Populations and metropolitan centers are accumulated in coastal areas around the world. In view of the fact that they are geographically adjacent to coasts and intense anthropogenic activities, increasing global offshore pollution has been an important worldwide concern over the past several decades and has become a very serious problem that needs to be addressed urgently. Due to offshore pollution, various geological disasters occur in high frequency, including intensified erosion and salinization of coastal soils, frequent geological collapses and landslides and increasing seismic activities. Moreover, offshore pollution shows increasingly serious impacts on the topography and geomorphology of offshore and coastal areas, including coastal degradation, retreating coastlines and estuary delta erosion. Offshore sedimentation processes are strongly influenced by the pH changes of terrestrial discharges, and sedimentary dynamics have become extremely acute and complex due to offshore pollution. The seabed topography and hydrodynamic environment determine the fate and transport of pollutants entering offshore regions. Coastal estuaries, port basins and lagoons that have relatively moderate ocean currents and winds are more likely to accumulate pollutants. Offshore regions and undersea canyons can be used as conduits for transporting pollutants from the continent to the seabed. It is particularly noteworthy that the spatial/temporal distribution of species, community structures, and ecological functions in offshore areas have undergone unprecedented changes in recent decades. Due to increasing offshore pollution, the stable succession and development trend of marine ecosystems has been broken. It is thus important to identify and regulate the quantity, composition and transportation of pollutants in offshore regions and their behavior in marine ecosystems. In particular, crucial actions for stabilizing marine ecosystems, including increasing species and biodiversity, should be implemented to enhance their anti-interference capabilities. This review provides an overview of the current situation of offshore pollution, as well as major trends of pollutant fate and transportation from continent to marine ecosystems, transformation of pollutants in sediments, and their bioaccumulation and diffusion. This study retrospectively reviews the long-term geological evolution of offshore pollution from the perspective of marine geology, and analyses their long-term potential impacts on marine ecosystems. Due to ecological risks associated with pollutants released from offshore sediments, more research on the influence of global offshore pollution based on marine geology is undoubtedly needed.

Interactions between microorganisms and clay minerals influence the transport and cycling of metal contaminants in both marine and terrestrial environments. The present study was conducted to quantify the adsorption of dissolved cadmium, Cd(II), under seawater-like conditions to the marine cyanobacterium Synechococcus sp. PCC 7002, three common clay minerals (kaolinite, montmorillonite and illite), as well as cell-clay aggregates. We show here that the Synechococcus-only experiments removed the most Cd above pH 5.5, followed in decreasing order by aggregates of 50% cells:50% individual clays, aggregates of cells and all 3 clays, and individual clays. Electron microscope imaging showed that clays associated in a tangential edge-on orientation to the cells in Synechococcus-clay mineral aggregates. A non-electrostatic surface complexation modeling approach was used to fit Cd adsorption onto Synechococcus cells and individual clay minerals. The resulting Cd binding constants were then used in consort with surface functional group pKa values and site concentrations to accurately predict the extent of Cd adsorption onto the Synechococcus-clay mineral aggregates using the component additivity (CA) approach. We observed that the addition of cyanobacterial cells to clay mineral suspensions led to significantly larger mean aggregate sizes of clay minerals, enhancing the clay sedimentation rate. Although specifically focused on Cd, our study indicates that the ratio of bacterial plankton to clay minerals is an important determinant in terms of understanding the rate with which metals are transferred from the water column to the seafloor.

Marine bacterial plankton play a key role in elemental cycling through their ability to bind, assimilate, metabolize, and modify the redox state of trace metals in seawater. Of those processes, arguably the least studied are the mechanisms underpinning trace metal adsorption to planktonic marine bacteria, despite a plethora of literature pertaining to terrestrial species. Recently, Liu et al. (2015) demonstrated that the marine cyanobacterium Synechococcus sp. PCC 7002 has the capacity to remove appreciable amounts of Cd2+, a proxy for other divalent cations, from seawater by adsorption. In this study, we build on that work and employ a surface complexation modelling (SCM) approach using titration and pH adsorption edge experiments to calculate the thermodynamic binding constants of four bioessential transition metals (Co, Ni, Cu, Zn) to Synechococcus in simulated seawater. Based on the titration results, the major functional groups involved in metal binding were carboxyl groups with a pKa of 5.59 and phosphoryl groups with a pKa of 7.61. Metal adsorption experiments indicate that Synechococcus can bind considerable concentrations of Zn, Cu, Ni, and Co at pH 8. When all four metals are simultaneously added to solution, the same adsorption pattern of Zn > Cu > Ni > Co is maintained, and accurately predicted by the SCM. Based on average marine cell densities and turnover rates of Synechococcus cells in the photic zone, we calculate that Synechococcus, in the absence of competing ligands such as dissolved organic matter (DOM), has the theoretical capacity to remove nearly all of the free metal cations from seawater. These observations highlight the surface reactivity of marine cyanobacteria as a potentially important vector for the transfer of dissolved metals from the photic zone to deeper waters or the seafloor in modernoceans, but they also have implications for the Precambrian oceans as sinking cyanobacteria could have acted as an exit channel for trace elements into ancient sediments including banded iron formations (BIF).

In marginal marine settings, understanding the role that clay minerals play in the transfer of metal cations from the water column to the seafloor is important if the composition of modern muds is to be used as a proxy for the precursors of ancient shale deposits. In this study, we conducted potentiometric titrations of three naturally abundant clay minerals (kaolinite, montmorillonite and illite) in 0.56 M NaCl electrolyte solutions to ascertain the surface reactivity of each clay mineral at seawater ionic strength. Our results demonstrate that all three clay minerals were increasingly anionic as pH increases from 3 to 9, with montmorillonite having the highest negative-charge. The potentiometric titrations and adsorption data were modeled using both non-electrostatic (NEM) and electrostatic (constant-capacitance model, CCM) surface complexation models (SCMs). A two-site surface complexation model, that included one basal siloxane surface site (equivalent to X-) and one amphoteric edge site (equivalent to SOH), provided an excellent fit for the protonation data of each mineral. Cd(II) adsorption experiments were conducted to quantify the magnitude of cation adsorption, which showed that 10 g montmorillonite, illite, and kaolinite powder could bind an equivalent of 4.7x10(-4) g, 4.3 x 10(-4) g, and 4.0 x 10(-4) g of Cd, respectively, under conditions relevant to seawater (initial Cd concentration of 8.9 x 10(-6) M, and pH = 8). To place this value into the context of modern riverine clay inputs to the ocean, 13.5 x 10(9) tons of total suspended sediment are deposited annually (Milliman and Meade, 1983) of which 10 to 25% is clay (Manheim et al., 1970; Schroeder et al., 2015). The total amount of Cd adsorbed to suspended clay minerals entering the modern oceans could then amount to approximately 10(4) to 10(5) tons per year. The results of this study highlight the potential role of clay minerals in transporting metals from the ocean water column to the seafloor.

Potentiometric titrations are an effective tool to constrain the protonation constants and site concentrations for microbial surface ligands. Protonation models developed from these experiments are often coupled with data from metal adsorption experiments to calculate microbial ligand-metal binding constants. Ultimately, the resulting surface complexation models can be used to predict metal immobilization behavior across diverse chemical conditions. However, most protonation and metal-ligand thermodynamic constants have been generated in laboratory experiments that use cultured microbes which may differ in their chemical reactivity from environmental samples. In this study, we investigate the use of in situ field potentiometric titrations of microbial mats at a carbonate hot spring located at Fairmont Hot Springs, British Columbia, with the aim to study microbial reactivities in a natural field system. We found that authigenic carbonate minerals complicated the potentiometric titration process due to a "carbonate spike" introduced by the contribution of inorganic carbonate mineral dissolution and subsequent carbonate speciation changes during the transition from low to high pH. This inhibits the determination of microbial surface ligand variety and concentrations. Our preliminary study also highlights the need for developing novel probes to quantify in situ microbial mat reactivity in future field investigations.

Measuring the metal binding potential and reactivity of bacterial mats is challenging in alkaline and carbonate-rich systems. Traditional methods used to measure these parameters, such as potentiometric titrations and metal adsorption pH edges, are difficult to implement due to the presence of the carbonate minerals that buffer pH and prevent assessment of mat surface reactivity. Additionally, under alkaline conditions metals may form hydroxide and/or carbonate precipitates. In this study we examined the metal binding capacity of four distinct bacterial mats collected from Fairmont Hot Springs, BC, Canada. To prevent metal precipitation, the bacterial mat concentration was varied under a constant initial cadmium (Cd) concentration of 8.89μM and at pH8. In addition to the intact bacterial mats, a carbonate mineral sample and two bacterial mats in which the carbonate mineral was removed via acid-treatment, were used as end-members to assess the mechanisms of reactivity in the whole system. Freundlich adsorption isotherms were used to fit metal adsorption data and directly compare surface reactivity among intact mats and mat components. Two of the intact mats exhibited a higher affinity for Cd compared to the mineral at metal equilibrium concentrations above 2.5μM, while the other two intact mats had lower affinities under all experimental conditions. Generally, we found the acid-treated mats had higher Cd adsorption capacities than the carbonate mineral. When compared to their equivalent intact mats, only one acid-treated mat had a higher affinity for Cd. Further, we modeled whether metal adsorption in the intact mats, containing microbes and carbonate mineral, could be explained by a linear combination of the observed metal uptake by the organic and inorganic components through end-member experiments. Metal adsorption additivity results were mixed. Metal uptake by one intact mat was found to be additive, while for the other mat the additive model significantly underestimated the observed Cd accumulation. Our study demonstrates the potential, as well as the limitations, of using modified metal adsorption edges to determine the metal binding affinity and surface reactivity of bacterial mats in alkaline and carbonate-rich systems.

The distribution of many trace metals in the oceans is controlled by biological uptake. Recently, Liu et al. (2015) demonstrated the propensity for a marine cyanobacterium to adsorb cadmium from seawater, suggesting that cell surface reactivity might also play an important role in the cycling of metals in the oceans. However, it remains unclear how variations in cyanobacterial growth rates and nutrient supply might affect the chemical properties of their cellular surfaces. In this study we used potentiometric titrations and Fourier Transform Infrared (FT-IR) spectrometry to profile the key metabolic changes and surface chemical responses of a Synechococcus strain, PCC 7002, during different growth regimes. This included testing various nitrogen (N) to phosphorous (P) ratios (both nitrogen and phosphorous dependent), nitrogen sources (nitrate, ammonium and urea) and growth stages (exponential, stationary, and death phase). FT-IR spectroscopy showed that varying the growth substrates on which Synechococcus cells were cultured resulted in differences in either the type or abundance of cellular exudates produced or a change in the cell wall components. Potentiometric titration data were modeled using three distinct proton binding sites, with resulting pKa values for cells of the various growth conditions in the ranges of 4.96–5.51 (pKa1), 6.67–7.42 (pKa2) and 8.13–9.95 (pKa3). According to previous spectroscopic studies, these pKa ranges are consistent with carboxyl, phosphoryl, and amine groups, respectively. Comparisons between the titration data (for the cell surface) and FT-IR spectra (for the average cellular changes) generally indicate (1) that the nitrogen source is a greater determinant of ligand concentration than growth phase, and (2) that phosphorus limitation has a greater impact on Synechococcus cellular and extracellular properties than does nitrogen limitation. Taken together, these techniques indicate that nutritional quality during cell growth can noticeably influence the expression of cell surface ligands and their measurable densities. Given that cell surface charge ultimately affects metal adsorption, our results suggest that the cycling of metals by Synechococcus cells in the oceans may vary regionally.

The past two decades have seen a significant advancement in our understanding of bacterial surface chemistry and the ability of microbes to bind metals from aqueous solutions. Much of this work has been aimed at benthic, mat-forming species in an effort to model the mechanisms by which microbes may exert control over metal contaminant transport in soils and groundwater. However, there is a distinct paucity of information pertaining to the surface chemistry of marine planktonic species, and their ability to bind trace metals from the ocean’s photic zone. To this end, the surface properties of the cyanobacterium Synechococcus sp. PCC 7002 were studied as this genus is one of the dominant marine phytoplankton, and as such, contributes significantly to metal cycling in the ocean’s photic zone. Zeta potential measurement indicates that the cell surfaces display a net negative charge. This was supported by potentiometric titration and Fourier transform infrared spectroscopy analyses demonstrating that the cells are dominated by surface proton releasing ligands, including carboxyl, phosphoryl and amino functional groups, with a total ligand density of 34.18±1.62mmol/g (dry biomass). Cd adsorption experiments further reveal that carboxyl groups play a primary role in metal adsorption, with 1.0g of dry biomass binding an equivalent of 7.05×10−5M of Cd from solution at pH=8. To put this value into context, in 1L of seawater, and with an open-ocean population of Synechococcus of 105cells/mL in the photic zone, approximately 10nmol of Cd could potentially be adsorbed by the cyanobacteria; an amount equivalent to seawater Cd concentrations. Although we have only focused on one microbial species and one metal cation, and we have not considered trace element assimilation, our results highlight the potential role of surface sorption by phytoplankton in the cycling of metals in the ocean.

Veterinary antibiotics introduced into soil environment may change the composition and functioning of soil microbial communities and promote the spreading of antibiotic resistance. Actual risks depend on the antibiotic's bioaccessibility and sequestration in soils, which may vary with contact time and soil properties. We elucidated changes in the horsebean plant's bioaccessible oxytetracycline with increasing contact time in three different soils (cinnamon, red, and brown soil) and observed discrepancy in oxytetracycline dissipation using sequential extractions with H2O-, 0.01 M CaCl2-, and Mcllvaine- in the same three soils. The results showed lower quantities of oxytetracycline with increasing contact time over 20 days than the level in freshly contaminated soils but hugely discrepant quantities among the three tested soils. In addition, aging largely reduced dissipation of H2O-, 0.01 M CaCl2-, and Mcllvaine- extracted oxytetracycline in soils before planting. However, bioturbation helped increase the H2O-, CaCl2-, and Mcllvaine- extracted oxytetracyline from cinnamon and brown soils with aging. Lastly, correlation analysis indicated that bioaccessibility of oxytetracycline significantly correlates with the total of H2O-, CaCl2-, and Mcllvaine- extracted oxytetracycline (0.676**, p < 0.01) in soils, especially the H2O- (0.789**, p < 0.01) and Mcllvaine- (0.686**, p < 0.01) extracted oxytetracycline with aging. Overall, this study provides some basic understanding of the aging effect on sequestration and bioaccessibility of veterinary antibiotics in soils.

The binary competitive effect could obviously influence the fate and transport behavior of oxytetracycline (OTC) and cadmium (Cd2+) in cinnamon soil. However, two pollutants loading into soil usually are different, perhaps because of the three reasons including occurrence of OTC before Cd2+, simultaneous occurrence of OTC and Cd2+, or occurrence of Cd2+ before OTC. The purpose of the study was to predict the competitive adsorption and desorption of OTC and Cd2+ as a function of above input loadings on cinnamon soil.