Dissociation constants of protonated methionine species in seawater media

The dissociation constants (pK₁ and pK₂) for methionine have been measured in artificial seawater as a function of salinity (S = 5 to 35) and temperature (5 to 45 °C). The seawater pK₂ values were lower than the values in NaCl at the same ionic strength while the pK₁ values in seawater were lower only at S = 35. In an attempt to understand these differences, we have made measurements of the constants in Na–Mg–Cl solutions at 25 °C. The measured values have been used to determine the formation of Mg²⁺ complexes and Pitzer interaction parameters for Mg²⁺ with methionine. The seawater model with the interaction parameters accounts for the differences between the value of pK₁ and pK₂ between NaCl and seawater. This study demonstrates that it is important to consider all of the ionic interactions in natural waters when examining the dissociation of organic acids.     

Dissociation constants of protonated cysteine species in seawater media

The dissociation constants (pK₁, pK₂ and pK₃) for cysteine have been measured in seawater as a function of temperature (5 to 45 °C) and salinity (S = 5 to 35). The seawater values were lower than the values in NaCl at the same ionic strength. In an attempt to understand these differences, we have made measurements of the constants in Na–Mg–Cl solutions at 25 °C. The measured values have been compared to those calculated from the Pitzer ionic interaction model. The lower values of pK₃ in the Na–Mg–Cl solutions have been attributed to the formation of Mg²⁺ complexes with Cys²⁻ anions

Mg²⁺ + Cys²⁻ = MgCys

The stability constants have been fitted to

after corrections are made for the interaction of Mg²⁺ with H⁺.The pK₁ seawater measurements indicate that H₃Cys⁺ interacts with SO₄²⁻. The Pitzer parameters β⁰(H₃CysSO₄), β¹(H₃CysSO₄) and C(H₃CysSO₄) have been determined for this interaction. The formation of CaCys as well as MgCys are needed to account for the values of pK₂ and pK₃ in seawater.The consideration of the formation of MgCys and CaCys in seawater yields model calculated values of pK₁, pK₂ and pK₃ that agree with the measured values to within the experimental error of the measurements. This study shows that it is important to consider all of the ionic interactions in natural waters when examining the dissociation of organic acids.     

Association constant of fluoride and hydrogen ions in seawater

A method is described to obtain the association constant of fluoride and hydrogen ions and its influence on the total and free ion concentration. The following equation was found with an error of ± 0.05 for the salinity and temperature range 10–40 and 9–33°C, respectively In β_HF = -874/T - 0.111S^0.6 + 9.68 where T is the absolute temperature and S the salinity.     

The pH measurements in seawater on the NBS scale

A new standardization method for glass electrodes is proposed for pH measurements on the NBS scale. An expression is obtained to evaluate the apparent activity coefficient of hydrogen ions as a function of salinity and temperature, from determinations obtained by Mehrbach et al., 1973 (Limnol. Oceanogr., 18: 897–907). This expression must be used to estimate systematic errors produced by variations of residual liquid-junction potential by estimating the apparent activity coefficient of hydrogen ions. In this way, values of pH obtained in oceanographical cruises can be standardized in order to determine and compare different parameters of the CO₂ system.Some experiments to study the variation of pH with temperature are carried out to compare the different series of acid constants used at present. A simple and precise polynomial equation is also obtained to determine the variation of pH with temperature.     

Vertical distribution of the hydrogen sulphide sources in the Black Sea

Data on the diffusion coefficientK _zand the concentration of H₂S in the Black Sea are used to compute the depth distribution of the vertical flux, and the intensity of the H₂S sources and sinks. On average, the total production of H₂S in the Black Sea reaches 37×10⁶ t/year. The main bulk of H₂S is produced not at the bottom, but in the layer of 450–1300 m. Destruction of H₂S prevails above the 400 m layer. Dissolved oxygen penetrating the H₂S zone can oxidize only half of the hydrogen sulphide produced in the sea.Translated by Mikhail M. Trufanov.     

Photochemical production of molecular hydrogen in lake water and coastal seawater

Samples of lake water and coastal seawater from Nova Scotia, Canada, were irradiated with natural or artificial sunlight to investigate the potential for photochemical hydrogen production. Hydrogen photo-production was observed in all natural water samples. Rates of hydrogen formation were highest in coloured lake water (range: 98–163 pmol L^− 1h^− 1) and lower in seawater (range: 19–45 pmol L^− 1 h ^− 1). Dilutions of the most highly coloured lake sample (Kejimkujik Lake) showed a positive linear relationship between H₂ production rates and CDOM concentration. Photo-production rates normalised to UV absorption coefficients at 350 nm indicated that the photochemical efficiency of hydrogen formation varied between samples, perhaps due to differences in the CDOM composition. Photochemical hydrogen formation was also seen in solutions of syringic acid and acetaldehyde: two low-molecular-weight carbonyl compounds found in natural waters. Photochemistry may therefore offer least a partial explanation for the persistently high levels of hydrogen observed in the low-latitude surface ocean.     

Temperature coefficient of seawater pH as a function of temperature,pH, DIC and salinity

pH is a measure of the hydrogen ion activity in a solution, which is a function of temperature. Under normal seawater conditions, it is well constrained. Nowadays, with an increasing interest in complex environments(e.g.,sea ice), a better understanding of the temperature change on pH under extreme conditions is needed. The objective of this paper was to investigate the temperature coefficient of the seawater pH(?pH/?T) over a wide range of temperature, pH, dissolved inorganic carbon(DIC) and sa...     

The use of buffers to measure the pH of seawater

The pH of seawater can be measured in the field using potentiometric and spectrophotometric methods. The use of pH standards or buffers is an important aspect of the calibration of both methods in a laboratory on a common concentration scale. The buffers can also be used to monitor the performance of pH meter and spectrophotometer during a cruise. A procedure is described for the determination of the pH of seawater, where the proton concentration is expressed as moles kg-H₂O⁻¹ using seawater buffers. The buffers are prepared in synthetic seawater in the laboratory by the methods outlined by Bates and coworkers. We have prepared four buffers (Bis, Tris, Morpholine and 2-Aminopyridine) that cover a pH range from 6.8 to 8.8. The emf values of the buffers were measured with a H₂, Pt/AgCl, Ag electrode system after their preparation and bottling for use at sea. The measured emf values were found to be in good agreement (±0.05 mV) with the original measurements of Bates and coworkers from 0 to 45°C. The measured pH of these buffers are in good agreement (±0.001 pH units) with the values calculated from the equations of Dickson on the total pH scale based on Bates et al. Studies are underway to access the long term stability of these buffers. We have also used these buffers to calibrate systems used to make potentiometric and spectrophotometric measurements of pH on seawater relative to the H₂, Pt/Ag, AgCl electrode from 5 to 45°C.     

Kinetics of iron(II) oxidation in seawater of various pH

The rate of iron(II) oxidation in North Sea water of pH 5.5–10 in the range 10–25°C has been studied. The oxygenation rate depends linearly on the iron(II) and dissolved oxygen concentrations. The second-order dependence on [OH^?], found by several investigators for synthetic solutions, was confirmed in seawater, but only for pOH > 6.9. For pOH < 5.9 the rate appeared to be independent of the pOH. In the intermediate range, pOH 5.9–6.9, corresponding to the natural pH of seawater, a first-order dependence on the pOH is obeyed. The important discrepancy in the literature between the second-order rate constant for NaCHO₃ solutions and for seawater can be attributed predominantly to the incorrect assumption of a second-order pOH dependence in natural seawater. The results can be useful, for example, in predicting the effect of dumping acidic iron waste from the titanium-dioxide industry into the ocean.     

不同海水盐度和pH对文昌鱼精子寿命的影响

本文首次报道了正常文昌鱼精子的运动方式和寿命,以及海水盐度和pH值对其活动和寿命的影响。     

养殖海水初始pH值对硝化作用影响的研究

本工作进行了一系列实验,研究pH对养殖海水硝化作用的影响.结果表明,水体硝化作用受到pH的影响,硝化作用适宜的水体pH范围为弱碱性.在水体初始pH值为8.10时,硝化的速率为2.416μmol/(d·dm3),水体的硝化率达到最大.硝化作用基本符合一级反应的动力学模式.     

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.     

The hydrogen sulphide boundary in the Black Sea in the 1920s and 1980s

Maps of the boundary topography for anaerobic waters in the Black Sea are plotted for the summers of the 1920s and 1980s. The mean depths of the H₂S boundary for this period are determined. It is shown that the variation in the distribution and average location of the hydrogen sulphide zone has remained constant for the last 60 years.Translated by Mikhail M. Trufanov.     

Mathematical model for the ecosystem of the Black Sea hydrogen sulphide zone

A model for the ecosystem of the Black Sea hydrogen sulphide zone is suggested which incorporates seven components, namely, the concentrations of hydrogen sulphide, oxygen, dead organic matter, thiosulphates, molecular sulphur, and the biomass of sulphate-reducing and thiobacteria. With the minor terms neglected in the equations governing the system under consideration, the latter was divided into subsystems which allow an approximate calculation of the model components' vertical stationary profiles. The derived components' profiles agree qualitatively with available observations.Translated by V. Puchkin.     

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.     

模拟研究沙海蜇消亡过程中海水pH 变化及对海水酸化的影响

通过室内模拟实验,研究了不同pH、盐度、温度和氮磷比控制条件下沙海蜇(Nemopilema nomurai)消亡过程中水体pH的变化特征及对海水酸化的影响.结果表明,沙海蜇块体分解会造成pH的显著降低,水体出现明显酸化.随着沙海蜇的分解,本底海水组(本底海水+实验用沙海蜇)水体pH呈现先下降,后缓慢回升直至稳定的趋势,并在第2天形成最小值,且水体pH下降0.5～1.3.沙海蜇块体在不同pH、盐度、氮磷比、温度控制条件下分解时,水体pH变化趋势相似,均表现为先下降,达到最小值后再缓慢回升,但不同控制条件下水体pH出现最小值的时间并不一致,从先到后的顺序是温度组(第3天)、pH和盐度组(第4天)及氮磷比组(第5天),这与沙海蜇块体分解速率顺序一致.沙海蜇分解过程中,这4个实验组水体pH下降0.5～1.8,水体发生明显的酸化,这其中海水盐度、pH的变化及温度的降低所导致的沙海蜇消亡过程中海水酸化程度比较严重;因此,在当今海水富营养化及海水温度升高的情况下,沙海蜇的暴发及其消亡会造成海洋生态系统遭受更严重的破坏.     

Acute toxicity of bromochlorinated seawater to selected estuarine species with a comparison to chlorinated seawater toxicity

The acute toxicity of bromochlorinated estuarine water (ca. 20%) was determined for several estuarine organisms. The most sensitive species were oysters (Crassostrea virginica, larvae and juveniles) and copepods (Acartia tonsa) with 48-h LC₅₀'s of 0·10 to 0·21 mg BrCl/litre. Palaemonetes pugio was most tolerant with a 96-h LC₅₀ of 0·70 mg BrCl/litre. The fish species tested (Menidia menidia, Brevoortia tyrannus and Leiostomus xanthurus) all had a 96-h LC₅₀ of 0·21–0·23 mg BrCl/litre.The BrCl toxicity data are compared with Cl₂ toxicity data for the same species. When the LC₅₀'s are expressed as equivalents per litre, BrCl is found to be two to four times less toxic than Cl₂. The ranking of species in terms of sensitivity is the same for both disinfectants.Some data are provided concerning the decay rates of BrCl and Cl₂ in estuarine water. BrCl was found to decay more rapidly than Cl₂ at higher ammonia levels (0·25 mg NH₄-N/litre). The question of chemical speciation is discussed with particular reference to the differential toxicities.     

自研高精度pH传感器的标定、校正方法及其在海水原位观测中的应用

电化学方法是测量海水pH值的主要方法之一。针对自主研发的基于铱金属及其氧化物电极的pH传感器,建立了海水环境下仪器标定和数据校正的方法,并在近岸和大洋环境中进行了原位测试的应用。仪器标定包括：(1)依照海水pH分析的标度要求选取适当的标定缓冲试剂;(2)以标准海水替代常用的2-氨基吡啶(AMP)溶液制备标定缓冲体系。数据校正主要包括温度背景校正及误差校正。海区原位测试应用以及与其他同类仪器对比表明,标定体系差异带来的误差可达1.00 pH单位,数据校正可提升测试精度0.10～3.00 pH单位不等。仪器的标定与数据校正方法能有效提高该自研pH传感器的测量精度。     

A preliminary methods comparison for measurement of dissolved organic nitrogen in seawater

Routine determination of dissolved organic nitrogen (DON) is performed in numerous laboratories around the world using one of three families of methods: UV oxidation (UV), persulfate oxidation (PO), or high temperature combustion (HTC). Essentially all routine methods measure total dissolved nitrogen (TDN) and calculate DON by subtracting the dissolved inorganic nitrogen (DIN). While there is currently no strong suggestion that any of these methods is inadequate, there are continuing suspicions of slight inaccuracy by UV methods.This is a report of a broad community methods comparison where 29 sets (7 UV, 13 PO, and 9 HTC) of TDN analyses were performed on five samples with varying TDN and DIN concentrations. Analyses were done in a “blind” procedure with results sent to the first author. With editing out one set of extreme outliers (representing 5 out of 145 ampoules analyzed), the community comparability for analyzing the TDN samples was in the 8–28% range (coefficient of variation representing one standard deviation for the five individual samples by 28 analyses). When DIN concentrations were subtracted uniformly (single DIN value for each sample), the comparability was obviously worse (19–46% cv). This comparison represents a larger and more diverse set of analyses, but the overall comparability is only marginally better than that of the Seattle workshop of a decade ago. Grouping methods, little difference was seen other than inconclusive evidence that the UV methods gave TDN values for several of the samples higher than HTC methods. Since there was much scatter for each of the groups of methods and for all analyses when grouped, it is thought that more uniformity in procedures is probably needed. An important unplanned observation is that variability in DIN analyses (used in determining the final analyte in most UV and PO methods) is essentially as large as the variability in the TDN analyses.This exercise should not be viewed as a qualification exercise for the analysts, but should instead be considered a broad preliminary test of the comparison of the families of methods being used in various laboratories around the world. Based on many independent analyses here, none of the routinely used methods appears to be grossly inaccurate, thus, most routine TDN analyses being reported in the literature are apparently accurate. However, it is not reassuring that the ability of the international community to determine DON in deep oceanic waters continues to be poor. It is suggested that as an outgrowth of this paper, analysts using UV and PO methods experiment and look more carefully at the completeness of DIN conversion to the final analyte and also at the accuracy of their analysis of the final analyte. HTC methods appear to be relatively easy and convenient and have potential for routine adoption. Several of the authors of this paper are currently working together on an interlaboratory comparison on HTC methodology.