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.     

Contrasting behaviour of trace metals in the Scheldt estuary in 1978 compared to recent years

Dissolved and particulate trace metals (Cu, Cd, Pb, Zn, Ni, Fe and Mn) measured at six stations along the Scheldt estuary in October/November 1978 are compared with more recent data. Based on Ca content in the suspended matter, three distinct geochemical regions could be distinguished: the upper estuary (salinity 1–7) dominated by fluvial mud, mid-estuary (salinity 7–17) where the composition of the suspended matter remained relatively constant, and the lower estuary where marine mud prevailed. Re-suspension of sediments is the major factor controlling the composition of the particles in the upstream region. Anoxic conditions prevailed in the upper part of the estuary extending to a salinity of 15 in 1978, while at present the seaward boundary of the anoxic water body is located at less saline waters. Furthermore, the present-day metal load is much lower than in 1978. As a consequence of the changed situation, maxima in dissolved concentrations of redox-sensitive metals in the mid/lower estuary have moved as well, which affects the trace metal re-distribution pattern. In the anoxic zone, exchange processes between dissolved and particulate metal fractions were strongly redox regulated, with Fe and Mn as excellent examples. Iron was removed from the dissolved phase in the early stages of mixing resulting in an increase in the suspended particulate matter of the leachable ‘non-residual' Fe fraction from 2 to 3.5%. Due to its slower kinetics, removal of Mn from solution occurred in mid-estuary where oxygen concentrations increased. Cu, Cd and Zn on the contrary were mobilised from the suspended particles during estuarine mixing. External inputs of Pb, and to a lesser extent of Cu, in the lower estuary resulted in the increase of their particulate and the dissolved concentrations. Calculated K_d (distribution coefficient) values were used to assess the redistribution between the dissolved and particulate phase of the investigated metals. Due to the existence of the anoxic water body in the upper estuary, the importance of redox processes in determining the K_d values could be demonstrated. The sequence of K_d values in the upper estuary (Fe, Cd, Zn, Pb > Cu > Ni, Mn) is significantly different from that in the lower estuary (Fe > Mn > Pb, Ni, Zn, Cu, Cd). Thus, in such a dynamic estuary single metal-specific K_d values cannot be used to describe redistribution processes.     

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.     

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.     

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.     

Trace elements in ferromanganese nodules from the central indian ocean basin

Thirty-three bulk ferromanganese nodules from the sediment–water interface of siliceous sediment domain from the Central Indian Ocean Basin were analyzed for 50 elements including 6 new (Be, As, Se, Sn, Sb, and Bi) using inductively coupled plasma–mass spectrometer. The Mn/Fe ratio and triangular plot (Fe-Mn-{Cu+Ni+Co?×?10}) suggest that ferromanganese nodules are of hydrogenetic, early diagenetic, and diagenetic origin. In the ferromanganese nodules, Mo, Sb, Bi, and As are highly enriched ～320, 160, 90, and 50 times compared with upper continental crust, respectively. A majority of the elements such as Be, Sc, Ti, V, Co, As, Se, Sr, Y, Zr, Nb, Sn, rare earth elements (REEs), Pb, Bi, P, Th, U, Hf, and Ta are associated with Fe, whereas, Cu, Ni, Zn, Mo, Li, Ga, Sb, Mg, and Cs are associated with Mn in the ferromanganese nodules. Redox proxies such as U/Th (0.14) and Mo/Mn (0.0019) ratio in the ferromanganese nodules suggest their formation under oxic conditions.     

MarinevsFluvial Suspended Matter in the Scheldt Estuary

The ratio of marine to fluvial suspended matter in the Scheldt Estuary was calculated by applying factor analysis to a data set of elemental concentrations. The data set consisted of 98 samples collected under various river discharge conditions. Each sample was analysed for the concentration of Cr, Pb, Fe, Mn, Ni, Co, Ba, Zn, Cu, Cd, S, Ca, Sr, Ag, Sn and Na. Five linearly independent processes were found to describe the variability of the elemental concentrations: (1) the supply of fluvial material to the mixing zone; (2) manganese oxidation in the transition area between the anoxic upper estuary and the oxic lower estuary; (3) the supply of marine material to the mixing zone; (4) a phytoplankton bloom in the lower estuary; and (5) the formation of insoluble metal sulphides in the anoxic high-turbidity zone. Scores of the first and third factor were used to calculate the ratio of marine to fluvial suspended matter in the mixing zone. Information on the origin of both the inorganic and organic fraction of suspended matter was obtained in this way.     

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...     

Trace element diagenesis in pyrite-rich sediments of the Achterwasser lagoon, SW Baltic Sea

The early diagenesis of trace elements (V, Cr, Co, Cu, Zn, As, Cd, Ba, U) in anoxic sediments of the Achterwasser, a shallow lagoon in the non-tidal Oder estuary in the Baltic Sea, was investigated in the context of pyrite formation. The dissolved major redox parameters show a two-tier distribution with transient signals in the occasionally re-suspended fluid mud layer (FM) and a permanently established diagenetic sequence in the sediment below. Intense microbial respiration leads to rapid depletion of O₂ within the uppermost mm of the FM. The reduction zones of Mn, Fe and sulfate overlap in the FM and in the permanently anoxic sediment section which appears to be a typical feature of estuarine sediments, under low-sulfate conditions. Degrees of pyritization (DOP) range from 50% in the FM to remarkably high values > 90% at 50 cm depth. Pyrite formation at the sediment surface is attributed to the reaction of Fe-monosulfides with intermediate sulfur species via the polysulfide pathway. By contrast, intense pyritization in the permanently anoxic sediment below is attributed to mineral growth via adsorption of aqueous Fe-sulfide complexes onto pyrite crystals which had originally formed in the surface layer.The studied trace elements show differential behavior patterns which are closely coupled to the diagenetic processes described above: (i) Zn, Cu and Cd are liberated from organic matter in the thin oxic layer of the sediment and diffuse both upwards across the sediment/water boundary and downwards to be trapped as monosulfides, (ii) V, Cr, Co and As are released during reductive dissolution of Mn- and Fe-oxyhydroxides, (iii) U removal from pore water occurs concomitantly to Fe reduction in the FM and is attributed to reduction of U(VI) to U(IV), (iv) the Ba distribution is controlled by reductive dissolution of authigenic barite in the sulfate reduction zone coupled with upward diffusion and re-precipitation. The incorporation of trace elements into pyrite is most intense for Co, Mn and As, intermediate for Cu and Cr and little to negligible for U, Zn, Cd, V and Ba. The observed trend is largely in agreement with previous studies and may be explained with differing rates for ligand exchange. Slow and fast ligand exchange and thus precipitation kinetics are also displayed by downcore increasing (Mn, Cr, Co and As) or constantly low (Zn, Cu, Cd) pore water concentrations. The downward increasing degrees of trace metal pyritization (DTMP) for Co, Cu, Zn and As are, in analogy to pyrite growth, assigned to adsorption of sulfide complexes or As oxyanions onto preexisting pyrite minerals.     

Concentrations of suspended matter and particulate cadmium,copper, lead and zinc in the Indian sector of the antarctic ocean

The concentrations of suspended matter and particulate Cd, Cu, Pb and Zn were determined for 36 samples collected at 6 stations in the Antarctic Ocean during December, 1970 and January, 1971 using membrane filters. The concentration of suspended matter was determined gravimetrically and trace metal levels were determined using anodic stripping voltammetry. For waters deeper than 100 m the concentration of suspended matter was < 100 μg l^?1. Concentrations up to 542 μg l^?1 were recorded between surface and 100 m. Individual concentrations of the metals were scattered with depth. Average concentrations of particulate metals were: Cd, 3.5 ng l^?1; Cu, 100 ng l^?1; Pb, 35 ng l^?1; and Zn, 230 ng ;l^?1 These measurements represent non-steady state conditions of early Antarctic summer as the ice pack disintegrates and biological activity increases.     

Vertical physicochemical parameter distributions and health risk assessment for trace metals in water columns in eastern Lake Tanganyika,Tanzania

The vertical distributions of trace metals and physicochemical parameters in water columns in Kigoma Bay and Kungwe Bay in eastern Lake Tanganyika, Tanzania, were studied. The Al, Ba, Ca, Co,K, Mg, Mn, Mo, Na, Sn, Sr, and V concentrations were low and varied very little with depth. The toxic heavy metal(As, Cr, Cu, Ni, Pb, and Zn) concentrations were relatively high in the surface water, and the Cu, Ni, Pb, and Zn concentrations decreased with depth. Principal component and cluster analyses indicated that the metals in the lake had three main sources. Al, Ba, Ca, Co, Cu, Cr, Mn, Sr, Sn, and V were found to be geogenic; As, Cr, Cu, Mo, Ni, Pb, Sn and Zn anthropogenic; and As, Ca, Co, Mg, and Na biogenic.Human health risk assessments were performed, and it was found that trace metals in the water at most of the sampling sites would cause no potential adverse ef fects or non-carcinogenic health risks through dermal contact or ingestion. However, trace metals in surface water in Kungwe Bay could have certain adverse ef fects on human health through the ingestion pathway(the total hazard quotient for ingestion(ΣHQi ng)was 1.75(a value >1 was de?ned as possibly indicating adverse ef fects). The Pb HQi ng for surface water in Kungwe Bay was 1.50 and contributed >80% of the ΣHQ_(ing_, implying that Pb pollution is a water quality and safety problem that needs to be carefully monitored and the potential sources identi?ed.     

Input of particulate heavy metals from rivers and associated sedimentary deposits on the Gulf of Lion continental shelf

Fluxes of the heavy metals chromium (Cr), cobalt (Co), nickel (Ni), copper (Cu), lead (Pb), cadmium (Cd) and zinc (Zn) delivered by rivers to the Gulf of Lion (NW Mediterranean Sea) were estimated over a three year study of the River Rhone and its smaller tributaries. Most of the particulate metal fluxes (80–90%) delivered by these rivers occurred within a very short period of time (less than 12%), a typical trend for the Mediterranean environment, where highly contrasting hydrological regimes were observed over the year. Temporal and spatial variations in the fluxes of these particulate metals were driven by the fluxes in both water discharge and suspended particulate matter load. On the shelf, these particulate metal fluxes, largely arising from the Rhone watershed, were two to ten times more important than those resulting from atmospheric deposition. Co, Cr and Ni in the rivers and on the shelf surface sediments were mainly natural and associated with the finest particles. Cd and Phosphorus appeared to be associated with the silt fraction and to be enriched in the prodelta areas. Pb, Zn and Cu were more closely associated with the organic matter content and also showed enrichment in the organic rich prodeltaic sediments. Anthropogenic influences diminished offshore, except for Pb and Zn which could be supplied from the atmosphere by man-made aerosols. Although most of the metals tended to be enriched in the prodelta areas, these did not constitute a permanent sink due to resuspension processes affecting these shallow depths. A resuspension experiment conducted on sediment cores from the Rhone prodelta demonstrated that metal deposited on the surface layer, especially those associated with the organic matter, may be resuspended; this should be taken into account for a complete understanding of the biogeochemical cycle of these metals.     

Phosphorus and metals bound to organic matter in coastal sediments - An investigation of complexes of P,Cu, Zn,Fe, Mn,Ni, Co and Ti by inductively coupled plasma-atomic emission spectrometry with sephadex gel chromatography

Phosphorus and metals bound to organic matter were separated from coastal sediments of Harima Sound in Seto Inland Sea, Japan by extraction with NaOH and fractionated by Sephadex G-25 chromatography. Phosphorus and metals were determined in the eluates by a multi-channel, inductively coupled plasma-atomic emission spectrometer. Phosphorus and Cu, Zn, Fe, Mn, Ni, Cr, Co and Ti bound to organic matter with high molecular weights (OMHMW) (MW ? 5000) were found to be present in the sediments, but no Mo or V were found. The technique provides minimum estimates of the amounts of P and metals bound to organic matter. These organic complexes show surface enrichment in a sediment core (0–20 cm) and their contents decrease with depth. Also, the amounts of eighteen elements, namely: P, Fe, Mn, Zn, Cu, Si, Al, Ti, Pb, Co, Ni, Cr, Mo, V, Na, K, Ca and Mg, in H₂O, ammonium acetate at pH 7 and 5, hydrogen peroxide, hydroxylamine hydrochloride and hydrogen fluoric acid soluble fractions have been determined with a selective chemical leaching technique for the ²¹⁰Pb-dated sediment core sample. Considerable amounts of P (6–19%) and Cu (5–21%) were associated with organic matter, in contrast to other metals such as Fe, Mn, Zn, Ni, Cr, Co and Ti which were associated with sulfide and silicate.     

Forms of some metals in the suspended sediments of the Northern Dvina River and their seasonal variations

The results of the analysis of samples of the Northern Dvina River’s suspended particulate matter obtained by the sedimentation method from large water volumes in the periods of the spring high water and summer low water are presented. By the method of sequential leaching using different reagents, four fractions have been separated: the F1 is the sorbed complex and carbonates, the F2 is the amorphous hydroxides of Fe and Mn, the F3 is the form connected with the organic matter, and the F4 is the residual or silicate-detrital (inert) form. The data have shown that all ten elements determined were grouped with respect to the ratio of the distinguished forms: F4 is the predominant form for Al and Fe (73–88% of all the forms; however, the summer sample contains only 38% of this form of iron, and F2 is the predominant form for this period with 46.6%). As to Mn, the F1, F2, and F4 are nearly equally distributed in the spring high water samples, and only the F3 form is less important (5.4%). In the summer sample, the manganese sorbed complex is predominant (53.5%); for Cu, Ni, Cr, and Co, the inert F4 form is predominant (60–70%) in the sample of the spring suspended matter. The summer low water suspended matter has a lower F4 contribution (25–45%); for Zn, Pb, and Cd, the equal distribution of the forms in the spring samples is typical, while the summer suspended matter differs by the F2 form’s predominance (53–61% for Zn and Pb). The main conclusion from the acquired data is that the geochemical mobility of all the studied elements, except for cadmium, in the summer low water suspended matter is higher than in the spring suspended matter. The more intensive biogeochemical processes in August, the high level of organic matter, and the higher contribution of phytoplankton lead to the intensification of the metals’ geochemical activity in the Northern Dvina suspended matter in the end of the summer compared to the spring high water period when the physical processes are predominant over the biogeochemical ones due to the high speeds of the freshened waters flow.     

九龙江口和厦门西港海域若干重金属元素的生物地球化学特性

根据１９８７年３月至１９８８年１２月九龙江口，厦门西港海域的调查资料，初步探讨该海域Ｆｅ，Ｍｎ，Ｃｕ，Ｚｎ，Ｎｉ，Ｃｏ，Ｐｂ，Ｃｄ等重金属元素的生物地球化学特性，及其与磷的生物地球化学的关系。结果表明该海域重金属元素的分布主要受九龙江径流的影响。在河水与海水混合过程中，悬浮颗粒态重金属元素发生明显转移，Ｆｅ，Ｍｎ，Ｃｏ，Ｚｎ等元素自悬浮颗粒物上解吸，Ｃｕ可能被吸附，颗粒态重金属元素与颗粒态磷呈良好     

Biomonitoring of trace metals using transplanted mussels, <Emphasis Type="Italic">Mytilus galloprovincialis</Emphasis>, in coastal areas around Ulsan and Onsan Bays,Korea

Mediterranean (blue) mussels (Mytilus galloprovincialis) collected from a reference site were transplanted to 15 stations in coastal areas around Ulsan and Onsan Bays, an extensively metal polluted area in Korean coastal waters, to assess metal contamination in the coastal oceans of Korea. During the biomonitoring periods (June 30 to July 20, 2003; 21 days), transplanted mussels, seawater, and particulate materials were collected for analysis of 15 metals (Ag, As, Cd, Co, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Sb, Se, Sn, and Zn). Transplanted mussels showed metal enrichment compared to initial concentrations and spatial gradients consistent with dissolved and/or particulate metal concentrations in seawaters. Based on Q mode factor analysis, stations were clustered into three groups. The first group, located on Onsan Bay, showed high Ag, Cd, Cu, Hg, Pb, Sb and Zn enrichment, presumably arising from non-ferrous metal refineries and chemical industries in this area. The second group was located near the mouth of the Oehwang River and was enriched in Co from petrochemical industries. The third group comprised a site intermediate between Group 1 and Group 2, an isolated station with independent metal sources located in Jangsaengpo harbor, where a number of ship repairing and building companies operate, and a less contaminated station near a small fishing village. Metal accumulation rates (%·day^-1) in mussels were estimated to be between 8% (Cr) and 281% (Pb), based on accumulated metal concentrations over 21 days. The active biomonitoring technique using M. galloprovincialis demonstrated here is a useful monitoring method because it reflects the present status of seawaters; furthermore, physiological factors can be standardized, and bioavailable and time-integrated metal concentrations can be obtained. Furthermore, this method can be applied even in coastal seawaters so heavily contaminated that living organisms would not normally survive.     

The geochemistry of deepwater particulate matter over the hydrothermal field at 9°d50′ N (the East Pacific Rise)

The results of geochemical studies of particulate matter in the water mass over the hydrothermal field at 9°50′ N on the East Pacific Rise are presented. The particulate matter was tested in background waters, in the buoyant plume, and in the near-bottom waters. The contents of Si, Al, P, C_org, Fe, Mn, Cu, Zn, Ni, Co, As, Cr, Cd, Pb, Ag, and Hg were determined. No definite correlations were found between the ele-ments in the background waters. Many of the chemical elements correlated with Fe and associated with its oxyhydroxides in the buoyant plume. In the near-bottom waters, microelements are associated with Fe, Zn, and Cu (probably, to their sulfides formed under fluid mixing with seawater). The matter precipitated in a sed-imentation trap was similar to the near-bottom particulate matter in the elemental composition.     

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.     

Trace metals in seawater and copepods in the ocean outfall area off the northern Taiwan coast

The distribution, partitioning and concentrations of trace metals (Cd, Cr, Cu, Fe, Mn, Pb and Zn) in seawater, including dissolved and particulate phases, and in copepods in the ocean outfall area off the northern coast of Taiwan were investigated. Normalization of metal concentrations to the background metal concentration to yield relative enrichment factors (EF), which were used to evaluate the contamination of dissolved and particulate trace metals in seawater around the ocean outfall. The EF results indicated that the outfall area was significantly contaminated by dissolved Fe and Zn, and by particulate Fe, Cr, Cu, Pb and Zn. In addition, most trace metals were chiefly in the particulate phase. The average percentage of total metal concentrations (dissolved plus particulate phases) bound by suspended particulate matter followed the sequence Al(95%) = Mn(95%) > Pb(88%) > Cu(86%) > Fe(72%) > Zn(32%) > Cr(17.5%) > Cd(3.4%). Therefore, metal contamination is better evaluated in solid phase than in the dissolved phase. The concentration ranges of trace metals in the copepods, Temora turbinata, Oncaea venusta and Euchaeta rimana, near the outfall were: Cd, 0.23-1.81 microg g(-1); Cr, 16.5-195 microg g(-1); Cu, 14-160 microg g(-1); Fe, 256-7255 microg g(-1); Mn, 5.5-80.8 microg g(-1); Pb, 2.6-56.2 microg g(-1); Zn, 132-3891 microg g(-1); and Al, 0.21-1.13%. Aluminum, and probably Fe, seemed to be the major elements in copepods. The concentrations of trace metals in copepods, especially Temora turbinata, near the outfall were generally higher than those obtained in the background station. The mean increase in bioconcentration factor of metals in copepods ranged from 4 to 7 and followed the sequence Al(6.4) > Cu(6.2) > Fe(6.0) > Zn(5.7) > Pb(5.6) > Cr(5.5) > Cd(5.1) > Mn(4.7). Therefore, marine copepods in the waters of northern Taiwan can accumulate trace metals over background concentrations and act as contamination indicators.     

Elemental mass-balance of material carried by major world rivers

An estimate of average river particulate matter (RPM) composition was bàsed on analyses of more than 40 elements in the Amazon, Congo, Ganges, Magdalena, Mekong, Parana and Orinoco rivers, to which were added literature data for 13 other major world rivers, covering the whole spectrum of morphoclimatic features. Geographic variations of major elements in RPM are mostly linked to weathering types and to the balance between weathering rate and river transport. As a result of chemical erosion, Al, Fe and Ti are enriched in RPM with respect to the average parent rock, while Na, Ca, Mg and Sr are strongly depleted. These figures are directly related to the relative importance of dissolved and particulate transport in rivers; this has been computed for each of 40 elements. In order to study weathering on a global scale, the total observed elemental fluxes (dissolved + particulate) have been computed and compared to theoretical ones. The latter were derived from the elemental content in the average parent rock and the total quantity of weathered material, computed from the Al ratio in RPM and in parent rock. Observed and theoretical fluxes are balanced for the less mobilized elements (rare earths, Co, Cr, Cs, Fe, Mn, Rb, Si, Th, Ti, U and V) for which no enrichment relative to Al is noted in RPM, and for B, Ba, Ca, K, Mg, Na, Sr which are relatively depleted in RPM due to their high dissolved transport. Additional fluxes have been found for Br, Sb, Pb, Cu, Mo, Zn and are possible also for Ni and P. This is reflected by marked enrichments in RPM relative to Al for the poorly or moderately dissolved transports (Pb, Cu, Zn). Several hypotheses involving either the natural origin (volcanic dust, marine aerosols, geochemical fractionation) or the artificial origin (worldwide pollution) are discussed to explain these discrepancies, assuming river transport and weathering either to be in a steady state on a global scale or not. However, none of them can fully account for these additional fluxes. It is most likely that these excesses have multiple origins, anthropogenic or natural or both. The comparison between RPM and deep-sea clay compositions emphasizes the prime influence of river input on oceanic sedimentation of Si, Al, Fe, Ti, lanthanides, Sc, Rb, V, etc. A few elements such as Zn, Sb, occur in excess in RPM as compared to deep-sea clays; in order to balance this excess, a remobilization of these elements out of the sediment can be considered. Finally, the enrichment of Co, Cu, Mn and Ni in deep-sea clays compared to RPM is discussed and attributed to several sources and processes.