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.

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.

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.

How aquaculture impacts the coastal phosphorus (P) cycle remains poorly understood. Here we compared different P species from two sedimentary records off Nan'ao Island, South China, with core S1 collected in a large seaweed cultivation area and core S2 in a non-mariculture area. The results showed that the concentration of total P (TP) in sediment cores varied from 143.67 to 400.92 μg/g, and organic P (OP) was the dominant P species. The TOC/OP ratios in the two sediment cores were higher than the Redfield ratio in 26 samples (52%) from core S1 and 39 samples (78%) from core S2, suggesting that terrestrial organic matter was an important carbon source to Shen'ao Bay. The lack of change in Ex-P (exchangeable or loosely sorbed P) and OP in the area around core S1 since the 2000s may be due to the large-scale seaweed cultivation.

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.

Fluxes of dissolved trace metals (Cd, Co, Cr, Cu, Mn, Ni, Pb, and Zn) via groundwater discharge along the southern Baltic Sea have been assessed for the first time. Dissolved metal concentrations in groundwater samples were less variable than in seawater and were generally one or two orders of magnitude higher: Cd (2.1–2.8nmolL−1), Co (8.70–8.76nmolL−1), Cr (18.1–18.5nmolL−1), Mn (2.4–2.8μmolL−1), Pb (1.2–1.5nmolL−1), Zn (33.1–34.0nmolL−1). Concentrations of Cu (0.5–0.8nmolL−1) and Ni (4.9–5.8nmolL−1) were, respectively, 32 and 4 times lower, than in seawater. Groundwater-derived trace metal fluxes constitute 93% for Cd, 80% for Co, 91% for Cr, 6% for Cu, 66% for Mn, 4% for Ni, 70% for Pb and 93% for Zn of the total freshwater trace metal flux to the Bay of Puck. Groundwater-seawater mixing, redox conditions and Mn-cycling are the main processes responsible for trace metal distribution in groundwater discharge sites.

The present study aimed to geochemical speciation of metals in the surface sediments of the northern Persian Gulf. Metal contents in the sediment were observed in the order: Al>Fe>Cr>Ni>V>Zn>Cu>Co>As>Pb>Cd. The results of sequential extraction procedure revealed that all metals were predominantly associated with the residual fraction. Among the metals, Cu and As exhibited higher bioavailability. The risk assessment code (RAC) indicated that Cu, As and Cd had medium environmental risk at some sampling sites. Based on enrichment factor (EF), Cd and As had moderate to significant enrichment.

Metals are non-degradable in the aquatic environment and play a vital role in estuarine biogeochemistry but could also be detrimental to associated biota. A comparative evaluation of the trace metal concentrations (Fe, Mn, Zn, Cu, Ni, and Co) was carried out in the Zuari estuary, Goa during the post-monsoon season of 2013 at six locations, each representing three mangrove and three mudflat regions. In addition, fractionation of trace metals in sediments was performed to provide information on the mobility, distribution, bioavailability and toxicity. Special attention was paid to the marine mollusks viz. bivalves and gastropods that are extensively used as bio-indicators in coastal pollution. Considering the percentage of metals in the sequentially extracted fractions, the order of mobility from most to least bioavailable forms was Mn > Zn > Cu > Ni > Co > Fe. Mn maintained high bioavailability (average around 60%) in Fe–Mn oxide and carbonate bound forms indicating that Mn is readily available for biota uptake. The bioavailability of Fe was on an average of around 6% whereas other metals like Cu, Zn, Ni and Co were around 19% to 34%. When the bioavailable values were compared with standard Screening Quick Reference Table (SQUIRT), Zn showed higher toxicity level and bioavailability in the lower estuary. On the basis of calculated Bio Sediment Accumulation Factors (BSAF's), overall trend in bioaccumulation was in the order of Cu > Zn > Mn > Ni > Co > Fe. Metal Pollution Index (MPI) computed was higher for gastropods than bivalves.