM from terrestrial C3 sources. These correlations, together with high percentages of heavy metals in the oxidizable fraction (~33-50%), indicated that the erosive washout of OM and fine sediments ladened with heavy metals from the adjoining degraded mangrove ecosystem contributed significantly to the increased contents of heavy metals in surface sediments of the study area.

Geochemical discrimination of bulk organic matter in surface sediments of the Cross River estuary system and adjacent shelf, South East Nigeria (West Africa).

Knowledge of the sources, distribution and fate of organic matter (OM) in estuarine and adjacent shelf sediments are important for the understanding of the global biogeochemical cycles. Bulk organic carbon (C-org), total nitrogen (TN), biogenic silica (BSi), stable carbon (δ13C-org) and nitrogen (δ15N) isotopes, and sediment grain sizes were measured to study the spatial distributions and sources of sediment OM in the Cross River estuary system (CRES) and adjacent shelf. Surface sediments in the CRES were composed of clayey silt and sandy silt, while the adjacent shelf sediments were mainly silty sand. The range of the studied parameters was -28.79‰ to -22.20‰ for δ13C-org, -1.32‰-6.31‰ for δ15N, 6.7-29.2 for C-org/N ratios, 0.08%-0.33% for TN, 0.24‰-0.74‰ for BSi, and 0.47%-5.28% for C-org, and their spatial distributions showed a general decreasing trend in both the terrestrial and estuarine OM from the riverine regions to the adjacent shelf. Based on the three-end-member mixing model using the δ13C and δ15N isotopic values, ~58.01 ±â€¯15.32% of sediment OM are derived from terrestrial sources dominated by C3 vascular plants, while ~26.34 ±â€¯9.71% are attributed to estuarine sources dominated by aquatic macrophytes, and ~15.65 ±â€¯12.37% for marine plankton source. Other sources of OM identified included soils underlain C3 vascular plants and agricultural farms enriched with N, sewage, and petroleum hydrocarbons. The relationship between C-org vs. BSi, and the atomic BSi/Corg ratios suggested that diatoms also play an important role in OM sequestration in surface sediments of the CRES and adjacent shelf. The correlations of the δ13C-org and δ15N isotopic values vs. C-org/N ratios resulted in scatter plots, indicating that the distributions of sediment OM in the CRES and adjacent shelf are influenced by post depositional processes, fixed inorganic N adsorbed on fine-grained sediments, microbial degradation, as well as sediment grain size.