Vacuum extraction of natural levels of radon from seawater

A vacuum extraction system has been constructed which rapidly and quantitatively extracts radon and other gases from water. The time required to extract radon from a 23-1 sample is 15 minutes with an extraction efficiency of 0.985. Total sample processing time (sample preparation, extraction, purification, and transfer of radon to a counting cell) is 40 minutes for the 23-1 sample. The system has been field tested and used routinely to analyze several hundred seawater samples for radon. The combined variability of sampling and extraction efficiency in the field was determined to be 2 to 3%, from three sets of replicate measurements.     

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 copper complexation with natural organic ligands in seawater by equilibration with MnO2 I. Theory

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.     

海水中-氧化氮的化学发光法测定

基于鲁米诺-H2O2混合溶液作为发光液与海水中NO发生反应产生发光信号的原理,提出了一种测定海水中痕量NO的化学发光法.确定了化学发光法测定NO的最佳条件:pH9.2、浓度1×10-2 mol/dm3的碳酸盐为缓冲体系,鲁米诺浓度为8.4×10-5 mol/dm3,H2O2浓度为1×10-2 mol/dm3,测定温度为...     

Hunnebotn: a seawater basin transformed by natural and anthropogenic processes

The lake Hunnebotn (A=1 km², z_max=11 m) has become separated from the sea by isostasis, but a 1.5-m-deep channel is held open by periodic dredging. Water exchange is minor due to the small tidal range (21 cm) and the length of the channel (1.8 km), but there may be an inflow of seawater at spring tides. The terrestrial watershed runoff may be fertilized by sewage and agricultural runoff despite some measures taken to prevent this. Historical and new records of biological communities indicate variations in sensitivity to different phases of the isolation and eutrophication process. The native oyster was most sensitive and disappeared first. Later, the eelgrass disappeared possibly due to overgrowth by epiphytic algae, and finally there was a massive littoral–sublittoral invasion of green algae. The lake should not be left in this condition, for aesthetic reasons and because marine inlets and eutrophic brackish water may serve as refugia for spore populations of toxic microalgae. Improving surface water quality will require better control of anthropogenic sources, but bursts and leaks of nutrients from the anoxic monimolimnion cannot be controlled.     

A comparison of diatom colonization on natural and artificial substrata in seawater

Experiments to investigate diatom colonization on various substrata in seawater are described. No differences were found due to different methods of preparation of the substrata. Differences in the numbers of diatoms colonizing the different substrata emphasize the care needed in selecting a substratum on which to study the settlement of organisms, especially if the experiments are to be used for subsequent prediction.     

适用于快速远程检测海水中氰化物的方法研究

建立了一种适用于海洋远程快速检测氰化物的检测方法,设计了一体化检测装置,未来可搭载到无人艇上实现自动快速检测。针对最佳检测条件进行了一系列优化,得到最佳检测条件:对于100 mL的待测样品,加入酒石酸固体1.5 g;用1～2滴浓度为150 g/L的碳酸钠溶液浸润苦味酸试纸;加热温度80℃,加热时间10min。在最佳检测条件下,检测检出限达0.3mg/L。该方法实现了适用于海水氰化钠的远程检测,大大提高了检测效率,无需人员进入污染现场,安全性高。可广泛用于海洋危化品泄漏、湖泊污染、现场应急筛选等场合的水体样品快速检测。     

天然海水河蟹工厂化育苗研究——大水体生产性育苗试验

本文报导了利用对虾育苗设施，进行天然海水河蟹工厂化育苗生产性试验。试验结果令人满意，６９６只亲蟹产出蟹苗１７６４万只。文中讨论了亲蟹的暂养与促产、幼体孵化、幼体培育等主要技术环节。     

Analysis of seawater and different highly saline natural waters by capillary zone electrophoresis

Innovative applications of capillary zone electrophoresis (CZE) to the determination of inorganic ions in environmental aquatic samples of high salinity and, particularly, in seawater are reviewed. Emphasis is placed on advanced approaches utilized for securing separation performance from being degraded by the presence of matrix salts and for simultaneous separation of ions different in natural abundance. Also covered are methodologies of present or possible use to evolve the method's practical utility to trace-level ions. Surveyed procedures are tabulated for the purpose of facilitating the method selection or further development. In addition, brief background information on basic methodological principles of CZE in inorganic ion analysis is given for a better orientation of those intending or just beginning to put CZE to work. Finally, possible future research trends and developments of CZE in the area are briefly discussed.     

Starvation effects on pathogenic Vibrio alginolyticus in natural seawater

To get a better understanding of the starvation survival strategy of pathogenic Vibrio alginolyticus, log-phase cells were inoculated into sterile natural seawater for starvation studies. The results showed that all of total bacteria number, viable bacteria number and CFU number of V. alginolyticus increased remarkably at the initial starvation stage; after reaching their peaks at 5 d, both total bacteria number and viable bacteria number of V. alginolyticus fell slowly, while the CFU number fell more quickly after reaching its peak at 10 d; V. alginolyticus elongated their cells at the prophase of starvation, and then shrunk their volume and turned their shapes into ovals from rods at the anaphase of starvation; starved cells showed more sensitivity to heating and UV; starved cells showed no significant difference from unstarved ones at the lowest detection limit determined by indirect enzyme-linked immu- nosorbent assay （ELISA） ; starved cells＇ ability to adhere to the skin mucus of large yellow croaker （ Pseudosciaena crocea） showed a sharp decline as the starvation time increases; the cellular protein of V. alginolyticus increased remarkably at the ariaphase of starvation. The results indicated that pathogenic V. alginolyticus could survive in starvation for relatively long periods of time （ ≥2 months） in 28℃ natural seawater due to the morphological and physiological changes; however, starved V. alginolyticus cells showed less virulence and higher sensitivity under environmental stresses.     

Determination of the complexing capacity and conditional stability constants of complexes of copper(II) with natural organic ligands in seawater by cathodic stripping voltammetry of copper-catechol complex ions

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 K′_CuL) of 12.2 and 10.2, respectively.     

The determination of sulfide in seawater by flow-analysis with voltammetric detection

Preliminary measurements of sulfide in seawater using cathodic stripping voltammetry and a hanging mercury drop electrode (HMDE) in batch-mode showed that the sulfide peak decreased rapidly with time. This decrease was not caused by O₂, H₂O₂ or IO₃⁻, and the sulfide peak was not stabilised by trace metal additions. A home-made flow-cell was constructed to enable the determination of sulfide in seawater using voltammetry with an HMDE. A stable sulfide peak was obtained by flow-analysis with voltammetric detection, with a precision of 2.8% and detection limit of 0.5 nM at a 60 s adsorption time. Several thiol compounds were found to produce a peak at, or very close to, the peak potential for sulfide. Their interference was evaluated by allowing the sulfide peak in conventional (batch) voltammetry to decay. Comparative experiments showed that waste metallic mercury is responsible for removal of sulfide in batch-mode analysis due to formation of insoluble mercuric sulfide salts causing the rapid decay of the sulfide peak. The problem is circumvented by using flow-analysis to determine sulfide.     

Gypsum-organic interactions in natural seawater: Effect of organics on precipitation kinetics and crystal morphology

Organic compounds which are chloroform extractible from seawater affect gypsum precipitation by inhibiting the nucleation of crystals. The effect is selective towards calcium-populated crystal habit faces and results in the growth of more tabular, equidimensional crystals. Studies using model organic compounds suggest that the inhibition takes place through an adsorption mechanism and show that longer-chained n-fatty acids are more actively adsorbed. The specific adsorption mechanism (at Ca²⁺ habit faces) is also supported by the fact that the free-acid (base-soluble) fraction of the chloroform extractibles from seawater is more active than the neutral fraction. The calcium ion complexing ability of model organic compounds is not correlatable with their inhibitory effects on gypsum crystal nucleation.     

In situ chemisorption of radiocesium from seawater

A novel approach to in situ extraction of Cs radionuclides from seawater is described which offers many advantages over previous methods. Cesium (stable and radioactive) is partially stripped from seawater as it passes in series through a tandem cartridge consisting of twin beds of ion exchange resin impregnated with cupric ferrocyanide. It is demonstrated that, when seawater passes through this cartridge at a constant flow-rate, collection efficiencies of each bed are the same, allowing the calculation of the seawater Cs nuclide concentration. The cartridge is made of inexpensive, readily available, PVC pipe fittings and is easily deployed under various field conditions. Procedures are described for resin preparation and desorption and radiochemical purification of the collected Cs. Thousands of liters of seawater can be stripped of Cs in this way, permitting substantial improvement in the sensitivity of measurement of ¹³⁴Cs and ¹³⁷Cs.     

国产沸石的改性处理及其在海水硝酸盐氮同位素预处理中的应用

使用多种改性方法对几种国产天然沸石进行改性处理,提高其铵氮吸附率,制备符合海水硝酸盐氮同位素预处理要求的沸石。发现重力筛选可提高沸石铵氮吸附率16%以上,钠改性及酸改性后钠改性可提高沸石铵氮吸附率80%以上,微波改性和超声波改性均可进一步提高沸石铵氮吸附率。改性处理后,几种沸石在酸性条件下对低浓度铵氮吸附率达90%以上,其氮同位素分馏较美国UOP沸石分馏系数更小,且更稳定。改性后的国产沸石更适于海水硝酸盐氮同位素预处理。应用改性后沸石对长江口海域硝酸盐水样进行了分析,结果表明,改性后沸石可以应用于海水中溶解态硝酸盐的氮同位素分析,为海水中溶解态氮的来源问题及循环机理研究等提供了有效信息。     

Reactions which remove dissolved alumina from seawater

Dissolved alumina can coprecipitate with dissolved silica from seawater enriched with both compounds. This coprecipitation is almost complete within 1h and maintains the concentration of dissolved alumina near naturally occurring oceanic concentrations, well below the alumina concentration of 0.50 ppm A1 found to be stable in filtered Sargasso seawater at 2°C. Only 0.5 ppm Si is necessary to initiate this coprecipitation, which indicates that the concentrations of dissolved alumina that occur in seawater and in interstitial water are a function of the concentration of dissolved silica as well as of the alumina solubility.Dissolved alumina is also quickly removed by solid amorphous silica from solutions of seawater enriched in dissolved alumina and also by several marine sediments in contact with the solution. This process may be an important factor in authigenic mineral formation in marine sediments.     

Comparison of techniques for pre-concentrating radium from seawater

In the framework of the KEOPS project (KErguelen: compared study of the Ocean and the Plateau in Surface water), we aimed to provide information on the water mass pathways and vertical mixing on the Kerguelen Plateau, Southern Ocean, based on ²²⁸Ra profiles. Because ²²⁸Ra activities are extremely low in this area (~ 0.1 dpm/100 kg or ~ 2.10^− 18 g kg^− 1), the filtration of large volumes of seawater was required in order to be able to detect it with minimal uncertainty. This challenging study was an opportunity for us to test and compare methods aimed at removing efficiently radium isotopes from seawater. We used Mn-fiber that retains radium and that allows the measurement of all four radium isotopes (²²⁶Ra, ²²⁸Ra, ²²³Ra, ²²⁴Ra). First, we used Niskin bottles or the ship's seawater intake to collect large volumes of seawater that were passed onto Mn-fiber in the laboratory. Second, we filled cartridges with Mn-fiber that we placed in tandem on in situ pumps. Finally, we fixed nylon nets filled with Mn-fiber on the frame of in situ pumps to allow the passive filtration of seawater during the pump deployment.Yields of radium fixation on the cartridges filled with Mn-fiber and placed on in situ pumps are ca. 30% when combining the two cartridges. Because large volumes of seawater can be filtered with these pumps, this yields to effective volumes of 177–280 kg (that is, higher than that recovered from fourteen 12-l Niskin bottles). Finally, the effective volume of seawater that passed through Mn-fiber placed in nylon nets and deployed during 4 h ranged between 125 and 364 kg. Consequently, the two techniques that separate Ra isotopes in situ are good alternatives for pre-concentrating radium from seawater. They can save ship-time by avoiding repeated CTD casts to obtain the large volumes of seawater. This is especially true when in situ pumps are deployed to collect suspended particles. However, both methods only provide ²²⁸Ra/²²⁶Ra ratios. The determination of the ²²⁸Ra specific activity is obtained by multiplying this ratio by the ²²⁶Ra activity measured in a discrete sample collected at the same water depth.     

Determination of iron in seawater by flow injection analysis using in-line preconcentration and spectrophotometric detection

A highly sensitive flow injection analysis (FIA) method for determining the concentration of iron in seawater has been developed. The technique is a modification of the catalytic batch method previously reported by Hirayama and Unohara. By optimising the chemistry for FIA and incorporating in-line preconcentration of the iron from seawater onto a column of resin-immobilised 8-hydroxyquinoline, the detection limit of the method has been reduced to 0.025 nM. The typical precision of the method for a 0.35 nM Fe sample is 2.5% (n = 6). The method has been used at sea in its preconcentration mode to determine iron in open ocean water samples from the equatorial Pacific and the North Atlantic. It has also been used in a direct injection mode for hydrothermal plume samples from around Loihi Seamount in the Central Pacific.     

The effect of seawater magnesium on natural fluorescence during estuarine mixing,and implications for tracer applications

Natural fluorescence, which is thought to result from low molecular weight humic and fulvic compounds, can be used as a tracer to distinguish between individual river waters. Natural fluorescence exhibits conservative mixing with seawater, except for a slight fluorescence increase which is sometimes observed in the low salinity range (0–5‰). This increase is not due to the inner filter effect (internal quenching). Laboratory experiments can reproduce this low-salinity natural fluorescence increase. Of the major seawater ions, only magnesium can cause a similar natural fluorescence increase. Variation in sample pH, ionic strength, or particle content cannot explain the natural fluorescence increase, nor does it appear to be related to the estuarine flocculation of humic material. Addition of seawater magnesium to the fluorescent material with subsequent loss of hydrogen ions could enhance fluorescence by adding crosslinking to the structure. Replacement of a fluorescence-depressing metal like copper or iron by magnesium could also enhance fluorescence, essentially by removing the quenching effect of the metal. Experimental data in this study are consistent with both of these possible mechanisms. Calcium also enhances fluorescence, however the effect of seawater calcium during estuarine mixing is not as apparent as the magnesium effect. The implications of this low-salinity natural fluorescence increase with respect to estuarine and coastal tracer applications depend on whether individual rivers mix in the high or low salinity region of an estuary or coastal area.     

Flow injection analysis of nanomolar level orthophosphate in seawater with solid phase enrichment and colorimetric detection

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.