Trace Metal Budgets Research Articles

Long Distance Transport of Subsurface Sediment‐Derived Iron From Asian to Alaskan Margins in the North Pacific Ocean

AbstractThe international GEOTRACES program has been instrumental in demonstrating how marine sediments are a critical source of dissolved Fe to the world's oceans. Here, we present dissolved iron (dFe) from the GEOTRACES North Pacific GP15 section, which, alongside other sediment‐source tracers (including dissolved δ56Fe, Mn, 228Ra, and particulate Fe), allows for identification of the dFe provenance of three distinct dFe depth maxima at the Alaskan margin. Two of these (shelf and abyssal depths) are of local Alaskan sedimentary origin. The third, a mid‐depth dFe maximum with an absence of 228Ra, is an advected signal that, based on tracer data from Western Pacific GEOTRACES transects and circulation models, must be advected from sedimentary sources on the Asian margin, ∼5,000 km away. This study illustrates the importance of measuring diagnostic sedimentary tracers like radium when assigning local margins as sedimentary sources of marine trace metal budgets.

Surface reactivity of the anaerobic phototrophic Fe(II)-oxidizing bacterium Rhodovulum iodosum: Implications for trace metal budgets in ancient oceans and banded iron formations

It is widely accepted that anoxygenic photosynthetic bacteria (photoferrotrophs) oxidized dissolved Fe(II) in anoxic Archean seawater, leading to the sedimentation of cellular biomass and the Fe(III) minerals that comprised banded iron formations (BIF). However, it remains unknown to which extent the sedimented bacteria may have transported trace metals to BIF through their ability to sorb ions from seawater. We therefore chose the marine anoxygenic photoferrotroph Rhodovulum iodosum to quantify Cd2+, Co2+, Cu2+, Mn2+, Ni2+ and Zn2+ adsorption to bacteria/Fe(III)-oxyhydroxide composites at neutral pH and an ionic strength of 0.1M. Acid base titration data were modeled using a linear programming optimization method to yield pKa values of 4.83±0.13, 6.21±0.18, 7.74±0.24 and 9.28±0.27 and corresponding site densities of 5.7, 12.0, 3.3 and 6.5×10−4mol/g, respectively. FTIR spectroscopy confirmed the presence of carboxyl groups as the most acidic sites corresponding to the lowest pKa values. The analysis of Cd2+ sorption data showed two metal complexing sites with pKS values of 3.44±0.14 and 4.80±0.21 and corresponding binding site concentrations of 1.1±0.3×10−4 and 0.9±0.2×10−4mol/g on the ferrihydrite/R. iodosum composite. The pKS values were used to calculate metal-ligand binding constants, Km. This confirmed Cd2+ binding to the most acidic carboxyl groups on the ferrihydrite/R. iodosum composite surface, as the calculated Km was consistent with reported Cd2+ binding constants for simple organic acids (e.g., lactic, acetic, pyruvic and citric acid). This was used to further calculate the concentration of Co2+, Cu2+, Mn2+, Ni2+ and Zn2+ sorbed to ferrihydrite/R. iodosum composites. The resulting concentrations were ultimately compared to the concentrations of trace elements in BIF to demonstrate that is plausible that the trace metal content in BIF was derived from plankton growing in the ancient ocean's photic zone.

Trace Metal Budgets for Forested Catchments in Europe—Pb, Cd, Hg, Cu and Zn

Input/output budgets for cadmium (Cd), lead (Pb) and mercury (Hg) in the years 1997–2011 were monitored and determined for 14 small forest-covered catchments across Europe as part of the Integrated Monitoring program on the effects of long-range pollutants on ecosystems. Metal inputs were considered to derive from bulk deposition, throughfall and litterfall. Outputs were estimated from run-off values. Litterfall plus throughfall was taken as a measure of the total deposition of Pb and Hg (wet + dry) on the basis of evidence suggesting that, for these metals, internal circulation is negligible. The same is not true for Cd. Excluding a few sites with high discharge, between 74 and 94 % of the input Pb was retained within the catchments; significant Cd retention was also observed. High losses of Pb (>1.4 mg m−2 year−1) and Cd (>0.15 mg m−2 year−1) were observed in two mountainous Central European sites with high water discharge. All other sites had outputs below or equal to 0.36 and 0.06 mg m−2 year−1, respectively, for the two metals. Almost complete retention of Hg, 86–99 % of input, was reported in the Swedish sites. These high levels of metal retention were maintained even in the face of recent dramatic reductions in pollutant loads.

The particulate 7Be/ 210Pb xs and 234Th/ 210Pb xs activity ratios as tracers for tidal-to-seasonal particle dynamics in the Gironde estuary (France): Implications for the budget of particle-associated contaminants

The short-lived natural radionuclides 7Be ( T 1/2 = 53 days), 234Th xs ( T 1/2 = 24.1 days) and 210Pb xs ( T 1/2 = 22.3 years), i.e. 234Th and 210Pb in excesses of that supported within particles by the decay of their parent isotopes, were analysed in suspended particulate matter (SPM) to study the particle dynamics in the Gironde fluvial estuarine system (France), strongly impacted by heavy metal pollution. From surveys of this land–ocean interface in 2006 and 2007, we established a times series of these radioisotopes and of their activity ratios ( 7Be/ 210Pb xs and 234Th/ 210Pb xs ARs) in particles sampled under different hydrological conditions. The particulate 7Be/ 210Pb xs AR varies along the fluvial estuarine system mainly due to variations in 7Be activities, controlled by riverine, oceanic and atmospheric inputs and by resuspension of old 7Be-deficient sediments. These processes vary with river discharge, tidal cycle and season. Therefore, seasonal particle transport processes can be described using variations of the SPM 7Be/ 210Pb xs ARs. During high river discharge, the SPM 7Be/ 210Pb x ARs decrease from river to the ocean. The turbidity maximum zone (TMZ) is dispersed and the particles, and the associated contaminants, are rapidly transported from river to coastal waters, without significant retention within the TMZ. During low river discharge, the TMZ intrudes into the fluvial estuary, and the lowest 7Be/ 210Pb x ARs are observed there due to resuspension of 7Be-deficient sediments. Away from the TMZ, from the middle to lower estuary, SPM 7Be/ 210Pb x ARs increase, indicating that the particles have been recently tagged with 7Be. We explain this trend as being caused by marine input of dissolved radionuclides, as traced by SPM 234Th/ 210Pb xs ARs, followed by scavenging in the estuary. This result indicates that particle transport models based on 7Be and trace-metal budgets must consider oceanic dissolved inputs as an additional source of 7Be and, possibly, of contaminants to estuaries.

Geochemical Cycling of Arsenic in a Coastal Aquifer

Biogeochemically modified pore waters from subterranean estuaries, defined as the mixing zone between freshwater and saltwater in a coastal aquifer, are transported to coastal waters through submarine groundwater discharge (SGD). SGD has been shown to impact coastal and perhaps global trace metal budgets. The focus of this study was to investigate the biogeochemical processes that control arsenic cycling in subterranean estuaries. Total dissolved As, as well as a suite of other trace metals and nutrients, were measured in a series of wells and sediment cores at the head of Waquoit Bay, MA. Dissolved As ranged from below detection to 9.5 microg/kg, and was associated with plumes of dissolved Fe, Mn, and P in the groundwater. Sedimentary As, ranging from 360 to 7500 microg/kg, was highly correlated with sedimentary Fe, Mn, and P. In addition, amorphous Fe (hydr)oxides were more efficient scavengers of dissolved As than the more crystalline forms of solid-phase Fe. Given that dissolved As in the surface bay water was lower than within the subterranean estuary, our results indicate that the distribution and type of Fe and Mn (hydr)oxides in coastal aquifers exert a major influence on the biogeochemical cycling of As in subterranean estuaries and, ultimately, the fate of groundwater-derived As in marine systems influenced by SGD.

The groundwater geochemistry of the Bengal Basin: Weathering, chemsorption, and trace metal flux to the oceans

Sixty-eight groundwater samples from the Ganges-Brahmaputra floodplain in the Bengal Basin were analyzed to assess the groundwater geochemistry, the subsurface hydrology, the buffering effects of sediments on trace metal concentrations and their isotopic compositions, and the magnitude of the subsurface trace element flux to the Bay of Bengal and to the global ocean. Samples obtained from depths of 10 to 350 m were measured for major and trace elements, dissolved gas, and tritium. On the basis of the 3He/ 3H ages, the groundwater at depth (30–150 m) appears to be continually replenished, indicating that this recharge of groundwater to depth must ultimately be balanced by a significant quantity of submarine discharge into the Bay of Bengal. Using the 3He/ 3H groundwater age–depth relationship to calculate a recharge rate of 60 ± 20 cm/yr, we estimate a subsurface discharge into the Bay of Bengal of 1.5 ± 0.5 × 10 11 m 3/yr, or 15% of the surface Ganges-Brahmaputra river (GBR) flux. Several trace elements, especially Sr and Ba, display elevated concentrations averaging 7 to 9 times the surface GBR water values. The submarine groundwater fluxes of Sr and Ba to the oceans are 8.2 ± 2 × 10 8 and 1.5 ± 0.3 × 10 8 mol/yr, or 3.3 and 1.2%, respectively, of the world total, or equal to the surface GBR Sr and Ba estimated fluxes. Our groundwater flux for Ba agrees with the estimate of Moore (1997) (3 × 10 8–3 × 10 9 mol/yr), on the basis of measured Ba and Ra excesses in the Bay of Bengal. Other trace metals, such as U and Mo, are at low but measurable levels and are not major contributors to the global flux in this river system. A comparison of the Sr and Ba concentrations, plus 87Sr/ 86Sr ratios in groundwater to the oxalate extractable fractions of a coastal sediment core, suggests that weathering of carbonates and minor silicates, coupled with cation exchange plus adsorption and desorption reactions, controls the trace element concentrations and 87Sr/ 86Sr isotopic compositions in both the groundwater and river water. Our data also imply that other coastal floodplains (e.g., the Mekong and the Irrawaddy rivers) that have high precipitation rates and rapid accumulation of immature sediments are likely to make significant contributions to the global oceanic trace metal budgets and have an impact on the Sr isotopic evolution in seawater.

Trace metal fluxes to the ocean: The importance of high‐standing oceanic islands

Trace metal analyses of river channel sediments from Taiwan and New Zealand provide new estimates for global budgets of trace metal inputs to the world's ocean. Mean trace metal values from high standing island river sediments are less chemically weathered than observed in sediments collected from large, continental, rivers and more similar to upper continental crust (UCC) values. Our mean values for Cu, Mn, Co and Pb are similar to the UCC; Zn, Ni and Cr are more highly enriched, compared to UCC values. Our new estimates of global trace metal budgets, combining previous estimates with these new data, show that geochemical fluxes of metals into the oceans are lower than previous estimates, ranging from 9% lower for Co to 24% lower for Cu.

A Reassessment of Trace Metal Budgets in the Western Mediterranean Sea

This paper presents inputs and output fluxes of dissolved metals (As, Cd, Co, Cu, Fe, Mn, Ni, Pb and Zn) into and out the Western Mediterranean. These flux estimates are based on the most recently published concentrations and fluxes for the atmosphere, the rivers and the straits. Comparison of the different sources shows the predominance of the inputs through the straits over other sources. The river input is smaller than the atmospheric input except for As. For all elements except Fe, output flux and input flux are balanced; iron budget indicates transfer from the dissolved to the particulate phase.

The effect of river liming on the trace metal budgets of a down stream lake

Sediment cores from two lakes, connected by a limed river, were analyzed for organic matter, calcium (Ca), iron (Fe), manganese (Mn), zinc (Zn), copper (Cu), lead (Pb), cadmium (Cd), and ion exchange capacity. The distribution of trace metals in the pristine upper lake is governed primarily by changes in the long distance atmospheric transported pollutants. In the lake down stream of the liming station the distribution of trace metals in sediments deposited before liming started (1985) is similar to that in the pristine lake. Liming of the connecting river raises the pH value by about 1.8 units from 5.1 enhancing the accumulation rate of trace metals in the downstream lake. Iron enriched acid insoluble particles are likely to be important carriers of trace metals. The liming agent itself is the most important source for Pb, while increased accumulation of Zn and Cd is caused primarily by enhanced scavenging of dissolved metals. For Cu the two sources are of about equal importance.

Sorption of trace metals (Cu, Pb, Zn) by suspended lake particles in artificial (0.005 M NaNO 3) and natural (Esthwaite Water) freshwaters

The sorption of Cu, Pb, and Zn onto natural lake particles, suspended in 0.005 M NaNO 3 solution and in a natural lake water (Esthwaite Water, Cumbria, UK), was studied as a function of pH and time in a series of laboratory experiments, under environmentally realistic conditions. The sorption of all three metals increased with increasing pH and reaction time (2 h and 7 days). In 0.005 M NaNO 3 solution, the well-defined sorption edges spanned 2–2.5 pH units for Cu and Pb, and ≈ 4 pH units for Zn. In the natural lake water, the Cu sorption edge was broader and both Cu and Zn were less strongly sorbed. The binding stability decreased in the order Pb>Cu>Zn. Competitive adsorption onto surface sites appeared to be the main factor determining the observed sorption behaviour. Application of a macroscopic metal exchange model to the 7 day NaNO 3 results enabled the surface site concentration to be estimated as 0.79 ± 0.07 mmol g −1. The modelling exercise suggested that an observed shift in the sorption edge of Zn, in the presence of Pb and Cu, was due to competition for surface sites. The experimental data are in good general agreement with field observations of trace metal behaviour in Cumbrian lakes. The almost total sorption of Pb by lake particles throughout the in-situ pH range is compatible with previous field measurements including trace metal budgets and residence times. Dissolved Zn concentrations in the lake are lower than predicted by the sorption experiments, but the lower lake concentrations are consistent with the previously observed scavenging of Zn by planktonic algae. Both the decreased sorption of Cu in the experiments with natural lake water, compared to that in NaNO 3 solution, and the relatively small-scale removal of dissolved Cu by particles in the lake itself can partially be explained by humic complexation.

Trace metal distributions at an Arctic Ocean ice island

The concentrations of Cd, Cu, Co, Mn, Ni and Zn have been determined in water samples collected at the Canadian Ice Island in the Arctic Ocean north of Ellesmere Island in June 1985. Two sets of measurements were made, one at the Bedford Institute of Oceanography and the other at the University of Goteborg. The agreement between the two sets of results is good. The origin and persistence of a distinct trace metal maximum coincident with the nutrient maximum in the upper halocline is discussed. Trace metal budgets calculated for the Arctic Ocean help to identify the most important sources of metals in the Arctic.

Separate dissolved and particulate trace metal budgets for an estuarine system: An aid for management decisions

The sources and sinks of dissolved and particulate Pb, Cu and Zn were determined for the main basin of Puget Sound to understand the effect man has had on metal concentrations in both the water column and in the sediments. Municipal, industrial and atmospheric sources contributed about 66% of the total Pb added to the main basin of Puget Sound during the early 1980s. Advective inputs were the major sources of total Cu and Zn (∼40%) while riverine and erosional sources contributed about 30%. The discharge of the particle-bound trace metals from rivers minimized the influence of particulate anthropogenic sources, which constituted 50%, 23% and 18% of the total particulate Pb, Cu and Zn inputs, respectively. While advective transport was the major source of dissolved Cu and Zn (∼60% of all dissolved inputs), industrial, municipal and atmospheric inputs contributed about 85%, 30% and 38% of the dissolved Pb, Cu and Zn inputs, respectively. The sources of dissolved and particulate Cu and Zn were comparable with the sinks within the errors of the analyses indicating their quasi-conservative nature. Advection removed about 60% of the total Cu and Zn added to the main basin while 40% was deposited in the sediments of Puget Sound. Because of this quasi-conservative nature of Cu and Zn, anthropogenic inputs of Cu and Zn were dispersed from the system more than they were contained within main basin sediments. About 75% of the dissolved Pb discharged into the main basin of Puget Sound was lost from the dissolved phase and was balanced by a similar gain in the particulate phase. Because of this extensive scavenging and the effective retention of particles within the main basin, about 70% of the total Pb added to the main basin was retained within its sediments. These separate mass balances have utility in management decisions because they show the relative contributions from different sources and demonstrate whether the influences of dissolved and particulate inputs are reflected solely in the water column or the sediments, respectively.

The impact of scavenging on trace metal budgets in Puget Sound

The distributions of dissolved and particulate Mn, Pb, Cu and Zn in Puget Sound, its tributaries, and its sediments were determined to illustrate the impact of scavenging reactions on trace metal budgets of a large fjordlike estuary. About 75% of the dissolved Pb discharged into the main basin of Puget Sound was scavenged from the dissolved phase. The high particulate Pb concentrations in regions of high particulate Mn concentrations and the significant correlations between Pb and Mn concentrations on suspended particles demonstrate the importance of hydrous manganese oxide phases in scavenging dissolved Pb. Since particles are effectively retained within the main basin, scavenging results in the sedimentation of about 70% of the total Pb added to the main basin. Only isolated instances of scavenging of dissolved Cu and Zn were observed and the discharge rates of dissolved Cu and Zn from known sources were equal to their rates of advective removal within the errors of the budget. The remineralization of organically-bound particulate Cu is partly responsible for its quasi-conservative behavior within the main basin of Puget Sound. The fates of Cu and Zn are controlled mainly by physical processes such as advection and settling of particles. Advection removes about 60% of the total Cu and Zn added to the main basin while 40% is deposited in the sediments of Puget Sound.

Trace metal budgets for a forested watershed in the New Jersey pine barrens

Deposition of Pb, Cu, Ni, Fe, Mn, and Cd on the McDonalds Branch Basin in bulk precipitation was 25.4, 5.3, 6.6, 64.6, 20.7, and <2 mg m−2 yr−1 for a 1 year period in 1978–1979. Output in streamflow was 1.7, 0.7, 1.9, 148, 12.8, and <1 mg m−2 yr−1, respectively, and loss to deep groundwater was 1.4, 1.9, 2.3, 123, 20.4, and <1 mg m−2 yr−1. Pb, Cu, and Ni accumulated in the basin, while there was a net loss of Fe and Mn from the ecosystem. The major mechanism for movement of Fe and Pb out of the basin was interpreted to be complexation with and transport by mobile organic matter.