Speciation of cadmium in seawater — a direct voltammetric approach

The present report deals with differential pulse anodic stripping voltammetry (DPASV) applied for the analysis of cadmium in open ocean seawater. Evaluation of different Cd species can generate information about distribution and speciation of Cd in the open ocean. Distribution of Cd was investigated in surface waters of the Atlantic Ocean over a wide geographical range as well as in the water column. Surface water sampling on board the research vessel Polarstern was performed from the bow boom of the ship as well as with a snorkel system which allowed continuous sample-taking. Two different Cd species could be differentiated in the voltammograms. UV-irradiation experiments allowed the identification of an inorganic and organic Cd form, the latter caused by the association between Cd and organic matter as e.g. humic substances (HS). Atlantic ocean surface seawater normally contains between 2 and 4 ng organically complexed Cd/kg and no detectable inorganic Cd. Some areas however showed readings of up to 14 ng inorganic Cd/kg in addition. Water column samples exhibited an enrichment of inorganic Cd by depth. Occurrence of inorganic Cd at the surface could be related to specific oceanographical conditions. Together with analytical results of trace metal contents in the particulate phases of surface seawater, new aspects could be established about the biogeochemical cycling of Cd in the sea.     

Biomethylation of thallium by bacteria and first determination of biogenic dimethylthallium in the ocean

To investigate a possible biomethylation of thallium, incubation experiments were carried out under aerobic conditions with a sewage sludge and with a mixed bacterial culture isolated from a sewage sludge, as well as under anaerobic conditions with a fresh‐water lake sediment, by adding Tl(I) nitrate to these systems. Only in the case of the anaerobic sediment was a significant production of dimethylthallium observed (after three‐weeks). Analysing different surface seawater samples and those from a single depth profile down to 4000 m, dimethylthallium was determined above the detection limit of 0.4 ng L⁻¹ in about 20% of all samples, ranging from 0.5 to 3.2 ng l⁻¹. The proportion of dimethylthallium in these samples, compared with the total thallium concentration, varied from 3 to 48%. The determination of such low dimethylthallium content was possible by applying a new sensitive analytical method of positive thermal‐ionization isotope‐dilution mass spectrometry connected with a species‐unspecific thallium enrichment by anion‐exchange chromatography and a species‐specific extraction step. This is the first time that dimethylthallium could be detected in environmental samples. In surface seawater samples the occurrence of dimethylthallium correlated well with relatively high concentrations of chlorophyll‐a, used as an indicator for bioactivity. Mostly, other biomethylated compounds such as trimethyl‐lead, monomethylcadmium and dimethyl sulphide were also found with peak concentrations at these locations. The depth profile of dimethylthallium shows a maximum in concentration between 40 and 200 m, which corresponds with the highest level of bioactivity normally found in the water column of the ocean. However, even at depths of 1000 and 4000 m significant amounts of dimethylthallium could be analysed, which suggest bacteria as the biogenic source in the deep sea. Copyright © 2000 John Wiley & Sons, Ltd.     

A new methodology for precise cadmium isotope analyses of seawater

Previous studies have revealed considerable Cd isotope fractionations in seawater, which can be used to study the marine cycling of this micronutrient element. The low Cd concentrations that are commonly encountered in nutrient-depleted surface seawater, however, pose a particular challenge for precise Cd stable isotope analyses. In this study, we have developed a new procedure for Cd isotope analyses of seawater, which is suitable for samples as large as 20 L and Cd concentrations as low as 1 pmol/L. The procedure involves the use of a ¹¹¹Cd–¹¹³Cd double spike, co-precipitation of Cd from seawater using Al(OH)₃, and subsequent Cd purification by column chromatography. To save time, seawater samples with higher Cd contents can be processed without co-precipitation. The Cd isotope analyses are carried out by multiple collector inductively coupled plasma mass spectrometry (MC-ICP-MS). The performance of this technique was verified by analyzing multiple aliquots of a large seawater sample that was collected from the English Channel, the SAFe D1 seawater reference material, and several samples from the GEOTRACES Atlantic intercalibration exercise. The overall Cd yield of the procedure is consistently better than 85% and the methodology can routinely provide ε ^114/110Cd data with a precision of about ±0.5 ε (2sd, standard deviation) when at least 20–30 ng of natural Cd is available for analysis. However, even seawater samples with Cd contents of only 1–3 ng can be analyzed with a reproducibility of about ±3 to ±5 ε. A number of experiments were furthermore conducted to verify that the isotopic results are accurate to within the quoted uncertainty.     

Photochemistry of organic iron(III) complexing ligands in oceanic systems

Iron is a limiting nutrient for primary production in marine systems, and photochemical processes play a significant role in the upper ocean biogeochemical cycling of this key element. In recent years, progress has been made toward understanding the role of biologically produced organic ligands in controlling the speciation and photochemical redox cycling of iron in ocean surface waters. Most (>99%) of the dissolved iron in seawater is now known to be associated with strong organic ligands. New data concerning the structure and photochemical reactivity of strong Fe(III) binding ligands (siderophores) produced by pelagic marine bacteria suggest that direct photolysis via ligand-to-metal charge transfer reactions may be an important mechanism for the production of reduced, biologically available iron (Fe[II]) in surface waters. Questions remain, however, about the importance of these processes relative to secondary photochemical reactions with photochemically produced radical species, such as superoxide (O2-). The mechanism of superoxide-mediated reduction of Fe(III) in the presence of strong Fe(III) organic ligands is also open to debate. This review highlights recent findings, including both model ligand studies and experimentallobservational studies of the natural seawater ligand pool.     

Speciation of major arsenic species in seawater by flow injection hydride generation atomic absorption spectrometry

Arsenic present at 1 microg L(-1) concentrations in seawater can exist as the following species: As(III), As(V), monomethylarsenic, dimethylarsenic and unknown organic compounds. The potential of the continuous flow injection hydride generation technique coupled to atomic absorption spectrometry (AAS) was investigated for the speciation of these major arsenic species in seawater. Two different techniques were used. After hydride generation and collection in a graphite tube coated with iridium, arsenic was determined by AAS. By selecting different experimental hydride generation conditions, it was possible to determine As(III), total arsenic, hydride reactive arsenic and by difference non-hydride reactive arsenic. On the other hand, by cryogenically trapping hydride reactive species on a chromatographic phase, followed by their sequential release and AAS in a heated quartz cell, inorganic As, MMA and DMA could be determined. By combining these two techniques, an experimental protocol for the speciation of As(III), As(V), MMA, DMA and nonhydride reactive arsenic species in seawater was proposed. The method was applied to seawater sampled at a Mediterranean site and at an Atlantic coastal site. Evidence for the biotransformation of arsenic in seawater was clearly shown.     

Determination of trace metals in seawater by graphite furnace atomic absorption spectrometry with preconcentration on silica-immobilized 8-hydroxyquinoline in a flow-system

Summary A flow-system utilizing a miniature column packed with silica-immobilized 8-hydroxyquinoline (I-8-HOQ) was used for the preconcentration of Cd, Pb, Zn, Cu, Fe, Mn, Ni, and Co from seawater prior to their determination by graphite furnace atomic absorption spectrometry (GFAAS). Enrichment factors sufficient to permit the analysis of an open ocean seawater reference material using 50 ml sample volumes (100 ml for Co determinations) were obtained. Recoveries of the above elements from seawater averaged 93% (range 87–97%) with absolute blanks ranging between 0.04 ng (Ni) and 4.0 ng (Fe). Estimated detection limits for these elements vary from 0.2 ng l^–1 (Co) to 40 ng l^–1 (Fe) based on a 50 ml sample volume (100 ml for Co).

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Bestimmung von Spurenmetallen in Meereswasser durch Graphitofen-AAS mit Anreicherung an Kieselgel-immobilisiertem 8-Hydroxychinolin in einem Durchflu\system

     

Determination of trace metal complexes by natural organic and inorganic ligands in coastal seawater.

It is well-documented that organic compounds form strong complexes with most metals in aquatic systems, and that seawater is a complex medium which contains a large variety of organic and inorganic ligands, including colloidal matter. We suggest that most trace metals are complexed in seawater and that some inorganic metals complexes are either labile or not stable. In contrast, metal-organic complexes are often stable and need various and specific treatments to be dissociated. In this paper we try to illustrate a good tendency of some trace metals to be complexed by organic ligands in seawater. A solid-phase extraction method was applied using a C18 column as a resin that is able to separate metals complexed by neutral organic ligands, and the chelamine resin to separate metal species that are present as labile inorganic complexes. The determination of total dissolved metal concentrations was achieved by formatting a metal-8-hydroxyquinoline complex, followed by adsorption on C18 columns and ICP-AES analysis.     

Speciation of major arsenic species in seawater by flow injection hydride generation atomic absorption spectrometry

Arsenic present at 1 μg L^–1 concentrations in seawater can exist as the following species: As(III), As(V), monomethylarsenic, dimethylarsenic and unknown organic compounds. The potential of the continuous flow injection hydride generation technique coupled to atomic absorption spectrometry (AAS) was investigated for the speciation of these major arsenic species in seawater. Two different techniques were used. After hydride generation and collection in a graphite tube coated with iridium, arsenic was determined by AAS. By selecting different experimental hydride generation conditions, it was possible to determine As(III), total arsenic, hydride reactive arsenic and by difference non-hydride reactive arsenic. On the other hand, by cryogenically trapping hydride reactive species on a chromatographic phase, followed by their sequential release and AAS in a heated quartz cell, inorganic As, MMA and DMA could be determined. By combining these two techniques, an experimental protocol for the speciation of As(III), As(V), MMA, DMA and non-hydride reactive arsenic species in seawater was proposed. The method was applied to seawater sampled at a Mediterranean site and at an Atlantic coastal site. Evidence for the biotransformation of arsenic in seawater was clearly shown.     

Lead in Atlantic surface waters as a tracer for atmospheric input

Summary The present report provides information about lead concentrations in Atlantic surface waters over a wide geographical range. Differential pulse anodic stripping voltammetry (DPASV) was applied for the analysis of lead in surface water of the Atlantic Ocean. Sampling on board of the research vessel Polarstern was performed from the bow boom of the ship but also with a newly installed snorkel system which allowed continuous sampletaking. In both cases special precautions were taken in order to avoid contamination by the ship. A limited number of samples could immediately be measured aboard Polarstern in a newly constructed clean room laboratory container. A part of the samples had to be irradiated before the voltammetric measurement. In 1989 lead concentrations in the North Atlantic between 22° N and 46° N continuously increased from 42.5 pmol/kg up to 147 pmol/kg. The comparison with results from a cruise in 1981 shows that the lead concentration in the eastern North Atlantic has diminished by more than 50%. A similar trend is documented for the consumption of alkyl leaded gasoline in the United States of America. Seawater samples from a cruise in 1990 exhibited a very low background concentration of 6.1–14 pmol/kg Pb in the middle Atlantic, while higher values were measured in the Intertropical Convergence Zone (ITCZ). In a certain area of the Atlantic Ocean lead has been identified as a tracer for terrigenous input, in another area, however, as a transient tracer for anthropogenic input. This demonstrates that atmospheric input of lead into the surface water of the Atlantic can have different origins.     

Seasonal Changes in Methylarsenic Distribution in Tosa Bay and Uranouchi Inlet

The distribution of arsenic species, including trivalent methylarsenicals, was observed in coastal seawater of Tosa Bay and Uranouchi Inlet Japan. In Tosa Bay, most arsenic was dissolved in the inorganic form throughout the year and the concentration of total dissolved arsenic was higher than that in Uranouchi Inlet. The sum of methylarsenicals found in surface waters comprised 2–25% and 10–82% of the total dissolved arsenic in Tosa Bay and Uranouchi Inlet, respectively. In Uranouchi Inlet, seasonal variations in the concentrations of arsenicals were observed both in the water column and in surface sediments. The maximum concentrations of methylarsenicals appeared during summer, and became comparable to those of inorganic arsenicals in surface water. The concentration of trivalent methylarsenicals was usually low, and their seasonal changes seemed to be independent of those of the pentavalent species. The variations in methylarsenic(V) concentration did not coincide with those of chlorophyll a in either Tosa Bay or Uranouchi Inlet. These results suggested that methylarsenic(V) in natural waters was produced not directly by the activity of phytoplankton but through decomposition of organic matter by bacteria.