Application of trichloroacetic acid (TCA) to extraction of soft body for the determination of tissue Cd, Cu, Pb and Zn in the prosobranch Hydrobia ulvae (Pennant)

The application of trichloroacetic acid (TCA) as a shell extractant for preparation of soft body parts with reference to tissue metal concentrations (Cd, Cu, Pb, Zn) in shellfish has been evaluated on the example of the mud snail Hydrobia ulvae, a small marine prosobranch densely present in rocky and soft-bottom habitats of the eastern Atlantic. A solution of 0.1 M TCA was tested on individuals treated according to two different protocols: (1) thawed after freezing ("non-dried") and (2) thawed and air-dried to a constant weight ("dried"). Two points were investigated in detail to improve the method: individual soft tissue dry weight and tissue metal concentration following a standard digestion method. In both instances, the results were compared with those from manually dissected snails. Conditions for total shell decalcification of 60 individuals (3-4 mm long) were 5.5 h in 20 ml of 0.1 M TCA.No differences in individual soft tissue weight were observed between the treatments, indicating good efficiency of the TCA extraction with respect to weight of soft body parts. In contrast, tissue metal concentrations varied among treatments. The TCA extraction of the dried animals had a good recovery for Cd, most likely due to the lower solubility of Cd vital cellular components (proteins and mineral concretions) from the dried tissue. Satisfactory recoveries of the tissue concentrations of Cu and Pb were obtained for the non-dried individuals. This might be related to the specific distribution of metals in the organism (namely in the digestive glands and gonads) and their different chemical reactivity with TCA after the tissue was dried. Limited susceptibility of Zn-bearing protein bindings to complexing with TCA also accounts for significantly lower concentrations of Zn in the mud snail's soft tissue that was extracted. The 0.1 M TCA solution is therefore recommended for extraction of the shells of Hydrobia ulvae for tissue determination of Cd, Cu and Pb; however the treatment protocol does affect metal recovery and thus a consistent procedure should be followed.The extracted metals from the soft tissues and shells of the mud snails (on the basis of both metal concentrations and contents) were ranked in order of increasing contribution of soft body parts to the total (shell+tissue): Pb相似文献   

Comparison of metal accumulation between 'Artificial Mussel' and natural mussels (Mytilus galloprovincialis) in marine environments

The passive sampler called 'Artificial Mussel' (AM) developed by Wu et al. (2007) can provide a time-integrated estimate of metal concentrations in the marine environment, and offers a potential device to assess and compare metal concentration in different marine environments worldwide. The aim of this study was to compare metal accumulation on AM and natural mussel Mytilus galloprovincialis at three sites with different metal loads along the Portuguese coast for four months. M. galloprovincialis were placed in cages alongside AMs at each site. Samples were collected monthly and Cd, Cr, Cu, Pb, and Zn concentrations in whole soft tissues and AMs compared. For both Cu and Cd, the results were similar between AMs and natural mussels. Higher concentrations of Zn were observed in natural mussels, whereas the inverse was shown for Pb (about 10-fold higher). Our results showed that AMs are promising tools for assessing metal concentrations in marine environments.     

Trace metals in the living and nonliving components of scleractinian corals

Trace metals in coral tissue and skeleton have been investigated in various ways since the early seventies. More recently it has been suggested that the symbiotic zooxanthellae may play an important role in the accumulation and regulation of trace metals. Furthermore gamete development and mucus production may influence the metal accumulation and loss in corals. Many studies have attempted to use the annual growth bands in coral skeletons to investigate historical pollution events. However the relationship between the metal concentrations in the surrounding environment and the incorporation of this into coral skeleton is not well understood. This paper explains a method for investigating metal loads in coral tissue, zooxanthellae and skeleton. Furthermore, it presents new information suggesting that zooxanthellae accumulate most metals (Al, Fe, As, Mn, Ni, Cu, Zn, Cd, Pb) in greater concentrations than the coral tissue. Coral skeletons had consistently lower metal concentration than the zooxanthellae, tissue and gametes. The loss of zooxanthellae during stress events may have a significant contribution to the total metal loads in corals. The use of corals as biomonitors should carefully factor in zooxanthellae densities and gamete development before conclusions are drawn.     

Seasonal studies on cadmium concentration and toxicity, oxygen consumption, digestive gland glycogen, and lipid in dog whelks collected at Aberystwyth, Wales

The concentration of cadmium in Nucella was investigated at different times of the year at one site. There was no significant difference in tissue cadmium at the times of the year investigated but tissue zinc was more variable. Accumulation and toxicity of cadmium were studied using 50–600 μg Cd l⁻¹ for 21 days. There was no significant seasonal difference in the rate of cadmium uptake but mortality appeared to vary with the season. Nucella did not survive 21 days at 600 μg Cd l⁻¹, but at lower concentrations 50–100 μg Cd l⁻¹ all survived.

Although there was significant drop in oxygen consumption between 7 and 14 days it did not appear to be related to the cadmium exposure. Glycogen levels on the other hand showed a decrease after cadmium treatment, while lipid values remained unchanged. Results are discussed in relation to energy source, season, and adaptation to the environment.     

Contaminant exposures at the 4H shell mounds in the Santa Barbara Channel

Remobilization, bioavailability, and potential toxicity of chemical contaminants were evaluated at the 4H shell mounds – the site of abandoned offshore oil and gas production platforms in the Santa Barbara Channel region of the Southern California Bight. Evaluations used a weight-of-evidence approach based on results from bulk phase chemical analyses and laboratory toxicity testing of shell mound cores, in situ field bioassays using caged mussels, and surficial sediment chemistry. Shell mound cores contained elevated concentrations of metals associated with drilling wastes (e.g., Ba, Cr, Pb, and Zn), as well as monocyclic and polycyclic aromatic hydrocarbons (PAHs). The highest concentrations along with pockets of free oil were associated with the middle “cuttings” stratum. Sediments composited from all core strata caused significant acute toxicity and bioaccumulation of Ba and PAHs in test organisms during laboratory exposures. In contrast, caged mussels placed at each of the shell mounds for a period of 57–58 days had greater than 90% survival, and there were no significant differences in survival of mussels placed at the shell mounds and corresponding reference sites. While all mussel samples exhibited increases in shell length, whole animal weight, and tissue lipid content, in some cases growth metrics for the shell mound mussels were significantly higher than those for the reference sites. Concentrations of metals, PAHs, and polychlorinated biphenyls (PCBs) in tissues of the shell mound mussels were not significantly different from those at reference sites. The presence of labile aromatic hydrocarbons in shell mound cores and absence of significant contaminant accumulation of tissues of caged mussels indicated that chemical contaminants are not being remobilized from the 4H shell mounds. Surficial bottom sediments near the shell mounds contained elevated Ba concentrations that probably were associated with drilling wastes. However, concentrations did not exhibit clear spatial gradients with distance from the shell mounds. Despite a number of storm events during the mussel exposures, maximum currents were 34 cm s⁻¹ and unlikely to erode materials from the shell mounds. Thus, Ba distributions in bottom sediments probably were due to episodic disturbance such as platform removal or trawling rather than ongoing erosion and dispersion of shell mound solids by near-bottom currents. These results suggest that, in the absence of physical disturbances, contaminants are expected to remain sequestered in the shell mounds.     

Sediment pollution and its effect on fish through food chain in the Yangtze River

Suspended sediment adsorbs pollutants from flowing water in rivers and deposits onto the bed. However, the pollutants accumulated in the river bed sediment may affect the bio-community through food chain for a long period of time. To study the problem the concentration of heavy metals （Cr, Cd, Hg, Cu, Fe, Zn, Pb and As） in water, sediment, and fish/invertebrate were investigated in the middle and lower reaches of the Yangtze River during 2006-2007. The concentrations of heavy metals were 100-10,000 times higher in the sediment than in the water. Benthic invertebrates had relatively high concentrations of heavy metals in their tissues due to their proximity to contaminated sediments. Benthic invertivore fish had moderately high concentrations of heavy metals whereas phytoplanktivore fish, such as the silver carp, accumulated the lowest concentration of heavy metals. The concentrations of Cu, Zn, and Fe were higher than Hg, Pb, Cd, Cr, and As in the tissue samples. The concentration of heavy metals was lower in the river sediments than in the lake sediments. Conversely, the concentration of heavy metals was higher in river water than in lake water. While a pollution event into a water body is often transitory, the effects of the pollutants may be long-lived due to their tendency to be absorbed in the sediments and then released into the food chain. The heavy metals were concentrated in the following order： bottom material 〉 demersal fish and benthic fauna 〉 middle-lower layer fish 〉 upper-middle layer fish 〉 water.     

Heavy metal concentrations in water and bivalved mollusks in different channel reaches of the Southern Bug River

Variations in Cd, Cr, Cu, and Fe concentrations in water and the soft tissues of bivalved mollusks Anodonta anatina and Unio tumidus along the Southern Bug River channel are examined. Fe concentration was found to be somewhat higher than the MAC. Cd, Cr, and Cu concentrations in water met the drinking water standards. The comparison of individual reaches of the channel in terms of heavy metal concentrations in mollusks allowed polluted river reaches to be identified. The highest Fe concentrations in the soft tissues of mollusks were recorded near the river source. The mollusks in the middle and lower reaches of the Southern Bug featured high accumulation of Cd, Cr, and Cu.     

Effects of Lime‐Based Waste Materials on Immobilization and Phytoavailability of Cadmium and Lead in Contaminated Soil

Low cost lime‐based waste materials have recently been used to immobilize metals in contaminated soils. This study was conducted to evaluate the effects of oyster shells and eggshells as lime‐based waste materials on immobilization of cadmium (Cd) and lead (Pb) in contaminated soil, as well as their effects on metal availability to maize plants (Zea mays L.). Oyster shells and eggshells were applied to soils at 1 and 5% w/w, after which they were subject to 420 days of incubation. The toxicity characteristic leaching procedure (TCLP) test was employed to determine the mobility of Cd and Pb in soils. The results showed that the addition of waste materials effectively reduced the metal mobility as indicated by the decrease in the concentration of TCLP‐extractable Cd and Pb, and this was mainly due to significant increases in soil pH (from 6.74 in untreated soil to 7.85–8.13 in treated soil). A sequential extraction indicated that the addition of such alkaline wastes induced a significant decline in the concentration of Cd in the exchangeable fraction (from 23.64% in untreated soil to 1.90–3.81% in treated soil), but it increased the concentration of Cd in the carbonate fraction (from 19.59% in untreated soil to 36.66–46.36% in treated soil). In the case of Pb, the exchangeable fraction was also reduced (from 0.67% in untreated soil to 0.00–0.01% in treated soil), and the fraction of Pb bound to carbonate was slightly increased (from 16.61% in untreated soil to 16.41–18.25% in treated soil). Phytoavailability tests indicated that the metal concentrations in the shoots of maize plant were reduced by 63.39–77.29% for Cd and by 47.34–75.95% for Pb in the amended soils, with no significant differences being observed for the amendment types and the application rates. Overall, these results indicate that oyster shells and eggshells can be used as low cost lime‐based amendments for immobilizing Cd and Pb in contaminated soils.     

Cadmium content, accumulation and toxicity in dog whelks collected around the Welsh coastline

The concentration of cadmium in sexually mature Nucella lapillus was investigated around the coast of Wales. Higher concentrations of cadmium were found in whelks located in the Bristol Channel compared with Cardigan Bay Nucella. Accumulation and toxicity of cadmium were investigated at 50–600 μg Cd l⁻¹ over a period of 21 days. At the lower concentrations of 50–100 μg Cd l⁻¹ all Nucella survived the 21 days of experimentation. The rate of cadmium uptake after exposure to cadmium was inconsistent and not related to the degree of site contamination. At all sites the concentration of cadmium in Nucella, after treatment with 50–600 μg Cd l⁻¹ for 21 days, was significantly different from controls, but after 7 days it varied with the site and cadmium concentration. Only samples collected at Fishguard, Dale, and Swansea survived 21 days at 600 μg Cd l⁻¹. Tissue cadmium concentrations did not significantly effect the whole body concentration of zinc.     

Histopathological effects of petroleum hydrocarbons and heavy metals on the American oyster (Crassostrea virginica) from Tabasco, Mexico

Oyster tissues may be affected by the concentration of ions in the water (i.e. salinity) and by contaminants such as petroleum hydrocarbons and heavy metals. Oyster populations from three coastal lagoons (Mecoacan, Camen and Machona) in the Mexican state of Tabasco, in the southern Gulf of Mexico, were sampled for pollution studies during June, September and November 1992 and May 1993. No statistically significant relationships were found between the concentration of contaminants in the body tissues of organisms and their shell length, soft tissue weight and particulate matter; however, a significant correlation was found between condition index and salinity (r = −0.72). Generally, the lowest weights, shell lengths and indices of condition were found in Mecoacan. The concentrations of cadmium and zinc were inversely related to salinity (r = −0.52 and r = −0.32, respectively), so a riverine input is suspected. On average, 63% of the individual oysters showed histopathological lesions, which can be related to salinity and to the concentrations of cadmium and the unresolved fraction of hydrocarbons (UCM). The response of each of the tissues analysed was different. The percentage of individuals with damage in the digestive diverticulum increased linearly with UCM (r = 0.71), but in a saturation-response fashion (Y = B₀ − B₀/(1 + X^B1) r = 0.66) with cadmium. The percentage of individuals with damage in the gills increased linearly with weight (r = 0.68), cadmium (r = 0.60) and UCM (r = 0.60). The lesions in the connective tissue decreased linearly (r = −0.82) with salinity, but increased in a saturation-response way (r = 0.83) with cadmium. Finally, the percentage of individuals with lesions in the digestive tube decreased linearly with salinity (r = −0.59). Only the damage to the gills and digestive diverticula were dependent on gonadal maturity, while damage to the connective tissue was dependent on the sex of the individual.     

The use of transplanted cultured tropical oysters (Saccostrea commercialis) to monitor Cd levels in North Queensland coastal waters (Australia)

Bivalves are commonly used to detect metal pollution in the marine environment. Commercially cultured Milky oysters (Saccostrea commercialis) were transplanted in various sites along the North Queensland coast and analyzed for two metals of potentially anthropogenic origin (Cd, Zn). To provide additional information, naturally occurring Black Lip oysters (Saccostrea echinata) were also collected at the transplantation sites. The study demonstrated that the oysters species transplanted are good bioindicators of these metal concentrations in tropical waters, sensitive to variations in the environment at concentrations which are much smaller than pollution signals commonly reported for temperate waters. Three transplant experiments were carried out from May 1999 to February 2000. Milky oysters transplanted to offshore areas (Orpheus Is., Kelso Reef) accumulated Cd in the soft parts whereas oysters sampled from cages placed in Ross Creek and the Herbert River estuaries showed a decrease in Cd concentration, which resulted from an increase in dry weight. Dry weight appeared to be an important covariant affecting Cd concentration in the oysters whereas it does not unambiguously affect Zn concentrations. For the duration of the experiments, oysters sampled from the Magnetic Is. reference site showed effectively constant Cd concentrations and total Cd contents which indicates that any seasonal cycle affecting metal concentration is weak. It was found that Cd accumulation in oysters increased as ambient dissolved Cd concentration decreased, from which it was concluded that for these oysters, the predominant source of Cd was from the particulate phase rather than the dissolved phase.     

Some results of bottom sediment monitoring in oil production area in the southeastern Baltic Sea

Monitoring studies in the area of Kravtsovskoe oil field in the southeastern Baltic Sea have been carried out since 2003. Terrigenous bottom sediments (0–5 cm layer) in the area (23 stations) are represented by all grain size types. Down to the depth of 30–50 m, these are mostly quartz sands; at depths of 60–110 m, these are terrigenous mud with C_org content of 1–3%. The concentration and distribution of toxic elements (Cu, Co, Cd, Pb, Ba, and Hg) over sediment types and bed area are the same as in the Baltic Sea as a whole: Cu, Co, Cd, Pb, and, partially, Hg are distributed in accordance with the “fraction rules” (with minimums in sands and coarse aleurites and maximums in mud); Ba distribution is independent of the sediment type. The concentrations of toxic elements tend to increase with time: the concentrations of such elements in samples (at the same stations) somewhat increase compared with their concentrations before the construction of D-6 oil platform, during its construction, and during oil production. This trend in the concentrations of toxic elements in sediments can be due to the steelwork of D-6 platform. The increase in Ba concentration is likely due to drill mud spills during exploration drilling. None of the elements shows sediment pollution in excess of MAC anywhere in the area.     

Occurrence of ten metals in Mytilus edulis L. and Cardium glaucum L. from the Gdańsk Bay

The determination of Fe, Mn, Ni, Pb, Cu, Co, Zn, Cd, Ca and Mg was carried out in the soft tissues and shells of Mytilus edulis and Cardium glaucum from Gdańsk Bay. This paper reports on the influence of size (age) on the metal concentration in molluscs. Both species-dependent variability and regional variations of metal concentrations in molluscs were observed. The correlation coefficients between the concentrations of metal in the soft tissues and shells were determined. The correlation coefficients between hard and soft parts metals were calculated for Mytilus edulis.     

Biomonitoring of metals under the water framework directive: Detecting temporal trends and abrupt changes,in relation to the removal of pollution sources

Temporal trends in metal concentrations, i.e. Ag, Cd, Cu, Cr, Hg, Ni, Pb and Zn, measured in soft tissues of Mytilus galloprovincialis mussels and Crassostrea gigas oysters collected from estuarine waters within the Basque Country (Bay of Biscay), have been investigated to determine if actions undertaken have improved the environmental quality of rivers and estuaries. Data compiled between 1990 and 2010 have been analysed statistically, applying the Mann–Kendall and the Mann–Whitney–Wilcoxon tests. Moreover, in those cases with significant trends, the Kolmogorov–Zurbenko Adaptive (KZA) filter was applied to detect abrupt changes. Results showed significant decreasing trends for some metals, i.e. Ni, Cu, Pb and Zn, and differences between medians. Trend lines showed abrupt changes occurring between 1998 and 2002. Therefore, observed downward trends were related to increased wastewater treatment and diversions of discharges to ocean, implemented mainly during 2000–2002.     

Chronological reconstruction of metal contamination in the Port of Maó (Minorca, Spain)

In this work we discuss the historical record of metals as derived from a sediment core from the Port of Maó (Minorca, Spain), the second natural largest harbour in Europe. The sedimentation rate derived from radionuclide profiles increased by a factor of five since the 1960s due to the urbanisation of the town waterfront. Metal concentrations showed two different trends: (i) Pb and Sn inputs started during the second half of the 19th century and remained relatively high until mid-20th century; and (ii) Ag, Cd, Ni, Zn, Cu and Cr accumulation began in the 1940s, peaking in the late 1970s. The commissioning of a submarine outfall in 1978 reduced metal concentrations in subsequently deposited sediments since, thereafter, urban and industrial wastes have been dumped out of the estuary. This study also shows that evaluating the quality of sediments on the basis of surface concentrations may be misleading.     

Centennial records of lead contamination in northern Atlantic bivalves (Arctica islandica)

In the study, we establish centennial records of anthropogenic lead pollution at different locations in the North Atlantic (Iceland, USA, and Europe) by means of lead deposited in shells of the long-lived bivalve Arctica islandica. Due to local oceanographic and geological conditions we conclude that the lead concentrations in the Icelandic shell reflect natural influxes of lead into Icelandic waters. In comparison, the lead profile of the US shell is clearly driven by anthropogenic lead emissions transported from the continent to the ocean by westerly surface winds. Lead concentrations in the European North Sea shell, in contrast, are dominantly driven by local lead sources resulting in a much less conspicuous 1970s gasoline lead peak. In conclusion, the lead profiles of the three shells are driven by different influxes of lead, and yet, all support the applicability of Pb/Ca analyses of A. islandica shells to reconstruct location specific anthropogenic lead pollution.     

Evaluations of heavy metal pollution in sediment and Mullus barbatus from the Izmir Bay (Eastern Aegean) during 1997-2009

Izmir Bay is one of the great natural bays of the Mediterranean. The surface sediment and fish samples were collected during 1997-2009. The sediment concentrations of inner bay showed significant enrichments during sampling periods. Outer and middle bays exhibited low levels of metal enrichments except the estuary of Gediz River. The concentrations were generally higher than the background levels from the Mediterranean and Aegean except Cd and Pb levels gradually decreased. Metal EF is used as an index to evaluate anthropogenic influences of metals in sediments. Maximum metal enrichment was found for Hg in the outer bay, while Pb indicated maximum enrichment in the middle-inner bays. Metal levels were evaluated in sediments in accordance with the numerical SQG of the USEPA. The levels of fish tissues were lower than the results reported from polluted areas of the Mediterranean. The highest BAFs were detected for Hg and Cd in fish.     

Effects of Animal Size on Concentrations of Metallothionein and Metals in Periwinkles Littorina littorea Collected from the Firth of Clyde, Scotland

Different sizes of Littorina littorea were collected from four areas in the Firth of Clyde, Scotland. Their metallothionein (MT) and heavy metal concentrations were analysed using the Silver Saturation Method and Atomic Absorption Spectrophotometry, respectively. Concentrations of MT, Cd and Zn (as μg g⁻¹ dry soft-body weight) generally decreased with an increase in size of L. littorea. MT concentrations were better correlated with Cd than with Zn or Cu concentrations. Nevertheless, MT and the metals in periwinkles (as μg individual⁻¹) increased significantly with increasing size. Concentrations of MT and the metals among the sampling areas were compared at a standardised soft-body weight (10 mg). The results from Discriminant Analysis based on all metal concentrations indicate that Largs is different from the other areas and characterised by high Fe concentrations in L. littorea. The problems and differences in using either soft-body weight or shell length as independent variable for size-standardisation are discussed.     

Zum Einfluß des pH-Wertes und des Calciumgehaltes auf Metall-Fulvinsäure-Bindungen — Inversvoltammetrische und chemometrische Untersuchungen

The Influence of pH and Calcium Concentration on Metal-Fulvic Acid Bonds – Stripping Voltammetric and Chemometric Investigations. Electrochemically available metal concentrations of Cd, Cu and Zn were analyzed in dependence of different concentrations of calcium, fulvic acids and pH by Differential Pulse Anodic Stripping Voltammetry (DPASV). A statistical experimental design was the base to minimize the number of experiments and to include the multifarious interactions between the independent variables (Ca concentration, concentration of fulvic acids and the pH value) and otherwise the electrochemically available metal concentrations of Cd, Cu and Zn. At first analysis of experimental data was carried out by multiple linear regression. The main influence on available metal concentrations is the pH value especially for Cu. The Ca ion influence has not competitive effect and is only significant for Cd and Cu. It has an effect on the metal-fulvic acid-bonds. Two factor interactions exist for pH/fulvic acids and for Ca/fulvic acids too. The partial least squares regression (PLS) model was used to include the interactions between the metals Cd, Cu and Zn. For proving these two models the three parameters pH, Ca and fulvic acid were varied within the calibration range of the models and predicted values were compared with the experimental values. The approach with the PLS model is better than the approach with the multiple linear regression (normally used mathematical method of analysis of a factorial plan) with a relative error of 9.7% for modelling of Cd, 6.0% for Zn and 58% for Cu in relation to multiple linear regression with errors of 12% for Cd, 8.6% for Zn and 65% for Cu. The PLS modelling is a suited tool for modelling chemical interactions also in simulated natural matrices.     

Biomonitoring with benthic macroalgae and direct assay of heavy metals in seawater of the Oporto coast (northwest Portugal)

The concentrations of dissolved Cd, Cu, Hg and Pb in seawater and algae (Enteromorpha spp. and Porphyra spp.) were determined in parallel on three beaches located in the Oporto coast (Portugal), during 8 successive months, comprising periods of low and high biological productivity. The concentrations of dissolved metals in seawater varied markedly during the sampling period and exhibited seasonality. The concentrations of Cd were high in autumn and winter, but low in spring. The concentrations of Cu and Hg were high in autumn, low in winter and peaked in May. The concentrations of Pb were low in autumn and winter, and also peaked in May. It is likely that biological activity was, at least partially, responsible for the observed seasonal changes. The mean concentrations of dissolved metals in seawater were similar to those reported for polluted and industrialized european coastal areas. Metal concentration factors, calculated month-to-month for each alga, metal and site, varied markedly during the sampling period, indicating that concentration factors based on single or few determinations could be misleading. On the contrary, mean concentration factors (calculated by dividing the mean metal concentration in the algae by the mean metal concentration in seawater) were relatively constant at all three sites, indicating that in the Oporto coast, Enteromorpha spp. can be used to estimate the mean concentration of dissolved Cd, Cu and Hg in seawater, and Porphyra spp., the mean concentration of Cd, Cu and Pb. However, considering that future estimates of the concentrations of these metals in seawater should be based on determinations of the metal contents in Enteromorpha spp. and Porphyra spp. carried out on several occasions spanning a considerable period of time, the use of these algae as monitors of heavy metal pollution can have limited practical advantages over the direct assay of the metals in seawater.