Chemical speciation of trace metals in seawater: Implication of particulate trace metals

Chemical speciation of particulate metals in seawater was examined theoretically. Mass balance considerations showed that the apparent conditional stability constant, defined for organically binding metals in suspended particles, coincides with the conditional stability constant determined for the corresponding metal-organic complexes dissolved in seawater. This hypothesis suggests that some metals, which are present as organic complexes (e.g. copper), are directly associated with particulate organic matter. Metals, whose free ion is buffered by organic and/or inorganic ligands, may be used as indicators of the presence of particulate organic matter in the marine environment.     

海水悬浮颗粒物中不同形态磷的测定

分别采用硫酸过硫酸钾作为氧化剂进行高压消解和用浓度为1 mol/dm³盐酸浸泡提取,然后用磷钼蓝分光光度法测定海水悬浮颗粒物、沉积物中的总磷和无机磷,用差减法得到有机磷。悬浮颗粒物总磷(PTP)和无机磷(PIP)质量浓度分别为(632.4～651.7)×10^-6和(436.6～452.6)×10^-6时,其相对标准偏差小于1.44%。悬浮颗粒物总磷、无机磷和有机磷的回收率分别为97.2%～101.3%,97.8%～100.4%和97.3%～102.3%。所建立的分析方法可用于海水、河口水悬浮颗粒物及沉积物中不同形态磷的测定。     

Characterization of the proteinaceous matter in marine aerosols

Marine aerosols play a dominant role in the transfer of oceanic material to the atmosphere. Most marine aerosol originates when air bubbles burst at the sea surface ejecting material from the sea surface microlayer and bubble surface layers into the air. Concentrations of chemical compounds in these surface layers often differ from their concentrations in bulk water. We examined the enrichment of aerosols with proteinaceous matter and attempted to characterize the physical nature and sources of this matter. We measured concentrations of dissolved free (DFAA), dissolved combined (DCAA), and particulate (PAA) amino acids, transparent stainable particles (TSP), and bacteria and virus-like particles as carriers of protein, in natural and simulated aerosols. We also evaluated D/L ratios certain amino acids in all amino acid fractions.DFAA and DCAA enriched the aerosols we sampled by 1.2–20 times compared to bulk seawater; PAA enrichment was usually higher (up to 50-fold). Aerosols contained particles typical of seawater, e.g., microorganisms, organic debris, inorganic particles with adsorbed organic matter, but also a large number of semitransparent gel-like particles, which all contained amino acids. Some of these particles were probably scavenged from bulk water, but new particles produced as bubbles burst at the surface comprised at least 10% of total proteinaceous matter in the aerosol. D/L ratios of certain amino acid suggested that the particles were most likely made from dissolved polymers secreted by phytoplankton that were concentrated on bubble surfaces and in the microlayer. Examination with Alcian Blue (a dye that targets carbohydrates) and Coomassie Blue (a dye that targets proteins) showed that most TSP in the aerosols contained both proteins and polysaccharides. Microorganisms enriched the aerosols by up to two orders of magnitude, but contributed less than 4% to the total protein pool.     

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.     

Acute toxicity of heavy metals to two species of marine nematodes

The acute toxicity of seawater solutions of copper, zinc, lead, cadmium and mercury to two species of free-living marine nematodes was studied. Enoplus brevis (Bastian) is a euryhaline species inhabitating intertidal estuarinemud. The closely related Enoplus communis (Bastian) is stenohaline and may be found as a commensal in the byssus threads of seed mussels. Specimens of both species were collected from two sites on the Northeast coast of England showing different levels of pollution by heavy metals. Both species were more susceptible to copper, lead and mercury than to zinc and cadmium, but the order of toxicity of the metals changed with exposure concentration. The euryhaline species survived better than the strictly marine species and there is a suggestion that animals from a polluted site were more tolerant of elevated of heavy metals.     

Trace elements in suspended matter from the anoxic hypersaline Tyro and Bannock Basins (eastern Mediterranean)

In the anoxic hypersaline Tyro and Bannock Basins of the eastern Mediterranean, extremely high concentrations of Co (0.015%), Cu (1.35%) and Zn (0.28%) were found in suspended matter collected at the sharp interface between seawater and the anoxic brine. The high particulate Co, Cu and Zn concentrations can be explained by the sharp increase in dissolved sulphide at these interfaces, and the resultant precipitation of metal sulphides. The particulate As, Sb and Mo concentrations also showed a sharp maximum at or close to the interface. However, the contributions of As, Sb and Mo contents in suspended matter to the total concentrations in the water column are small. Scanning electron microscopy-energy-dispersive X-ray analysis (SEM-EDAX) of suspended particulate matter from the Tyro Basin revealed spherical particles strongly enriched in Fe, Cu and Zn at the seawater-brine interface.     

An investigation of methods commonly used for the selective removal and characterization of trace metals in sediments

The characterization of solid phase-associated transition metals is important in understanding solid—seawater interactions. This has proven to be a difficult problem because of the complex nature of most sediments and suspended particulate matter. Many chemical techniques have been proposed to describe sedimentary metal phases. Most rely on characterizing equivalent chemical reactivities from the various metal phases rather than the characterization of the actual physical phases with which the metals are associated. In this study, several of the most widely used trace metal extraction techniques are compared for many of the most commonly measured transition metals using a variety of naturally occurring major marine sediment types. All solid concentrations are normalized to total metal values as obtained by neutron activation and X-ray fluorescence analyses.One weak, four intermediate strength, and two strong metal extraction methods were studied individually. The weak method had the lowest degree of extraction efficiency, but dissolved all solid carbonate phases. Its probable inability to retain released metals quantitatively in solution is a major problem. Three of the four intermediate methods are similar. The other and simplest of the four methods (0.5 N HCl), released much lower amounts of most metals studied when compared to these other three. It cannot be classified as a weak method, however, as it does attack some moderately resistant solid phases. Only one of the other three intermediate methods (a reducing acetic acid solution), was relatively free from analytical difficulties and it is preferred for this reason. The two strong extraction methods are quite similar, with neither yielding total metal concentrations.A five-step sequential extraction scheme was also evaluated. The results were generally quite good, both with regard to metal phase fractionation and overall total extraction of available metals. Based on the results of this study, a sequential extraction scheme is a useful method for characterizing solid phase-associated transition metals.     

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.     

Rain water-aerosol trace metal relationships at cap ferrat: A coastal site in the Western Mediterranean

The factors controlling the distributions of the trace metals Al, Co, Ni, Cu and Pb in a series of 25 individual rain water samples collected at Cap Ferrat, a site on the Western Mediterranean coast, are interpreted in relation to aerosols taken simultaneously at the same site. The trace metal chemistry and pH of the rain waters are constrained by the scavenged aerosols, which are composed of a mixture of urban-dominated (European) and crust-dominated (Saharan) components. Thus, the pH values of the rain waters, which range between 3.95 to 6.77, reflect the type of aerosol scavenged from the air; urban-dominated aerosol components giving rise to acidic rains, and crust-dominated aerosol resulting in neutral to basic rains. The average solubilities of the trace metals in the rain waters increase in the order Al (17%), Co (36%), Ni (53%), Pb (65%) and Cu (76%). The paniculate ↔ dissolved speciation of the non-crust-dominated metals Cu and Pb varies with pH, being more soluble at lower pH values, and exhibits the classical pH ‘adsorption edge’. However, the pH of rain can vary during an individual rain event in response to the sequential scavenging of crust-dominated and urban-dominated aerosol components. As a result, the solubility of non-crust-dominated trace metals, such as Pb, can also vary sequentially during an individual rain event; the maximum solubility being related to a ‘dip’ in pH associated with the scavenging of urban-rich aerosol components, followed by a return to the initial pH as the pH-influencing components are exhausted. Data from the present study therefore indicate that the pH-controlled trace metal solubility relationship reported for individual rain events can also occur sequentially in the same event. The particulate material in the rain waters does not contain the relatively high concentrations of Ni, Cu and Pb found in the parent aerosols, and its composition approaches that of crust-dominated aerosols transported to the Mediterranean. Data from the present study, together with those for other Western European coastal locations, indicate that there is a Pb-Cu fractionation between aerosols and rainwaters which results in a significantly greater fraction of the aerosol Pb, relative to Cu, escaping precipitation scavenging in the coastal zone and so becoming available for long-range atmospheric transport.     

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.     

宁波—舟山深水港海域水体有机物分布特征初探

本文根据1987年5月宁波—舟山深水港海域水体中有机物分布,初步讨论了有机物在水体中的行为。海水中溶解态的有机物与有机物总量存在如下关系:[DOM]/[TOM]=0.611[TOM]~(-0.899)。并且在通常状况下,调查海区水体中的有机物随悬浮颗粒物的增加而增高,其关系式为:[TOM]=0.65e~(0.0011〔SS〕)。认为该海区的悬浮物是制约有机物行为的主要因素之一。     

东海颗粒碳的垂直转移过程

在１９９３年和１９９４年两个航次中，利用震动式取样从东海陆架取得３个柱状岩芯样品。对其进行了ＰＯＣ，ＰＩＣ，ＰＯＮ含量和粒度分析，并同其上覆水体的ＰＯＣ，ＰＩＣ以及总颗粒物的垂直通量和悬浮体作了比较。     

The association of copper,mercury and lead with surface-active organic matter in coastal seawater

Significant fractions of copper (6–30%), lead (3–12%) and mercury (4–50%) were associated with surface-active dissolved or colloidal organic matter isolated from the water column of a controlled experimental ecosystem. Changes in the concentration of surface-active forms of these metals were attributed to release of surface-active metal-binding organic matter during the collapse of a phytoplankton bloom and early diagenesis of settled detritus. Naturally occurring surface-active organic matter can be expected to significantly influence the chemical speciation and transfer of metals across air-water and solid-water interfaces in the marine environment.     

Removal of trace metals from seawater during a phytoplankton bloom as studied with sediment traps in Funka Bay,Japan

To study biological effects on the particulate removal of chemical elements from seawater, sediment trap experiments were carried out successively ten times throughout the spring phytoplankton bloom in Funka Bay. Sediment traps were deployed every one to two weeks at 1, 40 and 80 m depths. The settling particles obtained were analyzed for trace metals, phosphate and silicate. The propagation of diatoms in spring results in larger particulate fluxes than that of dinoflagellates. The biogenic silicate concentration is higher in the earlier period, when diatoms are predominant, than in the subsequent period, when dinoflagellates are predominant. The concentrations of aluminum, iron, manganese and cobalt in the settling particles comprising largely biogenic particles are lower during phytoplankton bloom. The concentration of copper is not reduced by the addition of biogenic particles, and its vertical flux is approximately proportional to the total flux, indicating that its concentration in the biogenic particles is nearly equal to that in the non-biogenic particles. The results for nickel and lead show the same tendency as for copper. Cadmium is more concentrated in biogenic particles than in non-biogenic particles, and the concentration of cadmium in the settling particles decreases with depth, similarly to phosphate and organic matter. Thus, metals in seawater are segregated by biological affinities, and the degree of incorporation into biogenic particles is in the order Cd > Pb, Ni, Cu > Co > Mn, Fe, Al. Biogenic particles are the most important agent controlling the vertical distribution of metals in the ocean. They remove the metals from the surface water, transport them through the water column, and regenerate them in the deep.     

Seasonal changes in phosphatase activities in Toulon Bay (France)

We studied the characteristics of the phosphatase activity (Km and Vmax) in total seawater and in particulate material of the three main plankton classes (0.25-5, 5-90 and >90 microm) in a coastal marine ecosystem of Toulon Bay (French Mediterranean Sea). The measurement of the hydrolysis of sodium paranitrophenylphosphate (pNPP), a substrate of phosphatase, revealed low and high affinity components in unfiltered seawater and in particulate matter. In unfiltered seawater, the low affinity activity was predominant from October to March during phytoplankton development. The high affinity activity dominated from April to June and was significantly correlated with the bacterial abundances. The phosphatase behaviour in the particulate material differs from that in the unfiltered seawater. The activity of the three particulate classes was generally much lower than that of unfiltered seawater, particularly the low affinity activity. The >90 microm size fraction consisted in greater part of zooplankton. In this size class, the activity (nmol l(-1) h(-1)) of the low affinity component was predominant from May to August, when the abundance of the larvae of copepods (copepodites) was highest. Its high specific activity (Activity/Protein concentration as nmol l(-1) h(-1) microg(-1)) was particularly elevated during this period. The 5-90 microm fraction consisted of phytoplankton cells, especially Dinoflagellates. Between September and January, the activity (nmol l(-1) h(-1)) of this size class was mostly supported by the low affinity component. The specific activity (nmol l(-1) h(-1) microg(-1)) of the high affinity component was highest in June and August. No significant correlation was found between phosphatase activities and chlorophyll a or total cell abundance. In return temporary relationships with specific taxa exist in particular with Ceratium spp., Gymnodinium spp. and Protoperidinium spp. The contribution of the 0.25-5 microm size class exceeded rarely 20% of the total particulate activity. Between June and August, high specific activities (nmol l(-1) h(-1) microg(-1)) were observed for its high affinity component. In autumn, strong rainfall increased the phosphate and nitrate concentrations and led to a drop in salinity, which probably explains the low phosphatase activities (nmol l(-1) h(-1)) and cell densities observed during this period.     

The role of suspended matter in the biogeochemical cycles in the Adige River estuary (Northern Adriatic Sea)

Suspended matter and sediments from the Adige River mouth were analysed in an attempt to elucidate the transfer of heavy metals from the river to the sea. The vertical profile of grain-size spectra of suspended matter in front of the river mouth has shown that the riverine particles are limited to the upper brackish layer.Particulate matter was found to have a large specific surface area, up to 20 m² g⁻¹ in the estuarine sample. High quantities of quartz and phyllosilicates (micas and clay minerals) were found in the riverine suspended matter. The quartz content of the suspended matter from the brackish layer was found to be diminishing and with the organic matter becoming the essential component (22%). Higher levels of trace metals were usually detected in suspended matter samples (40 ppm Ni, 200 ppm Cr, 60 ppm Pb, 100 ppm Cu, 320 ppm Zn, and 0·9 ppm Cd) than in sediments.The observed similarity of physico-chemical, mineralogical and geochemical characteristics of riverine suspended matter and recent marine sediments, indicates that most of the riverborne particulate matter is deposited in the proximity of the Adige River mouth.The peculiar characteristics of the chromium level (high bulk concentration and its abundance in the organic fraction of the particular matter) when compared to the other trace metals, indicates the anthropogenic influence on its biogeocycle.     

Mercury distribution in seawater in Minamata Bay and the origin of particulate mercury

Horizontal and vertical distributions of mercury were determined in seawater in Minamata Bay and Yatsushiro Sea. The concentrations of total and particulate mercury respectively ranged from 56–285 ng l^–1 and 2.1–506 ng l^–1. They were both highest in the inner most part of Minamata Bay where the sediment was most heavily polluted, and decreased with increasing distance from there. Vertically, an evident increase in concentration was observed near the bottom. A good agreement was found between the mercury content in suspended matter and that in fine sediment particles.These facts show that the particulate mercury is supplied mostly from the bottom sediment, and that it is spreading offshore with dispersing in seawater. This process would eventually result in the pollution of sediment in Yatsushiro Sea.     

Seasonal and depth variations of copper,iron and nickel in ligurian coastal waters

The aim of this work is to study the seasonal variation of iron, copper and nickel in connection with those of other environmental parameters which characterize the coastal system studied; in particular, the phytoplankton biomass. Sampling was carried out from January to October with monthly periodicity, at a station 2 miles offshore of Portofino, Italy, to depths of 200 m.The results indicate that the concentrations of copper, iron and nickel in particulate matter show a marked increase compared to values reported in the literature for the open seawater of the Mediterranean. It is also possible to determine a relationship between the three metals and the seasonal and depth variations. In the particulate matter, there is a direct relationship between the phytoplankton biomass and the heavy metals in the photic layer.     

Hydrophysical and hydrochemical investigation on abiotic media of the Bay of Burgas

The results of field measurements in the Bay of Burgas (Bulgaria) are presented. The velocities and patterns of sea currents, the variation of the concentration of suspended organic matter, and the concentrations of mercury, copper, zinc, lead, and hydrocarbon in the water have been determined. The results show that the bay is polluted with heavy metals, which is especially dangerous since a cyclonic current exists there. Its pattern is revealed herein. Pollution accumulates in the water and is transported by currents longshore, producing a dangerous influence on the water ecosystems.Translated by mikhail M. Trufanov.