An international intercalibration for mercury in seawater

An intercalibration between 32 laboratories in 16 countries was conducted using acidified and ultraviolet-irradiated seawater. One sample was natural seawater but two were spiked with mercuric chloride, 15.4 and 143 ngl^?1, respectively. The results show, for the majority of the laboratories, good accuracy and precision in the recovery of spikes but they also demonstrate that the most serious errors in low-level determinations are systematic.     

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.     

Intercalibration of Bruevich’s method to determine the total alkalinity in seawater

In 2000, the Carbon Dioxide in the Ocean working group of the North Pacific Marine Science Organization (PICES) performed an international experiment on the intercalibration of the measurements of the total alkalinity in seawater using certified reference materials (CRM). Taking part in this experiment, Russian specialists presented the method by Bruevich. The results of the intercalibration showed that the alkalinity values obtained by Bruevich’s method using modern burettes, an Na₂CO₃ reactant of high purity as a standard to ascertain the acid titre, and corrections for the acid density and for the weights of the acid and seawater samples in vacuum are in agreement with the standard within ±1 μ M/kg.     

pH对SPE-HPLC-ESI-Q-TOF-MS检测海水中小分子活性物质的影响研究

海水溶解有机物(dissolvedorganicmatter,DOM)中含有的生物活性物质在海洋生态系统中作用巨大,但因缺乏适合的分离提取方法而严重阻碍了对其不同组分在生态系统中作用的探索。固相萃取法对富集提取海水DOM十分有效,在用其提取海水DOM时,海水pH对活性物质提取效果的影响很大,但目前针对海水的这种影响尚存在很大争议。本文以天然近海海水作为基质,探究不同pH条件下用亲水-疏水平衡(hydrophilic-lipophilicbalanced,HLB)固相萃取小柱萃取海水中活性分子的提取效率,并使用高效液相色谱-四极杆飞行时间质谱(HPLC-Q-TOF-MS)在负离子(ESI-)模式下检测解析提取物的组成。研究结果表明,当海水样品pH为中性和强酸性时都能获得较好的提取效率,随着pH的降低,提取物质谱的整体响应值降低,但可识别的谱峰数目增加,提取出有机物的分子量和性质差异都更广泛。分析提取物分子在范克雷维伦(van Krevelen)图和质荷比-氢碳比(m/z-H/C)图上的分布发现,中性条件适合提取饱和度较高的小分子化合物,而具有生物活性的带有不饱和基团的化合物及蛋白质、糖类等生物大分子在强酸性提取条件时提取效果和分辨率更好。综合提取效率、有效峰数目和分子组成特征考虑,用HLB固相萃取小柱提取近海海水中的小分子活性物质时,将海水样品pH调节为2较为适宜。     

The reliability of analytical data for tributyltin (TBT) in sea water and its implications on water quality criteria

To investigate the reliability of analytical data for tributyltin (TBT) in sea water, split water samples were distributed to ten laboratories in six countries. The sub-surface samples comprised: (i) an offshore (0·5 km) water sample, (ii) the same sample but spiked with an undisclosed quantity of TBT standard compound (175 ng TBT⁺ liter⁻¹), and (iii) a sample taken from a yacht marina. The seven acceptable data sets were in good agreement for the spiked sample (178 ± 26 ng TBT⁺ liter⁻¹) but showed a greater variation in concentrations reported for the yacht marina sample (366 ± 93 ng TBT⁺ liter⁻¹). Atomic absorption and gas chromatographic-flame photometric detection techniques produced results of similar accuracy and precision. Samples acidified with 1 ml of 10% (v/v) acetic acid appeared stable for more than 2 weeks when stored refrigerated and in darkness. Analyses of the offshore seawater sample revealed TBT contamination (9 ± 7 ng TBT⁺ liter⁻¹) indicating dispersion of the compound to the shelf waters off Monaco. The spread in values reported by the laboratories demonstrates inherent difficulties in obtaining good precision below approximately 20 ng TBT⁺ liter⁻¹. This observation is discussed with respect to the setting and enforcing of water quality standards.     

A community-wide intercomparison exercise for the determination of dissolved iron in seawater

The first large-scale international intercomparison of analytical methods for the determination of dissolved iron in seawater was carried out between October 2000 and December 2002. The exercise was conducted as a rigorously “blind” comparison of 7 analytical techniques by 24 international laboratories. The comparison was based on a large volume (700 L), filtered surface seawater sample collected from the South Atlantic Ocean (the “IRONAGES” sample), which was acidified, mixed and bottled at sea. Two 1-L sample bottles were sent to each participant. Integrity and blindness were achieved by having the experiment designed and carried out by a small team, and overseen by an independent data manager. Storage, homogeneity and time-series stability experiments conducted over 2.5 years showed that inter-bottle variability of the IRONAGES sample was good (< 7%), although there was a decrease in iron concentration in the bottles over time (0.8–0.5 nM) before a stable value was observed. This raises questions over the suitability of sample acidification and storage.     

LASER-INDUCED FLUOROMETRY FOR THE RAPID DETERMINATION OF TRACE LEVELS OF URANIUM IN SEAWATER

A laser-induced fluorometric method for the rapid determination of trace level? of uranium in seawater with the Modified Anti-interference Fluorometric Reagent for uranium (MAFG) is described. Only a sample volume of 1.5-2.5 ml is used in each determination and no pre-scparation and concentration steps are required. The analysis rate is a sample per 5 min. The relative standard deviation of ten replicate determinations on 3.44 ppb U of the natural seawater is 4.7%.     

Determination of the reduced sulfur species in the anoxic zone of the Black Sea: A comparison of the spectrophotometry and iodometry techniques

The report presents the results of the studies of the reduced sulfur species in the water of the anoxic zone of the Black Sea. The content of hydrogen sulfide was determined by means of spectrophotometry using dilution with oxygen-free distilled water. The detection limit of the H₂S amounted to 0.3 μM with the method’s precision below 3%. The accuracy of the spectrophotometric determination was verified by iodometry after the fixation of the hydrogen sulfide in zinc acetate under the distillation with argon from the acidified seawater sample.     

生物硅的生成与溶解速率的研究——以胶州湾为例

营养盐的含量与元素间的比值直接控制着生态系统的生产力和浮游植物的种类组成.近岸海区硅藻可占初级生产的75%,但其生长速率受Si(OH)4含量的限制.胶州湾浮游植物的物种组成以硅藻为主.用29Si同位素示踪培养方法,采用四极杆质谱同位素稀释技术同时测定了胶州湾硅的生成速率与溶解速率.胶州湾生物硅(BSi)的含量为0.90～1.14 μmol/L,岩成硅(LSi)的含量为46.3～52.3 μmol/L.岩成硅是生物硅的约50倍.胶州湾BSi的含量处于世界近岸海区的低值范围,LSi的含量与LSi/BSi的比值均处于高值区.BSi的绝对生成速率为4～6 nmol/L*d,比生成速率为6～17/d.BSi的绝对溶解速率为<9 nmol/d,比溶解速率为<23/d.进一步开展胶州湾不同季节水体中BSi的生成速率与溶解速率的研究,是深入认识海湾浮游植物生长限制及其资源可持续利用的基础.     

Determination of dissolved oxygen in seawater by direct spectrophotometry of total iodine

A modified procedure has been proposed for the colorimetric determination of dissolved oxygen in seawater to improve its precision and accuracy. When a pickled sample is acidified, iodine liberated in the iodometric reaction is measured by direct spectrophotometry at 456 nm. Loss of molecular iodine by volatilization is eliminated by transferring the sample to a flow cuvette without contact with air. The method was calibrated for oxygen by spiking known amounts of potassium iodate. Precision was found at better than 0.2% r.s.d. (full scale). Evaluation of accuracy was made by comparison with calculated oxygen solubilities, which shows a relative bias of no more than 0.5% for oxic waters. The analytical throughput was much faster than that of the standard titration procedure.     

Heavy metal analyses in the marine environment - approaches to quality control

The validity of analyses of elements in the femto- and picomolar ranges in waters and sediments can be assessed on the basis of several criteria: an evaluation of the chemical technique; the use of primary standards and intercalibration exercises; and chemical and geochemical coherence of the results. Herein are reported analyses of ruthenium, platinum, palladium, rhenium, iridium and gold in oceanic samples. The gold concentrations in surface seawaters, at least 25 times less than those previously reported, are in accord with the concentrations of their periodic table neighbors as well as with crustal and sedimentary contents. The remarkable concentration of rhenium in seawater, in relation to its very low crustal abundance, can be explained by the inertness of the perrhenate ion.     

Sugars and uronic acids in sediment and water from the black sea and north sea with emphasis on analytical techniques

Sugars and uronic acids have been extracted from marine sediment and seawater by various hydrolysis techniques and analyzed by ion-exchange chromatography. All stages of the extraction methods were examined for sources of error arising from contamination, destruction and incomplete extraction. Tested were: (1) sample drying procedure; (2) acid hydrolysis, i.e., effect of different acids, variations in acid concentration and hydrolysis time, and effect of variations in organic and CaCO₃ contents of sediment on the quantity of released sugars and uronic acids; (3) deionization, i.e., neutralization of acid by precipitation or by ion-exchange resins, separation of sugars from uronic acids; and (4) volume reduction, i.e., rotary evaporation, freeze-drying, effect of added glycerin. It is shown that the hydrolysis efficiencies of the acids tested varied with the nature of the organic matter in sediment. Simultaneous hydrolyses with different acids may give insights into the sources of the organic input and the environment of deposition. For all sediment types examined pretreatment with 72 w/w% H₂SO₄ gave the highest yields and is, thus the optimal hydrolysis method for sediment.Sugar and uronic acid yields from seawater varied with the type of acid used for hydrolysis. The highest yield for North Sea surface water was obtained with p-toluene sulfonic acid.Since most previous investigators employed non-optimal techniques, it is recommended that intercalibration studies be performed.     

Impact of environmental factors on in situ determination of iron in seawater by flow injection analysis

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 (C_p = 2.8 × 10^{− 5}P + 3.4 × 10^{− 2} s nmol^{− 1}, R² = 0.997, for Θ = 13 °C) and an exponential relation as a function of temperature (C_Θ = 0.009e^0.103Θ, 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 Fe_a (unfiltered seawater, acidified in line at pH 1.8 for 80 s). Most of Fe_a (71 ± 4%) was probably a fraction of total dissolvable iron (TDFe, unfiltered seawater, acidified and stored at pH 1.8).     

海水中溴离子气相色谱测定法的研究

研究了用气相色谱测定海水及天然水中溴离子含量的方法,确定了最佳条件。天然海水,稀释200倍后;取10ml稀释水样,用氯胺T为氧化剂,将Br-氧化为溴,在六次甲基四胺催化的条件下,溴与丁酮反应生成溴代丁酮;用环已烷萃取后,用ECD检测器测定。此方法简便快速,对溴离子含量较低的天然水尤为适用。方法与碘量法相对照,取得满意结果。     

Effects of acidified seawater on calcification,photosynthetic efficiencies and the recovery processes from strong light exposure in the coral Stylophora pistillata

The aim of this study was to investigate whether coral photosynthetic efficiencies and recovery processes are affected by CO₂‐driven ocean acidification in symbiont photosynthesis and coral calcification. We investigated the effects of five CO₂ partial pressure (pCO₂) levels in adjusted seawater ranging from 300 μatm (pre‐industrial) to 800 μatm (near‐future) and strong and weak light intensity on maximum photosynthetic efficiency and calcification of a branching coral, Stylophora pistillata, as this species has often been used in rearing experiments to investigate the effects of acidified seawater on calcification and photosynthetic algae of corals. We found that, the photosynthetic efficiencies and recovery patterns under different light conditions did not differ among pCO₂ treatments. Furthermore, calcification of S. pistillata was not affected by acidified seawater under weak or strong light conditions. Our results indicate that the photosynthetic efficiency and calcification of S. pistillata are insensitive to changes in ocean acidity.     

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.     

Quantitative adsorption of organic matter from seawater on solid matrices

The influence of several operational parameters, including pH, flow rate, total volume of water passed, and choice of eluants, upon the efficiency of extraction of organic matter from seawater by two forms of commercially-available resin, XAD-2 and XAD-8, is considered. The overall efficiency of adsorption is at best 40%. The main factor determining the adsorption efficiency of XAD resin for natural organic matter is pH. The efficiency at normal seawater pH is only half that at pH 2.0. Although the efficiency decreases with increasing flow rate, the decrease is not great up to 3 bed vol./min. With increasing volume of water passed, the adsorption capacity of the resin initially drops, but reaches an approximately constant level after 1000 bed volumes. Alkaline solutions, either NH₄OH or NaOH, followed by methanol, completely recover adsorbed organic material from the resin. There is no significant advantage of XAD-8 over XAD-2 for seawater extractions, and the materials adsorbed by the two forms of resin are not substantially different.A new separation method combining XAD-2 resin and activated carbon as adsorbents in series in a column has been developed. Efficiencies of up to 90% were obtained in the extraction of acidified seawater. When the volume of water passed was less than 500 bed volumes, the adsorption as measured by UV-oxidation was quantitative. Elution of 90–100% of the adsorbed organic carbon was possible when ammonium hydroxide (7 M), methanol and an ammonium hydroxide—methanol mixture were used sequentially.     

Monitoring trace metals in seawater using a diffusive gradient in thin film probe in Ulsan Bay,East Sea,Korea: Comparison with transplanted mussels

To evaluate the applicability of a diffusive gradient in thin film (DGT) probe for monitoring dissolved metals in coastal seawater, DGT-labile metal concentrations were compared with total dissolved metal concentrations using spiked and natural seawater samples in the laboratory and transplanted mussels (Mytilus galloprovincialis). This was achieved through the simultaneous deployment of DGT probes and transplanted mussels in Ulsan Bay during winter and summer. DGT-labile metal concentrations were 45% (Cu) ~ 90% (Zn) of total dissolved concentrations, and the order of non-labile concentrations was Cu > Pb > Co ~ Ni > Cd ~ Zn in both metal-contaminated and non-contaminated seawater samples, which was similar to the order of stability of metal complexes in the Irving–Williams series. The overall variability of the DGT probe results within and between tanks was less than 10% (relative standard deviation: RSD) for all the metals tested during a 48-h deployment. The accumulation of metals, as determined by DGT probes, represented the spatial gradients better than the transplanted mussels did for all of the metals tested, and the extent of metal accumulation in mussels differed depending on the metal. The comparison of results for the DGT probe and the transplanted mussels in two seasons (winter and summer) suggested that metal accumulation in mussels was controlled by the physiological factors of mussels and partly by their diet (particulate metal loadings). The DGT probe could be used as a monitoring tool for dissolved metals in coastal seawater because its results explained only labile species. When using the DGT probe, slightly more than half of the total dissolved concentration in seawater samples for all the metals investigated displayed timeintegrated properties and distinct spatial gradients from pristine to metal-contaminated seawater.     

高氮磷比与酸化共同作用对微小亚历山大藻生长和产毒的影响

通过实验室构建不同氮磷比条件下的酸化海水环境,培养麻痹性贝毒(paralytic shellfish toxin,PST)产毒藻微小亚历山大藻(Alexandrium minutum),采用藻细胞计数法、分光光度法、高效液相色谱-质谱法等分析方法,探讨了不同氮磷比条件下的酸化海水对微小亚历山大藻的生长、氮磷营养盐吸收、产毒等参数的影响。结果表明,在一定程度上,酸化环境对A.minutum的生长、PST的胞内累积和胞外释放有促进作用,且胞外培养液中PST含量增加的程度更高;同时,酸化海水促进胞内毒性较低的N-H类膝沟藻毒素(GTX2和GTX3)被氧化成毒性较高的N-OH类膝沟藻毒素(GTX1和GTX4),导致A.minutum的细胞毒性和培养液毒性增加。而海水中氮磷比的进一步升高,在一定程度上促进了微小亚历山大藻细胞毒素含量和毒性的增加,但并未促进其生长,且降低了藻细胞内的磷储量。     

Centropages typicus (Crustacea,Copepoda) reacts to volatile compounds produced by planktonic algae

Volatile organic compounds (VOCs) may play the role of infochemicals and trigger chemotaxis and ecologically relevant responses in freshwater and marine invertebrates. Aquatic grazers use these signals as chemical cues to trace the presence of their food or to detect their predators. However, detailed data are still needed to fully understand the role of these relationships in marine plankton. We investigated the ability of the copepod Centropages typicus to perceive the odour of three planktonic diatoms (Skeletonema marinoi, Pseudonitzschia delicatissima and Chaetoceros affinis) and a dinoflagellate (Prorocentrum minimum). This information is ecologically relevant for orientation, habitat selection, predator avoidance and communication. In addition, as the pH of the medium influences the perception of chemical cues in aquatic environments, we tested the effect of seawater acidification resulting from increasing levels of CO₂, and its influences on the olfactory reactions of copepods. For this reason, our tests were repeated in normal (pH 8.10) and acidified (pH 7.76) seawater in order to simulate future ocean acidification scenarios. Using replicated chemokinetic assays we demonstrated that VOCs produced by Ps. delicatissima and Pr. minimum attract copepods at normal pH, but this effect is lowered in acidified water. By contrast, the odour of S. marinoi mainly induces a reaction of repulsion, but in acidified water and at higher concentrations this toxic diatom becomes attractive for copepods. Our experiments demonstrate, for the first time, that copepods are sensitive to the volatile compounds contained in various microalgae; VOCs prompt chemokinesis according to algal species and odour concentrations. However, seawater acidification induces changes in copepods' perception of odours. These findings highlight the sensitivity of chemically mediated interactions to global changes