Biogeochemical Cycling Of Trace Metals Research Articles

Distribution and off–shelf transport of dissolved manganese in the East China Sea

To gain a better understanding of the geochemical behavior of dissolved manganese (Mn) in the marginal seas with respect to distribution and exchange fluxes, more than 200 water samples were collected in the East China Sea (ECS) in May, August, and October of 2013. The concentration of dissolved Mn in the ECS ranged from 1.1 to 81.5 nM, with a gradual decrease with distance from the shore. Seasonal distribution of dissolved Mn varies significantly in the Changjiang estuary, mainly regulated by freshwater input from the Changjiang (Yangtze River) and redox variations. The ECS continental shelf is an important source of Mn for adjacent waters, and the export of Mn–rich coastal waters had an important effect on its re-distribution and internal cycling. The dynamic variation fluxes of water and dissolved Mn across the 100– and 200–m isobaths in the ECS were calculated with an aid of the Finite−Volume Coastal Ocean Model (FVCOM). The ECS continental shelf exported (5.69 ± 1.14) × 108 mol/yr of Mn into the East/Japan Sea from the Tsushima Strait. The Kuroshio surface waters receive an additional (1.02 ± 3.12) × 108 mol/yr of Mn from the ECS continental shelf through a cross–shelf exchange process, which could potentially affect dissolved Mn in the Northwest Pacific. Our data suggest that off-shelf transport from the ECS continental shelf is essential for understanding the biogeochemical cycles of trace metals in the Northwest Pacific Ocean and the East/Japan Sea.

Distribution and ecological health risk assessment of dissolved trace metals in surface and bottom seawater of Yantai offshore, China

The biogeochemical cycle of trace metals plays an important role in the coastal zone. The distribution, interaction, and biogeochemical behavior of dissolved trace metals in surface and bottom seawater are still unclear. This study analyzed the distribution and performed an ecological health risk assessment of dissolved trace metals (Zn, Cd, Co, Pb and Cr) in surface and bottom seawater in the summer (August) of 2019 and 2020 in the seawater of the Yantai offshore area, China. Zinc (Zn), cadmium (Cd), cobalt (Co), lead (Pb) and chromium (Cr) ranged from 23.76–117.47 μg/L (42.67 μg/L ± 15.15), 0.21–0.51 μg/L (0.30 μg/L ± 0.05), 0.90–2.94 μg/L (1.09 μg/L ± 0.31), 0.13–1.06 μg/L (0.39 μg/L ± 0.17), and 2.00–9.9 μg/L (5.38 μg/L ± 2.99) in the summer of the two years. The average metal (Zn and Co) concentrations were slightly higher than the other Chinese coastal areas, while the major contamination pressures were from Zn and Pb. The largest contaminants were in the following order: Zn > Pb > Cd > Cr > Co. Correlation analysis, principal component analysis and hierarchical cluster were used to determine the potential origins and cause the spatial distribution of the multiple dissolved trace metals. The major sources of the trace metal contamination in study area were identified as external inputs from natural human and atmospheric settling and the natural release of the trace metals in sediments under external disturbances. Riverine inputs, the Lubei coastal current and aquaculture significantly influenced the multi-parameter horizontal distributions of the dissolved trace metals and dissolved organic carbon. Although the growth of phytoplankton was strong in summer, the uptake of Zn, Cd, Co and Pb was negligible compared with the exogenous input. The concentrations of Zn, Cd, Co and Pb were higher in the surface than those in the bottom. Monsoons, tides and wind waves also influence the migration, transformation and distribution of dissolved trace metals and dissolved organic carbon. This study provides important information on the biogeochemical cycle process (migration and conversion) and distribution of dissolved trace metals at different depths in coastal and marine pasture areas.

Anthropogenic activities influence the mobilization of trace metals and oxyanions in coastal sediment porewaters

The biogeochemical cycle of trace metals and oxyanions in marine sediments is mainly controlled by early diagenesis of organic material, but anthropogenic activities such as dumping of dredged sludge or shipyard activities can strongly perturb these natural processes. Therefore, the impact of dumping of dredged sludge, shipyard activities such as blasting of boat hulls and the mixing of polluted Scheldt estuary water with less polluted coastal water on the mobilization of trace metals and oxyanions in the sediments was studied in the pre- and post-bloom period (March and October) in Belgian Coastal Zone (BCZ). Vertical profiles of total and labile dissolved trace element concentrations, dissolved sulfide, pH and redox potential were assessed in sediment porewaters. Generally, total and labile dissolved element profiles in the porewaters are well correlated, showing higher concentrations in March when the redox potential is lower and sulfide concentrations higher. Low pH levels were documented together with high amounts of Fe and associated elements in March at the dumping station. At the coastal station in the vicinity of the shipyards, sediment porewaters are enriched in dissolved Zn while at the mouth of the Scheldt estuary the highest dissolved Cu levels were found. Theoretical calculations with Visual MINTEQ confirm the increased Fe and associated element concentrations in March (lower pH) and the lower metal concentrations in October (lower Eh). R values, ratio of labile dissolved to total dissolved concentrations, reflect the potential of the solid sediment phase to supply labile elements to the porewater. They were lowest for Cu and highest for V. This study showed that anthropogenic activities in the BCZ such as dumping of dredged sludge and blasting of boat hulls have a serious impact on the levels, distribution and bioavailability of contaminants in the sediments, which may form a real threat to the benthic ecosystem.

Photodecomposition of natural organic metal-binding ligands from deep seawater

To reveal the effect of solar irradiation on the biogeochemical cycling of trace metals in the open ocean, the photodecomposition of organic iron- and copper-binding ligands was examined in an experiment using filtered seawater collected from a deep layer of the East China Sea. Six days of natural solar irradiation caused a significant decrease in the concentrations of both ligands, along with the loss of fluorescent dissolved organic matters. The relative decrease of iron-binding ligands, which are considered to be mainly composed of humic substances, was larger than that of copper-binding ligands or humic-like fluorescence. This may be attributable to relatively high photoreactivity of hydrophilic fluvic acids, which have higher affinity to ferric ions. Surprisingly, an accumulation of both iron- and copper-binding ligands was observed in the dark control bottles, but without a significant change in the fluorescence of humic-like substances. In conclusion, the upwelling of deep seawater into the sunlit surface layer can result in the rapid loss of the complexation capacity for both iron and copper ions. The stronger ligands for both metals, which were readily decomposed by sunlight irradiation, appears to have a similar composition, suggesting that competition could be important to determine the solubility and bioavailability of iron and copper.

Two Approaches to Measure Trace Metals Fluxes at the Sediment–Water Interface: Sediment Porewater Profile and Benthic Incubation

The biogeochemical cycle of trace metals is very likely affected by the global change in the ocean, especially due to the increasing of sea surface temperature and acidity. Thus, assessing biogeochemical cycle of trace metals will beneficial in elucidating the potential impact of climate change as well as ocean acidification. The assessment of the biogeochemical cycle of trace metals can be performed by measuring trace metals fluxes crossing the sediment–water interface. The main challenge in this measurement is the difficulty of measuring metal concentrations at trace levels due to either physical factors or biological factors that can affect the total flux. Sediment porewater profile and in situ benthic incubation are the two most commonly used methods for measuring trace metals fluxes from sediment to the overlying water or vice versa. The coefficient of diffusion and gradient of concentration are the two most important values in the sediment porewater profile method, while the constant volume involved in the container during the experiment is an important part of the in situ benthic incubation method. The purpose of this review is to provide an overview of both measurement methods deeply and predict the challenges faced in its implementation in Indonesia.

Plutonium in Southern Yellow Sea sediments and its implications for the quantification of oceanic-derived mercury and zinc

The spatial distributions of mercury (Hg) and zinc (Zn) concentration and the isotopic composition of plutonium (Pu) were investigated in surface sediments and sediment cores collected from the Southern Yellow Sea (SYS) during May 2014. The variation of the 240Pu/239Pu atom ratio (0.18–0.31) in the surface sediments of the SYS clearly indicated a signal of close-in fallout input from the Pacific Proving Ground (PPG). The buried 239+240Pu in the sediment of the SYS was estimated to be (4.7 ± 0.5) × 1010 Bq y−1 during the period from 2011 to 2014, of which ∼33% (1.5 × 1010 Bq y−1) was derived from the PPG by long-range transport via ocean currents (e.g., the North Equatorial Current and Kuroshio Current). The concentrations of Hg and Zn varied from 0.003 to 0.067 mg kg−1 and from 43.9 to 137 mg kg−1, respectively, and exhibited positive correlations with the 239+240Pu activity both in the surface sediments (0–1 cm) and upper layers (7 cm) of the sediment cores. Therefore, by using Pu as a tracer, we estimated that the oceanic input contributed 2.0 tons y−1 of Hg and 1.0 × 103 tons y−1 of Zn to the SYS sediments between 2011 and 2014, which accounted for 33% and 3% of total buried Hg and Zn, respectively. These findings indicate that environmental pollution control should also consider the oceanic contribution of some pollutants. The results of the present work help to elucidate the biogeochemical cycling of trace metals in marginal seas, and are helpful for managing environmental pollution in marine environments.

Elemental characteristics and biogeochemical cycles of trace metals in coastal seawater around coral reefs elucidated by multi-element profiling analyses

The present study applied multi-element profiling analysis to the monitoring of coastal seawater around coral reefs to elucidate the elemental characteristics and the biogeochemical cycles. In temporal concentration variation, the long-term monitoring (monthly over one year) and short-term monitoring (3-hourly over two days) were subjected to multi-element determination by ICP-MS with solid phase extraction using chelating resin. In the long-term monitoring, the nutrient-type elements Fe, Ni, Cu, Zn, and Cd and the scavenging-type elements Mn, Co, and Pb showed wide variations in their total, dissolved, and acid-soluble concentrations. The elevated total concentrations of Mn, Fe, Ni, Cu, Zn, Cd, and Pb in short-term variation of October 2011 were possibly caused by mucus secreted from coral. The increased concentrations of trace metals in the coastal seawater around the reefs might play important role to provide bio-essential trace metals to zooxanthellae living in symbiotic animals, such as corals, anemones, and giant clams.

Nickel and iron partitioning between clay minerals, Fe-oxides and Fe-sulfides in lagoon sediments from New Caledonia

In the tropics, continental weathering and erosion are major sources of trace metals towards estuaries and lagoons, where early diagenesis of sediments may influence their mobility and bioavailability. Determining trace metals speciation in tropical sedimentary settings is thus needed to assess their long-term fate and potential threat to fragile coastal ecosystems. In this study, we determined Fe, Ni and S speciation across a shore-to-reef gradient in sediments from the New Caledonia lagoon that receive mixed contribution from lateritic (iron-oxyhydroxides and clay minerals), volcano-sedimentary (silicates) and marine (carbonate) sources. Sulfur K-edge XANES data indicated a major contribution of pyrite (FeS2) to S speciation close to the shore. However, this contribution was found to dramatically decrease across the shore-to-reef gradient, S mainly occurring as sulfate close to the coral reef. In contrast, Fe and Ni K-edge XANES and EXAFS data indicated a minor contribution of pyrite to Fe and Ni speciation, and this contribution could be evidenced only close to the shore. The major fractions of Fe and Ni across the shore-to-reef gradient were found to occur as Ni- and Fe-bearing clay minerals consisting of smectite (~nontronite), glauconite and two types of serpentines (chrysotile and greenalite/berthierine). Among these clay minerals, greenalite/berthierine, glauconite and possibly smectite, were considered as authigenic. The low contribution of pyrite to trace metals speciation compared to clay minerals is interpreted as a result of (1) a reduced formation rate due to the low amounts of organic carbon compared to the Fe pool and (2) repeated re-oxidation events upon re-suspension of the sediments top layers due to the specific context of shallow lagoon waters. This study thus suggests that green clay authigenesis could represent a key process in the biogeochemical cycling of trace metals that are delivered to lagoon ecosystems upon continental erosion and weathering.

Specific Effect of Trace Metals on Marine Heterotrophic Microbial Activity and Diversity: Key Role of Iron and Zinc and Hydrocarbon-Degrading Bacteria.

Marine microbes are an important control on the biogeochemical cycling of trace metals, but simultaneously, these metals can control the growth of microorganisms and the cycling of major nutrients like C and N. However, studies on the response/limitation of microorganisms to trace metals have traditionally focused on the response of autotrophic phytoplankton to Fe fertilization. Few reports are available on the response of heterotrophic prokaryotes to Fe, and even less to other biogeochemically relevant metals. We performed the first study coupling dark incubations with next generation sequencing to specifically target the functional and phylogenetic response of heterotrophic prokaryotes to Fe enrichment. Furthermore, we also studied their response to Co, Mn, Ni, Zn, Cu (individually and mixed), using surface and deep samples from either coastal or open-ocean waters. Heterotrophic prokaryotic activity was stimulated by Fe in surface open–ocean, as well as in coastal, and deep open-ocean waters (where Zn also stimulated). The most susceptible populations to trace metals additions were uncultured bacteria (e.g., SAR324, SAR406, NS9, and DEV007). Interestingly, hydrocarbon-degrading bacteria (e.g., Thalassolituus, Marinobacter, and Oleibacter) benefited the most from metal addition across all waters (regions/depths) revealing a predominant role in the cycling of metals and organic matter in the ocean.

Accumulation processes of trace metals into Arctic sea ice: distribution of Fe, Mn and Cd associated with ice structure

Biogeochemical cycling of trace metals in sea ice is important to the productivity of the Arctic Ocean. Unfortunately, the processes by which trace metals accumulate into sea ice are poorly understood. To gain a clearer understanding of the mechanisms behind trace metal accumulation, dissolved (D, <0.2 μm), and labile particulate (LP = Total Dissolvable – Dissolved) iron (Fe), manganese (Mn), and cadmium (Cd) concentrations were compared to the structure observed in sea ice. Samples were pre-concentrated via solid-phase extraction on NOBIAS Chelate PA-1 resin and analyzed on a Graphite Furnace Atomic Absorption Spectrometer. Using photographic analysis for the percentage of pore microstructure and δ18O analysis, sea ice structure was determined to be snow ice, granular ice (frazil ice), mixed ice (granular and columnar ice) and columnar ice. Salinity and nutrients were low, indicating brine drainage and multi-year ice. High trace metal concentrations in snow ice indicated meteoric snow was a source of trace metals to sea ice. High concentrations of LPFe in granular ice indicated entrainment of suspended particulate trace metals by frazil ice during the formation of the granular ice structure. Whereas the high concentrations of DFe and DMn in granular ice may have been due to reduction from LPFe and LPMn after particle entrainment, indicating chemical transformation processes. Low dissolved and labile particulate trace metal concentrations in mixed and columnar ice indicated a release due to brine drainage. Our study clearly indicates that the differences observed in trace metals among sea ice structures, showed that sea ice formation, chemical reduction and brine release were the processes driving trace metal accumulation and release in the Arctic sea ice.

Trace metal partitioning in the top meter of the ocean

Understanding the biogeochemical cycles and distribution of trace elements in the marine environment is one of the main challenges in chemical oceanography. We describe herein the trace metal composition of the uppermost surface ocean of various oceanographic regions (Arctic and Southern Oceans, subtropical Atlantic Ocean, and Mediterranean Sea). Our results show that trace metals in the top meter of the ocean are found in two clearly differentiated layers according to metal abundance and stoichiometry, namely the surface microlayer (SML) and its underlying subsurface water (SSW). Although metal concentrations in the subsurface dissolved fractions vary regionally and globally, it shows a singular metal stoichiometric signature. This work emphasizes the need to study of the SML as unique compartment to improve our understanding of the biogeochemical cycle of trace metals in the surface ocean, especially for metals, such as Pb, Fe and Cu, which are abundant in the SML.

Custom-made PTFE filters for ultra-clean size-fractionated aerosol sampling for trace metals

Atmospheric deposition of marine aerosols is one of the important sources of dissolved trace metals in the ocean. Analyses of trace metals and stable isotope ratios in size-fractionated aerosol particles using extraction experiments are useful to understand the dissolution behavior and biogeochemical cycles of trace metals in the marine environment. These analyses require sample treatments in clean environment without contamination of target metals from the sampling filter. However, the contamination of target metals from sampling filter is not low enough to determine the fractional solubility (extractive metal/total metal) and the stable isotope ratio of trace metals. In this study, we optimized the acid-washing procedure of hydrophobic PTFE filter for the Sierra-type cascade impactor. The results showed that the filter blanks of the custom-made PTFE filters used for the upper stages (= PTFE-ST) in the cascade impactor were about 10–1000 times lower than those of cellulose filters. In addition, the filter blanks of major ions and water-soluble organic carbon were also decreased by using PTFE-ST. Trace metal concentrations in size-fractionated (7 fractions) aerosol particles with very short sampling periods have been successfully determined except for the backup stage. Thus, aerosol sampling with PTFE filter with only a tiny contamination is a useful method to obtain chemical and isotopic compositions of various elements in marine aerosol particles.

Quantitative analysis of Fe, Mn and Cd from sea ice and seawater in the Chukchi Sea, Arctic Ocean

Sea ice is important for the health of the polar oceans yet its role in the biogeochemical cycling of trace metals is not so clear. To understand the geochemical behaviour of trace metals and their accumulation into sea ice, dissolved (D, < 0.2 μm), and labile particulate (LP, Total Dissolvable - Dissolved) Fe, Mn, and Cd were examined in sea ice and seawater collected from the Chukchi Sea in the Arctic Ocean. Samples were pre-concentrated utilizing the solid-phase extraction NOBIAS Chelate PA-1 resin (Hitachi High-Technologies Corporation) and analyzed on a Graphite Furnace Atomic Absorption Spectrometer. Chukchi seawater showed high percentage for DMn (71.5%) and DCd (66.3%) with a high percentage of LPFe (94.1%). In seawater, DCd was the only metal to correlate with phosphate (R2 = 0.78) indicating a biogeochemical cycling source. Chukchi seawater concentrations of Fe and Mn may have been controlled through external sources such as sediments (shelf or river) and/or sediment reductive processes. Trace metal concentrations in Chukchi sea ice were heterogeneous. Sea ice showed high percentages for the LP fraction (99.2% Fe, 63.6% Mn and 71.2% Cd). This data indicated that, regardless of the trace metal behaviour in Chukchi seawater, Chukchi sea ice was observed to have a preference for the LP trace metal fraction.

Copper adsorption on composites of goethite, cells of Pseudomonas putida and humic acid

In the soil environment, iron oxides co‐occur commonly with different types of organic constituents to produce iron oxide–organic composites that play an important role in the biogeochemical cycling of trace metals. We investigated copper (Cu) adsorption on synthetic goethite, Pseudomonas putida (CCTCC M209319) bacterial cells, humic acid (HA) and their binary and ternary composites with batch adsorption experiments coupled with isothermal titration calorimetry (ITC). Morphological characterizations show that the three components can form closely combined and heterogeneous aggregates with one another. The kinetics of sorption of Cu to these composite materials conforms to the pseudo‐second‐order model, whereas the Cu sorptivities deviate from linear additivity. Specifically, Cu sorptivities on the binary goethite–P. putida and P. putida–HA and ternary goethite–P. putida–HA composites are less than expected assuming additivity, whereas the opposite is seen for the binary goethite–HA composite. There is considerable masking of adsorption sites in the ternary goethite–P. putida–HA system, but the binding sites on bacteria are not completely covered, as shown by the adsorption enthalpy and entropy (19.60 kJ mol−1 and 120.9 J mol−1 K−1, respectively) for the ternary composite. We conclude that the binding affinity of Cu for the binary goethite–humic acid composite is larger than that for the bacterial composites with goethite or humic acid, or both. This research indicates that bacteria, iron oxide and humic substances exhibit different behaviour in the sequestration of heavy metals when they form various binary and ternary complexes in natural environments.HighlightsHow does mineral–organic interaction affect the binding behaviour of trace elements? First investigation of Cu sorption to goethite–bacteria–humic acid composites. Goethite–HA shows enhanced Cu adsorption, whereas the opposite is true for bacterial complexes. Various bacteria–iron oxide–humic substance composites behave differently in metal sequestration.

Automated preconcentration of Fe, Zn, Cu, Ni, Cd, Pb, Co, and Mn in seawater with analysis using high-resolution sector field inductively-coupled plasma mass spectrometry

A rapid, automated, high-throughput analytical method capable of simultaneous analysis of multiple elements at trace and ultratrace levels is required to investigate the biogeochemical cycle of trace metals in the ocean. Here we present an analytical approach which uses a commercially available automated preconcentration device (SeaFAST) with accurate volume loading and in-line pH buffering of the sample prior to loading onto a chelating resin (WAKO) and subsequent simultaneous analysis of iron (Fe), zinc (Zn), copper (Cu), nickel (Ni), cadmium (Cd), lead (Pb), cobalt (Co) and manganese (Mn) by high-resolution inductively-coupled plasma mass spectrometry (HR-ICP-MS). Quantification of sample concentration was undertaken using isotope dilution for Fe, Zn, Cu, Ni, Cd and Pb, and standard addition for Co and Mn. The chelating resin is shown to have a high affinity for all analyzed elements, with recoveries between 83 and 100% for all elements, except Mn (60%) and Ni (48%), and showed higher recoveries for Ni, Cd, Pb, Co and Mn in direct comparison to an alternative resin (NOBIAS Chelate-PA1). The reduced recoveries for Ni and Mn using the WAKO resin did not affect the quantification accuracy. A relatively constant retention efficiency on the resin over a broad pH range (pH 5–8) was observed for the trace metals, except for Mn. Mn quantification using standard addition required accurate sample pH adjustment with optimal recoveries at pH 7.5 ± 0.3. UV digestion was necessary to increase recovery of Co and Cu in seawater by 15.6% and 11.4%, respectively, and achieved full break-down of spiked Co-containing vitamin B12 complexes. Low blank levels and detection limits could be achieved (e.g., 0.029 nmol L−1 for Fe and 0.028 nmol L−1 for Zn) with the use of high purity reagents. Precision and accuracy were assessed using SAFe S, D1, and D2 reference seawaters, and results were in good agreement with available consensus values. The presented method is ideal for high throughput simultaneous analysis of trace elements in coastal and oceanic seawaters. We present a successful application of the analytical method to samples collected in June 2014 in the Northeast Atlantic Ocean.

A simple and rapid method for isotopic analysis of nickel, copper, and zinc in seawater using chelating extraction and anion exchange

Stable isotope ratios of nickel, copper, and zinc are powerful tools for elucidating the biogeochemical cycling of trace metals in the ocean. However, analytical difficulties have impeded isotopic studies of these metals. We present a simple and rapid method for simultaneous analysis of Ni, Cu, and Zn isotope ratios in seawater using NOBIAS Chelate-PA1 resin and anion exchange resin. A NOBIAS Chelate-PA1 resin column was used to quantitatively collect Ni, Cu, and Zn from seawater and thoroughly remove the seawater matrix. Subsequent anion exchange purified and separated the Ni, Cu, and Zn from each other. The blanks used in this method (0.22 ng for Ni, 0.29 ng for Cu, and 0.53 ng for Zn) were sufficiently low to determine the isotope ratios of Ni, Cu, and Zn in surface seawater. Using this method, we analyzed GEOTRACES reference seawater samples (i.e., SAFe D1 and SAFe D2), National Research Council Canada certified materials (i.e., CASS-5 and NASS-6), and seawater samples collected from different depths in the subarctic South Pacific. The results were consistent with previously reported values. This method is expected to accelerate isotopic research and contribute to our understanding of biogeochemical cycling in the ocean.

Diel Changes in Trace Metal Concentration and Distribution in Coastal Waters: Catalina Island As a Study Case

Understanding biogeochemical cycling of trace metals in the ocean requires information about variability in metal concentrations and distribution over short, e.g., diel, time scales. Such variability and the factors that influence it are poorly characterized. To address this shortcoming, we measured trace metal concentrations in the total dissolved, colloidal, and soluble fractions every 3-4 h for several consecutive days and nights in surface waters from a coastal station. Our results show that both the concentration and the size partitioning of some biologically essential (Fe, Cu, Co, and Cd) and anthropogenic (Pb) metals are subjected to diel variations that may be related to both inorganic and biological processes (e.g., photolysis of high-molecular-weight dissolved organic matter, photoinduced reduction/oxidation of metal(hydrous)oxides, uptake by growing phytoplankton, degradation of organic matter, lysis, and grazing). The largest fluctuations were observed in the soluble and colloidal pools. Soluble Fe varied during the day-night cycle by a factor of 40, and the contribution of colloidal Pb to the total dissolved fraction increased from 6±3% during the day to as much as 70-80% during the night. Our results suggest that changes occurring over time scales of hours need to be considered when collecting and interpreting trace metal data from the surface ocean.

Assessing Effects of Climate Change on Biogeochemical Cycling of Trace Metals in Alluvial and Coastal Watersheds

Assessing the impacts of climate changes on water quality requires an understanding of the biogeochemical cycling of trace metals. Evidence from research on alluvial aquifers and coastal watersheds shows direct impacts of climate change on the fate and transformation of trace metals in natural environments. The case studies presented here use field data and numerical modeling techniques to test assumptions about the effects of climate change on natural arsenic contamination of groundwater in alluvial aqui fers and mercury bioaccumulation in coastalsalt marshes. The results show that the rises of sea level and river base during the warm Holocene period has led to an overall increase in groundwater arsenic concentration due to the development of reducing geo chemical

Behaviors of dissolved and particulate Co, Ni, Cu, Zn, Cd and Pb during a mesoscale Fe-enrichment experiment (SEEDS II) in the western North Pacific

During mesoscale Fe enrichment (SEEDS II) in the western North Pacific ocean, we investigated dissolved and particulate Co, Ni, Cu, Zn, Cd and Pb in seawater from both field observation and shipboard bottle incubation of a natural phytoplankton assemblage with Fea ddition. Before the Fe enrichment, strong correlations between dissolved trace metals (Ni, Zn and Cd) and PO43-, and between particulate trace metals (Ni, Zn and Cd) and chlorophyll-a were obtained, suggesting that biogeochemical cycles mainly control the distributions of Ni, Zn and Cd in the study area. Average concentrations of dissolved Co, Ni, Cu, Zn, Cd and Pb in the surface mixed layer (0–20m) were 70 pM, 4.9, 2.1, 1.6, 0.48 nM and 52 pM, respectively, and those for the particulate species were 1.7 pM, 0.052, 0.094, 0.46, 0.037 nM and 5.2 pM, respectively. After Fe enrichment, chlorophyll-a increased 3 fold (up to 3 mg/L) during developing phases of the bloom (12 days). Mesozooplankton biomass also increased. Particulate Co, Ni, Cu and Cd inside the patch increase in the concentrations, but there were no analytically significant differences between concentrations inside and outside the patch. The bottle incubation with Fe addition (1 nM) showed an increase in chlorophyll-a (8.9 mg/L) and raised the particulate fraction up to 3–45% for all the metals, accompanying changes in Si/P, Zn/P and Cd/P. These results suggest that Fe addition lead to changes in biogeochemical cycling of trace metals. The comparison between the mesoscale Fe enrichment and the bottle incubation experiment suggests that although Fe was a limiting factor for the growth of phytoplankton, the enhanced biomass of mesozooplankton also limited the growth of phytoplankton and the transformation of trace metal speciation during the mesoscale Fe enrichment. Sediment trap data and the elemental ratios taken up by phytoplankton suggest that export loss was another reason that no detectable change in the concentrations of particulate trace metals was observed during the mesoscale Fe enrichment.

Gel‐Integrated Voltammetric Microsensors and Submersible Probes as Reliable Tools for Environmental Trace Metal Analysis and Speciation

AbstractThis article gives a review of the analytical and environmental criteria which must be considered and the relevant specific developments needed for direct, reliable voltammetric measurements of trace metal speciation in environmental systems. In particular, this article will focus on the tools which enable remote, long‐term in situ measurements. The development of such tools is a challenging task. The strategies that can be used to achieve this goal are described for the development of innovative and versatile gel‐integrated voltammetric microsensors, micro‐/mini‐integrated analytical systems, and submersible probes. The advantages of these new tools with respect to selectivity, sensitivity, reliability, spatial and temporal resolution of data, and thus efficient environmental monitoring of the biogeochemical cycle of trace metals are demonstrated by providing examples of measurements made in various aquatic samples in laboratory (water, soils, solid–liquid interface) and in situ in fresh and seawaters.