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1.
Distribution coefficients, iKFe, were measured for sorption of yttrium and the rare earth elements (YREEs) on hydrous ferric oxide (HFO) in 0.5 M NaCl solutions over the pH range 3.9–8.4 (T = 25 °C). An existing, non-electrostatic model [Quinn, K.A., Byrne, R.H., Schijf, J., 2006. Sorption of yttrium and rare earth elements by amorphous ferric hydroxide: influence of pH and ionic strength. Mar. Chem. 99, 128–150] was modified to account for sorption of YREE–chloride complexes, as well as YREE–hydroxide complexes at elevated pH. The extended model, which allows calculation of iKFe as a function of [H+], contains two parameters, SK1 and SK2, to describe the equilibrium between positive, neutral, and negative forms of the hydroxyl functional groups on the HFO surface. In addition, it contains several composite, conditional stability constants, An, that represent YREE bonding to the neutral groups with release of n protons and/or to the negatively charged groups with release of n ? 1 protons.In 0.5 M NaCl solutions, YREE sorption on HFO is weaker and less pH dependent, yielding only 0.7–0.9 protons per YREE cation on average, vs. about 1.5 at low ionic strength. This is due to enhanced deprotonation of the HFO surface (SK1 ~ 0, pSK2 = 6.16), leading to an increase in the proportion of negatively charged groups, which release fewer protons per YREE cation sorbed. On a logarithmic scale, iKFe is a nearly linear function of pH, except at pH > 8 where cumulative sorption of YREE–hydroxide complexes causes it to rise more rapidly, especially for the heavy REEs. Both our own data and prior results from the literature are well described by the extended model, using only three adjustable parameters, A1–A3. The constant A3, representing YREE bonding to the negatively charged groups with release of two protons, shows an excellent linear free-energy relation when plotted against the first YREE hydrolysis constant, β1*. There is no evidence for YREE bonding to the positively charged groups (i.e., A0 = 0).  相似文献   

2.
The biogeochemistry of trivalent iron, manganese, and cobalt in the oceans is dominated by soluble complexes formed with high-affinity organic ligands that are believed to be microbial siderophores or similar biogenic chelating agents. Desferrioxamine B (DFOB), a trihydroxamate siderophore found in both terrestrial and marine environments, has served as a useful model for a large class of microbial siderophores in studies of 1:1 complexes formed with trivalent iron and manganese. However, no data exist concerning DFOB complexes with Co(III), which we hypothesize should be as strong as those with Fe(III) and Mn(III) if the current picture of the ocean biogeochemistry of the three trivalent metals is accurate. We investigated the complexation reaction between DFOB and Co(III) in aqueous solution at seawater pH using base and redox titrations, and then characterized the resulting 1:1 complex Co(III)HDFOB+ using X-ray absorption, resonance Raman spectroscopy, and quantum mechanical structural optimizations. We found that the complex stability constant for Co(III)HDFOB+ (log K [Co(III)HDFOB+] = 37.5 ± 0.4) is in fact five and seven orders of magnitude larger than that for Fe(III)HDFOB+ (log K[Fe(III)HDFOB+] = 32.02) and Mn(III)HDFOB+ (log K[Mn(III)HDFOB+] = 29.9), respectively. Spectroscopic data and the supporting theoretical structural optimizations elucidated the molecular basis for this exceptional stability. Although not definitive, our results nevertheless are consistent with the evolution of siderophores as a response by bacteria to oxygenation, not only because of sharply decreasing concentrations of Fe(III), but also of Co(III).  相似文献   

3.
The results of a potentiometric investigation (by ISE-H+, glass electrode) on the speciation of phytate ion (Phy12−) in an ionic medium simulating the major components (Na+, K+, Ca2+, Mg2+, Cl− and SO42−) of natural seawater, at different salinities and t = 25 °C, are reported. The work was particularly aimed at determining the possible formation of mixed Ca2+–Mg2+–phytate ion pairs, and to establish how including the formation of these mixed species would affect the speciation modeling in seawater media. After testing various speciation models, that considering the formation of the MgCaH3Phy5−, MgCaH4Phy4−, Mg2CaH3Phy3− and Mg2CaH4Phy2− species was accepted, and corresponding stability constants were determined at two salinities (S = 5, 10). A discussion is reported both on the choice of the experimental conditions and on the possibility to extend these results to those typical of real seawater. A detailed procedure is also described to demonstrate that the stability of these species is higher than that statistically predicted. As reported in literature, a parameter, namely log X, has been determined in order to quantify this extra stability for the formation of each mixed species at various salinities. For example, at S = 10, log X113 = 2.67 and log X114 = 1.37 for MgCaH3Phy5− and MgCaH4Phy4− (statistical value is log Xstat = 0.60), and log X213 = 6.11 and log X214 = 2.15 for Mg2CaH3Phy3− and Mg2CaH4Phy2− (log Xstat = 1.43), respectively. Results obtained also showed that the formation of these species may occur even in conditions of low salinity (i.e. low concentration of alkaline earth cations) and low pH (i.e., more protonated ligand).  相似文献   

4.
Iron chemistry in seawater has been extensively studied in the laboratory, mostly in small-volume sample bottles. However, little has been reported about iron wall sorption in these bottles. In this paper, radio-iron 55Fe was used to assess iron wall adsorption, both in terms of capacity, affinity and kinetics. Various bottle materials were tested. Iron sorption increased from polyethylene/polycarbonate to polymethylmetacrylate (PMMA)/high-density polyethylene/polytetrafluoroethylene to glass/quartz, reaching equilibrium in a 25–70 h period. PMMA was studied in more detail: ferric iron (Fe(III)) adsorbed on the walls of the bottles, whereas ferrous iron (Fe(II)) did not. Considering that in seawater the inorganic iron pool mostly consists of ferric iron, the wall will be a factor that needs to be considered in bottle experiments.The present data indicate that for PMMA with specific surface (S)-to-volume (V) ratio S/V, both iron capacity (42 ± 16 × 10− 9 mol/m2 or 1.7 × 10− 9 mol/L recalculated for the S/V-specific PMMA bottles used) and affinity (log KFe'W = 11.0 ± 0.3 m2/mol or 12.4 ± 0.3 L/mol, recalculated for the S/V-specific PMMA bottles used) are of similar magnitude as the iron capacity and -affinity of the natural ligands in the presently used seawater and thus cannot be ignored.Calculation of rate constants for association and dissociation of both Fe'L (iron bound to natural occurring organic ligands) and Fe'W (iron adsorbed on the wall of vessels) suggests that the two iron complexes are also of rather similar kinetics, with rate constants for dissociation in the order of 10 −4–10− 5 L/s and rate constants for association in the order of 108 L/(mol s). This makes that iron wall sorption should be seriously considered in small-volume experiments, both in assessments of shorter-term dynamics and in end-point observations in equilibrium conditions. Therefore, the present data strongly advocate making use of iron mass balances throughout in experiments in smaller volume set-ups on marine iron (bio) chemistry.  相似文献   

5.
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6.
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7.
The apparent solubility product K′sp of calcite in seawater was measured as a function of temperature, salinity, and pressure using potentiometric saturometry techniques. The temperature effect was hardly discernible experimentally. The value of K′sp at 25°C was 4.59·10−7 mole2/(kg seawater)2 at 35‰S, 5.34·10−7 at 43‰S, and 3.24·10−7 at 27‰S. The apparent partial molal volume was found to be −34.4 cm3 at 25°C and −42.3 cm3 at 2°C from a linear fit of log(K′sp P/K′sp 1). These results were used in conjunction with field data to calculate the degree of saturation in the oceans and showed undersaturation at shallower depths than previously reported.  相似文献   

8.
An interaction of dissolved natural organic matter (DNOM) with copper ions in the water column of the stratified Krka River estuary (Croatia) was studied. The experimental methodology was based on the differential pulse anodic stripping voltammetric (DPASV) determination of labile copper species by titrating the sample using increments of copper additions uniformly distributed on the logarithmic scale. A classical at-equilibrium approach (determination of copper complexing capacity, CuCC) and a kinetic approach (tracing of equilibrium reconstitution) of copper complexation were considered and compared. A model of discrete distribution of organic ligands forming inert copper complexes was applied. For both approaches, a home-written fitting program was used for the determination of apparent stability constants (Kiequ), total ligands concentration (LiT) and association/dissociation rate constants (ki1,ki- 1).A non-conservative behaviour of dissolved organic matter (DOC) and total copper concentration in a water column was registered. An enhanced biological activity at the freshwater–seawater interface (FSI) triggered an increase of total copper concentration and total ligand concentration in this water layer. The copper complexation in fresh water of Krka River was characterised by one type of binding ligands, while in most of the estuarine and marine samples two classes of ligands were identified. The distribution of apparent stability constants (log K1equ: 11.2–13.0, log K2equ:8.8–10.0) showed increasing trend towards higher salinities, indicating stronger copper complexation by autochthonous seawater organic matter.Copper complexation parameters (ligand concentrations and apparent stability constants) obtained by at-equilibrium model are in very good accordance with those of kinetic model. Calculated association rate constants (k11:6.1–20 × 103 (M s)− 1, k21: 1.3–6.3 × 103 (M s)− 1) indicate that copper complexation by DNOM takes place relatively slowly. The time needed to achieve a new pseudo-equilibrium induced by an increase of copper concentration (which is common for Krka River estuary during summer period due to the nautical traffic), is estimated to be from 2 to 4 h.It is found that in such oligotrophic environment (dissolved organic carbon content under 83 µMC, i.e. 1 mgCL− 1) an increase of the total copper concentration above 12 nM could enhance a free copper concentration exceeding the level considered as potentially toxic for microorganisms (10 pM).  相似文献   

9.
Samples of dead biomass from the marine brown algae Fucus ceranoides, Fucus vesiculosus and Fucus serratus were studied for their ability to remove cadmium from aqueous solutions. The metal sorption process is rapid, with 90% of the metal uptake completed within the first 25 min of contact. The kinetic data was described successfully by a pseudo second order chemical sorption process with rate constants of ca. 0.6 g mmol− 1 min− 1. At pH 4.5, the raw biomass of the three species exhibited equilibrium uptake capacities for Cd as high as 0.8 mmol g− 1 (90 mg g− 1), on a dry weight basis, without chemical pretreatment. These sorption capacities are much higher than those reported for activated carbon and chitin. The sorption of Cd was found to increase as pH increases, reaching a plateau at pH 5.Batch sorption experiments and continuous potentiometric titrations of acid-treated biomass samples in 0.05 M NaNO3 were used to derive thermodynamic binding parameters according to the NICCA model. The total amount of acid sites was 2.4–2.9 mmol g− 1, with median values of the affinity distribution for protons and cadmium ions, log K˜H and log K˜Cd, of 3.7 and 2.69, respectively (conditional values). The apparent heterogeneity of the sorbent was successfully taken into account by the empirical NICCA isotherm, which described very well the competition between protons and metal ions, in contrast with a simpler discrete competitive Langmuir model.The experimental results demonstrate that these seaweeds constitute a promising, efficient, cheap and biodegradable sorbent biomaterial for cadmium removal from wastewaters. This use would represent an example of exploitation of a renewable marine resource in water treatment technologies for the prevention of heavy metal pollution in the environment.  相似文献   

10.
The hydrolysis of silicic acid, Si(OH)4, was studied in a simplified seawater medium (0.6 M Na(Cl)) at 25°C. The measurements were performed as potentiometric titrations (hydrogen electrode) in which OH− was generated coulometrically. The total concentration of Si(OH)4, B, and log[H+] were varied within the limits 0.00075 B 0.008 M and 2.5 -log[H+] 11.7, respectively. Within these ranges the formation of SiO(OH)3− and SiO2(OH)22− with formation constants log β−11(Si(OH)4 SiO(OH)3− + H+) = −9.472 ±0.002 and log β−21(Si(OH)4 SiO2(OH)22− + 2H+) = −22.07 ± 0.01 was established. With B > 0.003 M polysilicate complexes are formed, however, with -log[H+] 10.7 their formation does not significantly affect the evaluated formation constants. Data were analyzed with the least squares computer program LETAGROPVRID.  相似文献   

11.
Iron solubility equilibria were investigated in seawater at 36.22‰ salinity and 25°C using several filtration and dialysis techniques. In simple filtration experiments with 0.05 μm filters and Millipore ultra-filters, ferric chlorides fluorides, sulfates, and FeOH2+ species were found to be insignificant relative to Fe(OH)2+ at p[H+] = ?log [H+] greater than 6.0. Hydrous ferric oxide freshly precipitated from seawater yielded a solubility product of 1Kso = [Fe3+][H+]?3 = 4.7 · 105. Solubility studies based on the rates of dialysis of various seawater solutions and on the filtration of acidified seawater solutions indicated the existence of the Fe(OH)30 species. The formation constant for this species can be calculated as 1β3 = [Fe(OH)30] [H+]3/[Fe3+] = 2.4 · 10?14. The Fe(OH)4? species is present at concentrations which are negligible compared to Fe(OH)2+ and Fe(OH)30 in the normal pH range of seawater. However, there is at least one other significant ferric complex in seawater above p[H+] = 8.0 (possibly with bicarbonate, carbonate, or borate ions) in addition to the Fe(OH)2+ and Fe(OH)30 species.  相似文献   

12.
Estimating nitrogen transformation rates in aquatic ecosystems by isotope dilution techniques is simplified by directly measuring nitrogen isotopic ratios for NH4+ in the water using high performance cation exchange liquid chromatography (HPLC). Modifications of HPLC conditions and implementation of a median-area method for retention time determination improved and linearized a previously reported sigmoid relationship between the retention time shift (RTshift) of the NH4+ peak and the ratio of [15NH4+]: [Total NH4+] in seawater fortified with 15NH4+. Increasing the temperature of the HPLC column from 47 to 85 °C increased mobile phase buffer flow rate relative to column back pressure, decreased the retention time for NH4+, and allowed the buffer pH to be optimized relative to the pK of NH4+. The use of median-area rather than maximum-height to define the retention time of NH4+ further improved the linearity (r > 0.995) of the relationship between the ratio [15NH4+]: [Total NH4+] and RTshift over the range of isotope ratios. Reduction of NO3− to NH4+ by adding zinc dust to acidified (pH 2) seawater or lakewater samples, followed by pH neutralization, and subsequent analysis of NH4+ isotope ratios by HPLC, extended application of the method to isotope dilution experiments with NO3−. Advantages of this direct-injection method over mass-measurement approaches traditionally used for isotope dilution experiments include small sample size and minimal sample preparation.  相似文献   

13.
The effect of a sudden increase in salinity from 10 to 37 in porewater concentration and the benthic fluxes of ammonium, calcium and dissolved inorganic carbon were studied in sediments of a small coastal lagoon, the Albufera d'Es Grau (Minorca Island, Spain). The temporal effects of the changes in salinity were examined over 17 days using a single diffusion-reaction model and a mass-balance approach. After the salinity change, NH4+-flux to the water and Ca-flux toward sediments increased (NH4+-flux: 5000–3000 μmol m−2 d−1 in seawater and 600/250 μmol m−2 d−1 in brackish water; Ca-flux: −40/−76 meq m−2 d−1 at S=37 and −13/−10 meq m−2 d−1 at S=10); however, later NH4+-flux decreased in seawater, reaching values lower than in brackish water. In contrast, Ca-flux presented similar values in both conditions. The fluxes of dissolved inorganic carbon, which were constant at S=10 (55/45 mmol m−2 d−1), increased during the experiment at S=37 (from 30 mmol m−2 d−1 immediately after salinity increase to 60 mmol m−2 d−1 after 17 days).In brackish conditions, NH4+ and Ca2+ fluxes were consistent with a single diffusion-reaction model that assumes a zero-order reaction for NH4+ production and a first-order reaction for Ca2+ production. In seawater, this model explained the Ca-flux observed, but did not account for the high initial flux of NH4+.The mass balance for 17 days indicated a higher retention of NH4+ in porewater in the littoral station in seawater conditions (9.5 mmol m−2 at S=37 and 1.6 mmol m−2 at S=10) and a significant reduction in the water consumption at both sites (5 mmol m−2 at S=37; 35/23 mmol m−2 at S=10). In contrast, accumulation of dissolved inorganic carbon in porewater was lower in seawater incubations (−10/−1 meq m−2 at S=37; 50/90 meq m−2 at S=10) and was linked to a higher efflux of CO2 to the atmosphere, because of calcium carbonate precipitation in water (675/500 meq m−2). These results indicate that increased salinity in shallow coastal waters could play a major role in the global carbon cycle.  相似文献   

14.
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.  相似文献   

15.
The pK1* and pK2* for the dissociation of carbonic acid in seawater have been determined from 0 to 45°C and S = 5 to 45. The values of pK1* have been determined from emf measurements for the cell:
Pt](1 − X)H2 + XCO2|NaHCO3, CO2 in synthetic seawater|AgC1; Ag
where X is the mole fraction of CO2 in the gas. The values of pK2* have been determined from emf measurements on the cell:
Pt, H2(g, 1 atm)|Na2CO3, NaHCO3 in synthethic seawater|AgC1; Ag
The results have been fitted to the equations:
lnK*1 = 2.83655 − 2307.1266/T − 1.5529413 lnT + (−0.20760841 − 4.0484/T)S0.5 + 0.08468345S − 0.00654208S1
InK*2 = −9.226508 − 3351.6106/T− 0.2005743 lnT + (−0.106901773 − 23.9722/T)S0.5 + 0.1130822S − 0.00846934S1.5
where T is the temperature in K, S is the salinity, and the standard deviations of the fits are σ = 0.0048 in lnK1* and σ = 0.0070 in lnK2*.Our new results are in good agreement at S = 35 (±0.002 in pK1*and ±0.005 in pK2*) from 0 to 45°C with the earlier results of Goyet and Poisson (1989). Since our measurements are more precise than the earlier measurements due to the use of the Pt, H2|AgCl, Ag electrode system, we feel that our equations should be used to calculate the components of the carbonate system in seawater.  相似文献   

16.
We examine the concentration variations of the different parameters X of the carbonate system in seawater when calcium carbonate precipitation occurs. Variations are expressed as ∂[X]/∂[Ca2+]. Four different cases are considered: spontaneous chemical precipitation; calcification combined with photosynthetic activity under a constant ΔCT/Δ[Ca2+] ratio; precipitation under constant pCO2 and precipitation under constant [Ca2+]·[CO32−] ionic concentration product. The last condition should be maintained by an ecosystem which, thanks to the regulation of its calcifying and photosynthetic activity, would absorb 1 mol of carbon for organic tissue each time 1 mol of CaCO3 is formed. This stoichiometric ratio would allow the activity of these biological communities to go on in practically closed systems during periods compatible with their growth or development cycles.  相似文献   

17.
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 At, total carbonate Ct, 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. Cx=20 μmol kg−1, pKx=6.2) produces a deviation approaching 20 μmol kg−1 at constant Ct; however, adjustment of Ct 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 Ct 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 At, Ct, 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.  相似文献   

18.
The seasonal and interannual variability of the air–sea CO2 flux (F) in the Atlantic sector of the Barents Sea have been investigated. Data for seawater fugacity of CO2 (fCO2sw) acquired during five cruises in the region were used to identify and validate an empirical procedure to compute fCO2sw from phosphate (PO4), seawater temperature (T), and salinity (S). This procedure was then applied to time series data of T, S, and PO4 collected in the Barents Sea Opening during the period 1990–1999, and the resulting fCO2sw estimates were combined with data for the atmospheric mole fraction of CO2, sea level pressure, and wind speed to evaluate F.The results show that the Atlantic sector of the Barents Sea is an annual sink of atmospheric CO2. The monthly mean uptake increases nearly monotonically from 0.101 mol C m− 2 in midwinter to 0.656 mol C m− 2 in midfall before it gradually decreases to the winter value. Interannual variability in the monthly mean flux was evaluated for the winter, summer, and fall seasons and was found to be ± 0.071 mol C m− 2 month− 1. The variability is controlled mainly through combined variation of fCO2sw and wind speed. The annual mean uptake of atmospheric CO2 in the region was estimated to 4.27 ± 0.68 mol C m− 2.  相似文献   

19.
Dissolved Al carried in river water apparently undergoes a fractional removal at the early stages of mixing in the Conway estuary. On the other hand, dissolved Al behaves almost conservatively in high salinity (>13) estuarine waters. In order to understand the geochemistry of Al in these estuarine waters, simple empirical sorption models have been used. Partitioning of Al occurs between solid and solution phases with a distribution coefficient, Kd, which varies from 0.67 × 105 to 3.38 × 106 ml g−1 for suspended particle concentrations of 2–64 mg l−1. The Kd values in general decrease with increasing suspended particulate matter and this tendency termed the “particle concentration effect” is quite pronounced in these waters. The sorption model derived by previous workers for predicting concentrations of dissolved Al with changing suspended sediment loads has been applied to these data. Reasonable fits are obtained for Kd values of 105, 106 and 107 ml g−1 with various values of α. Further, a sorption model is proposed for particulate Al concentrations in these waters that fits the data extremely well defined by a zone with Kd value 107 ml g−1 and C0 values 16 × 10−6 mg ml−1 and 92 × 10−6 mg ml−1. These observations provide strong evidence of sorption processes as key mechanisms influencing the distribution of dissolved and particulate Al in the Conway estuary and present new insight into Al geochemistry in estuaries.  相似文献   

20.
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 (Cp = 2.8 × 10− 5P + 3.4 × 10− 2 s nmol− 1, R2 = 0.997, for Θ = 13 °C) and an exponential relation as a function of temperature (CΘ = 0.009e0.103Θ, 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 Fea (unfiltered seawater, acidified in line at pH 1.8 for 80 s). Most of Fea (71 ± 4%) was probably a fraction of total dissolvable iron (TDFe, unfiltered seawater, acidified and stored at pH 1.8).  相似文献   

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