Intercomparison of different methods for the determination of trace metals in seawater

During a cruise on the North Sea and the North East Atlantic, about 90 samples were obtained from various depths. Concentrations of cadmium, copper, lead, nickel and zinc were determined by atomic absorption spectroscopy after separation/concentration using two different extraction methods. One, using APDC and MIBK, was applied directly on board while the other, using a mixture of dithiocarbamates and freon, was applied after storage under acid conditions. About half of the samples were also analysed for cadmium, copper and lead using ASV. The results of these determinations are intercompared. Consistent results were obtained for cadmium with the two extraction methods and for lead with the freon extraction method and ASV. In the other cases discrepancies were found.     

An intercalibration for trace metals in seawater

This paper describes the results of a recent international intercalibration experiment for trace metals in seawater. The results show that considerable improvements in analytical ability have been made for several metals at concentrations close to those found in offshore marine waters. Some systematic differences between the results of analyses of frozen and acidified samples are evident for most metals. The application of two different analytical techniques, atomic absorption spectrophotometry and anodic stripping voltammetry, appears to introduce relatively small differences in the results for copper and cadmium at near-natural concentrations.Two factors limiting our ability to conduct trace metal intercalibrations at the levels found in the deep ocean are the extent of tolerable contamination, especially for zinc and lead, and the degree to which the overall homogeneity of a group of intercalibration samples can be assured. Some reexamination of methods of sample preparation needs to be carried out before such low level calibrations can be effectively conducted.     

Variations des teneurs en Cd,Pb et Cu dans les eaux de l'estuaire maritime du St-Laurent Durant l'ete 1972

Concentrations of cadmium, lead and copper have been determined in the lower estuary of the St. Lawrence River during the summer of 1972 (from May to August). Seven sample stations distributed in the estuary have been studied. Analysis measurements have been made using atomic absorption spectrophotometry and are related to the soluble metals. The concentrations of cadmium are low and no important variations occur. Mean analysis of cadmium abundance gives a value of 1.05 μg/l. Similar variations are observed for copper and lead contents with a Cu/Pb ratio which is nearly equal to unity. Average concentrations for all the stations are 3.11 μg/l for copper and 3.48 μg/l for lead. Higher values are measured for copper and lead during the month of May and these are related to the fresh-water inflow arising from the thawing period. The lowest concentrations are observed during the months of June and July and are in correspondence with the spring period of intense primary production. The biologic-dynamic conditions affecting the concentrations of cadmium seem to be different from those affecting copper or lead contents (without considering pollution phenomena). The highest average values for copper and lead have been found on the south shore of the estuary. The values obtained in this work compared favourably with other results gathered in the neighbouring area.     

浙江西沪港重金属铜的配位容量和形态分析

根据2000年6月10～14日在浙江省西沪港采集的海水样品,利用AA-800石墨炉原子吸收分光光度技术和阳极溶出伏安法测定样品中重金属铜的含量,获得铜在海水中受不同的有机配体控制.不同粒级的铜表观配位容量表明西沪港海水过孔径1.00μm微孔膜的(ACuCC)较高,为144.4nmol/dm3;过0.40和0.20μm滤膜的(ACuCC)分别为103.0和102nmol/dm3;铜的有机配体条件稳定常数的对数值在7.25～9.14之间.铜的总量为21.72nmol/dm3.铜全部为稳定溶解态,其中pH2酸溶态占95.0%,强有机结合态占5.0%.溶解态铜中有机结合态占过滤海水中总铜的61.6%.     

An experimental study on the speciation of dissolved zinc,cadmium, lead and copper in river rhine and north sea water,by differential pulsed anodic stripping voltammetry

Dissolved electroactive concentrations of zinc, cadmium, lead and copper in river Rhine and North Sea samples have been measured at natural and lower pH values by differential pulsed anodic stripping voltammetry using a Kemula-type hanging mercury drop electrode. Average concentrations detected in North Sea samples at salinities $\text{? 32‰ S}$ and their range are (in μgl^?1): 3.9 (2.0–7.5) for zinc, 0.23 (0.13–0.31) for cadmium, 0.3 (0.1–0.6) for lead and 0.3 (0.25–0.60) for copper (pH 8.1). The APDC-MIBK extracting/concentrating method, followed by AAS measurement applied to the same samples, resulted in 3.9 (2.0–7.5) for zinc, 0.11 (0.01–0.27) for cadmium, 0.5 (0.2–0.9) for lead and 1.6 (0.7–3.2) for copper. A fraction of the electroactive concentrations at pH 2.7 (6.1 for Zn) is electroactive at pH 8.1. The fractions are 100% for Cd, 20% for Cu, 13% for Pb and 40% for Zn. The remaining fractions are partly composed of organically bound species in solution. The low value for lead may be caused by the presence of particulate lead that is dissolved at low pH.Ionic copper and lead species, added separately to seawater at pH 8.1 are removed from the electroactive form, and taken up in (organic) complexes in the same ratio (at least for copper) as the species already present. Added ionic zinc is not removed within the time scale of the measurements (30 min). North Sea water at the natural pH has a complexing capacity, probably due to the presence of dissolved organic compounds, in a concentration equivalent to 3.10^?7M copper. The complexing capacity is zero at pH 2.7. The usual method of standard addition for the determination of electroactive copper and lead concentrations may lead to erroneous results in samples where complexation of this type occurs.     

Cadmium,cobalt, copper,iron, lead,nickel and zinc in Indian Ocean water

Results of trace-metal analyses of water samples obtained during a cruise with the Soviet R.V. “Akademik Kurchatov” in the Indian Ocean are presented. The determinations were performed on board with atomic absorption spectrophotometry after a two-stage dithiocarbamate—Freon extraction procedure. Trace-metal concentrations found are in the same range as those found recently for similar open-ocean areas by other workers. The values for lead and zinc are probably high due to contamination. Vertical profiles indicate biogenic processes as controlling factors for the increase of cadmium, copper and nickel concentrations with depth. Iron shows an irregular depth distribution as a result of large random variations in concentration.     

Partitioning of trace metals released from polluted marine aerosols in coastal seawater

Mobilization and transfer of atmospherically transported metals to major suspended particulate matter components in seawater have been studied in a multichamber leaching experiment. Data on the meteorological air mass history, enrichment factors and sequential extraction analysis indicate that the highly polluted marine aerosol samples collected on Helgoland are of anthropogenic origin. A significant fraction of the total cadmium (81%), zinc (58%), copper (41%), and lead (40%) was released in seawater within 1 h. When exposed to the aerosol and artificial suspended particulate matter components for another 100 h, a portion of the released metals ranging from 10 to 60% was readsorbed. Zinc and lead were scavenged by iron/manganese oxides or readsorbed by the aerosol particulates. Of the total scavenged copper portion 67% was bound to phytoplankton cell walls which evidences an ecological impact of the polluted marine aerosols even in the coastal environment.     

Copper, lead and cadmium in coastal waters of the western North Sea

Cadmium, lead and copper have been determined in both dissolved and particulate phases for 130 surface-water samples from the coastal zone of Scotland and England in the western North Sea. The concentrations reported are, in general, lower than those published previously for the same area.The distribution of total metal concentration between the dissolved and particulate phases varies for the three elements. The lead distribution is dominated by its associations with particulate material while cadmium shows the reverse behaviour, existing almost totally in the dissolved phase. Copper is intermediate in behaviour, with the dissolved phase generally being dominant.An inverse relationship between salinity and dissolved copper concentration suggests a freshwater origin for this element. It is suggested that sedimentary and/or anthropogenic sources affect dissolved copper concentrations in coastal waters. The dissolved lead distribution reveals plumes of contaminated coastal water. The lead distribution is, however, dominated by associations with particulate material and sediments which produce a sharp concentration gradient close to the coast. The Humber estuary is identified as a significant source of cadmium to the North Sea.     

Cadmium,copper and lead in the western Mediterranean Sea

The results of determinations of cadmium, copper and lead in western Mediterranean waters collected during the PHYCEMED 81 cruise are discussed in this paper. The analyses were carried out according to two different methods: flameless atomic absorption and anodic stripping voltammetry. Very strict conditions of sampling and treatment were maintained in order to reduce the chance of contamination. The concentrations found are considerably lower than those usually reported for Mediterranean waters. The distributions are homogeneous, both vertically and from one station to another. The average concentrations are 8 ng 1^?1 for Cd, 90 ng 1^?1 for Cu and 30–40 ng^?1 for Pb. This homogeneity, as well as the concentrations of cadmium and lead, may be explained by the hydrological conditions of the Mediterranean Sea.     

A simplified resorcinol method for direct spectrophotometric determination of nitrate in seawater

A direct, spectrophotometric method has been adapted for quantitative determination of nitrate concentrations in seawater. The method is based on nitration of resorcinol in acidified seawater, resulting in a color product. The absorption spectrum obtained for the reaction product shows a maximum absorption at 505 nm, with a molar absorptivity of 1.7 × 10⁴ L mol^− 1 cm^− 1. This method has a detection limit of 0.5 μM and is linear up to 400 μM for nitrate. The advantage of this method is that all reagents are in aqueous solutions without involving cadmium granules as a heterogeneous reactant, as in conventional methods, and therefore is simple to implement. Application of the resorcinol to seawater analysis demonstrated that the results obtained are in good agreement with the conventional approach involving the reduction of nitrate by cadmium followed by diazotization.     

Determination of copper complexation with natural organic ligands in seawater by equilibration with MnO2 II. Experimental procedures and application to surface seawater

The MnO₂ adsorption method combined with voltammetry is proposed for the direct determination of metal complexation in seawater of various salinities as a more satisfactory alternative to direct voltammetric measurements and bioassay methods. A small quantity of MnO₂ is equilibrated with copper ions in filtered seawater. Natural organic ligands in the seawater compete for copper with the MnO₂. Total dissolved copper is measured by differential pulse anodic stripping voltammetry after filtration and acidification of the sample. Preconcentration of natural water samples is unnecessary and measurement is performed at the natural equilibrium pH of the aerated sample. The analytical limit of detection of the method depends on contamination from the filtration step, and for copper complexation a ligand concentration of 5 × 10^?8 M was obtained. The sensitivity can be increased by use of radioisotopes as tracers. The method is very versatile in that complexation of various metals may be determined by any analytical method that measures total dissolved metal concentrations. Neither organic ligands nor their complexes with copper adsorb on the MnO₂ at pH8, but at pH 1.8 MnO₂ is an efficient scavenger for electroactive organic material.Samples of surface water from the Irish Sea and the Atlantic Ocean were found to contain ligand concentrations of 1.7 × 10^?7 and 1.1 × 10^?7 M, with conditional stability constants (log values) of 9.84 ± 0.13 and 9.86 ± 0.23, respectively, at pH 8.0.     

Determination of cadmium,lead and copper in interstitial water by anodic stripping voltammetry

This paper gives the results of determination of cadmium, lead and copper in interstitial water of the coastal sediment, Seto Inland Sea, Japan by using anodic stripping voltammetry. An aliquot of 4–5 ml interstitial water separated from 30–70 ml of sediment is used for the simultaneous determination of ionic cadmium, lead and copper. No significant differences were observed on the content of trace metals between surface water and interstitial water of the top of the sediment.     

Announcement

Cadmium, lead and copper have been determined in both dissolved and particulate phases for 130 surface-water samples from the coastal zone of Scotland and England in the western North Sea. The concentrations reported are, in general, lower than those published previously for the same area.The distribution of total metal concentration between the dissolved and particulate phases varies for the three elements. The lead distribution is dominated by its associations with particulate material while cadmium shows the reverse behaviour, existing almost totally in the dissolved phase. Copper is intermediate in behaviour, with the dissolved phase generally being dominant.An inverse relationship between salinity and dissolved copper concentration suggests a freshwater origin for this element. It is suggested that sedimentary and/or anthropogenic sources affect dissolved copper concentrations in coastal waters. The dissolved lead distribution reveals plumes of contaminated coastal water. The lead distribution is, however, dominated by associations with particulate material and sediments which produce a sharp concentration gradient close to the coast. The Humber estuary is identified as a significant source of cadmium to the North Sea.     

Concentrations of cadmium,copper, lead and zinc in surface waters of the Northwest Atlantic Ocean — A comparison of Go-flo and teflon water samplers

The concentrations of cadmium, copper, lead and zinc were measured at two locations in surface waters of the western North Atlantic. Samples were collected upstream of the research vessel in 1-1 teflon bottles, and in a 30-1 teflon-coated Go-flo bottle. Surface mixed-layer samples were also collected at each location by ship cast using this same Go-flo sampler. A comparison of the three sampling modes shows that all the samples taken with the Go-flo sampler possessed much higher concentrations of zinc (7–10-fold) and lead (2–3-fold) than those collected directly in teflon bottles. No apparent differences were noted at each station in the concentrations of either copper or cadmium among the samples collected by the three different procedures. The measured values for copper and cadmium in these waters are in good agreement with recent reports for the western North Atlantic.     

Quantification of cadmium-induced metallothionein in crustaceans by the silver-saturation method

Metallothionein (MT) has been proposed as a specific biochemical probe for metal exposure of aquatic organisms. It is recognized that its usefulness as a monitoring tool depends on the full understanding of its function and on the possibility of measuring its concentration in tissues. Therefore the study of MT in crustaceans is interesting from two different points of view: the need to understand mechanisms associated with the toxicology of metals, and the potential use of this protein for monitoring metal-contamined environments. Several methods have been developed for quantitative measurements of MT in biological samples. Immunochemical and electrochemical procedures are reliable techniques but they require sophisticated equipment and highly trained staff. In the present work, modifications to the silver-saturation method have been developed for the quantitative determination of MT in crustacean tissues, estimating silver concentrations by flame in an atomic absorption spectrophotometer. Cadmium and MT were measured both in Artemia and Procambarus clarkii after sublethal exposure to cadmium. An increase in MT content was recorded in crustacean tissues after 12 h of cadmium exposure. A high responsiveness was found in MT induction by cadmium in the two crustaceans and there was a clear relationship between cadmium concentration in water and MT levels in tissues. The silver-saturation assay may be a rapid assay technnique for biomonitoring purposes.     

Effects of heavy metal ions on larval Penaeus chinensis and comparative study on their elimination methods

In order to establish a new method to eliminate toxicities of heavy metal ions to larval penaeid shrimp, the effects of copper, zinc, lead and cadmium ions on larval metamorphosis of Penaeus chinensis at each stage were determined in detail, and two methods eliminating toxicities were compared. The results indicate that sensitivity of larvae to heavy metal ions decreases in the order of nauplii, protozoea, mysis and postlarvae. The phytoplankton food can reduce, by chetating, the toxicities of heavy metal ions. Both EDTA chelation and PHMA absorption can be used to eliminate the toxicities effectively and there is no significant difference between the two methods. EDTA is harmful to larval P. chinensis at high concentration but affects neither survival nor metamorphosis at below 10 mg/dm3. It is preliminarily observed that copper and zinc ions at low concentration are beneficial to the development of larvae after protozoea stage. It is suggested that it is unnecessary to e-liminate the effects of heavy     

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.     

Kinetic studies of lead(II) uptake by the seagrass Zostera muelleri in water by radiotracing,atomic absorption spectrometry and electrochemical techniques

Evidence was found that uptake of lead from seawater in both model and natural systems by the leaves of the seagrass Zostera muelleri does occur for live, dead and scraped leaves at all the lead concentrations tested. Positive uptake of lead was measured using the three analytical techniques of radio-tracer, differential pulse anodic stripping voltammetry and atomic absorption spectrometry; similar uptake profiles were obtained for each technique. Profiles always showed an initial rapid uptake phase followed by a gradual transition to a plateau phase at which an approximate equilibrium between lead attached to seagrass and free ionic lead in seawater was reached. The presence of active lead uptake processes was indicated in experiments which attempted to remove lead from leaves by a chelating agent.     

Lead, cadmium, copper, nickel and iron in limpets, mussels and snails from the coast of ras Beirut, Lebanon

Samples of Patella coerulea (Linnaeus), Brachydontes variabilis (Krauss), Monodonta turbinata (Born) and surface seawater were collected at eight locations along the coast of Ras Beirut, Lebanon, and analysed for lead, cadmium, copper, nickel and iron. With the exception of cadmium, the metal levels found in the three molluscs appear to be high in relation to levels reported by investigators from other coastal areas. The average values for lead, cadmium and nickel within these animals were quite similar. Concentrations of copper in P. coerulea were lower, but concentrations of iron were much higher than those found in both B. variabilis and M. turbinata. Further studies of metal levels in various other intertidal organisms from Ras Beirut, together with investigations into the possible effects of seasonal changes on metal concentration and distribution, are currently under way.     

DIRECT DETERMINATION OF TRACE MERCURY IN SEAWATER BY DIFFERENTIAL COLD VAPOR ATOMIC ABSORPTION METHOD

A low-absorbance differential cold vapor atomic absorption method is developed for direct determination of trace mercury in seawater. The sensitivity of the method is good at 1 ng mercury per liter and precision is excellent with a relative standard deviation of 13.9% at 12 ng Hg/1 level and 3.2% at 39 ng Hg/1 level respectively. The method is proved to be rapid and simple, and has been applied to the analysis of mercury in seawater from Xiamen Harbor and the Central Pacific Ocean.