Carbon-capture and storage is considered to be a potential mitigation option for climate change. However, accidental leaks of CO2 can occur, resulting in changes in ocean chemistry such as acidification and metal mobilization. Laboratory experiments were performed to provide data on the effects of CO2-related acidification on the chemical fractionation of metal(loid)s in marine-contaminated sediments using sequential extraction procedures. The results showed that sediments from Huelva estuary registered concentrations of arsenic, copper, lead, and zinc that surpass the probable biological effect level established by international protocols. Zinc had the greatest proportion in the most mobile fraction of the sediment. Metals in this fraction represent an environmental risk because they are weakly bound to sediment, and therefore more likely to migrate to the water column. Indeed, the concentration of this metal was lower in the most acidified scenarios when compared to control pH, indicating probable zinc mobilization from the sediment to the seawater.

Estuarine sediments can be a source of Phosphorus (P) to coastal waters, contributing to nutrient budgets and geochemical cycles. In this work, the concentration and speciation of P in 47 cores were examined from the inter-tidal mud flats of the tidal river Thames (~120km). Results of P concentration and speciation were combined with published data relating to known sediment dynamics and water chemistry (salinity) within the estuary to produce a conceptual model of sediment-P behaviour. Results demonstrated significant P desorption occurring after sediment passed through the Estuarine Turbidity Maximum and when the salinity of the river water exceeded ~6ppt. It was found that organic P was desorbed to a greater extent than inorganic P in the lower estuary. Models were used to identify those geochemical parameters that contributed to the Total P (R²=0.80), oxalate extractable P (R²=0.80) and inorganic P (R²=0.76) concentrations within the Thames estuary.

Geochemical speciation of As, Cd, Co, Cr, Cu, Ni, Pb, V and Zn were determined in the surface sediments of the southern Caspian Sea. A five-step sequential extraction technique was used to determine the chemical forms of metals. Mean concentrations (ppm) of heavy metals were (mean±S.D.) As: 9.94±1.71, Cd: 0.87±0.23, Co: 14.85±2.80, Cr: 72.29±19.48, Cu: 18.91±4.48, Ni: 32.87±5.25, Pb: 12.48±3.22, V: 86.07±20.71 and Zn: 66.85±10.11. Among the metals, Cu, As, Pb and Zn exhibited relatively higher mobility, while Cd, Co, Cr, Ni and V were found mainly in the residual fractions. Cu and As showed the highest percentages in the exchangeable phase while Co and Cr had the lowest percentages in the phase. The Risk Assessment Code (RAC) values indicated that As, Cu and V had medium risk at some sampling sites. According to pollution load index (PLI), sediments from some sampling sites were polluted.

Sediment collected from the estuarine mangroves of the Zuari estuary and Cumbharjua canal were analyzed to assess the concentration, contamination and bioavailability of metals. Mangrove pneumatophores were also analyzed to understand the metal bioaccumulation in mangrove plants. The results indicated the variation of metal concentrations in sediment along the estuary was attributed to changing hydrodynamic conditions, type of sediment and metal sources. Further, speciation studies revealed that Fe, Cr, Co, Ni, Cu and Zn were mainly of lithogenic origin and less bioavailable while high Mn content in the sediment raised concerns over its potential mobility, bioavailability and subsequent toxicity. The mangrove plants exhibited difference in metal accumulation due to variations in sediment parameters and metal availability, in addition to difference in plant species and tissue physiology that affect metal uptake. Moreover, the mangrove plants reflected the quality of the underlying sediment and can be used as a potential bio-indicator tool.

The bioavailability and risk assessment of As were studied in sediments of the Yangtze River estuary (YRE). Results showed that residual fractions dominated the As partition (>85%), which attenuated overall bioavailability. After the residual fraction, As mainly partitioned into the Fe-Mn oxides fraction (3.16–4.22%). Arsenic bound to Fe-Mn oxides was higher in wet seasons. The carbonate fraction was minimal, which may result from the negative state presence of As in sediments. According to the risk assessment code, the YRE was classified as low risk. Additionally, the reduction of As(V) to As(III) may occur due to the reducing condition in wet seasons. Considering As(III) is more toxic and mobile, As bound to the exchangeable and Fe-Mn oxides fractions may have more potential ecological risk. Thus, the speciation and fraction should be both considered on the ecological risk of As in sediments of the YRE.

Mercury and its speciation were studied in surface and deep waters of the Adriatic Sea. Several mercury species (i.e. DGM – dissolved gaseous Hg, RHg – reactive Hg, THg – total Hg, MeHg – monomethyl Hg and DMeHg – dimethylmercury) together with other water parameters were measured in coastal and open sea deep water profiles. THg concentrations in the water column, as well as in sediments and pore waters, were the highest in the northern, most polluted part of the Adriatic Sea as the consequence of Hg mining in Idrija and the heavy industry of northern Italy. Certain profiles in the South Adriatic Pit exhibit an increase of DGM just over the bottom due to its diffusion from sediment as a consequence of microbial and/or tectonic activity. Furthermore, a Hg mass balance for the Adriatic Sea was calculated based on measurements and literature data.

The present study investigated the concentration, distribution and speciation of metals (Fe, Mn, Cu, Pb, Co, Zn and Cr) in sediments of Mumbai region. Pearson’s correlation matrix and cluster analyses showed good association of metals with grain size and organic matter. Factor analysis applied to the speciation data helped to identify the role of different sediment fractions in metal retention. The environmental risks of metals, evaluated by sediment quality guidelines, revealed some contamination in the region. However, the Individual and Global Contamination Factors and the Risk Assessment Code, suggested low risk to the aquatic environment, except of Mn in the creek sediments.

One of the main risks associated with carbon capture and storage (CCS) activities is the leakage of the stored CO2, which can result in several effects on the ecosystem. Laboratory-scale experiments were performed to provide data on the possible effects of CO2 leakage from CCS on the mobility of metals previously trapped in sediments. Metal-contaminated sediments were collected and submitted to acidification by means of CO2 injection using different pH treatments. The test lasted 10days, and samples were collected at the beginning and at the end of the experiment for metal analysis. The results revealed increases in the mobility of metals such as Co, Cu, Fe, Pb and Zn due to pH decreases. Geochemical modeling demonstrated that acidification influenced the speciation of the metals, increasing the concentrations of their free forms. These data suggest the possible sediment contamination consequences of accidental CO2 leakage during CCS activities.

Marine mercury (Hg) concentrations have been monitored in the French coastline for the last half a century using bivalves. The analyses presented in this study concerned 192 samples of bivalves (mussels: Mytilus edulis and Mytilus galloprovincialis and oysters: Crassostrea gigas and Isognomon alatus) from 77 sampling stations along the French coast and in the French Antilles sea. The goals of this study were to assess MeHg levels in various common bivalves from French coastline, and to identify possible geographic, taxonomic or temporal variations of concentrations. We show that the evolution of methylmercury (MeHg) concentrations covary with total mercury (HgT) concentrations. Moreover, in most of the study sites, HgT concentrations have not decreased since 1987, despite regulations to decrease or ban mercury used for anthropic activities.