Some peculiarities of the trace-metal distribution in Baltic waters and sediments

Between 1980 and 1984 extensive studies were carried out in the Baltic Sea on trace metals (Cd, Co, Cu, Fe, Hg, Mn, Ni, Pb and Zn) in water, suspended matter and sediments. The results enabled the influence of different factors on metal distribution patterns to be considered. The vertical profiles of dissolved and particulate metals in waters of the central deep basins reflect influences caused by oxygen deficiency and anoxic conditions in near-bottom water layers. Peculiarities at Station BY15 in the Gotland Deep included high dissolved Fe, Mn and Co concentrations and remarkable enrichment of Zn (0.64%), Cd (51 μg g⁻¹) and Cu (0.15%) in particulate matter from the anoxic zone. Manganese-rich particles were accumulated above this layer.In fine-grained soft sediments below anoxic deep waters, maximum contents of Cd, Cu and Zn were observed, relative to other coring sites, between Bothnian Bay and Lübeck Bight. The Hg content in sediments probably reflects the joint flocculation with organic matter. Land-based sources seem to play the leading part for maximum lead contents.     

海洋沉积物孔隙水中痕量金属元素的测试分析方法

孔隙水是沉积物-海水界面链接沉积物颗粒和上覆水体的一个重要过渡相态,针对其研究可更好地了解痕量金属在固-液界面的早期成岩过程。近年来,针对孔隙水中痕量元素研究的方法较为匮乏,为此建立了一种分析测定海洋沉积物孔隙水中7种痕量金属元素(Mn、Cu、Zn、Ni、Cd、Co、Pb)的方法,该方法使用Nobias PA1树脂进行富集分离,再使用电感耦合等离子体质谱(ICP-MS)进行测试,可针对孔隙水中的痕量金属元素进行准确分析。通过实验结果发现该方法最优实验条件为: Nobias PA1树脂富集时的pH值为5.5~6.0,洗脱酸浓度为1.3 mol/L硝酸,体积为1 mL。同时,样品需进行紫外消解4 h以上以分解有机络合物,该消解步骤对Cu和Co这两种元素尤其重要。该方法通过加标回收获得Mn、Cu、Ni、Co和Pb的回收率在92%~100%, Zn和Cd的回收率分别为72%和82%; Mn、Cu、Zn、Ni的方法检出限范围为0.03~0.53 nmol/L, Cd、Co、Pb的方法检出限范围为2.66×10^-3~8.60×10^-3 nmol/L,满足孔隙水中痕量金属浓度的测试需求。同时,根据检出限计算的结果显示,孔隙水样品只需1 mL,即可应用该方法进行测试。应用该方法测试了一根采集于北黄海中部沉积物短柱的孔隙水样品,测试结果显示其垂相分布合理、较符合早期成岩过程规律。此研究为分析海洋沉积物孔隙水中痕量金属元素提供了一种准确而简便的方法。     

Trends of trace metal (Mn, Fe, Co, Ni, Cu, Zn, Cd and Pb) distributions at the oxic-anoxic interface and in sulfidic water of the Drammensfjord

Anoxic sulfidic waters provide important media for studying the effect of reducing conditions on the cycling of trace metals. In 1987–1988, dissolved and particulate trace metal (Mn, Fe, Co, Ni, Cu, Zn, Cd and Pb) concentrations were determined in the water column of the anoxic Drammensfjord basins, southeastern Norway. The iminodiacetic acid type chelating resin (Chelex 100) was used for the preconcentration of trace metals. The trace metal concentrations were determined using atomic absorption spectrophotometry (AAS), differential pulse polarography (DPP), and differential pulse-anodic stripping voltammetry (DP-ASV).It was observed that the trace metals Mn and Fe were actively involved in the processes of redox cycling (oxidationreduction and precipitation-dissolution) at the O₂/H₂S interface. The dissolved concentrations of Mn, Fe and Co showed maxima just below the O₂/H₂S interface. The seasonal enhancement in the maxima of both dissolved and particulate Mn and Fe at the redox cline is mainly governed by the downward movement of water which carries oxygen. An association of Co with the Mn cycle was observed, while the total dissolved Ni was decreased by only 10–35% in the anoxic waters. The dissolved concentrations of Cu, Zn, Pb and, to a lesser extent, Cd decreased in the anoxic zone.     

Simplified synthesis of an 8-hydroxyquinoline chelating resin and a study of trace metal profiles from Jellyfish Lake, Palau

We report a simplified synthesis, and some performance characteristics, for 8-hydroxyquinoline (8-HOQ) covalently bonded to a chemically resistant TosoHaas TSK vinyl polymer resin. The resin was used to concentrate trace metals from stored, acidified seawater samples collected from Jellyfish Lake, an anoxic marine lake in the Palau Islands. The Mn, Fe, and Zn profiles determined from the 8-HOQ resin extraction were similar to those determined using Chelex-100 resin. The Zn and Cd profiles did not exhibit removal by sulfide “stripping” in contrast to other anoxic marine basins. The profiles of Co and Ni also exhibited elevated concentrations in the anoxic hypolimnion. The solution speciation and saturation states for the metals were calculated using revised metal-bisulfide stability constants. The calculations suggest that the MS(HS)⁻ species dominates the solution speciation for Mn, Co, Ni, Zn, Cd, and Pb. Cu(I) is modeled as the CuS⁻ or Cu(HS)₂⁻ species, while Fe(II) behaves as the free Fe²⁺ cation. The Mn, Co, Ni, Cu and Cd concentrations appeared to be at least 10-fold undersaturated, while the Fe(II), Zn, and Pb concentrations were close to saturation with respect to their metal sulfides.     

Heavy metals in mussels (Mytilus galloprovincialis) from the gulf of la spezia and from the promontory of Portofino,Italy

In different samples of Mytilus galloprovincialis Cd, Co, Cr, Cu, Hg, Mn, Ni, Pb and Zn were determined by AAS. The mussels were taken from 11 sites in the Port of La Spezia. Typical concentration ranges (μ/g dry weight) were as follows: Cd, 2.0–6.8; Co, 0.8–3.2; Cr, 5.8–19.5; Cu, 6.9–33.7; Hg, 0.15–0.38; Mn, 11.8–37.8; Ni, 1.3–10.9; Pb, 13.9–44.6 and Zn, 203–379.Other samples were collected at 4 sites on the Promontory of Portofino and the following values were obtained: Cd, 0.8–1.1; Co, 2.6–2.9; Cu, 3.3–4.2; Hg, 0.09–0.15; Mn, 6.3–9.1; Ni, 1.2–2.4; Zn, 120–140.     

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 Fe addition. 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 (0–20 m) 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 μg L⁻¹) during developing phases of the bloom (<12 days). Mesozooplankton biomass also increased. Particulate Co, Ni, Cu and Cd inside the patch hinted at an 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 μg L⁻¹) 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.     

粤西湛江港海底沉积物重金属的分布特征与来源

2004年9月23日至10月5日对湛江港海洋沉积物中金属元素的含量及分布进行了调查。共采集样品20个,采用王水-氢氟酸消解,电感耦合等离子体发射光谱法测定样品中的金属元素As、Cd、Co、Cr、Cu、Ni、Pb、Zn、Al、Ca、Fe、Mg和Mn。结果发现,湛江港大多数区域的沉积物未受污染,但霞山区港务局码头附近海域受到Cd、Cu和Pb的轻度污染,特呈岛养殖区也受到Cu的轻度污染。主成分分析结果表明,Al、Cd、Co、Cr、Cu、Fe、Ni、Pb和Zn主要通过陆源输入进入近岸水域的沉积相中,Ca、As、Mg和Mn主要通过海洋环境中水相和沉积相的相互作用进入沉积相中。结合其它调查结果认为,湛江港的Cd污染在水相、沉积相和生物相中均已存在,应引起有关部门的高度重视。     

RELEASE OF HEAVY METALS FROM HARBOUR''S SEDIMENT TO SEAWATER: A LABORATORY STUDY

The release and removal behaviour of Cd, Cu, Co, Ni, Pb and Zn from the sediment of Xiamen Harbour to sea water have been studied under ultra-clean laboratory condition within 168 b. Initial rapid increases in dissolved Cu, Pb, Zn and Co were observed in the first six hours and twelve hours respectively after addition of various amounts of sediment. Then Pb and Co decreased to background values, while Zn decreased to less than the background value and Cu remained unchanged. Cd and Ni did not increase during the experiment. The results indicated that the weakly bound heavy metals were released from the sediment through desorption or exchange. Simultaneously, they might form complexes or be adsorbed in colloids or particles. The two processes existed simultaneously, changing with time and conditions.     

The behavior of Zn,Cd, Cu,Ni, Co,Fe, and Mn in anoxic baltic waters

In June 1981, dissolved Zn, Cd, Cu, Ni, Co, Fe, and Mn were determined from two detailed profiles in anoxic Baltic waters (with extra data for Fe and Mn from August 1979). Dramatic changes across the O₂H₂S interface occur in the abundances of Cu, Co, Fe, and Mn (by factors of ?100). The concentrations of Zn, Cd, and Ni at the redox front decrease by factors between 3 to 5.Equilibrium calculations are presented for varying concentrations of hydrogen sulfide and compared with the field data. The study strongly supports the assumption that the solubility of Zn, Cd, Cu, and Ni is greatly enhanced and controlled by the formation of bisulfide and(or) polysulfide complexes. Differences between predicted and measured concentrations of these elements are mainly evident at lower ΣH₂S concentrations.Cobalt proved to be very mobile in anoxic regions, and the results indicate that the concentrations are limited by CoS precipitation. The iron (Fe²⁺) and manganese (Mn²⁺) distribution in sulfide-containing waters is controlled by total flux from sediment-water interfaces rather than by equilibrium concentrations of their solid phases (FeS and MnCO₃). The concentrations of these metals are therefore expected to increase with prolonged stagnation periods in the basin.     

Chemical fractionation of zinc versus cadmium among other metals nickel, copper and lead in the northern North Sea

Concentrations of dissolved Ni, Cu, Zn, Cd and Pb were measured in water samples collected during a cruise with R.V Pelagia (29-6/14-7-1993) in the northern North Sea and N.E. Atlantic Ocean. At least six depths (0–90 m) were sampled with modified Go-Flo samplers from a rubber zodiac. In the study area, the first 25 m were well mixed and stratification occurred below this depth. The local bloom of Emiliania huxleyi hardly affected the trace metals concentration, except for some removal of Cd as seen from its correlation with nitrate. The mean dissolved concentrations were for Ni (3.66 nM), Cu (1.61 nM), Zn (4.5 nM), Cd (48 pM) and Pb (108 pM). These concentrations are among the lowest reported for the North Sea and are of similar magnitude to those found in the eastern North Atlantic at the same latitude. Zn was the only exception with values 10 times higher compared to those in the Atlantic Ocean, suggesting external inputs, mainly atmospheric and possibly from surrounding land masses. The observed ratio Zn:Cd in the North Sea and estuaries is in between the high ratio 600–900 for continental sources and the low ratio 5–10 for oceanic waters. Latter low ratio is consistent with the 21-fold stronger inorganic complexation of Cd in seawater which, in combination with the preferential biological uptake of Zn, may lead to the observed about hundredfold fractionation of Zn versus Cd in the marine system. Other processes may play a role but would need further investigation. The dissolved Pb values tend to be lower than found before in the North Sea, indicating decreasing inventories due to reduced anthropogenic emissions.     

Geochemistry of suspended matter from the Baltic Sea 2. Results of bulk trace metal analysis by AAS

In 1984, on a transect covering the whole Baltic Sea and parts of the adjacent North Sea, 160 water samples were taken and analysed for their concentrations of particulate and dissolved metals. In addition, the suspended materials were investigated for their elemental bulk composition.The particulate fractions represented from about 5% (Cd, Cu and Ni) to 50% (Fe and Pb) of the total (particulate plus dissolved) concentrations. For some elements (Ba, Cd, Cu, Pb and Zn), the particulate matter from the surface microlayer was enriched with respect to those suspended materials taken from 0.2 m depth. This could reflect the atmospheric input of metal-rich aerosols. In anoxic deep waters, maximum contents of Zn (6400 μg g⁻¹), Cu (1330 μg g⁻¹) and Cd (12 μg g⁻¹) were observed in the particulate matter, indicating sulphidic forms. On the other hand, under oxic conditions the distribution coefficients (K_d) decreased with the water depth (Cd, Fe and Pb).Relative to global background levels, the particulate matter contained metal “excesses” amounting to more than 90% of the total contents (Cd, Mn, Pb and Zn). Automated electron probe X-ray microanalysis (EPXMA) revealed that the elemental composition of sediments is mainly governed by post-depositional processes of early diagenesis and is only weakly related to the composition of suspended matter in the overlying water body. For instance, in relation to surface mud sediments of the central Baltic net-sedimentation basins, Zn, Cd, Cu and Mn had 30–100% higher levels in the suspended materials. The general pattern of metal contents of particulate matter taken from 10 m depth on a transect between the Bothnian Bay and the North Sea were—possibly as a result of anthropogenic inputs—rather similar for Pb, Zn and Cu. For Fe and Mn, the distribution patterns along the transect were probably governed by the natural loading characteristics and by the biogeochemistry of those elements.     

Trace metal concentrations in sediments of the Eastern Mississippi Bight

Sediments collected from 3 onshore-offshore transects (12 stations total) in the Eastern Mississippi Bight at 5 different times during 1987–1988 have been analyzed for total Ag, As, Ba, Cd, Co, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Sb, Se, Sn, Th and Zn. The data show considerable variation both spatially and temporally, largely as a result of natural variability in grain size and mineralogy. Clay-rich samples from deep water were always more metal-rich than sandy samples from shallow areas. Many samples from near the Mississippi River Delta appeared to be enriched in Ba by about a factor of two, probably as a result of contamination from oil well drilling mud, but there were few other indications of pollution influences. Many samples from throughout the area gave Mn/Fe and Cd/Fe ratios a factor of two or more lower than their Mississippi River source material. This shows that biochemical activity in the sediment is capable of solubilizing reducible and adsorbed metals.     

Heavy metals in sinking particles and bottom sediments from the eastern Turkish coast of the Black Sea

Concentrations of Cd, Cu, Cr, Co, Ni, Zn, Fe, Mn, Pb, As, and Sb were determined in sediment trap and bottom sediment samples collected seasonally from a station on the eastern Turkish coast of the Black Sea. Cd, Pb and Mn concentrations were highest in the sediment trap samples except during the summer period, whereas Co, Ni, Zn and Fe levels were much lower than corresponding levels found in the surface sediments. Cu, Cr, As and Sb levels showed no definite trend with sediment type. In general, with the exception of Cr, relatively lower metal concentrations in the sediment trap material were determined in the summer period. The highest mass flux, 56.5 g m⁻² day⁻¹, was measured during autumn. The highest flux of heavy metals also occurred during autumn and was strongly dependent on particle mass flux. Based on these results, we suggest that the downward vertical transport of particulate heavy metals in this region is related to the high degree of land erosion and the resultant particulate flux dynamics, which occur here. It was noteworthy that the highest concentrations of Cd, Cu, Co, Zn, Fe and Sb in particles were measured during winter a finding which suggests that enhanced fossil fuel combustion, which occurs during this period in adjacent urban and industrial areas plays an important role in the metal composition of sinking particles in nearshore waters.     

Monitoring trace metals in seawater using a diffusive gradient in thin film probe in Ulsan Bay,East Sea,Korea: Comparison with transplanted mussels

To evaluate the applicability of a diffusive gradient in thin film (DGT) probe for monitoring dissolved metals in coastal seawater, DGT-labile metal concentrations were compared with total dissolved metal concentrations using spiked and natural seawater samples in the laboratory and transplanted mussels (Mytilus galloprovincialis). This was achieved through the simultaneous deployment of DGT probes and transplanted mussels in Ulsan Bay during winter and summer. DGT-labile metal concentrations were 45% (Cu) ~ 90% (Zn) of total dissolved concentrations, and the order of non-labile concentrations was Cu > Pb > Co ~ Ni > Cd ~ Zn in both metal-contaminated and non-contaminated seawater samples, which was similar to the order of stability of metal complexes in the Irving–Williams series. The overall variability of the DGT probe results within and between tanks was less than 10% (relative standard deviation: RSD) for all the metals tested during a 48-h deployment. The accumulation of metals, as determined by DGT probes, represented the spatial gradients better than the transplanted mussels did for all of the metals tested, and the extent of metal accumulation in mussels differed depending on the metal. The comparison of results for the DGT probe and the transplanted mussels in two seasons (winter and summer) suggested that metal accumulation in mussels was controlled by the physiological factors of mussels and partly by their diet (particulate metal loadings). The DGT probe could be used as a monitoring tool for dissolved metals in coastal seawater because its results explained only labile species. When using the DGT probe, slightly more than half of the total dissolved concentration in seawater samples for all the metals investigated displayed timeintegrated properties and distinct spatial gradients from pristine to metal-contaminated seawater.     

Analytical fractionation of dissolved copper, lead and cadmium in coastal seawater

The speciation of dissolved Cu, Pb and Cd in twelve seawater samples from the Inner Oslofjord, Norway, has been examined by an operational scheme which involves ultrafiltration followed by determination of labile, acid soluble and total Cu, Pb and Cd by differential pulse anodic stripping voltammetry (DPASV). The techniques employed are discussed and evaluated. It was found that Cd was present entirely in low molecular weight (LMW) labile species; Pb was mainly in non-labile LMW species, with half of the total Pb probably occurring in LMW organo-metallic compounds; Cu distribution was irregular, with extensive organic and colloidal association.     

碱蓬（Suaeda salsa）对胶州湾滨海湿地重金属的富集与迁移作用

通过对胶州湾东北部滨海湿地5个采样点生长的碱蓬中10种重金属Cu、Zn、Pb、Cd、As、Cr、Co、Ni、V、Mo的系统研究,发现碱蓬对Cu,Zn的吸收明显高于其它重金属,这可能与Cu和Zn是植物生长发育必需的微量元素有关,碱蓬体内Cr、Pb、V和Ni的含量也相对较高。碱蓬对Mo的富集效果最为显著,对Cu、Zn、Cd...     

Stoichiometry among bioactive trace metals in seawater on the Bering Sea shelf

The distribution of Al, Mn, Fe, Co, Ni, Cu, Zn, Cd, and Pb in seawater was investigated on the Bering Sea shelf (56–64°N, 165–169°W) in September 2000. The unfiltered and filtered seawater samples were used for determination of total dissolvable (TD) and dissolved (D) metals (M), respectively. The TD-M concentrations were generally higher than in the Pacific Ocean. TD-Cd was highest in deep water of the outer shelf domain and dominated by dissolved species. The other TD-M were highest at stations close to the Yukon River delta and had higher fractions of labile particulate (LP) species that were obtained as the difference between TD-M and D-M. Dissolved Al, Ni, and Cu were characterized by input from the Yukon River. Dissolved Mn and Co showed maximums on the bottom of the coastal domain, suggesting influence of sedimentary Mn reduction. The correlations of D-Zn, D-Cd, and macronutrients indicated their distributions were largely controlled through uptake by microorganisms and remineralization from settling particles. All these three processes (river input, sedimentary reduction, and biogeochemical cycle) had an influence on the distribution of D-Fe. D-Pb was fairly uniformly distributed in the study area. The stoichiometry of D-M in the Bering Sea shelf showed enrichment of Co and Pb and depletion of Ni, Cu, Zn, and Cd compared with that in the North Pacific. The LP-M/LP-Al ratio revealed significant enrichment of the other eight metals relative to their crustal abundance, suggesting importance of formation of Fe–Mn oxides and adsorption of trace metals on the oxides.     

Metals background and enrichment in the Chiloé Interior Sea sediments (Chile). Is there any segregation between fjords,channels and sounds?

The range and spatial distribution of metal concentrations in the Chiloé Interior Sea were investigated from 37 surface sediment samples collected during the ‘CIMAR 10 Fiordos’ cruise. Grain size distribution, total organic carbon and nitrogen, δ¹³C, major (Al, Fe, and biogenic opal) and trace (Cd, Co, Cu, Ni, Pb, and Zn) elements were determined. Metal background concentrations of each metal in sediment were defined from linear regression equations of metal versus Al, as baseline information for future research on the status of sediment contamination in the Northern Patagonian marine area. Metal levels in Chiloé sediments were of the same order of magnitude as uncontaminated sediments around the world and contamination can be considered negligible-moderate (normalized enrichment factors lower than 3) in this Southern Pacific Region. The Chiloé Interior Sea can be segregated into two zones on the basis of metal content by applying a principal component analysis. The first pertains to inner fjords and it has terrestrial origin (associated to Co, Cu, Pb, Zn) and the second zone features channels and gulfs of a predominantly marine source (Cd, Cu). Nevertheless, only one background equation is needed to predict metal concentrations in the natural sediment of the Chiloé Interior Sea.     

Bioaccumulation of trace metals in the Antarctic amphipod Orchomene plebs: evaluation of toxicokinetic models

Bioaccumulation of Cd, Co, Cu, Ni, Pb and Zn in Antarctic gammaridean amphipod collectives, Orchomene plebs (Hurley, 1965), was investigated during a cruise of RV "Polarstern" to the Wedell Sea. With the sole exception of Cd the organisms accumulated metals during exposure and depurated them in uncontaminated seawater. Four independent toxicokinetic experiments and one field study were modelled simultaneously to calculate the following size-dependent bioconcentration factors for organisms with body length 10 mm (BCF(10 mm)): 130 (Co), 4030 (Cu), 190 (Ni), 2900 (Pb), and 5210 (Zn). On the time scale of our experiments the data suggest an increased metal uptake by previously exposed test organisms. The collectives investigated may be regarded as potentially suitable biomonitors for Co, Cu, Ni, Pb and Zn but not for Cd. An approach to evaluate the sensitivity of Orchomene plebs as a biomonitor of waterborne metals in the field indicates minimal increments of the ambient exposure concentrations of 0.01 microg Co l(-1), 0.2 microg Cu l(-1), 0.4 microg Ni l(-1), 0.6 microg Pb l(-1) and 0.3 microg Zn l(-1).     

The determination of Cd,Cu, Fe,Ni, Pb and Zn in Baltic Sea water

Cd, Cu, Fe, Ni, Pb and Zn were determined in 123 samples from the Baltic Sea proper. The trace metals were extracted directly on board the vessel, using a dithiocarbamate-Freon procedure. Final analyses of the extracts are performed onshore by atomic absorption spectrometry.Similar trace-metal concentrations are found in different areas of the Baltic proper. Most values fall in the following ranges: Cd, 30–60 ng 1^?1; Cu, 0.6–1.0 μg 1^?1; Fe, 0.3–0.9 μg 1^?1; Ni, 0.6–0.9 μg 1^?1; Pb, 0.05–0.2 μg 1^?1; and Zn, 1.5–3.5 μg 1^?1. The metal-concentrations are generally independent of depth. However, copper exhibits a small but significent decrease in concentration below 80 m.Filtration did not affect trace-metal concentrations, with the exception of iron in waters from lower layers. Similarly, storage under acid conditions was shown to affect only the concentration of iron. An electro-chemical technique was also used to determine Cu in some samples.