Determination of alkalinities of estuarine waters by a two-point potentiometric titration

Gran plots of titrations of seawater with acid are straight lines after protonation of all weak acids when ion-pairing is taken into account. This property is used to calibrate the pH electrode and to determine the endpoint of what is essentially a two-point alkalinity titration of the sample. First the initial sample pH is measured; then a standard addition of acid is made giving a pH near 3.2 (pH₁); a further acid addition is made giving a pH near 2 (pH₂). The slope of the electrode response and the total alkalinity are calculated from pH₂ and pH₁. The advantages of this method are that no separate calibrations are necessary: no corrections for variations in activity coefficients are needed because pH values are obtained on the seawater pH scale; and the instruments used for the determinations are very simple. The standard deviation of the alkalinity determination of seawater by the proposed technique was − 0.10%.     

Rapid, high-precision potentiometric titration of alkalinity in ocean and sediment pore waters

A system for rapid, high precision potentiometric determination of alkalinity in sea water and sediment pore water is presented. Two titration units were used: a 40 ml unit for seawater and a small volume unit for sediment pore water. Titration time was normally less than 10 minutes per sample, including sample exchange. With a 40 ml sample volume, the relative standard deviation of the alkalinity obtained in the laboratory was 0.05% and at sea 0.1 %. The small-volume system (0.5–1.5 ml) gave a precision of 0.07%. Five titration points, in two groups after the second equivalence point, were used to evaluate the equivalence volume. Results from equilibrium calculations and computer simulated alkalinity titrations show that it was possible to use a non-modified Gran function [(V₀ +v)^*10^(E/Z)] and still achieve good accuracy and precision.     

Calibration of a chalcogenide glass membrane ion-selective electrode for the determination of free Fe in seawater: I. Measurements in UV photooxidised seawater

Calibration of a chalcogenide glass membrane, Fe(III)ISE [Fe_2.5(Ge₂₈Sb₁₂Se₆₀)_97.5], in buffered saline media has been undertaken in order to assess the suitability of this ISE for seawater analyses. The electrode slopes in saline citrate and salicylate buffers were 26.3 and 28.2 mV/decade, respectively, for Fe³⁺ concentrations ranging from 10⁻¹⁰ M to less than 10⁻²⁵ M Fe³⁺. The calibration lines in the citrate and salicylate buffers were essentially collinear with the response in unbuffered chloride-free standards containing >10⁻⁵ M Fe³⁺, demonstrating that the response of the FeISE is unaffected by chloride ions. A mechanism involving a combination of charge transfer and ion-exchange of Fe(III), at the electrode diffusion layer, can be used to explain the ≈30 mV/decade slope of the FeISE. The response of the FeISE in UV photooxidised seawater containing 8 nM total Fe was measured as the pH was changed from 8.27 to 3.51. The slope of the response was 24.2 mV/decade [Fe³⁺] calculated as a function of pH using Fe(III) hydrolysis constants for seawater. Moreover, the response was essentially collinear with that in citrate buffers and in unbuffered solutions containing >10⁻⁵ M Fe³⁺ and the slope for the combined data was 26.2 mV/decade. This study was restricted to organic-free seawater because the certainty in Fe(III)–ligand stability constants is insufficient to warrant the selection of an ideal calibration buffer system, and there is evidence that powerful chelating ligands (e.g., EDTA along with humic and fulvic acids) may alter the response of the Fe(III)ISE. The Fe dissolution rate of the FeISE in UV photooxidised seawater was found to be 1.6×10⁻² nmol Fe/min, as measured by cathodic stripping voltammetry (CSV). This would contaminate a 100-ml sample by 0.8–1.6 nM Fe over a typical measurement period of 5–10 min obtained using a stability criterion of 0.5 mV/min. Various methods are proposed for reducing the level of contamination in open ocean samples that contain sub-nanomolar concentrations of iron. The FeISE has the potential to detect free Fe³⁺ at concentrations typically found in natural seawater.     

End point and equivalence point: a tribute to John Lyman

Lyman's 30-year-old seawater titration is sufficiently precise to reveal a 4 micromolar discrepancy (theoretically supported) between observed end point and zero-alkalinity equivalence point. Accurate measure of alkalinity requires correction for the difference, either by assuming the constancy of relative proportions and multiplying the end-point alkalinity by 1.002, or by careful fitting of data far from the end point.     

Dissociation of hydrogen sulphide in seawater and comparison of pH scales

The protonization constant of HS^? (K₁₂) has been determined potentiometrically (glass electrode) at atmospheric pressure in synthetic seawater in the salinity range 2.5–40‰ at 5 and 25°C and in NaCl solutions in the formal ionic strength of 0.1–0.8 M at 5 and 25°C. The difference between synthetic seawater and an NaCl solution with the same formal ionic strength can be explained in terms of the complexation of H⁺ by sulphate in seawater. These results can be used to compare the pH scales suggested by Hansson (1973c) and Bates (1975). Furthermore, comparison between the present values of K₁₂ and those of Goldhaber and Kaplan (1975) makes it possible to compare the conventional pH scale with Hansson's titration pH scale. The conditional protonization constant of HS^? in seawater of different salinities can be used to modify the Gran plots (Hansson and Jagner, 1973) for alkalinity measurements in anoxic seawater. Ion-pair formation between HS^? and Mg²⁺ or Ca²⁺ seems to be very weak.     

Alkalinity titration in seawater: How accurately can the data be fitted by an equilibrium model?

Displaying “calculated minus observed” data for precise titrations of seawater with strong acid permits direct evaluation of important parameters and detection of systematic errors.At least two data sets from the GEOSECS (Geochemical Ocean Sections) program fit an equilibrium model (which includes carbonate, borate, sulfate, silicate, fluoride, and phosphate) within the most stringent experimental error, less than 2 μmol kg⁻¹. The effect of various parameters on the fit of calculated to observed values depends strongly on pH. Although standard potential E₀, total alkalinity A_t, total carbonate C_t, and first acidity constant of carbon dioxide pK₁ are nearly independent, and can be determined for each data set, other parameters are strongly correlated. Within such groups, all but one parameter must be determined from data other than the titration curve.Adding an acid-base pair to the theoretical model (e.g. C_x=20 μmol kg⁻¹, pK_x=6.2) produces a deviation approaching 20 μmol kg⁻¹ at constant C_t; however, adjustment of C_t by about −18 μmol kg⁻¹ to produce a good fit leaves only ± 1.5 μmol kg⁻¹ residual deviation from the reference values. Thus, at current standards of precision, an unidentified weak acid cannot be distinguished from carbonate purely on the basis of the titration curve shape.There are few full sets of numerical data published, and most show larger systematic errors (3–12 μmol l⁻¹) than the above; one well-defined source is experiments performed in unsealed vessels. Total carbonate can be explicitly obtained as a function of pH by a rearrangement of the titration curve equation; this can reveal a systematic decrease in C_t in the pH range 5–6, as a result of CO₂ gas loss from the titration vessel. Attempts to compensate for this by adjustment of A_t, C_t, or pK₁ produce deviations which mimic those produced by an additional acid-base pair.Changing from the free H⁺ scale (for which [HSO₄⁻] and [HF] are explicit terms in the alkalinity) to the seawater scale (SWS) (where those terms are part of a constant factor multiplying [H⁺]) requires modification of the titration curve equation as well as adjustment of acidity constants. Even with this change, however, omission of pH-dependent terms in [HSO₄⁻] and [HF] produces small systematic errors at low pH.Shifts in liquid junction potential also introduce small systematic errors, but are significant only at pH <3. High-pH errors due to response of the glass electrode to Na⁺ as well as H⁺ can be adequately compensated to pH 9.5 by a linear selectivity expression.     

Potentiometric determination of calcium and magnesium in seawater

Methods are described for the complexometric determination of calcium and magnesium in seawater, using an amalgamated silver electrode for end-point detection. In the presence of a small amount of mercury(II)-chelonate, the amalgamated silver electrode serves as a pM indicator during the complexometric titration, the Hg complex being stronger than Ca, Mg and Sr complexes. Calcium is determined by titration with EGTA, calcium+magnesium+strontium by titration with EDTA and magnesium is obtained by difference. Average values of 0.02120 (standard deviation 0.00004) for Ca:Cl‰ and 0.06671 (standard deviation 0.00014) for Mg:Cl‰ were obtained for samples from tropical North Atlantic Ocean.     

用Ag2S电极电位滴定法测定海水氯度

本文以Ag_2S银离子电极为指示电极,第二种离子选择电极为参比电极组成无液接测量系统,对海水中高含量氯的测定进行了研究。试验表朋,以氟电极或玻璃电极作参比电极,在酸性溶液中,电位突跃约为140mV,终点明显,尤其是氟电极作参比电极,电位较稳定。证明了在酸性溶液中,可以不加有机试剂直接测定海水中高含量氯。     

The calculation of carbonate ion concentration from total CO2 and titration alkalinity

A direct method involving a single iteration (a quadratic equation solved twice) is given for the calculation of carbonate ion concentration from total CO₂ and titration alkalinity. The simplified calculation should allow wider use of existing total CO₂ and titration alkalinity data.     

Characterization of multiple functional groups on kaolinite

Multiple proton functional group conditional binding constants (K′_i) and their concentrations (C_i) are determined from detailed acid/base titration data. The C-K′ information is obtained for kaolinite by assuming that the distribution can be approximated by cumulative independent mono protic groups. Linear programming optimization techniques are used to Fit the data. In addition, the electrode calibration is optimized in the data fit. This adjustment is important for high and low pHs. Discrete concentration dependent pXs of about 3.4, 4.5, 6.7 and 9.8 are determined for a reference kaolinite. These correspond reasonably well to designations made by Wehrli et al. (1990, Aquatic Sciences, Vol. 52, pp. 1–31 ) to A10H2 and AlOH proton reactions at edge and surface sites and to silanol exchange. There is an ionic strength effect for one site. Long and short reaction times and reversibility affect the results.     

RESEARCH ON THE DETERMINATION OF Pb, Cd, Cu AND Zn IN SEAWATER BY STRIPPING VOLTAMMETRY

In this paper, a comparison viral made between the two results of determining Pb, Cd, Cu and Zn in seawater by direct current (tripping voltammetry (DCS) with rotating glass carbon electrode and by differential pulse stripping voltammetry (DPS) with hanging mercury drop electrode (HMDE). By DCS, the range of linear calibration curves obtained was 4×10-3 M-2×10-7M for Cu, Zn and Cd, and 4× 10-9M-2×10-3M for Pb. By using DPS, the range of linear calibration curve was as follows: Cu 0.65-1.9 ppb; Pb 1.0-10 ppb; Zn 0.65-2.0 ppb; Cd 0.02-0.14 ppb. It was found that DCS could be used for determining Pb, Cu, Zn in coastal waters, but it is necessary to add gallium ion to it to eliminate the interference of Cu-Zn inter-metallic compound for determining Zn. The DPS is better for determinig Cd.     

Coulometric total carbon dioxide analysis for marine studies: maximizing the performance of an automated gas extraction system and coulometric detector

A global survey of the distribution of dissolved CO₂ taking advantage of sampling opportunities provided by the World Ocean Circulation Experiment: World Hydrographic Program (WOCE-WHP) is being carried out through 1995. Goals include the measurement of oceanic inorganic carbon transport and the development of a data base from which future fossil-fuel CO₂ build-up can be monitored. The analytical method selected for total carbon dioxide (C_T) is gas extraction of acidified seawater with coulometric titration of the acid formed by the resultant carbon dioxide and monoethanolamine. To combine high accuracy and precision (± 1.5 μmol/kg for C_T ≥ 2000 μmol/kg) with a high rate of analysis, we have modified an automated single-parameter system. Following prototype development between 1987 and 1990, an instrument emerged with the acronym Somma standing for single-operator multiparameter metabolic analyzer. Improved functional and operating procedures have integrated electronic calibration, CO₂ gas calibration, and sample analysis with automated pressure, temperature, and conductivity (salinity) sensing into a single convenient transportable package.     

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。     

Indication of thiols in black sea deep water

Potentiometric titrations of deep Black Sea water give reasonably precise values of sulphide in the concentration range 30–300 μmol l⁻¹ and a strong indication of thiols in the concentration range 10–30 μmol l⁻¹. Organic analysis of Black Sea water should therefore include the search for compounds containing SH groups. A simple stoichiometric model indicates that sulphur-containing proteins might be the main source of thiols after hydrolysis and deamination. The alkalinity and total sulphide are simply related by A_t = 3287 ± 30 + (3.84 ± 0.10) [H₂ S]_t μmol kg⁻¹. The slope of 3.84 instead of the stoichiometric slope of 2.31 indicates a lack of reduced sulphate in the form of hydrogen sulphide.     

The international at-sea intercomparison of fCO2 systems during the R/V Meteor Cruise 36/1 in the North Atlantic Ocean

The ‘International Intercomparison Exercise of fCO₂ Systems’ was carried out in 1996 during the R/V Meteor Cruise 36/1 from Bermuda/UK to Gran Canaria/Spain. Nine groups from six countries (Australia, Denmark, France, Germany, Japan, USA) participated in this exercise, bringing together 15 participants with seven underway fugacity of carbon dioxide (fCO₂) systems, one discrete fCO₂ system, and two underway pH systems, as well as systems for discrete measurement of total alkalinity and total dissolved inorganic carbon. Here, we compare surface seawater fCO₂ measured synchronously by all participating instruments. A common infrastructure (seawater and calibration gas supply), different quality checks (performance of calibration procedures for CO₂, temperature measurements) and a common procedure for calculation of final fCO₂ were provided to reduce the largest possible amount of controllable sources of error. The results show that under such conditions underway measurements of the fCO₂ in surface seawater and overlying air can be made to a high degree of agreement (±1 μatm) with a variety of possible equilibrator and system designs. Also, discrete fCO₂ measurements can be made in good agreement (±3 μatm) with underway fCO₂ data sets. However, even well-designed systems, which are operated without any obvious sign of malfunction, can show significant differences of the order of 10 μatm. Based on our results, no “best choice” for the type of the equilibrator nor specifics on its dimensions and flow rates of seawater and air can be made in regard to the achievable accuracy of the fCO₂ system. Measurements of equilibrator temperature do not seem to be made with the required accuracy resulting in significant errors in fCO₂ results. Calculation of fCO₂ from high-quality total dissolved inorganic carbon (C_T) and total alkalinity (A_T) measurements does not yield results comparable in accuracy and precision to fCO₂ measurements.     

Chemical speciation of copper and zinc in surface waters of the western Black Sea

The chemical speciation of Cu and Zn was investigated by voltammetric titration methods in the surface waters (10 m) of the western Black Sea during an Istanbul–Sevastopol cruise conducted in November 1998. Supporting parameters (temperature (T), salinity (S), pH, alkalinity (Alk), suspended particulate matter (SPM) and dissolved and particulate ²³⁴Th) were obtained in order to distinguish hydrographic features against involvement of the metals in biogeochemical processes. In the Turkish continental slope region, the cruise track intersected a narrow vein of colder water originating on the western shelf. The core of this cold water vein was characterised by a relatively low salinity, higher specific alkalinity and higher metal (especially Cu) and metal-binding ligand concentrations.A very large portion of Cu (93–99.8%) and Zn (82–97%) was organically complexed. The degree of complexation was highest in shelf waters and lowest in the central gyre. Titration data for Cu were modelled by two classes of organic binding ligands characterised by (C_L1=3–12 nM, log K₁′=13.1–13.9) and (C_L2=20–70 nM, log K₂′=9.4–11.2). These ligands occurred mainly in the ‘dissolved’ phase, as defined by 0.4-μm filtration. The stronger Cu-binding ligand seemed to be produced in situ in response to Cu concentration, whereas the weaker Cu-binding ligand appeared to be derived from terrestrial sources and/or reducing shelf sediments. Titration results for Zn were generally represented by one class of ligands (C_L1=8–23 nM, log K₁′=9.4–10.2), which were almost uniformly distributed between the ‘dissolved’ (78±8%) and the particulate phase (22±8%). The concentration of these strong Zn-binding ligands showed a very good correlation with SPM (r²=0.64), which improved when the dissolved ligands alone were considered (r²=0.78). It is hypothesised that these ligands were produced in situ by the bacterial breakdown of particulate organic matter.     

The effect of analytical error on the evaluation of the components of the aquatic carbon-dioxide system

A study has been made of the effect of error in the measurement of the determinable parameters of the marine CO₂ system on the calculation of the remaining parameters from equations such as those of Park (1969). This approach can be used either to assess and compare experimental data, or to aid in the choice of suitable combinations of determinable parameters for solving any particular problem. Now that the total alkalinity and total inorganic carbon (C_T) can be determined extremely accurately by titration, a combination of carbonate alkalinity and C_T is the most satisfactory combination for the majority of applications. If, however, P_CO2 is required it should be measured directly.     

The behaviour of a Cu(II) ion selective electrode in seawater; copper consumption capacity and copper determinations

Determinations of copper consumption capacity (CuCs.C) and labile copper concentrations in surface coastal seawater, using a copper ion selective electrode (Cu-ISE) potentiometric method under predominantly diffusive conditions, are reported. For evaluation of the copper concentrations, the points of the endpoint contiguity zone of the CuCs.C titration curve were treated by an ISE multiple standard addition technique. The results were compared with those obtained by means of a Chelex-100 (calcic form) ‘batch’ procedure-potentiometric stripping analysis.The labile copper of the sample was determined at concentrations down to 10.70 nM with an average RSD of 12%, independent of the Cu-ISE employed. For adjacent subsamples, the mean CuCs.C values obtained for El Way seawater were equivalent to 81.05 and 48.00 nM copper, with an RSD of 4 and 7%, and for Isla Santa Maria seawater the value was equivalent to 70.27 nM copper, with an RSD of 7%. The theoretical approach of the electrode diffusive mechanism proposed, which would depend, fundamentally, on the adsorptive, complexing and reducing properties of the dissolved organic matter in the seawater sample, allows simultaneous analytical determination of CuCs.C and labile copper concentration in seawater.     

A new look at the alkalinity of the Sea of Japan

The most important feature of the distribution of the alkalinity and calcium in the Sea of Japan—the increase in the potential alkalinity with depth under the conditions when the waters are supersaturated in relation to calcium carbonate—is considered. It is demonstrated that this fact cannot be accounted for by the reaction of the formation-dissolution of calcium carbonate. A new concept explaining the alkalinity distribution in the sea is proposed. According to it, the biological pump is the basic process responsible for the alkalinity transport from the euphotic layer into the interior of the sea. Photosynthesis is the driving force for this process. The role of the active element transporting the alkalinity is not calcium carbonate, as has been claimed elsewhere, but extracellular polysaccharides (EPSs) produced by phytoplankton. EPSs bind to calcium and other cations to form transparent exopolymer particles (TEPs). The proposed conception makes it possible to explain the following: (a) the vertical flux of calcium carbonate that is independent of the super-saturation—undersaturation state of the ambient water regarding calcium carbonate; (b) the existence of the calcium carbonate flux regardless of the nature of the plankton skeletons; (c) the nonstoichiometric ratio between the alkalinity and calcium fluxes.     

Calibration and evaluation of a carbonate microsensor for studies of the marine inorganic carbon system

Accurate and rapid determination of inorganic carbon constituents in ocean environments is important for understanding the carbon cycle, especially in the context of ocean-acidification research. A microsensor capable of directly measuring carbonate ion (CO₃ ^2–) concentrations would be desirable. In this study, a carbonate microsensor with a polymeric liquid membrane was fabricated, and two calibration methods were used to evaluate its performance. The first method was based on continuous titration. Small increments of HCl were added to seawater or Na₂CO₃ solution to adjust the total alkalinity and pH values and thus obtain a series of carbonate concentrations. The second method used a series of discrete standards. Varying amounts of HCl or NaOH were added to separate seawater aliquots, and the CO₃ ^2– concentration of each standard was calculated from the resulting total alkalinity and total dissolved inorganic carbon. Both methods were found to be adequate for achieving accurate calibration of the CO₃ ^2– sensor, and both are suitable for field work. The discrete standards method, however, is more convenient and may provide a better linear range at low CO₃ ^2– concentrations (detection range: 2–300 μmol/kg) than the continuous titration method in seawater (detection range: 10–250 μmol/kg). This CO₃ ^2– microsensor can be used for 5–7 d and detects changes in carbonate concentration as low as 2 μmol/kg in the inorganic carbon constituents of the environments where marine calcareous organisms grow. The CO₃ ^2– microelectrode was further assessed by applying it to the measurement of pore-water CO₃ ^2– concentration profiles in a marine sediment core.