Trace metals in the Göta river estuary

The concentrations of the trace metals Cd, Cu, Fe, Ni, Pb and Zn in the Göta River estuary have been investigated. The following metal fractions have been determined: acid-leachable, dissolved, labile and particulate.The estuary represents a salt wedge type estuary and is situated in a densely populated region of Sweden. The metal concentrations found for the dissolved fraction is in the range of what can be considered as background levels for freshwater. It is difficult to evaluate any estuarine processes other than conservative mixing for Cd, Cu, Ni and Zn. The dissolved levels in the freshwater end member are Cd, 9–25 ngl^?1; Cu, 1·1–1·4 μgl^?1; Fe, 20–75 μg l^?1: Ni, 0·7–0·9 μg l^?1: Pb 0·09–0·2 μg l^?1; and Zn, 6–7 μg l^?1:The results from the acid-leachable fraction show that at high suspended load the particles sediment in the river mouth. The trace metal levels in this fraction are subject to large variations.     

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.     

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.     

The distribution of Mn,Fe, Zn,Cd and Cu in Baltic seawater; a study on the basis of one anchor station

A total of 150 samples were collected at a 10-days' anchor station in the Bornholm basin (55° 31.1′N, 15° 32.1′E) and analyzed for dissolved (< 0.4 μm) and particulate trace metals. For dissolved Mn, large gradients have been found in the vertical distribution with minimum concentrations (< 0.2 μgl^?1) in the halocline zone and considerably higher values in the deep waters (up to 50 μgl^?1). Ultrafiltration studies indicate that dissolved Mn is probably present as Mn²⁺ in the oxygenated bottom layer. The primary production process was not evident in the particulate Mn profile; the suspended particulate material (SPM), however, shows a considerable enrichment with depth, apparently due to Mn-oxide precipitation.The distribution of dissolved Fe was rather homogeneous, with average concentrations throughout the water column between 0.86 and 1.1 μgl^?1, indicating that the oxidation of Fe²⁺ ions released from the sediments must already be complete in the very near oxidation boundary layer. Relatively high concentrations of particulate Fe were actually measured in the bottom layer, with the maximum mean of 11.2 μgl^?1 at 72 m. Similarly to Mn, the profile of particulate Fe does not reflect the SPM curve of the eutrophic layer. On average, about 70% of the total Fe in surface waters was found to be particulate.The average concentrations of dissolved Zn, Cd and Cu were found to be rather homogeneous in the water column but showed a relatively high variability with time. A simplified model on trace-metal uptake by phytoplankton indicates no significant change in dissolved metal concentrations during the period of investigation. On average, only 1.7% Zn, 3.3% Cd and 9.8% Cu of the total metal concentrations were found in particulate form. SPM analyses showed significant correlations of Zn, Cd and Cu with Fe, indicating that particulate iron is an important carrier for particulate trace metals in Baltic waters.     

The spatial and seasonal variation of trace metals in coastal seawater and soft tissue of <Emphasis Type="Italic">Chthamalus montagui</Emphasis> around the northwest coast of Portugal

Metal concentrations (Cd, Cr, Cu, Fe, Mn and Zn) were determined in seawaters and soft tissues of Chthamalus montagui from the northwest coast of Portugal during the four seasons of 2011. The main objectives of this work were to assess seasonal and spatial variations of metals in order to detect hot spots of contamination, to establish correlations between metals in coastal seawaters and C. montagui and to calculate metal bioaccumulation factors (BAFs) in each season. Metal concentrations in coastal seawaters ranged within Cd: 1.2–35 ng L^?1; Cr: 15–87 ng L^?1; Mn: 77–1763 ng L^?1; Cu: 126–1819 ng L^?1; Fe: 430–4048 ng L^?1 and Zn: 2889–16867 ng L^?1 and in C. montagui ranged for Cd: 0.39–1.98 mg kg^?1; Cr: 0.45–3.13 mg kg^?1; Cu: 0.93–5.70 mg kg^?1; Mn: 2.2–20.4 mg kg^?1; Fe: 135–707 mg kg^?1 and Zn: 119–782 mg kg^?1. Significant spatial and seasonal variations were found between: (i) metal concentrations in seawaters and C. montagui tissues; (ii) the distribution of metal concentrations in C. montagui tissues were Fe > Zn > Mn > Cu > Cr > Cd and (iii) C. montagui showed higher bioaccumulation factors for Fe and Cd than for Cu, Mn and Zn in all seasons. Regarding the metal concentrations accumulated in C. montagui tissues during each season of 2011, the ecological quality classifications of the NW coast of Portugal varied from “Class I–Unpolluted” to “Class III–Remarkably Polluted”.     

Accumulation of Zn,Cu and Cd by crabs and barnacles

The crab Carcinus maenas (L.) and the barnacle Elminius modestus Darwin were exposed to a range of dissolved concentrations of Zn, Cu and Cd for 21 days in artificial seawater. Accumulation of Zn and Cu by crabs has been interpreted in terms of the presence of a regulation mechanism to maintain constant body concentrations (83·2 ± 19·4 μg Zn g^?1 dry wt.; 39·8 ± 9·8 μg Cu g^?1 dry wt.) under varying external dissolved metal levels, until a threshold dissolved metal concentration (c. 400 μg Zn l^?1; c. 170 μg Cu l^?1) beyond which net accumulation of metal begins. Cadium appears to be accumulated by C. maenas at all exposures with no evidence for regulation of body cadmium concentrations. Exposure of E. modestus to Zn, Cu or Cd caused net accumulation of the respective metal in the bodies of the barnacles, with no evidence for regulation of body metal concentrations.     

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.     

Cadmium,lead, copper,and zinc in Elminius modestus Darwin (Crustacea,Cirripedia) from Waitemata and Manukau Harbours,Auckland, New Zealand

Abstract

Concentrations of cadmium (Cd), lead (Pb), copper (Cu), and zinc (Zn) were measured in adult barnacles (Elminius modestus Darwin) from Waitemata and Manukau Harbours in the Auckland area, New Zealand. As in studies on sediments reported in the literature, it was possible to identify areas of likely anthropogenic influence, e.g., around the Auckland Harbour Bridge for Pb, Cu, and Zn. Groups of individuals with highest concentrations for these metals showed 19.8–23.8 mg Pb kg^?1, 198–266 mg Cu kg^?1, and 4460–6530 mg Zn kg^?1 (95% confidence limits, dry weight basis). Cd concentrations found for all barnacles from the Auckland area ranged from 0.8 to 3.1 mg kg^?1. Two samples from Omaha Beach, 60 km north of Auckland, were used as a reference. Accordingly, groups of individuals with lowest concentrations for Pb, Cu, and Zn could be allocated to this site using the Student‐Newman‐Keuls Multiple Range Test (0.5–1.3 mg Pb kg^?1, 8–10 mg Cu kg^?1, and 144–214 mg Zn kg^?1 ; 95% confidence limits). Only Cd concentrations were highest at Omaha Beach (8.6–12.1 mg Cd kg^?1 ). This result may have arisen from “naturally” increased bio‐availabilities of certain metals in mangrove systems which are reported in the literature. Generally, metal concentrations in barnacles from the Auckland Harbour area and from Omaha Beach were within the wider range for E. modestus as well as other barnacle species reported in the international literature.     

Impact of submarine hydrothermal vents on the metal composition of krill and its excretion products

We have measured the metal composition and estimated the excretion rate of trace elements (Ag, Cd, Co, Cu, Ni, Pb, V and Zn) by Antarctic krill (Euphausia superba) in three locations (two located within a submarine hydrothermal vent field and one away from it) along the Antarctic Peninsula region of the Southern Ocean. Results indicated that krill excreted large amounts of Ag, Cu, Pb and Zn, (range: 1.9–41.2 pmol Ag g DW^? 1 h^? 1, 15.3–26.8 nmol Cu g DW^? 1 h^? 1, 308.7–1118.3 pmol Pb g DW^? 1 h^? 1 and 24.4–76.5 nmol Zn g DW^? 1 h^? 1), compared with the non-significant or undetectable release rates of Cd, Co, Ni and V. The metal composition of the excreted material from krill collected in the area of hydrothermal activity was similar to the metal composition reported for suspended particles emitted from those vents. Our results suggest that krill recycling of Ag, Cu, Pb and Zn could potentially influence trace metal concentrations in the water column of the Bransfield region of the Southern Ocean, and that the original source of metals to these waters may be hydrothermal vents.     

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.     

Seasonal variability in the kinetics of Cu,Pb, Cd and Hg accumulation by macroalgae

Here it is demonstrated that both Porphyra spp. and Enteromorpha spp. of macro-algae display similar and very marked seasonal variations in their concentration factor (CF) of Cu, Pb, Cd and Hg in field conditions. The CF variations are specific for each metal and reproducible over several years. The way variations in the biological activity affect the equilibrium and kinetics of the interaction between trace metals and live algae was studied in vitro. Natural seawater was used as the culture medium. Voltammetry was used for the determination of natural organic ligands and trace metals except Hg, which was determined by mercury cold vapour after on-line pre-concentration. Titrations with the relevant metal demonstrated that the maximum binding capacity of the algae was not significantly dependent on the season for Pb (ca. 100 μmol g_{dry algae}⁻¹), Cd (ca. 50 μmol g⁻¹) and Hg (80–100 μmol g⁻¹). Marked seasonal variations were observed for Cu (ca. 40 μmol g⁻¹ in January; 70 μmol g⁻¹ in May; and 100 μmol g⁻¹ in August). The conditional stability constants of metal–algae complexation sites were seasonally independent and similar for both algae: logK_MS′=8.5±0.3 (Cu), 5.6±0.2 (Pb), 5.3±0.2 (Cd) and 18.0±0.3 (Hg). Exudates with a strong Cu complexing capacity (logK′_CuL=12.47±0.06) were determined in cultures with added Cu, Pb or Cd concentrations, and identified by cathodic stripping voltammetry (CSV) as cysteine or glutathione. All the tested metals promoted the liberation of exudates, both cysteine- and glutathione-like ligands were exuded in the presence of Cu, only cysteine-like ligands in the presence of Pb, and only glutathione-like ligands in the presence of Cd, the rise depending of the season of the year, particularly for Cu. Highest levels were produced in the presence of added Pb. When exposed to either 1- or 100-μM total dissolved metal concentrations, the metal uptake, and its rate, varied with the season and the algae.     

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.     

Distribution and partitioning of trace metals (Cd,Cu, Ni,Pb, Zn) in Galveston Bay waters

The distribution of several trace metals has been studied in the surface waters of Galveston Bay, Texas, in order to assess the impact of complexation with organic and reduced sulfur species on the partitioning of trace metals between particulate and aqueous species. The distribution of trace metals in the filter-passing fraction (<0.45 μm) showed two apparent trends: (1) the carrier phase metals (i.e., Fe and Mn) were largely removed in the Anahuac Channel region, which was dominated by direct Trinity River inputs; (2) the other metals (Cd, Cu, Ni, Pb, and Zn) showed non-conservative mixing behaviour, with mid-salinity maxima, within the estuarine regions of Galveston Bay. The average percentage of metal in the filter-passing fraction, as compared to the total metal load, decreased in that region from 95% to 9% in the order Ni>Cu>Cd>Zn>Pb>Mn>Fe, while an increasing trend was found in the same sequence for the acid-leachable fractions. The average values of K_d1, the particle-water partition coefficient, expressed as the ratio of weak acid-leachable particulate fractions to the filter-passing fractions, increased in the order Ni<Cu<Cd<Zn<Mn<Pb<Fe. This sequence is consistent with the relative importance of particulate transport of these trace metals from estuaries to coastal oceans. The observed decrease of K_d1 of Cu with increasing concentrations of suspended particulate matter (SPM), also called the “particle concentration effect” (PCE), can be eliminated when the free ionic, rather than the total concentration of Cu in the filter-passing fraction is used for calculating this ratio. A particle concentration effect would be expected if the binding of these trace metals by particles is mediated by solution (i.e., filter-passing) phase ligands. Complexation of Cd, Cu, Ni, Pb, and Zn with reduced sulfur species could be one of the causes for the observed linear correlations between metals and reduced sulfur species in both the filter-passing and filter-retained fractions. Significant correlations between Cu in the weak acid-leachable fraction and chlorophyll a (Chl a) concentrations suggest biological mediation of Cu uptake into the particulate fraction.     

Metal distributions and their fluxes at the coastal boundary of a semi-enclosed ria

Water column samples have been collected in the outer channel of the Ferrol Ria (NW Spain) during four occasions over a tidal cycle. The objective was to study the exchange of dissolved and particulate Cd, Cu, Pb and Zn and particulate Al, Fe and Si between the ria and the adjacent coastal waters. This study provides the first extensive dataset on dissolved and particulate metal concentrations in the water column of a Galician ria. Typical concentrations of dissolved Cd (96 ± 31 pM), Cu (8 ± 4 nM), Pb (270 ± 170 pM) and Zn (21 ± 10 nM) were similar than in other European Atlantic shelf and coastal waters. The fraction of metals in the particulate phase followed the trend: Pb > Cu Zn > Cd. The outgoing water from the ria was enriched in dissolved and particulate Cu, Pb and Zn compared with incoming waters, whereas Cd concentrations were similar for both waters. The suspended particulate matter was composed of a mixture of marine and continental material. The latter end-member was found to arise from the metal-rich ria bed sediments, which is diluted by the dominant metal-poor marine end-member. The net output flux of Cu from the channel is balanced by the freshwater inputs to the ria, and the net Zn flux gave a positive output to coastal waters. For Pb, the net flux to the coastal waters is less than that input from the rivers, as a result of its particle reactivity and deposition in sediments. On the contrary, a net input flux of dissolved Cd from coastal waters was observed, highlighting the oceanic source of this metal in the Galician rias. Results from the budget calculations are in agreement with the differential geochemical behavior of these elements in coastal waters.     

Chlorinated hydrocarbons in the seawater and surface sediments of Blanca Bay,Argentina

In order to characterize our study area and to provide reference values to be used in the future to measure the changes produced by an increase in contamination, the concentrations of chlorinated hydrocarbons have been investigated in fifty-one samples of seawater, taken at four different depths: air-sea interface, surface, one metre and bottom waters, and in twenty-three samples of surface sediments from Blanca Bay, Argentina. Of eleven organochlorine compounds we were looking for (α BHC, lindane, heptachlor, δ BHC. aldrin, heptachlor epoxide, dieldrin, o-p′DDD, p-p′DDD, o-p′DDT and p-p′DDT), seven could be detected in seawater and three in surface sediments with the following mean concentrations: α-BHC=48·2 ng l^?1; lindane=54·2 ng l^?1; heptachlor=45·0 ng l^?1; δ BHC=12·5 ng l^?1; aldrin=61·8 ng l^?1 and ΣDDT=67·0 ng l^?1; and δ BHC=3·2 ng g^?1; lindane=4·2 ng g^?1 and heptachlor=1·0 ng g^?1 for seawater, regarding the surface waters, and sediment samples, respectively.Concentration factors among the different water layers were also studied to see if there was any correlation between chlorinated hydrocarbon contents and the water depths from which the samples were taken. As a mean value, the air-sea interface water contains 18 times more of these compounds than that of the water near the bottom. A comparison of the values corresponding to seawater and surface sediments from our study area with those levels measured in samples from other geographic locations is also presented.With the purpose to detect a relationship between chlorinated hydrocarbon concentrations and the contents of particulate matter (PM) on the one hand, and particulate organic material (POM) on the other hand, four groups of samples containing different amounts of PM and POM, respectively were formed. From a comparison of the results obtained, lindane, heptachlor and δ BHC showed a tendency to lower concentrations in those samples containing little PM whereas α BHC and aldrin remained without important changes. No significant correlation was found between organochlorine levels and contents of POM.     

Mobilization of metals from riverine suspended matter in seawater

Suspended matter from rivers in the Russian Far East was leached by seawater to assess the extent of Zn, Cd, Pb, and Cu release from the land-derived solids to estuarine and coastal waters. The concentration of solids in the leaching experiments was 0.25 g/l. The suspended matter used varied in metal content from background levels to heavily contaminated.The concentration of Zn, Cd, Pb, and Cu in the leaching solution after 1, 4, 24, 48, and 96 h was determined by anodic stripping voltammetry. Measurable Cd was transferred from river suspended matter to seawater with both background and elevated Cd concentrations, though the amount of Cd released was different. The increase in Zn and Pb in solution was observed only at the enriched concentration of metals in the suspended solids. The Cu transfer into solution was more pronounced from material with elevated Cu concentration, but the amount of degradable organic matter in the solid phase was more important.The losses of metals from the riverine solids varied from 60% to 80% of total concentration for Cd to negligible for Pb, independent of contamination. The Zn loss depended on the initial concentration in the solids and decreased from 11–16% for the heavily contaminated suspended matter to 3–8% for the moderately enriched ones and to negligible for the pristine solids. Cu loss varied from 1% to 30% of total content, with no clear dependence on concentration in the suspended matter.The significance of additional input of dissolved metals to estuarine and coastal waters from remobilization was assessed by comparison with the initial concentration of dissolved metals in river water. Such experiments could be used to assess the water quality impact of atmospheric fallout of contaminated solids and storm drainage from the urbanized areas, in addition to river suspended matter studies.     

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.     

海口湾海水重金属的行为特征

本文对海口湾溶解态铜、铅、锌、镉进行了测定.铜的变化范围为:0.47～1.16μg/dm3,平均值为0.78μg/dm3;铅的变化范围为:0.94～2.36μg/dm3,平均值为1.36μg/dm3;锌的变化范围为:1.28～4.83μg/dm3,平均值为3.14μg/dm3;镉的变化范围为:0.005～0.072μg/dm3,平均值为0.030μg/dm3,Cu、Zn的溶解态含量在龙昆路生活污水排污沟口、秀英工业排污沟口及海甸溪口的测站相对较高,Pb、Cd溶解态含量较低,湾内各站平面分布较为均匀.它们的溶解态含量垂直变化趋势为:Cu、Pb、Zn底层大于表层,而Cd表层大于底层.对Cu、Pb、Zn、Cd的颗粒态含量也进行了测定,指出海口湾海水中的颗粒物对重金属的净化起一定作用.对铜的溶解态中的强络合态和不稳态铜也进行了研究,强络合态占总溶解态的比例均在85%以上,对生物起毒性作用有关的不稳态铜含量很低,均小于5nmol/dm3,表明目前海口湾海水中的重金属铜不会对生物生长产生影响.     

Sea-surface microlayer metals enrichments in an urban and rural bay

The sea-surface microlayer is an important interface between the atmosphere and ocean and a collection point for many anthropogenic materials including potentially toxic metals. We developed a glass plate sampler to collect the upper 30 to 55 micrometers of the sea surface. Samples of the microlayer and subsurface bulk water from an urban and rural bay were analysed for concentrations of Pb, Zn, Cu, Cd and Fe. Metal concentrations in both the microlayer and bulk water were generally 2 to 15 times greater in the urban than in the rural bay. Concentrations of metals in the microlayer of both bays averaged 6 to 65 times greater than those in the bulk water. In the urban bay, microlayer concentrations of Pb, Zn and Cu from 10 to > 100 μg 1^?1 were common. Measured microlayer metals concentrations agree well with those predicted from atmospheric deposition rates using a previously derived empirical model developed from laboratory microcosm studies. Further work will be required to determine whether or not these high microlayer metal concentrations contain significant biologically available fractions which could impact fisheries recruitment of larval icthyoneuston.     

Urban stormwater quality I. Hillcrest,Hamilton, New Zealand

Water quality parameters associated with siltation (non‐volatile and volatile suspended solids), oxygen depletion (chemical and biochemical oxygen demand), nutrient enrichment (N, P), toxicity (Pb, Zn, Cu, Cr, Ni, Cd), and human pathogenic micro‐organisms (coliforms, faecal coliforms, faecal streptococci) were measured in baseflow and stormflow from a residential catchment in Hamilton, New Zealand, from November 1979 to December 1981. A macro‐invertebrate survey was conducted. All parameters, except nitrogen, were predominantly associated with particulate material, and closely followed suspended solids behaviour during storm runoff. The concentrations of these particulate parameters are linearly related to suspended solid concentrations, which implies a reasonable consistency in the particulate source material, probably attributable to the uniform stable land use. The runoff was enriched with nitrate (from septic tank seepage) and the particles by Zn, Pb, and Cu. There was little or no enrichment of the particulates with phosphorus, nitrogen, organic matter, Cr, or Ni relative to catchment soils. Ni, Cr, and Cd were generally below detection limits. Dissolved reactive phosphorus and NH₄ ⁺‐N levels were low and unimportant in total P or N leaving the catchment. Most organic matter was particulate and only slowly degraded, and consequently the biological oxygen demand was only a small fraction (c. 13%) of chemical oxygen demand. Interpretation of the water quality data allows some tentative predictions to be made of potential receiving water impacts. It is doubtful that urban runoff will cause significant oxygen depletion, although the high level of organic‐rich particulate material could lead to a deterioration of receiving water sediments and affect benthic invertebrates. Urban runoff may be an important source of nutrients, but (apart from nitrate) its importance depends on the amount of suspended material in the runoff rather than increased input of nutrients from urban‐related activities. Bacterial counts indicate a poor water quality. The impact of metals will depend largely on the bioavailability of the particulate‐bound fraction. The key to the understanding of transport, treatment, and impact of most potential pollutants in urban runoff is probably their association with particulate materials.