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1.
Isotope dilution mass spectrometry (IDMS) and ultra-clean room approach are successfully used in the determination of Cd, Pb and Zn in seawater and the sample pretreatment of analysis. The precision in the determination of Cd, Pb and Zn in seawater is better than±3% and the limits of detection are 6×10-12, 6×10-11 and 2.4×10-10 respectively. The effects of sample pretreatment such as filtration and acidification on the results of determination of Cd- Pb and Zn in seawater are disscussed.  相似文献   

2.
Uptake and loss kinetics of cadmium were studied in Paracentrotus lividus exposed for 24 d to different stable Cd concentrations (0 to 1.14 μg Cd l−1) and 109Cd tracer added to seawater. The whole-body uptake kinetics were linear over the time course of the experiment. The whole-body 109Cd concentration factor was independent of the stable Cd concentration in ambient seawater. Bioconcentration of Cd in whole individuals and their body compartments was directly proportional to the Cd concentration added to the seawater. The echinoid digestive tract wall showed the highest degree of Cd uptake. Whole-body loss kinetics were described by a 2-component exponential equation. The loss kinetics were similar for each of the treatments examined. Cadmium was found to display a long biological half-life in echinoid tissues; the major fraction (73 to 85%) of the Cd taken up by echinoids was eliminated following a loss component whose biological half-life was of the order of 1 year, regardless of the absolute Cd concentration accumulated by the echinoid. Paracentrotus lividus is suggested as a valuable biomonitor of Cd, particularly where knowledge of Cd concentration variations over long-term is of interest.  相似文献   

3.
A sensitive method for iron determination in seawater has been adapted on a submersible chemical analyser for in situ measurements. The technique is based on flow injection analysis (FIA) coupled with spectrophotometric detection. When direct injection of seawater was used, the detection limit was 1.6 nM, and the precision 7%, for a triplicate injection of a 4 nM standard. At low iron concentrations, on line preconcentration using a column filled with 8-hydroxyquinoline (8HQ) resin was used. The detection limit was 0.15 nM (time of preconcentration = 240 s), and the precision 6%, for a triplicate determination of a 1 nM standard, allowing the determination of Fe in most of the oceanic regimes, except the most depleted surface waters. The effect of temperature, pressure, salinity, copper, manganese, and iron speciation on the response of the analyser was investigated. The slope of the calibration curves followed a linear relation as a function of pressure (Cp = 2.8 × 10− 5P + 3.4 × 10− 2 s nmol− 1, R2 = 0.997, for Θ = 13 °C) and an exponential relation as a function of temperature (CΘ = 0.009e0.103Θ, R2 = 0.832, for P = 3 bar). No statistical difference at 95% confidence level was observed for samples of different salinities (S = 0, 20, 35). Only very high concentration of copper (1000 × [Fe]) produced a detectable interference. The chemical analyser was deployed in the coastal environment of the Bay of Brest to investigate the effect of iron speciation on the response of the analyser. Direct injection was used and seawater samples were acidified on line for 80 s. Dissolved iron (DFe, filtered seawater (0.4 μm), acidified and stored at pH 1.8) corresponded to 29 ± 4% of Fea (unfiltered seawater, acidified in line at pH 1.8 for 80 s). Most of Fea (71 ± 4%) was probably a fraction of total dissolvable iron (TDFe, unfiltered seawater, acidified and stored at pH 1.8).  相似文献   

4.
The spatial and temporal distribution of cadmium (Cd) and phosphate in the Southern Ocean are related to biology and hydrography. During a period of 18 days between transects 5/6 and 11, a phytoplankton spring bloom developed in the Polar Frontal region. Upper water Cd concentrations were not depleted and ranged from 0.2 to 0.8 nM at about 10 m depth. These relatively high Cd concentrations are attributed to upwelling of Upper Circumpolar Deep Water (0.5–1.2 nM in the core) in combination with low biological productivity (0.2 to 0.3 mg m−3 chlorophyll-a, 0.3 g C m−2 d−1). Total particulate Cd concentrations at 40 m depth were between 0.02 and 0.14 nM with the maximum in concentration in the Polar Frontal region. Most of the particulate Cd at this depth (85–94%) was detected in the first phase of a sequential chemical leaching treatment which includes adsorbed Cd as well as Cd incorporated in algae. The Polar Frontal region was characterized by minima in Cd concentration and Cd/phosphate ratio of seawater at both transects; values were the lowest at transect 11 after development of the spring bloom which was dominated by diatoms. This decreasing Cd/phosphate ratio in seawater during spring bloom development was attributed to preferential Cd gross uptake which more than compensated the process of preferential Cd recycling. Within the Upper Circumpolar Deep Water, Cd showed a maximum in concentration similar to that of the major nutrients. Both the Cd concentration and the Cd/phosphate ratio of the deeper water increased in southern direction, from 0.4 to 0.7 nM and from 0.2 to 0.3 nM/μM, respectively. Antarctic Intermediate Water has a Cd concentration of 0.21 nM with a Cd/phosphate ratio of 0.10 nM/μM. In Antarctic Bottom Water, Cd concentrations ranged from 0.60 to 0.82 nM.  相似文献   

5.
A method is described for the determination of Th isotopes (232Th,230Th,228Th and227Th) in seawater through analysis of Th adsorbed on MnO2-impregnated fiber that has been moored in the deep sea for up to 10 months. Since the MnO2-fiber adsorbs Th from seawater at a constant rate, natural234Th can be used as a yield monitor by making a correction for its decay during the period of deployment. The results obtained by the method showed good reproducibility and accuracy. The method has the advantage over the chemical coprecipitation method that the time and labor for sampling and processing a large-volume of seawater is reduced.  相似文献   

6.
A new method is proposed for the determination of complexing capacities and conditional stability constants for complexes of copper(II) with dissolved organic ligands in seawater. This method is based on ligand competition by the added ligand catechol for free metal ions. The concentration of copper-catechol complex ions is measured with great sensitivity by cathodic stripping voltammetry. The concentration of the free copper ion is calculated from the concentration of copper-catechol complex ions. Ligand concentrations and conditional stability constants are obtained from a titration of the ligands with copper. Two techniques for treatment of the data are compared. A seawater sample, originating from open oceanic conditions, is analysed and two complexing ligands were detected, having concentrations of 1.1 × 10?8 and 3.3 × 10?8 M, and conditional stability constants (log KCuL) of 12.2 and 10.2, respectively.  相似文献   

7.
A detailed examination of a high-temperature catalytic oxidation method for liquid samples in the analysis of total nitrogen dissolved in seawater is reported. The nitrogenous compounds in liquid samples are oxidized on a platinum catalyzer at 680°C under oxygen atmosphere and the generated NO2 is absorbed into a chromogenic reagent, followed by a spectrophotometric determination. The results of this method are much higher than those of wet oxidation methods. Molecular size dependency of the results clearly indicates that the above discrepancy is caused by the low oxidation capacity of the wet oxidation method against high-polymer organic matter dissolved in seawater. The results revealed that the concentration of total nitrogen in seawater is nearly constant from surface to bottom, ranging from 30 to 40 μM 1?1, which organic nitrogen concentration higher in the surface layer, and a rapid decrease with depth. An examination of molecular size distribution indicates that the concentration of high-polymer organic nitrogen decreases rapidly from surface to deeper layers, with molecular sizes ranging from 5 × 103 to 3 × 104. Because of the well-defined principle of the oxidation process, its reliability, ease of sample handling and of analytical procedure on board or in the land laboratory, the present method is much more suitable for the marine analytical chemistry of total and organic nitrogen than the other previous methods.  相似文献   

8.
This paper suggests direct and simultaneous determinations of the reducible species of Zn, Cd, Pb, Cu and Bi in seawater made by the derivative-differential pulse anodic stripping voltammetry with a hung mercury drop electrode. The influence of Cu on the determination of Zn in this experiment condition has been studied, of which both the accuracy and precision are satisfactory. The procedure of determination is so quick, simple and convenient that the background concentration of these five elements in coastal seawaters can be determined only by adjusting the acidity of seawater to pH 2.5 and by taking 10-minutes plating time. Actual measurement time of these five elements for every sample is approximately 25 min.  相似文献   

9.
An ion-exchange technique was used to concentrate ammonia from seawater. Precipitation of bivalent cations, prior to concentration, reduced the variability of ammonia recovery from the ion-exchange column and lengthened column life. Analysis of the eluate was by the phenolhypochlorite reaction. The method was designed for use with small seawater samples (>10ml) and has the advantage that it can be adapted for use with small volumes of seawater with no loss in sensitivity. In a 10 ml seawater example NH3-N concentrations of 10–150 μg l?1 were accurately determined.  相似文献   

10.
The concentrations of Cu, Ni and Cd were determined in Funka Bay during a spring phytoplankton bloom, consisting of diatoms. Just after the bloom, both dissolved Cd and nutrients were removed in the euphotic zone. However, the removal ratio of Cd to phosphate was very different from that in seawater. The removal of Cd took place at a Cd/phosphate ratio of 0.07×10−3, which was lower than in seawater before the bloom (0.25×10−3), leading to an increase in this ratio in seawater exceeding 0.7×10−3 at the end of the bloom. Elevated concentrations of Cd and phosphate were observed in the deeper layer after the bloom due to the decomposition of detrital materials produced in the bloom. The ratio of Cd/phosphate in the regeneration step was 0.24×10−3 which was different from the removal ratio of 0.07×10−3. These observations suggest that the high Cd/phosphate ratio in the regeneration would reflect a relatively high regeneration rate of Cd than that of phosphate. No significant decrease in Cu and Ni concentrations was observed during the development of the bloom, suggesting that biological removal of these metals was not so significant during the spring bloom. The concentrations of Cd, Cu and silicate in surface waters increased after the bloom with decreasing salinity due to the influence of a spring thaw.  相似文献   

11.
An improved Strickland and Parsons' method, in which silicate correction is made, is described for the colorimetric determination of phosphate in seawater. Silicate correction is made by subtracting the value of 0.025 (C/100)2, whereC is silicate concentration (µg atoms 1?1), from the observed phosphate concentration. The relative standard deviations are 2 % at the 1 µg atom PO 4 3? ?Pl?1 level and less than 1 % at the 3 µg atoms PO 4 3? ?Pl?1 level in seawater.  相似文献   

12.
海水中溶解有机碳(DOC)的测定方法主要有过硫酸盐氧化法;紫外光氧化法和高温氧化法。近年来,随着仪器分析的进步,国外已出现能自动连续测定DOC的商售设备。 Menzel等发展的过硫酸钾氧化法,由于设备简单,容易实施,至今仍为很多人采用。  相似文献   

13.
Solid-phase microextraction (SPME) is a simple, sensitive and less destructive method for the determination of dimethylsulfide (DMS) in seawater. Combined with detection by gas chromatography-mass spectrometry (GC-MS), the method had sufficient sensitivity (minimum detectable concentration of DMS was 0.05 nM), and practical levels of reproducibility (relative standard deviation ≤7%) and linearity (r 2 > 0.995) over a wide concentration range (0.5 to 910 nM). The protocol developed was applied to a Sagami Bay water sample to determine concentrations of DMS and DMSP, and in situ DMSP-lyase activity.  相似文献   

14.
A method for the determination of nanomolar concentrations of orthophosphate in oligotrophic seawater developed by Liang et al. (2007) has been modified to make it fully feasible for shipboard application and for faster sample throughput with minimized sample volume. The technique is based on the flow injection method with solid phase extraction on a Sep-Pak C18 cartridge and colorimetric detector. The Schlieren effect was minimized by rinsing the cartridge sequentially with 5 mL water and 2 mL 95% ethanol solution. With three micro pumps in parallel, savings of up to 80% in amount of reagents and 25% volume of seawater samples could be achieved in comparison to the previous method. Variation of stopped flow time and sample loading time gave 3 different standard curves, which corresponded to 3 linear ranges within 3.4 and 515 nM. The modified method permits the analysis of samples over a wide range of concentrations, and has been successfully applied to shipboard determination of trace orthophosphate in more than 200 seawater samples during a one-month cruise in the South China Sea. For seawater at concentrations of 20.6, 82.5, 206.2 nM orthophosphate, the relative standard deviations (RSD) (n = 6), determined daily for 6 days on board ship were 4.45%, 4.73% and 6.75%, respectively. Five seawater samples collected in the Station SEATS (South East Asia Time Series Station at 18°N, 116°E) were analyzed using the present method both on board and in a land-based laboratory, as well as with the magnesium hydroxide-induced coprecipitation (MAGIC) method, and showed no significant difference according to the statistical t-test.  相似文献   

15.
16.
镉能积累于人体及生物体内造成慢性中毒,引起严重的“骨头病”[1],并与严重的心血管病有连带关系[2].海洋中镉的污染问题已引起人们极大的重视.目前,我国与世界其他国家一样,已将镉的污染列为国家海洋环境重点监测项目之一.  相似文献   

17.
The separation and simultaneous determination of the traces of U and Th in seawater by IDMS is described. The detection limits of this method are 2.4×10-9 g for Th and 1.1×10-8 g for U. The concentrations of U and Th in seawater nearby Xiamen were measured, which are 3.20 ppb and 7.73 ppt respectively. The precisions fo the method are ±1.7% for U and ±3.6% for Th respectively.  相似文献   

18.
《Marine Chemistry》2007,103(1-2):122-130
Phosphomolybdenum blue (PMB) paired with cetyltrimethylammonium bromide (CTAB) can be extracted using a solid phase extraction technique on C18 sorbent. Based on this, a novel on-line solid phase extraction method coupled with flow injection (FI) analysis and colorimetric detection has been established to determine nanomolar level orthophosphate in seawater. A stopped flow technique was employed to assure the complete formation of the PMB–CTAB compound, which was sequentially extracted on an in-line Sep-Pak C18 cartridge. The adsorbed PMB–CTAB can be rapidly eluted by 0.56 mol/L H2SO4 in ethanol, and determined with a spectrophotometer at 700 nm. Experimental parameters, including reaction temperature, sample loading flow rate, stopped time and eluting flow rate, were optimized throughout the experiments based on univariate experimental design. The results show that reaction temperature and stopped time were the major factors affecting the formation of PMB–CTAB. Silicate concentration up to 5000 times higher than that of orthophosphate would not interfere with the determination of orthophosphate. Using artificial seawater with salinity of 35 as a matrix under the optimized conditions, the standard curve shows a linear range between 3.2 and 48.5 nmol/L, and the recovery and the detection limit of the proposed method are 96.4% and 1.57 nmol/L, respectively. The relative standard deviation (RSD) (n = 8), which was determined daily for 8 days, was 4.52% for the artificial seawater at a concentration of 32.4 nmol/L orthophosphate. Two typical seawater samples were analyzed using both the proposed method and the MAGnesium hydroxide-Induced Coprecipitation (MAGIC) method. The results of the two methods show no significant difference using the t test. Compared to the MAGIC method, the proposed method has the advantage of being more sensitive, faster, sample saving and easy for on-line analysis.  相似文献   

19.
Experiments on the uptake of Zn and Cd by synthetic hydrous Mn oxides were carried out in an ionic medium at pH 3.5 and at pH 4. A slight preference for uptake of Cd2+ over Zn2+ was observed with both birnessite and nsutite, the Cd/Zn ratio being different for each mineral. Subsequently, the desorption of Zn and Cd from the obtained products in artificial seawater was studied. In this medium Cd is desorbed from the Mn oxides to a much higher extent than is Zn. The latter observations can be satisfactorily explained by the large difference of complex formation for the two metals in seawater, slightly counteracted by the preferential uptake of Cd2+ over Zn2+. The order of magnitude of the Zn/Cd ratio in natural manganese nodules is compatible with the ratio calculated on the basis of experimental results, taking fair estimates of the actual inorganic Zn/Cd ratio in seawater and of the pH of deep ocean water.  相似文献   

20.
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.  相似文献   

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