Influence of m-cresol purple indicator additions on the pH of seawater samples: correction factors evaluated from a chemical speciation model

The perturbation of the indicator m-cresol purple on the pH in seawater is illustrated in diagrams, representing measurements in 1-cm and 5-cm cells. The diagrams apply to a measured pH interval of 7.4–8.4 using a 2-mM stock solution of m-cresol purple sodium salt dissolved in seawater. The magnitude of the perturbation is described as correction values, i.e., the change in seawater pH caused by the indicator. The diagrams are based on calculations made by using the equilibrium speciation programme, MARINHALT. From these calculations, and least squares fitting methods, pH correction values are described in terms of the pH difference between each seawater sample and the pH of an indicator stock solution. Calculations are performed for a typical high latitude water and a north Pacific deep water. Diagrams are presented for a salinity of 35 and a temperature of 15°C. Responses to salinities between 32 and 36 and temperatures 15–25°C are illustrated as well. A ±0.05 pH difference between a seawater sample and an indicator stock solution gives a correction of less than 0.001 pH unit for a 1-cm cell. For a 5-cm cell, pH differences between the indicator stock solution and a seawater sample as large as ±0.3 cause corrections smaller than ±0.001 pH unit. Calculations demonstrate that the five-fold lower indicator concentration used with 5-cm cells decreases the perturbation effect by approximately a factor of five relative to 1-cm cells.     

Spectrophotometric determination of pH in seawater off Taiaroa Head,Otago, New Zealand: Full-spectrum modelling and prediction of pCO2 levels

Accurate measurement of seawater pH has long been sought by marine chemists (for example: [Dickson, A.G. 1993a. The measurement of sea water pH. Marine Chemistry, 44, 131–142, Dickson, A.G. 1993b. pH buffers for sea water media based on the total hydrogen ion concentration scale. Deep-Sea Research, 40, 107–118; Zhang, 1996; Tapp, M., Hunter, K.A., Currie, K. and Macaskill, B. 2000. Apparatus of continuous-flow underway spectrophotometric measurement of surface water pH. Marine Chemistry 72(2–4), 193–202; Friis, K., Koetzinger, A., Wallace, D.W.R. 2004. Spectrophotometric pH measurement in the ocean: Requirements, design and testing of an autonomous charge-coupled device detector system. Limnology and Oceanography: Methods 2, 126–136]. Recently, such attempts have taken on greater significance as anthropogenic carbon dioxide emissions may create rapidly changing oceanic pH. Spectrophotometric techniques have been accepted generally as the best for determination of seawater pH. Here we report a new technique using thymol blue as the indicator dye and fitting the entire spectrum from 400 to 900 nm rather than measuring the absorbance values at only two or three points in the spectrum. This full-spectrum modelling enables a reduction in signal to noise over other techniques. In the laboratory, we find with seawater samples a pH precision increase of five-fold “within” a sample and seven-fold “between” samples when comparing the full spectrum to the three-point method of analysis [Zhang, H., Byrne, R.H. 1996. Spectrophotometric pH measurements of surface seawater at in-situ conditions: absorbance and protonation behaviour of thymol blue. Marine Chemistry 52, 17–25].     

pH 胁迫对脊尾白虾抗氧化酶活力的影响

为了了解pH胁迫下脊尾白虾(Palaemon(Exopalaemon)carinicauda Holthuis)的适应性,作者采用静水毒性的实验方法确定了脊尾白虾的半致死pH,分析了pH胁迫对脊尾白虾抗氧化酶活力的影响。设置pH4~11.1共17个胁迫组,统计脊尾白虾24、48、72和96 h的死亡率。结果显示,脊尾白虾24、48、72和96 h酸性半致死pH值分别为4.25、4.64、4.71和4.78,碱性半致死pH分别为10.87、10.55、10.38和10.29。将脊尾白虾暴露于低pH 6.5、高pH9.5的水体,以pH8.0作为对照,分别于胁迫后0、3、6、12、24、48、72和96 h测定鳃、肝胰腺、肌肉和血淋巴中总抗氧化力、过氧化氢酶、抗超氧阴离子活力。结果发现,pH胁迫后,在3~6 h内各组织中抗氧化酶活力均显著上升,24~48 h开始回落,到96 h之前,各组织中抗氧化酶水平基本恢复到对照组水平。整个实验过程中肝胰腺中抗氧化酶活力水平明显高于其他组织。本实验结果表明,脊尾白虾对pH有很强的适应性,pH胁迫3~24 h之内抗氧化酶活力反馈性升高清除体内多余的活性氧。     

In situ experimental decomposition studies in estuaries: A comparison of Phragmites australis and Fucus vesiculosus

The decomposition rates of Phragmites australis and Fucus vesiculosus were experimentally determined in an estuarine system using the leaf-bag technique. The study was conducted in fifteen sites arranged in five areas, extending from freshwater, outside the tidal range, to the marine environment, near the mouth of the estuary. The leaf-bags (5 mm mesh), were set up with 3.0 g of dried substrate, submerged in the experimental sites at day 0 and collected at days 3, 7, 15, 30 and 60, to follow biomass loss. The biomass loss through the leaching phase (day 3) was about 16% for Phragmites australis and 33% for Fucus vesiculosus and was independent of salinity for both substrates. The difference in the remaining biomass between the two species increased with time and the decomposition rates differed along the salinity gradient. For F. vesiculosus, the decomposition rate was highest near the mouth of the estuary, corresponding to the preferential distribution area of the algae, and decreased towards freshwater. For Phragmites australis, the fastest decay was observed in the mid estuary, where Phragmites australis occurs naturally, confirming previous studies. The decomposition rates measured at different time intervals (0–15, 0–30 and 0–60 days) were always higher for the algae and decreased with time for both species. These results indicate that the use of decomposition rates as a measure of ecosystem integrity or quality status in transitional waters will not be straightforward and must take into account, among others, the test species, the study area positioning along the estuarine gradient, and the time interval for the calculation of the decomposition rate.     

Alterations in seawater pH and CO2 affect calcification and photosynthesis in the tropical coralline alga, Hydrolithon sp. (Rhodophyta)

Calcification in the marine environment is the basis for the accretion of carbonate in structures such as coral reefs, algal ridges and carbonate sands. Among the organisms responsible for such calcification are the Corallinaceae (Rhodophyta), recognised as major contributors to the process world-wide. Hydrolithon sp. is a coralline alga that often forms rhodoliths in the Western Indian Ocean. In Zanzibar, it is commonly found in shallow lagoons, where it often grows within seagrass beds and/or surrounded by green algae such as Ulva sp. Since seagrasses in Zanzibar have recently been shown to raise the pH of the surrounding seawater during the day, and since calcification rates are sensitive to pH, which changes the saturation state of calcium carbonate, we measured the effects of pH on photosynthetic and calcification rates of this alga. It was found that pH had significant effects on both calcification and photosynthesis. While increased pH enhanced calcification rates both in the light and in the dark at pH >8.6, photosynthetic rates decreased. On the other hand, an increase in dissolved CO₂ concentration to 26 μmol kg⁻¹ (by bubbling with air containing 0.9 mbar CO₂) caused a decrease in seawater pH which resulted in 20% less calcification after 5 days of exposure, while enhancing photosynthetic rates by 13%. The ecological implications of these findings is that photosynthetically driven changes in water chemistry by surrounding plants can affect calcification rates of coralline algae, as may future ocean acidification resulting from elevated atmospheric CO₂.     

Simultaneous vertical measurements of in situ pH and CO2 in the sea using spectrophotometric profilers

We have developed new systems capable of profiling to >1000 m for measuring in situ pH and fugacity of CO₂ (fCO₂) in the ocean using spectrophotometric analysis (pH and CO₂ profilers). The in situ pH is determined by detecting the color change of the pH indicator (m-cresol purple). It can withstand ambient pressure to 1000 m depth. The CO₂ profiler analyzed in situ fCO₂ by detecting the change of pH in an inner solution, equilibrated with the seawater through a gas permeable membrane. It can be operated to 2500 m depth. We used an amorphous fluoropolymer tubing form of AF-2400 for the gas permeable membrane due to its high gas permeability coefficients. The inner solution was a mixture of 2 μM bromocresol purple (BCP) and 5 μM sodium hydroxide. This system gave us a response time of 1 minute, which is twice as fast as previous systems. The precisions of pH and CO₂ profilers were within 0.002 and 2.5% respectively. We have used these profilers to study the North Pacific, obtaining good agreement with the difference between the data from profilers and a discrete bottle of 0.002 ± 0.005 pH (SE, n = 25) and −0.4 ± 3 μatm (SE, n = 31).     

温度及pH对杀鲑气单胞菌生长的影响研究

利用A值法与活菌平板计数法,测定了杀鲑气单胞菌在不同条件下的生长曲线,研究了不同温度及pH对杀鲑气单胞菌(Aeromonas salmonicha)生长的影响。结果表明,活菌计数法更能真实的反映细菌数量的动态变化。在28℃,15℃,10℃,5℃条件下,随着温度降低,杀鲑气单胞菌生长速率明显下降;在pH6.0~8.0时,酸性条件能明显抑制杀鲑气单胞菌的生长;在28℃、pH7.5条件下,杀鲑气单胞菌生长速率最快,达到稳定期时细菌数量也最多。在养殖生产过程中,为了抑制杀鲑气单胞菌的生长繁殖,建议在不影响鱼类正常生长的条件下,尽量降低养殖水体温度并合理控制水体pH,以降低养殖鱼类发病率。     

Impurities in indicators used for spectrophotometric seawater pH measurements: Assessment and remedies

Spectrophotometric pH measurements have been widely used in oceanic CO₂−system research. However, impurities in indicator dyes from different manufacturers may cause uncertainty in measured pH values. In this work we report initial findings surrounding the potential significance of indicator sources (manufacturers) on pH measurements obtained with the sulfonephthalein indicator m-cresol purple. HPLC analyses were used for comparative assessments of impurities in m-cresol purple obtained from a range of manufacturers. Results indicate that m-cresol purple from different manufacturers, and perhaps from different batches of the same manufacturer, have different types and quantities of light-absorbing impurities. Impurities can contribute to pH offsets as large as 0.01 pH units. The pH offset caused by impurities decreases with decreasing sample pH. Indicators can be purified using preparative HPLC. Until purified indicators and refined indicator calibrations become available, we suggest that investigators should reserve some portion of each indicator batch for comparison with the properties of purified indicators.     

海洋真菌Rhodotorulamucilageinosa GIM 2.157介导邻-、间-、对-溴苯乙酮的不对称还原反应

研究了海洋真菌介导邻-、间-、对-溴苯乙酮的不对称还原反应。具体考察了Rhodotorulamucilageinosa GIM 2.157对邻-、间-、对-溴苯乙酮的催化活性和对映选择性,并综合考察了反应温度、pH、反应时间和底物浓度等因素对还原产物的产率及立体选择性的影响。确定最佳反应条件:反应温度为25℃,反应体系的pH为7,反应时间为24 h,底物浓度为10 mmol/L。在最佳条件下,产率以及立体选择性均99%。     

大菱鲆精子运动特征与精液pH的相关性研究

为探究大菱鲆(Scophthalmus maximus)精液质量与pH的关系及甘油对大菱鲆精子激活的影响,本研究通过计算机辅助精子分析系统分析检测了威海和烟台4家大菱鲆育苗场(A、B、C、D)的精子质量。研究发现,不同育苗场的大菱鲆精子活力存在显著的差异,A2A1DCB,精子预测寿命分别为11.7、7.1、6.8、4.6、3.3 min,所取精子的质量的存在显著差异。研究结果发现,大菱鲆精子运动特性与精子活化率相关性显著,其中精子活化率与平均曲线运动速度、平均直线运动速度、平均路径速度、精子头侧摆幅度、精子平均鞭打频率呈显著正相关(P0.05),与运动直线性、运动摆动性、运动前向性等参数无显著相关性;大菱鲆精子运动特性受pH影响显著,精液pH与平均曲线运动速度、平均直线运动速度、平均路径速度、精子头侧摆幅度、精子平均鞭打频率呈显著正相关(P0.05),而与运动直线性、运动摆动性、运动前向性等参数无显著相关性。同时还发现,精子活化率高、寿命长的大菱鲆精液pH偏弱碱性(pH=8.0),即大菱鲆精子适宜在弱碱性环境中活动。除此之外,向激活海水中加入梯度甘油(0.1、1、10、100、500、1 000 mmol/L),发现可以显著提高大菱鲆精子寿命,其中甘油浓度为100 mmol/L时,精子寿命延长至15.17 min±0.29 min,推测甘油在精子激活后可能被精子吸收并氧化分解提供能量。     

盐度对拟穴青蟹幼蟹存活、生长和Na+/K+-ATP 酶活性的影响

研究了盐度(6、13、20、27和33)对拟穴青蟹(Scylla paramamosain)幼蟹生长发育和Na+/K+-ATP酶活性的影响。结果表明,盐度对拟穴青蟹幼蟹甲宽和体质量特定生长率、C3蜕壳间期、甲宽增量(C1至C2和C2至C3)及Na+/K+-ATP酶活性有显著影响(P<0.05),但对幼蟹存活率、C2蜕壳间期及C3至C4甲宽增量无显著影响(P>0.05)。盐度13处理组特定生长率最高、蜕壳间期最短,盐度6处理组特定生长率最低,但与盐度20、27和33处理组无显著差异(P>0.05),而盐度33处理组蜕壳间期最长;第一次蜕壳后盐度20处理组甲宽增量最大,后两次蜕壳盐度13处理组均是最大;盐度处理0.5、4、7和11 d时,Na+/K+-ATP酶活性分别表现为盐度6>13>20>27>33、6>13>27>20>33、6>13>20>27>33和6>13>33>20>27的趋势,低盐环境下Na+/K+-ATP酶活性的升高有助于拟穴青蟹幼蟹对低渗环境的适应。     

Predicting oxygen in small estuaries of the Baltic Sea: a comparative approach

Coastal eutrophication, manifested as hypoxia and anoxia, is a global problem. Only a few empirical models, however, exist to predict bottom oxygen concentration and percentage saturation from nutrient load or morphometry in coastal waters, which are successfully used to predict phytoplankton biomass both in lakes and in estuaries. Furthermore, hardly any empirical models exist to predict bottom oxygen from land-use. A data set was compiled for 19 estuaries in the northern Baltic Sea, which included oxygen concentration and percentage saturation, water chemistry, estuary morphometry, and land-use characteristics. In regression analyses, bottom oxygen was predicted both as a function of the percentage of watershed under agriculture and of mean depth. These models accounted for ca. 55% of the variation in oxygen. Additionally, oxygen was linked to fetch (diameter of the area in the direction of the prevailing wind), which accounted for 30% of the variation in oxygen. This suggests that shallow Finnish estuaries are wind-sensitive. In ‘pits’ (sub-thermocline waters of deep basins), near-bottom total nitrogen strongly correlated with oxygen percentage saturation (R²=0.81). Neither chlorophyll a, total phosphorus nor nutrient loading explained oxygen variation in entire estuaries or in ‘pits’, probably mainly due to annual sedimentation/sediment–water flux dynamics. On the basis of the results of cross-validation, the models have general applicability among Finnish estuaries.     

两种体色三疣梭子蟹线粒体DNA 部分片段序列的比较分析

三疣梭子蟹(Portunus trituberculatus)作为重要的海洋经济动物,其常见体色(头胸甲)为茶绿色。近年来在我国沿海海域海捕三疣梭子蟹中开始出现体色为紫色的一类梭子蟹,除体色不同外,二者表型特征并无显著差异。对两种体色三疣梭子蟹不同个体的线粒体COI和16S rRNA基因进行了序列比对分析以判定二者之间的亲缘关系。结果发现COI和16S rRNA基因在两种体色三疣梭子蟹群体中的核苷酸序列一致性分别为99.87%和99.88%,表明紫色三疣梭子蟹并未发生亚种的分化,即紫色和茶绿色群体属于同一个种。并利用GenBank数据库检索了梭子蟹科其他15种海产蟹的16S rRNA序列,进行了序列同源性比对分析和分子系统学方面的探讨,为梭子蟹种属分类学研究提供分子依据。     

渗透压、pH、葡萄糖及离子溶液对夏牙鲆精子激活及运动特征的影响

作者通过渗透压计分别测定各溶液的渗透压值,通过CASA精子分析系统,测定精子运动参数,分析、比较了渗透压、pH、葡萄糖及离子溶液对夏牙鲆(Paralichthys dentatus)精子激活及运动特征的影响。结果表明:夏牙鲆精子激活的渗透压范围为581~1260 mosm/kg;在特定的渗透压范围内(单位为mosm/kg),A组(581~650),B组(762~877),C组(931~1060),D组(1117~1260)中,与NaCl和KCl溶液相比较,葡萄糖溶液可以显著提高夏牙鲆精子激活后的运动率;在相对高渗条件下(1091~1180),经Ca Cl2400、EGTA400和无Ca~(2+)人工海水激活的夏牙鲆精子运动率存在显著差异;且夏牙鲆精子最适的激活p H范围是7~7.5。综上,激活剂的渗透压决定了夏牙鲆精子能否激活并显著影响了激活后精子的运动率,同时葡萄糖、外源Ca2+及p H均在一定程度上影响了精子的运动率。     

Experiments on the ocean sequestration of fossil fuel CO2: pH measurements and hydrate formation

We have carried out a series of in situ experiments to investigate the formation of a CO₂ hydrate (CO₂:5.75 H₂O) for the purpose of evaluating scenarios for ocean fossil fuel CO₂ disposal with a solid hydrate as the sequestered form. The experiments were carried out with a remotely operated vehicle in Monterey Bay at a depth of 619 m. pH measurements made in close proximity to the hydrate–seawater interface showed a wide range of values, depending upon the method of injection and the surface area of the hydrate formed. Rapid injection of liquid CO₂ into an inverted beaker to form a flocculant mass of hydrate resulted in pH initially as low as 4.5 within a few centimeters of the interface, decaying slowly over 1–2 h towards normal seawater values as dense CO₂ rich brine drained from the hydrate mass. In a second experiment, slower injection of the liquid CO₂ to produce a simple two-layer system with a near planar interface of liquid CO₂ with a thin hydrate film yielded pH values indistinguishable from the in situ ocean background level of 7.6. Both field and laboratory results now show that the dissolution rate of a mass of CO₂ hydrate in seawater is slow but finite.     

考洲洋牡蛎养殖海域海-气界面CO2交换通量的时空变化

根据2018年7月、11月和2019年1月、4月对广东考洲洋牡蛎养殖海域进行4个季节调查获得的p H、溶解无机碳(DIC)、水温、盐度、溶解氧(DO)及叶绿素a(Chla)等数据,估算该区域表层海水溶解无机碳体系各分量的浓度、初级生产力(PP)、表层海水CO₂分压[p(CO₂)]和海-气界面CO₂交换通量(FCO₂),分析牡蛎养殖活动对养殖区碳循环的影响。结果表明:牡蛎养殖区表层海水中Chl a、DIC、HCO₃^–和PP显著低于非养殖区;养殖淡季表层海水中pH、DO、DIC、HCO₃^–、和CO₃^2–显著大于养殖旺季,养殖旺季的p(CO₂)和FCO₂显著大于养殖淡季。牡蛎养殖区表层海水夏季、秋季、冬季和春季的海-气界面CO₂交换通量FCO₂平均值分别是(42.04±9.56)、(276...     

一种新型电镀法制备的Ir/Ir(OH)x pH电极及其在加州纽波特港海域的应用研究

Resulting from the rising levels of atmospheric carbon, ocean acidification has become a global problem. It has significant impacts on the development, survival, growth and physiology of marine organisms. Therefore, a highprecision sensor is urgently needed to measure the pH of sea-water. Iridium wire with a diameter of 0.25 mm is used as the substrate, and an Ir/Ir(OH)_x pH electrode is prepared by a one-step electrochemical method in a Li OH solution at the room temperature. A scanning electron microscope(SEM) observation reveals that it is coated with nanoscale particles. In laboratory tests, the electrode exhibits a very promising pH response, with an ideal Nernst slope(56.14–59.52), fast response, good stability and long life-span in tested pH buffer solutions. For a sea trial,four pH electrodes and one Ag/Ag Cl reference electrode are integrated with a self-made chemical sensor, and a profile detection of nearly 70 m is implemented near Newport Harbor, California on August 3, 2015. The results reflect that the pH value measured by the sensor is very close to the data given by Sea-Bird 911 plus CTD, with a difference value ranging from 0.000 075 to 0.064 719. And the sensor shows a better data matching degree in 0–40m water depth. In addition, the high precision and accuracy of the sensor make it possible to use in the ocean observation field.     

海底环境促使C4, C5异构体分异因素的研究

模拟海底微环境,研究促使C4,C5异构体分异的因素。39 d后,i-C4/n-C4变化率:灭菌固液混合组为1.67%,灭菌固液分离组为7.96%,未灭菌固液混合组为2.54%,未灭菌固液分离组为14.21%;i-C5/n-C5变化率:灭菌固液混合组为1.19%,灭菌固液分离组为8.18%,未灭菌固液混合组为2.26%,未灭菌固液分离组为10.19%。表明海底环境对烷烃组分产生复杂的溶解、吸附和生物降解作用,使异构体产生分异效应;碳原子数增加,综合作用相对减弱;同碳原子数,对正构烷烃的作用效果更显著。碳同位素分析发现:i-C4,n-C4,i-C5,n-C5的δ13C均有微弱的变重趋势,CO2的δ13C则发生明显的变轻趋势,并且未灭菌组比灭菌组变化大。表明海底环境使烷烃组分发生了碳同位素分馏,生物降解作用显著。     

长短期记忆神经网络在叶绿素a浓度预测中的应用

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