Trace Metals In Seawater Research Articles

Environmental characteristics of trace metals in seawater from the Ninety East Ridge in the Indian Ocean

Environmental characteristics of trace metals in seawater from the Ninety East Ridge in the Indian Ocean

Metal Organic Complexation in Seawater: Historical Background and Future Directions.

The speciation of most biologically active trace metals in seawater is dominated by complexation by organic ligands. This review traces the history of work in this area, from the early observations that showed surprisingly poor recoveries using metal preconcentration protocols to the present day, where advances in mass spectroscopy and stable isotope geochemistry are providing new insights into the structure, origin, fate, and biogeochemical impact of organic ligands. Many long-standing hypotheses about the specific biological origin of ligands such as siderophores in seawater are finally being validated. This work has revealed the complexity of organic complexation, with multiple ligands and, in some cases, timescales of ligand exchange that are much slower than originally thought. The influence of organic complexation on scavenging is now a key parameter in biogeochemical models of biologically essential metals, especially iron. New insights about the sources and sinks of ligands are required to enhance the usefulness of these models.

Dissolved and particulate heavy metal pollution status in seawater and sedimentary heavy metals of the Bohai Bay

Heavy metal contamination has been the focus of many studies owing to its potential risk on the health of coastal ecosystems. The Bohai Bay (BHB) is the second largest bay of Bohai Sea and subjected to serious anthropogenic perturbations. The aim of this study was to evaluate the distribution and pollution status of toxic heavy metals in seawater with two fractions (dissolved and suspended particulate phases) and surface sediments of this coastal system. Therefore, several hydrochemical parameters and concentration of seawater metals and sediment metals were measured at two cruises of 2020 summer and autumn. The spatial distribution and potential ecological risks were examined and their inter-element relationships were analyzed to identify potential geochemical processes. By comparing historical data since 1978, we find declining trends in contents of most trace metals in seawater and sediments, suggesting that recent pollution control in BHB have an effect on diminishing metal pollution. Dissolved metals showed no significant dependence on their particulate phase. The seawater posed a moderate to high level of ecological risk. The hydrochemical factors mainly had a greater impact on dissolved metals during summer, whereas they influenced suspended metals more significantly during autumn. These results provide fundamental information to support environmental quality management and ecological protection in coastal systems.

Coral skeletons reveal the impacts of oil pollution on seawater chemistry in the northern South China Sea

Oil pollution can release trace metals (TMs) with cumulative toxicity into seawater, harming marine ecosystems in the long term. However, the lack of studies has inhibited our understanding of the effects and mechanisms of oil pollution on TMs in seawater. Hence, we investigated the 10-year monthly variation of TMs in Porites coral skeletons from the northern South China Sea (SCS), complemented by spatial distribution of TMs in seawater, sediments and characterization of TMs in fuel oil. The results of principal component-multivariate linear regression showed that the total contribution of oil pollution as a source to TMs in surface seawater was 77.2%, where the residence time of TMs (Ni, V, Cr, Co, Cu, Mn, Fe, and Mo) released from oil spills in surface seawater was approximately 1.4 months. Due to the geochemical nature of the metals, their seasonal variations are controlled by tropical cyclones (Ni, V, Cr, Co, Cu, Mn, Fe, and Mo), winter monsoons (Pb, Cd, Ba, and Zn) and sea surface temperature (Sr). This study shows that coral skeletons can be used as a new tool to study marine oil pollution. This provides valuable reference data for accurately identifying and quantifying the effects of oil pollution on TMs in seawater from a spatial and temporal perspective.

A Chelating Resin of EDTA-Type Modified Cross-Linking Polystyrene to Preconcentrate Trace Metals for Seawater Detection.

The determination of trace metals in seawater is an important project of marine environmental monitoring. However, the presence of many alkali metal ions with high concentration, such as sodium ion, seriously interferes with the detection limit and accuracy of atomic absorption spectrometry (AAS, flame/graphite furnace integrated). The conventional chemical methods for the enrichment of trace metals are complex, and low boiling point organic solvents are used. In this paper, a kind of commercial cross-linked polystyrene resin microspheres was chloromethylated and aminated to introduce EDTA-type amino polycarboxylic groups and then loaded in a column as the absorption filler. A set of seawater pretreatment and enrichment devices was designed and assembled. The enriching process and conditions of trace Cu, Zn, Pb, and Cd in standard seawater were studied. 10 g of the modified resin could enrich the equivalent seawater and remove successfully the light metal ions. pH = 5∼9 and 0.2 mL/min of the flow rate were the suitable conditions for preconcentration. The enriched metal ions in the eluent were analyzed on the AAS. Compared with the conventional solvent method, the novel material and enrichment device have high preconcentration efficiency, strong anti-interference ability, and low cost and could be directly applied for routine seawater detection.

Determination of organic ligands of trace metals in seawater by using electroanalytical methods

Determination of organic ligands of trace metals in seawater by using electroanalytical methods

Mussel Caging and the Weight of Evidence Approach in the Assessment of Chemical Contamination in Coastal Waters of Finland (Baltic Sea)

Contamination status of coastal areas of Finland (northern Baltic Sea) markedly affected by anthropogenic activities (harbours, shipyards and maritime activity, industry, municipal and agricultural inputs, legacy contamination) was assessed for the first time using the weight of evidence (WOE) approach. The key element of the study was the caging (transplantation) of Baltic mussels (Mytilus trossulus) for the measurement of tissue accumulation of polycyclic aromatic hydrocarbons (PAHs) and applying a suite of biomarkers of biological effects of contaminants. Additional variables included in the assessment were trace metals in seawater, macrozoobenthos, near-bottom oxygen levels and eutrophication indicators. The chemical parameters were supported by passive sampling of PAHs and organotins at the study sites. The integrated approach combining all the line of evidence (LOE) variables into the WOE showed separation of some sites as more affected by hazardous substances than others, with the most contaminated areas found around harbour and ship yard areas. The contaminant levels measured in the different matrices were not alarmingly high at none of the areas compared to many other areas within or outside the Baltic Sea under more heavy anthropogenic impact, rarely exceeding any given threshold values for Good Environmental Status of the EU Marine Strategy Framework Directive. However, significant biological effects were recorded in mussels in the most contaminated sites, signifying that the combined effects caused by the contaminants and other environmental factors are disturbing the health of marine organisms in the area. The results of this successful combined application based on the mussel transplantation method and the WOE approach are highly encouraging for further trials in developing the monitoring of chemical contamination in the Baltic Sea.

Benthic trace metal fluxes in a heavily contaminated bay in China: Does the sediment become a source of metals to the water column?

Over three different seasons, seawater, porewater and sediment samples were collected from Jinzhou Bay, a previously heavily contaminated bay, to quantitatively assess the benthic flux of trace metals after a reduction in fluvial/sewage discharge for almost three decades. The spatial distribution patterns of trace metals in seawater, surface sediment, as well as the vertical distribution patterns of metals in porewater and solid phases in short sediment cores were reported. Metal concentrations in seawater and sediment all showed much higher Cd and Zn concentrations inside the Jinzhou Bay compared to the rest of Bohai Sea area. Zn, Ni, Pb and Co all had average benthic fluxes coming out of the sediments to the water column, contributing about 0.5%, 0.3%, 1.4% and 14% to their current standing stock in Jinzhou Bay. Seasonal difference was also identified in seawater and porewater, as well as in the benthic fluxes. In general, benthic fluxes and porewater concentrations all tended to be higher in summer, implying a close relationship between benthic flux and the temperature-dependent organic matter degradation process at the sediment-water interface.Currently, there are clearly still other sources, possibly fluvial/sewage discharge, as the main source of trace metals in Jinzhou Bay waters. For Cd and Cu, concentrations in the water column remain high on an annual basis indicating that sediment still acts as a sink. Conversely, for Pb, Zn, Co, and Ni, the sediment is beginning to act as a source to the water column. Although this may not yet be significant, it will become more and more important with time, and can last for hundreds to thousands of years.

Separation and determination of colloidal trace metals in seawater by cross-flow ultrafiltration, liquid-liquid extraction and ICP-MS

In this study, a method was developed for the desalination and pre-concentration of three colloidal trace metals in seawater, namely Cd, Cu and Pb, using diethylammonium diethyldithiocarbamate and ammonium 1-pyrrolidine dithiocarbamate as chelates. Seawater samples were first treated with cross-flow ultrafiltration (CFUF) for the separation of the colloidal matter of different molecular weights, i.e. 1–3 kDa, 3–10 kDa and 10 kDa-0.22 μm. Then, after acid digestion, the organic chelates and the extracting agent chloroform were added at pH = 3.8. Finally, the organic phase was back extracted, and the target metals in all samples were measured using inductively coupled plasma mass spectrometry (ICP-MS) with low detection limits in the range of 0.13–1.18 pmol L−1. The extraction efficiencies for the three metals were in the range of 92.2%–100.3% with an enrichment factor of 40, and their mass recoveries in the studied colloidal fractions were in the range of 83.1%–103.5%. The developed method has been successfully applied for the analysis of seawater samples collected from the sites off the south coast of North Yellow Sea in Shandong Peninsula, China. For the first time, the distribution of colloidal Cd, Cu and Pb in different molecular weights in this area is reported. The results obtained from real samples demonstrate that the developed method is simple, efficient and convenient for routine analysis with low detection limit.

Distribution of copper-complexing ligands in Canadian Arctic waters as determined by immobilized copper(II)-ion affinity chromatography

Complexation by dissolved organic ligands affects the bioavailability and distribution of copper and other bioactive trace metals in seawater. However, relatively little is known about the origin and identity of marine copper-complexing ligands, particularly in Arctic waters. We used immobilized copper(II)-ion affinity chromatography (IMAC) to isolate dissolved (< 0.2 μm) copper ligands from seawater samples collected during the 2015 Canadian Arctic GEOTRACES expedition. UV detection at 254 nm was employed to monitor elution of the compounds retained by IMAC. The areas of the resulting peaks were used to generate depth profiles that show, for the first time, how copper ligands are distributed across the Canadian Arctic. Copper ligand concentrations ranged from 0.9 to 4.8 nM, the depth of highest ligand concentration often coinciding with the chlorophyll maximum depth. Correlations between ligand concentration and in situ chlorophyll-a fluorescence suggest that marine phytoplankton or cyanobacteria could be an important source of copper ligands. A correlation was also observed between copper ligand and dissolved copper concentrations in Baffin Bay. Comparison of these results with published data for humic substances and other dissolved organic matter suggests that terrestrial input contributes to the pool of ligands captured by IMAC, particularly in the Canada Basin and Canadian Arctic Archipelago.

Evaluation of trace metals in seawater, sediments, and bivalves of Nellore, southeast coast of India, by using multivariate and ecological tool

Urbanization in recent years has driven us to investigate metal contamination on Nellore coast by collecting seawater, sediment, and bivalve samples monthly at five stations from 2015 to 2017. Non-metric multidimensional scaling and cluster analysis indicated that open sea (OS) samples were markedly different from the samples collected at other stations. Strong factor loadings of Al (0.76), Mn (0.79), and Cd (0.78) showed variability in seawater, while those for Fe (0.76), Ni (0.77), Zn (0.85), and Pb (0.81) showed variability in sediment. The mean values of Fe (346 ppm) and Mn (21 ppm) were high in bivalves compared to the mean values of other metals. A higher contamination factor was observed for Cd at Buckingham Canal, while the lowest was observed for sediment in OS. The order of trace metals in sediments according to risk index was Cd > Pb > Cu > Cr > Zn. The results obtained are essential to establish a reference for better comparison of tropical environments.

Adsorption of biologically critical trace elements to the marine cyanobacterium Synechococcus sp. PCC 7002: Implications for marine trace metal cycling

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).

Data trend shifts induced by method of concentration for trace metals in seawater: Automated online preconcentration vs. borohydride reductive coprecipitation of nearshore seawater samples for analysis of Ni, Cu, Zn, Cd, and Pb via ICP‐MS

AbstractThis research compares performance, reproducibility, and detection limits of ambient seawater analysis for trace metals using both borohydride reductive coprecipitation and an automated chelation column (seaFAST™ 2) preconcentration for matrix interferent elimination on total and dissolved grab samples in nearshore to marine waters, over a broad concentration range, prior to inductively coupled plasma mass spectrometry (ICP‐MS) injection. A move to an online preconcentration method both minimizes sample preparation, and eliminates correction errors when accounting for trace impurities in precipitated samples, induced via reagents. The reproducability of the online preconcentration method described, coupled with low blanks and method detection limits (MDLs), demonstrates the effectiveness of the automated procedure using ethylenediaminetriacetic and iminodiacetate acid chelation exchange resin and multianalyte determination by ICP‐MS for total and dissolved Ni, Cu, Zn, Cd, and Pb in marine water samples. Average CASS‐5 recoveries using the online preconcentration method (n = 9) were 109% ± 7%, 104% ± 5%, 103% ± 7%, 101% ± 3%, and 86% ± 8%, respectively. The MDLs obtained from the automated method for Ni, Cu, Zn, Cd, and Pb were 3.3, 1.8, 13.5, 4, and 10 times lower, respectively, than for the Borohydride method. There were statistically significant differences between the methods for CASS‐5 recoveries of Ni, Cu, Zn (p &lt; 0.0001), and Pb (p = 0.0024). Comparison of methods gave high concordance (rC ≥ 0.90) between methods for total and dissolved Ni, Cu, Zn, and Pb, and total Cd.

Chemical speciation of trace metals in seawater

Chemical speciation of trace metals in seawater

Effect of Acidic Industrial Effluent Release on Microbial Diversity and Trace Metal Dynamics During Resuspension of Coastal Sediment.

Both industrial effluent discharge and the resuspension of contaminated marine sediments are important sources of trace metals in seawater which potentially affect marine ecosystems. The aim of this study was to evaluate the impact of the industrial wastewaters having acidic pH (2–3) and containing trace metals on microbial diversity in the coastal ecosystem of the Gulf of Gabès (Tunisia, southern Mediterranean Sea) subjected to resuspension events of marine sediments. Four trace elements (As, Cd, U, and V) were monitored during 10-day sediment resuspension experiments. The highest enrichment in the seawater dissolved phase was observed for Cd followed by U, V, and As. Cd remobilization was improved by indigenous microbial community, while U release was mainly abiotic. Acidic effluent addition impacted both trace metal distribution and microbial diversity, particularly that of the abundant phylum Bacteroidetes. Members of the order Saprospirales were enriched from sediment in natural seawater (initial pH > 8), while the family Flavobacteriaceae was favored by acidified seawater (initial pH < 8). Some Flavobacteriaceae members were identified as dominant species in both initial sediment and experiments with acidic wastewater, in which their relative abundance increased with increasing dissolved Cd levels. It could be therefore possible to consider them as bioindicators of metal pollution and/or acidification in marine ecosystems.

Passive sampling monitoring of PAHs and trace metals in seawater during the salvaging of the Costa Concordia wreck (Parbuckling Project)

Passive sampling techniques were used for monitoring trace metals and polycyclic aromatic hydrocarbons (PAHs) in the seawater surrounding the Costa Concordia shipwreck (Isola del Giglio, Italy). The monitoring lasted two and a half years (2012–2014) and considered all four phases of the “parbuckling project”: stabilisation of the wreckage, installation of steel caissons on both sides of the wreck, parbuckling, and refloating. Dissolved trace metals (Cd, Cr, Cu, Hg, Ni, Pb, and V) were measured with diffusive gradients in thin films (DGT), while freely dissolved PAHs were measured with semi-permeable membrane devices (SPMDs). Passive sampling allowed to detect very low concentrations of contaminants, and indicated significant differences among the sampling stations and among the different steps for salvaging the wreck. The results suggested that the main source of contamination was the heavy working vessel traffic at the disaster site, rather than the release of contaminants from the wreck.

Inter-laboratory study for the certification of trace elements in seawater certified reference materials NASS-7 and CASS-6.

Certification of trace metals in seawater certified reference materials (CRMs) NASS-7 and CASS-6 is described. At the National Research Council Canada (NRC), column separation was performed to remove the seawater matrix prior to the determination of Cd, Cr, Cu, Fe, Pb, Mn, Mo, Ni, U, V, and Zn, whereas As was directly measured in 10-fold diluted seawater samples, and B was directly measured in 200-fold diluted seawater samples. High-resolution inductively coupled plasma mass spectrometry (HR-ICPMS) was used for elemental analyses, with double isotope dilution for the accurate determination of B, Cd, Cr, Cu, Fe, Pb, Mo, Ni, U, and Zn in seawater NASS-7 and CASS-6, and standard addition calibration for As, Co, Mn, and V. In addition, all analytes were measured using standard addition calibration with triple quadrupole (QQQ)-ICPMS to provide a second set of data at NRC. Expert laboratories worldwide were invited to contribute data to the certification of trace metals in NASS-7 and CASS-6. Various analytical methods were employed by participants including column separation, co-precipitation, and simple dilution coupled to ICPMS detection or flow injection analysis coupled to chemiluminescence detection, with use of double isotope dilution calibration, matrix matching external calibration, and standard addition calibration. Results presented in this study show that majority of laboratories have demonstrated their measurement capabilities for the accurate determination of trace metals in seawater. As a result of this comparison, certified/reference values and associated uncertainties were assigned for 14 elements in seawater CRMs NASS-7 and CASS-6, suitable for the validation of methods used for seawater analysis.

Impact of surface ocean conditions and aerosol provenance on the dissolution of aerosol manganese, cobalt, nickel and lead in seawater

Abstract Atmospheric deposition is an important pathway by which bioactive trace metals are delivered to the surface ocean. The proportions of total aerosol trace metals that dissolve in seawater, and thus become available to biota, are not well constrained and are therefore a key uncertainty when estimating atmospheric fluxes of these elements to surface waters. The aim of this study was to elucidate the main physico-chemical controls on the dissolution of the bioactive trace metals manganese (Mn), cobalt (Co), nickel (Ni) and lead (Pb). To this end, aerosol and surface seawater samples were collected in the Sargasso Sea and subsequently used in sequential seawater leach dissolution experiments to assess the role of aerosol source, seawater temperature, pH, and concentrations of dissolved oxygen and organic ligands, on aerosol trace metal dissolution. Results reveal that changes in key physico-chemical parameters in seawater leaches had little effect on the proportions of Mn, Co, Ni and Pb released from aerosols, although organic ligand amendments impacted the size distribution of aerosol-derived Mn in solution. Conversely, aerosol source and composition had the most significant effect on the dissolution of aerosol Co and Pb, with the most ‘anthropogenic’ aerosol samples displaying the highest fractional solubilities in seawater (up to 58% for Co and 112% for Pb). Fractional solubilities over the range of samples and conditions tested were in the range of 50–104% for Mn, 29–58% for Co, 40–85% for Ni and 67–112% for Pb. A large proportion (36–100%, median 89%) of the total dMn, dCo, dNi and dPb was mobilised rapidly during the first leaching step (5 min), with less dTM being released in leaches 2 through 4. Furthermore, investigation of the size distribution of the aerosol-derived trace metals in seawater showed that dissolved Pb was mostly colloidal (0.02–0.4 μm), dissolved Mn and Co were mostly soluble (

Evaluation of Immobilized Metal-Ion Affinity Chromatography and Electrospray Ionization Tandem Mass Spectrometry for Recovery and Identification of Copper(II)-Binding Ligands in Seawater Using the Model Ligand 8-Hydroxyquinoline

Complexation by organic ligands dominates the speciation of iron (Fe), copper (Cu), and other bioactive trace metals in seawater, controlling their bioavailability and distribution in the marine environment. Several classes of high-affinity Fe-binding ligands (siderophores) have been identified in seawater but the chemical structures of marine Cu-complexing ligands remain unknown. Immobilized metal-ion affinity chromatography (IMAC) allows Cu ligands to be isolated from bulk dissolved organic matter (DOM) in seawater and separated into fractions which can be characterized independently using electrochemical and spectroscopic techniques. Attempts have been made to combine IMAC with electrospray ionization mass spectrometry (ESI-MS) to characterize marine Cu ligands, but results have proven inconclusive due to the lack of tandem mass spectrometry (MS/MS) data to confirm ligand recovery. We used 8-hydroxyquinoline (8-HQ), a well-characterized model ligand that forms strong 1:2 metal:ligand complexes with Cu2+ at pH 8 (log β2 = 18.3), to evaluate Cu(II)-IMAC and ESI-MS/MS for recovery and identification of copper(II)-complexing ligands in seawater. One-litre samples of 0.45µm-filtered surface seawater were spiked with 8-HQ at low concentrations (up to 100 nM) and fractionated by IMAC. Fractions eluted with acidified artificial seawater were desalted and re-suspended in methanol via solid-phase extraction (SPE) to obtain extracts suitable for ESI-MS analysis. Recovery of 8-HQ by Cu(II)-IMAC was confirmed unambiguously by MS/MS and found to average 81% based upon accurate quantitation via multiple reaction monitoring (MRM). Cu(II)-IMAC fractionation of unspiked seawater using multiple UV detection wavelengths suggests an optimal fraction size of 2 mL for isolating and analyzing Cu ligands with similar properties.

Distribution of trace metals in surface seawater and zooplankton of the Bay of Bengal, off Rushikulya estuary, East Coast of India

Concentrations of trace metals such as iron (Fe), copper (Cu), zinc (Zn), cobalt (Co), nickel (Ni), manganese (Mn), lead (Pb), cadmium (Cd), chromium (Cr), arsenic (As), vanadium (V), and selenium (Se) were determined in seawater and zooplankton from the surface waters off Rushikulya estuary, north-western Bay of Bengal. During the study period, the concentration of trace metals in seawater and zooplankton showed significant spatio-temporal variation. Cu and Co levels in seawater mostly remained non-detectable. Other elements were found at higher concentrations and exhibited marked variations. The rank order distribution of trace metals in terms of their average concentration in seawater was observed as Fe>Ni>Mn>Pb>As>Zn>Cr>V>Se>Cd while in zooplankton it was Fe>Mn>Cd>As>Pb>Ni>Cr>Zn>V>Se. The bioaccumulation factor (BAF) of Fe was highest followed by Zn and the lowest value was observed with Ni. Results of correlation analysis discerned positive affinity and good relationship among the majority of the trace metals, both in seawater and zooplankton suggesting their strong affinity and coexistence.