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1.
The recently developed 2–5 L small-volume MnO2 coprecipitation method for determining 234Th in seawater has provided a new way to substantially increase, both temporally and spatially, the sampling resolution of 234Th and 234Th-based particulate organic carbon export estimates in the upper ocean. In this study, we further optimize the technique by reducing reagent quantities and the use of an additional water bath heating step. This optimization allows the filtration of the MnO2 precipitate onto a 25-mm diameter, 1.0 μm pore size QMA filter to be completed within < 30 min for unfiltered waters from the South China Sea. In addition, we have modified the MnO2 purification procedure to allow for alpha spectrometric measurements of 234Th recoveries. Results from recovery experiments suggest that reagent amounts can be reduced to 0.0375 mg KMnO4 and 0.1 mg MnCl2·4H2O per liter of sample, while still maintaining high 234Th recovery. This study further confirms that the addition of a yield monitor is necessary for the application of the small-volume method.  相似文献   

2.
234Th is a particle-reactive radionuclide widely used to trace biogeochemical oceanic processes occurring over short timescales. During the last few years, small-volume techniques based on the co-precipitation of 234Th with MnO2 coupled with beta-counting have been developed as an alternative to large volume gamma-spectrometric techniques. Here a procedure has been developed to enhance quantitative measurement of 234Th in MnO2 precipitates. The main objectives were to obtain a purified Th fraction for beta-counting and to determine the chemical recovery of 234Th using Th spikes and alpha-spectrometry as an alternative to ICP-MS based methods. Two variations of the procedure are presented. In the first “1 spike” method a 230Th tracer is added to the sample prior to precipitation of MnO2, and UTEVA® extraction chromatography is used to obtain a NdF3(Th) purified source that can be used for both beta-counting of 234Th and alpha-spectrometry of 230Th. In the “2 spike” method a 230Th spike is added and the MnO2(Th) precipitate is directly beta-counted for 234Th and subsequently spiked with 228Th or 229Th prior to UTEVA® purification and alpha-spectrometry. The results confirm the need to process small-volume seawater samples for 234Th measurement in presence of a yield tracer, and show that both the 1 spike and 2 spike methods allow an accurate and precise determination of 234Th (relative percent difference, RPD, between expected and mean measured value < 1%; CV between replicate samples < 3%). Our work also suggests that, although the combined analytical uncertainty on total 234Th measurements accomplished with both versions of the NdF3 procedure is promising (6% for 2-L samples), the precision of the 234Th flux estimation will ultimately depend on the degree of disequilibrium between 234Th and 238U.  相似文献   

3.
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   

4.
Using the moored MnO2-fiber method, we have obtained 38 determinations of Th and Pa isotope concentrations from 18 sites along the margin of the western North Pacific near Japan, from water depths of 1,330 to 5,873 m. From our data, we are able to show that (1)228Ra and227Ac are being supplied to the seawater from the slope sediments of Honshu, Japan, (2) our230Th and231Pa concentrations match those obtained byin situ pumping with a MnO2-fiber adsorber in the Japan and Izu-Ogasawara trenches but are significantly higher than those from the Panama and Guatemala basins, and (3) our232Th concentrations show a similar systematic decrease with depth as do those of trace metals like Mn, Al, Te and Bi whose concentrations are strongly controlled by particulate matter scavenging.In contrast, our data fail to show (1) that enhanced removal of230Th and231Pa by scavenging from the water column is taking place near the western margins and (2) that231Pa is being removed in preference to230Th from the water column to the marginal sediments. This is probably due to rapid mixing of the deep waters as compared to the scavenging rates of230Th and231Pa in the water column and at the sediment/seawater interface.  相似文献   

5.
Delayed coincidence counters (RaDeCC), used for measuring 223Ra and 224Ra preconcentrated from water onto MnO2-impregnated acrylic fiber (“Mn-fiber”), require a standard Mn-fiber column that has a precisely known activity of 224Ra for calibration. This may be done by adding an aged 228Th standard solution to adsorb both 228Th and its daughter 224Ra quantitatively onto a Mn fiber. We used both seawater and deionized water (DIW) for testing the adsorption efficiency of Th and Ra onto Mn fibers. Our experimental results show that more than 50% of thorium (232Th and 228Th) breaks through the Mn-fiber column when DIW is used as a medium. However, near quantitative recoveries are obtained if filtered (0.45 μm) seawater is used to prepare the standard. In the case of pure DIW, the pH (initial pH  5.3) rises to > 10 after passing through the column while seawater (initial pH  7.8) changes to  7.2. Thus, the lack of thorium adsorption in DIW may be attributed to this huge increase of pH and the consequent formation of Th(OH)4 and polyhydroxyl colloids. Based on these observations, we recommend that one should use either artificial seawater or natural seawater (which has negligible 224Ra and 228Th) as a loading solution after 0.45 μm filtration. In addition, the thorium adsorption efficiency should be confirmed either by thorium analysis of the effluent solution or long-term monitoring of the supported 224Ra on the Mn fiber using the RaDeCC. Similar cautions are likely necessary for making 223Ra standards by adsorption of 227Ac onto Mn fibers.  相似文献   

6.
The metal complexing ability of surface water of the Irish Sea has been measured by the MnO2 adsorption method. In all samples strong copper-chelating compounds are present at concentrations of 60–150 nM, with conditional stability constants (log values) of 10.0–10.4. The concentrations of Cu, Pb and Cd in the samples are 16–39 nM, 1–7 nM and 0.1–2 nM, respectively; much less than the ligand concentrations. The organic compounds form complexes with 94–98% of dissolved copper, and therefore constitute the major form of copper in surface water of the Irish Sea. Recalculation of speciation of the inorganic fraction of copper in seawater reveals that the major complex ion is that of CuCO30 (60%), followed by CuOH+ (16%) and Cu(OH)20 (16%). Complexes with borate ions form a small and rather insignificant fraction of 1%.  相似文献   

7.
本研究提出了一种用于检测海水中锌离子(Zn2+)含量的电化学检测方法。该方法首先应用水热法合成SiO2@PDA-Sb复合材料,然后将该复合材料修饰到玻碳电极上制备SiO2@PDA-Sb-Nafion/GCE,利用差分脉冲阳极溶出伏安法(DPASV)对珠江口海水水样中Zn2+进行测定。研究结果表明,Zn2+在SiO2@PDA-Sb-Nafion/GCE上具有较强的溶出峰。在最优条件下,SiO2@PDA-Sb-Nafion/GCE对Zn2+浓度在1～1 000 nmol/L范围内可实现灵敏、准确的检测,Zn2+的检测出限为0.71 nmol/L。加标回收率实验显示Zn2+加标回收率为93.19%～100.12%,表明该方法可应用于现场海水样品Zn2+测定。本方法具有电极制作简单、稳定性和抗干扰性良好,能够提高现有测定方法的检测限和精确度,在现场海水检测...  相似文献   

8.
运用实验模拟的手段,对铀(U)、钍(Th)在碳酸钙-海水界面的附着行为进行了初步研究,通过测定相关的分异系数(D)定量评估了文石和方解石两种碳酸钙矿物对U和Th的捕集作用。实验结果显示,不仅U和Th之间存在显著差异,而且两种碳酸钙矿物之间也存在明显不同。U介于碳酸钙和海水之间的分异系数(DU)分别在1.5~3.5(文石)和0.04~0.19(方解石)区间内变化,分异行为非常微弱但其分异系数随着碳酸钙沉淀速率的增加而逐渐上升。这表明U元素主要是以共沉淀的方式进入到文石或方解石沉淀中,但由于其在海水溶液中主要以2 22 3UO(CO)nn的形式存在,因而只能以占据晶格缺陷的方式进入碳酸钙。与之相反的是,文石和方解石都对Th表现出极强的捕集能力,所测定的分异系数(DTh)分别在240~6 330(文石)和430~6 160(方解石)范围内变化,但DTh与碳酸钙沉淀速率之间无明显关联。Th在碳酸钙表面的附着行为可界定为单纯的吸附作用,这一行为应与Th主要以Th(OH)4的形式赋存于溶液中有关。  相似文献   

9.
The theory is discussed which describes the distribution of copper ions between a weak ion exchanger, as exemplified by MnO2, and natural organic complexing material in seawater. Application of this theory and experimental procedures are outlined in part II of this series. It is apparent from the theory that titration with Cu2+ of one or more organic complexing ligands can be graphically represented by straight lines; slope and y-axis intercept provide information on the conditional stability constants and the ligand concentrations. Model calculations show that measurement of metal complexation at ligand concentrations higher than normally present in seawater may produce erroneous results because of possible changes in the metal to ligand ratio in the complexes. It is therefore advisable to measure metal complexation in the original, unaltered, water sample.  相似文献   

10.
The extent and kinetics of Np(V)O2+ adsorption from dilute aqueous solutions and seawater onto a variety of synthetic and natural solids were determined at 25°C and 1 atm total pressure. Extensive and complex adsorption reactions were found, contrary to speculations in the literature that NpO2+ should behave as a simple monovalent ion with a low affinity for surfaces. When normalized to adsorption per unit solid surface area, the ranking for the synthetic solids was aragonite ? calcite > goethite ? MnO2 ≈ clays. Natural materials generally followed the same behavior patterns as their synthetic counterparts. The dissolved/adsorbed ratio was found to be constant over a wide range (10?13–10?7M) of NpO2+ concentrations. At higher concentrations the extent of adsorption decreased until a solubility limit was reached at approximately 10?5 M.Solution composition had the most significant influence for NpO2+ adsorption on goethite, where much more extensive adsorption occurs in dilute solutions than in seawater. When seawater is added to a dilute solution, extensive desorption of NpO2+ from goethite occurs. Tests conducted on NpO2+ adsorbed on carbonates indicated that it remained in the V oxidation state.There is a growing consensus that Pu dissolved in natural waters also occurs dominantly in the V oxidation state as PuO2+ ion. Consequently, these results for NpO2+ may serve as a guide for Pu behavior when also in the V oxidation state. The fact that most adsorbed Pu is found in the III or IV oxidation states indicates that reduction of Pu may occur subsequent to adsorption in the V oxidation state.  相似文献   

11.
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   

12.
Self-diffusion coefficients of five major ions have been determined by a radioactive tracer method (capillary tube method) in seawater of salinity 34.86 at 25°C. Data are presented for Na+, Ca2+, Cl−, SO42, and HCO3−, which constitute about 95% by weight of sea salt. The influence of temperature and salinity on these coefficients has been studied for Na+ and Cl− which are the major components of sea salt: self-diffusion coefficients of these two ions have been measured in seawater, at different temperatures for a salinity of 34.86 and at different salinities for a temperature of 25°C. Diffusion coefficients of the same ions have been determined at 25°C by using another radioactive tracer method (quasi-steady cell method). In this experiment, seawater ions were allowed to diffuse from natural seawater into dilute seawater. Data have been obtained at 25°C for Na+, Ca 2+, Cl−, SO42− and HCO3−, corresponding to different salinity gradients.  相似文献   

13.
《Marine Chemistry》2007,103(1-2):1-14
We succeeded in determining the Ce isotopic composition (138Ce/142Ce) in seawater with an error of 2σm = 0.3–0.7 of ε unit. In this study, 1000–3000 L of seawater samples were passed through MnO2 fibers to concentrate Ce and Nd for precise measurement of their isotope ratios. Four surface seawater samples of the northwestern Pacific and a coastal sample in Tokyo Bay were analyzed. Most Ce isotope ratios in the surface water showed positive εCe values (+ 0.8 to + 1.4) in the northwestern Pacific Ocean. These values indicate that Ce in the surface water originates from the continental crust preferentially over mantle-derived materials. We examined binary mixing model between the continental crust and mid-ocean ridge basalt. However the model could not explain both isotopic compositions and concentrations, which implies that the atmospheric input was a possible pathway for Ce into the ocean. A negative εCe value was observed in Tokyo Bay, suggesting mantle-derived sources.  相似文献   

14.
基于模糊数学和改进层次分析法的海水入侵程度评价   总被引：1，自引：1，他引：0  
基于模糊数学基本思想,将海水入侵程度作为评价对象,选择Cl–、Br–、SO42–、K+、SAR等5项能敏感反映海水入侵过程的水化学指标作为评价指标,通过采用改进层次分析法计算各指标权重和运用模糊数学进行综合评价,构建海水入侵程度综合评价的数学模型。以山东省招远市作为研究区,运用评价模型对该地区海水入侵程度进行评判,评价结果较单一指标评价法更加合理准确,具有较好的实用性,可为当地海水入侵防控提供科学依据。研究表明,该模型是海水入侵程度评价的一种简易高效、科学合理的方法,可推广应用。  相似文献   

15.
234Th (T1/2=24.1 d) and 210Po (T1/2=138.4 d) are particle reactive radioisotopes that are used as tracers for particle cycling in the upper ocean. Particulate organic carbon (POC) export has frequently been estimated using 234Th/238U disequilibrium. Recent evidence suggests that 210Po/210Pb disequilibrium may be used as an additional tool to examine particle export, given the direct biological uptake of 210Po into cellular material. Differences in these two radioisotope pairs with regard to their half-lives, particle reactivity and scavenging affinity in seawater should provide complementary information to be obtained on the processes occurring in the water column. Here, we review eight different studies that have simultaneously used both approaches to estimate POC export fluxes from the surface ocean. Our aim is to provide a complete “dataset” of all the existing POC flux data derived from the coupled use of both 234Th and 210Po and to evaluate the advantages and limitations of each tracer pair. Our analysis suggests that the simultaneous use of both radiotracers provides more useful comparative data than can be derived from the use of a single tracer alone. The difference in half-lives of 234Th and 210Po enables the study of export production rates over different time scales. In addition, their different biogeochemical behaviour and preferred affinity for specific types of particles leads to the conclusion that 234Th is a better tracer of total mass flux, whereas 210Po tracks POC export more specifically. The synthesis presented here is also intended to provide a basis for planning future sampling strategies and promoting further work in this field to help reveal the more specific application of each tracer under specific water column biogeochemistries.  相似文献   

16.
The interaction of Mn2+ with the surface of calcite in aqueous solutions is complex. In dilute solutions the Mn2+ is rapidly absorbed, MnCO33 nucleates on the calcite surface and then grows by a first order reaction with respect to the initial Mn2+ concentration. At higher ionic strengths in NaCl solutions, the rate of these processes is slower, but the same general pattern persists. In solutions containing Mg2+, at the concentration of seawater and in seawater, the nucleation phase of the uptake process does not appear to occur. The long-term uptake rate of Mn2+ on the surface of calcite in seawater is first order with respect to the dissolved Mn2+ concentration. The rate constant is over three orders of magnitude smaller than that found in dilute Mg2+-free solutions. A probable explanation for the slower growth rate in seawater is that MnCO3 is not nucleated on the calcite surface due to the presence of high Mg2+ concentrations. The Mg2+, through site competition, prevents enough Mn2+ from being adsorbed to reach a critical concentration for MnCO3 nucleation. This behavior is similar to that found for orthophosphate with calcite surfaces in dilute solutions and seawater. It indicates that rhodochrosite cannot nucleate in carbonate-rich recent sediments unless the Mg2+ concentration is lowered below that of seawater.Measurements of the solubility of rhodochrosite in seawater gave results from an undersaturation approach to equilibrium in excellent agreement with those found in previous studies in dilute solutions. When equilibrium was approached from supersaturation, approximately fifty times more calcium was precipitated than Mn2+. The measured solubility was over twice that determined from undersaturation. It is possible that a Mn—calcite containing 25 to 30 mol% MnCO3 formed on the rhodochrosite from the supersaturated solutions. Consequently, it is doubtful that pure rhodochrosite controls the concentration of Mn2+ even in calcium carbonate-poor marine environments.  相似文献   

17.
氯离子和硫酸根离子是海水中重要的无机阴离子，在研究海洋生态变化、海洋循环作用过程与海洋全球气候变化等领域具有重要的指示意义。其测定方法较多，但缺少相应的测试方法。本文对测定海水中Cl-，SO42-的离子色谱方法进行了优化，选用IonPacAS14碳酸盐选择性离子色谱柱，以3.5 mmol/L Na2CO3+1 mmol/L NaHCO3为流动相，可消除海水样品中碳酸盐及其他阴离子的干扰。该方法对Cl-检出限为0.29 mg/L，线性相关系数r2=0.999 2，对SO42-检出限为0.42 mg/L，线性相关系数r2=0.997 9。样品的加标回收率在95%~102%，Cl-和SO42-的相对标准偏差分别为1.92%和4.18%。该方法简便、迅速、灵敏、准确度高，可满足批量海水样品中Cl-与SO42-的准确测试。  相似文献   

18.
A widely used method for determining iodate in seawater involves reaction of the IO3? with excess I?, under acid conditions, to form I2 which is measured colorimetrically. It is known that when the acidification is by mineral acid, nitrite can interfere with the method by oxidising I? to I2 in an analogous way to IO3?. Some workers have used sulphamic acid for acidification since it is reported to destroy nitrite in solution.We have investigated the extent of nitrite interference in the colorimetric determination of iodate using both mineral acid and sulphamic acid for acidifying the reaction mixture. In seawater the extent of the interference is equivalent to 0.212 μM 1?1 IO3? per μM 1?1 NO2? with sulphuric acid, and 0.128 μM 1?1 IO3? per μM 1?1 NO2? with sulphamic acid. This means that for a seawater containing 0.31 μM 1?1 (39 μg 1?1) IO3?, the presence of 0.5 μM 1?1 NO2? will lead to an error of 25% in the iodate determined colorimetrically in methods using sulphuric acid, and 15% in methods in which sulphamic acid is used.  相似文献   

19.
234Th (T1/2=24.1 d) and 210Po (T1/2=138.4 d) are particle reactive radioisotopes that are used as tracers for particle cycling in the upper ocean. Particulate organic carbon (POC) export has frequently been estimated using 234Th/238U disequilibrium. Recent evidence suggests that 210Po/210Pb disequilibrium may be used as an additional tool to examine particle export, given the direct biological uptake of 210Po into cellular material. Differences in these two radioisotope pairs with regard to their half-lives, particle reactivity and scavenging affinity in seawater should provide complementary information to be obtained on the processes occurring in the water column. Here, we review eight different studies that have simultaneously used both approaches to estimate POC export fluxes from the surface ocean. Our aim is to provide a complete “dataset” of all the existing POC flux data derived from the coupled use of both 234Th and 210Po and to evaluate the advantages and limitations of each tracer pair. Our analysis suggests that the simultaneous use of both radiotracers provides more useful comparative data than can be derived from the use of a single tracer alone. The difference in half-lives of 234Th and 210Po enables the study of export production rates over different time scales. In addition, their different biogeochemical behaviour and preferred affinity for specific types of particles leads to the conclusion that 234Th is a better tracer of total mass flux, whereas 210Po tracks POC export more specifically. The synthesis presented here is also intended to provide a basis for planning future sampling strategies and promoting further work in this field to help reveal the more specific application of each tracer under specific water column biogeochemistries.  相似文献   

20.
A practical method has been developed for the simultaneous determination of226Ra,234Th,210Pb and210Po in seawater. In the method, the samples are spiked with228Ra,230Th,208Po and common lead to determine chemical yield. These nuclides are coprecipitated with calcium carbonate and ferric hydroxide from 20 to 50 l of seawater and separated from one another by using coprecipitation and ion exchange techniques. Counting sources of Ra and the other nuclides are prepared by electrodeposition onto silver discs. Their radioactivities are counted with an-spectrometer and a low background-counter. This method gives a standard deviation of about 5% for replicate determination of226Ra and the other nuclides.  相似文献   

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