A comparison of two voltammetric techniques for determining zinc speciation in Northeast Pacific Ocean waters

Two independent voltammetric techniques, differential pulse cathodic stripping voltammetry (DPCSV) and differential pulse anodic stripping voltammetry (DPASV), determined that 95% of the dissolved zinc is organically complexed at two depths (60 and 150 m) within the surface euphotic zone at an open ocean station in the Northeast Pacific. Average values for the concentrations of the natural zinc-complexing organic ligands (C_L) obtained from duplicate determinations at these two depths by DPCSV versus DPASV are in excellent agreement: 1.60 ± 0.01 versus 1.76 ± 0.03 nM at 60 m, and 2.14 (n=1) versus 2.22 ± 0.06 nM at 150 m. Average values for the conditional stability constants (with respect to free Zn²⁺) of the natural zinc-organic complexes (log K^′_ZnL) from duplicate determinations at both depths by DPCSV versus DPASV are 10.3 ± 0.2 versus 11.2 ± 0.2. Additional research is required to assess the significance of the difference in the conditional stability constants determined by these two techniques. These results confirm recent observations that strong zinc complexes formed with an organic ligand class existing at nanomolar concentrations dominates zinc speciation in the North Pacific.     

Apparent copper complexation capacity and conditional stability constants in north atlantic waters

Surface water samples were collected in the north Atlantic Ocean in July–August 1983. Their apparent complexation capacity for copper (CC_Cu) was determined on board, using differential pulse anodic stripping voltammetry under clean room conditions. Measurements were carried out by direct titrations as well as after equilibration of copper spikes. CC_Cu and conditional stability constants (K′) were calculated, by means of three different methods, which are compared.On the basis of salinity, temperature, silicate and phosphate concentrations the following surface waters could be distinguished: North Atlantic Drift (I), East Greenland Current (II), Labrador Current (III) and Gulf Stream waters (IV, V). CC_Cu and K′ were found to differ between these waters. The range of values for CC_Cu and their mean values given in parentheses, as calculated from van den Berg plots for waters I–IV are: I, 53–65 (59); II, 47–66 (55); III, 37–53 (45); IV, 20–42 (33) nM Cu. The range and mean values for log K′ are: I, 8.23–8.33 (8.28); II, 7.89–8.11 (7.98); III, 8.40–8.41 (8.41); IV, 7.90–8.21 (8.06).Information on complexation kinetics extracted from the titration curve revealed that k_f^′ is area-specific. The complexation rate constant in the northern part (Area I) is about two times larger than that in the southern area IV, (3.6 ± 0.3) and (2.2 ± 0.2) × 10⁴s⁻¹M⁻¹ Cu, respectively.Preliminary results for deep water samples suggest smaller but still existent CC_Cu and higher K′ than those found for surface waters.     

Seasonal survey of copper-complexing ligands and thiol compounds in a heavily utilized, urban estuary: Elizabeth River, Virginia

Concentrations of thiol compounds, copper-complexing ligands, and total dissolved copper were followed over the course of 1 year (October 2002 until September 2003) in the Elizabeth River, Virginia to evaluate seasonality. Copper-complexing ligand concentrations were determined by competitive ligand equilibration-adsorptive cathodic stripping voltammetry (CLE/ACSV). Thiol detection was carried out by high performance liquid chromatography (HPLC) and calibration using a suite of nine thiol compounds (cysteine, glutathione, mercaptoacetic acid, 2-mercaptoethanesulfonic acid, 2-mercaptoethanol, 2-mercaptopropionic acid, 3-mercaptopropionic acid, mercaptosuccinic acid, and monothioglycerol). Total dissolved copper concentrations reached a January low of 13.1 nM to a June high of 24.7 nM and were found to vary seasonally with higher concentrations occurring from June to September. With a low of 26 nM during April to a high of 56 nM in October, copper-complexing ligand (average log K′_CuL of 12.0 ± 0.2) concentrations displayed a similar seasonal pattern to that of total dissolved copper. Free cupric ion concentrations remained below 1.5 pM for a majority of the year except during March, April, and December when values reached pM levels greater than 1.5. Six of the nine thiol compounds surveyed were detected in the Elizabeth River samples and ranged in concentration from below detectable concentrations (< 5 nM) to individual highs ranging from 25.3 to168.5 nM. The thiol compound concentrations displayed a clear seasonality fluctuating at below detection limits during November to February then increasing with increasing surface water temperatures from March to July. CLE/ACSV was used to assess whether or not the suite of thiol compounds detected by HPLC could contribute to the copper-complexing ligand pool. Conditional stability constants for each one of six thiol standards (average log K′_CuL  12.1 ± 0.5) were found to be statistically equivalent to the naturally occurring copper-complexing ligands (average log K′_CuL  12.0 ± 0.2). This suggests that these thiol compounds could act as copper-complexing ligands in natural samples and could contribute to the copper-complexing ligand pool detected by CLE/ACSV. This study involving seasonality of copper-complexing ligands and thiols in an industrialized, urban estuary underscored several points that have to be substantiated in future research efforts including copper-complexing ligands sources and the role that thiol compounds as well as other unidentified organic compounds play in the copper-complexing ligand pool.     

Determination of the zinc complexing capacity in seawater by cathodic stripping voltammetry of zinc—APDC complex ions

A novel technique to determine complexing capacities for zinc is presented. The free zinc concentration is determined by cathodic stripping voltammetry preceded by adsorptive collection of complexes of zinc with ammonium pyrrolidine dithiocarbamate (APDC). The reduction peak of zinc is depressed as a result of ligand competition by natural organic material in the sample. Sufficient time is allowed to reach equilibrium between this material and added APDC, and equilibrium is maintained during the measurement. Both electrochemically reversible and irreversible complexes can therefore be investigated. Values for K_ZnAPDC^′ are calibrated against NTA and EDTA in seawater of several salinities; log K_ZnAPDC^′ was found to be 4.40 at 36‰, 4.36 at 24‰, 4.43 at 12‰, and 4.87 at 2.3‰. The ligand concentration and conditional stability constant, K_ZnL^′, for complexing ligands in a sample from the Irish Sea were determined in the presence of 4 × 10^?5 M APDC and with added zinc concentrations between 5 × 10^?9 and 3 × 10^?7 M. The data best fitted a complexation model containing two ligands with concentrations of 2.6 and 6.2 and 10^?8 M, and with values for log K_ZnL^′ of 8.4 and 7.5, respectively. These results are comparable to those obtained with other equilibrium techniques, but the values of the constants are greater than those from ASV 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.     

Copper complexation profiles in the Atlantic Ocean: A comparative study using electrochemical and ion exchange techniques

The dissolved copper concentrations in several profiles of the water column in the Atlantic Ocean were between 1 and 6 nM, and indicate copper removal from the surface layer and mixing of water masses at greater depth. The ligand concentrations (C_L) decreased from a maximum of 1800 nM in surface waters to 6–20 nM in deeper waters, with values for log K′_CuL (conditional stability constants) between 9.4 and 11, as indicated by the MnO₂ technique. Ligand concentrations obtained with the DPASV (differential pulse anodic stripping voltammetry) technique showed more variability and were generally higher, whereas the log K′_CuL values were smaller at 7.5–10.3. Such differences in results obtained with different techniques may be due to certain operational parameters of each technique, which to some extent govern the detection window. Speciation calculations showed that the organic copper fraction at all depths amounts to 89–99.8% using data from the MnO₂ method, and 98.8–99.4% using data from the DPCSV (differential pulse cathodic stripping voltammetry) method. Comparison of the techniques used showed that the stronger ligands, or sites, detected by the DPCSV, and to a smaller extent MnO₂ procedures were of most relevance to the study of metal speciation, since these ligands form much more stable copper complexes than those detected by DPASV. The strong complexing ligands are not detected by DPASV due to lack of sensitivity. For reasons of convenience and sensitivity DPCSV is to be preferred over the MnO₂ method.     

Cu complexation by organic ligands in the sub-arctic NW Pacific and Bering Sea

Cu speciation was characterized at three stations in the sub arctic NW Pacific and Bering Sea using cathodic stripping voltammetry with the competing ligands benzoylacetone and salicylaldoxime. A single ligand model was fit to the titration data, yielding concentrations throughout the water column of ∼3–4 nM, and conditional stability constants ranging from 10^12.7 to 10^14.1, this range being partly due to the choice of competing ligand. Free Cu²⁺ in surface waters was 2–4×10⁻¹⁴ M, in close agreement with values reported by previous workers in the NE Pacific using anodic stripping voltammetry (ASV). However, those results showed that complexation by strong organic ligands becomes unimportant below 200–300 m, while our data indicated Cu is strongly complexed to depths as great as 3000 m. Free Cu²⁺ concentrations in surface waters reported here and in previous work are close to the threshold value where Cu can limit the acquisition of Fe by phytoplankton.     

Evidence for organic complexation of iron in seawater

Iron occurs at very low concentrations in seawater of oceanic origin and its low abundance is thought to limit primary production in offshore waters (Martin and Fitzwater, 1988). A new electrochemical method, cathodic stripping voltammetry (CSV), is used here to determine the speciation of iron in seawater originating from the Western Mediterranean taking advantage of ligand competition of an added electroactive ligand with the natural organic complexing matter to evaluate whether iron is organically complexed. The measurements indicate that iron occurs 99% (or 99.9% depending on which value is selected for α_Fe′) complexed by organic complexing ligands throughout the water column of the Western Mediterranean and by analogy probably also in other oceanic waters. The composition of the organic complexing ligands is as yet unknown, but the data indicate a major source from microorganisms (bacteria or phytoplankton) in and immediately below the fluorescence maximum in the upper water column. The organic complexes are apparently reversible releasing iron when the competing ligand is added and binding more iron when its concentration is increased. The organic complexing ligands occur at concentrations well above those of iron ensuring full complexation of this biologically essential element, and buffer the free iron concentration at a very low level against fluctuations as a result of removal by primary producers or inputs from atmospheric sources. The new data indicate that a re-evaluation of the concept of the bioavailable fraction of iron is required.     

Complexation of calcium and copper with carbohydrates: Implications for seawater speciation

The extent of complexation of calcium(II) and copper(II) with 33 carbohydrates found in seawater has been determined potentiometrically using calcium and copper ion-selective electrodes. The measurements were performed in an essentially neutral aqueous medium at 25°C in 0.70 M KNO₃.Neutral sugars form very weak 1:1 complexes with Ca(II) and Cu(II) ions. Sugars with carboxylate groups from much stronger complexes. K′_Cu(II) >K′_Ca(II)) for a given sugar. The extent of complexation is dependent on the conformation of the sugar ligand.     

Complexation of mercury by dissolved organic matter in surface waters of Galveston Bay, Texas

The chemical speciation of dissolved mercury in surface waters of Galveston Bay was determined using the concentrations of mercury-complexing ligands and conditional stability constants of mercury-ligand complexes. Two classes of natural ligands associated with dissolved organic matter were determined by a competitive ligand exchange-solvent solvent extraction (CLE-SSE) method: a strong class (L_s), ranging from 19 to 93 pM with an average conditional stability constant (K_HgLs) of 10²⁸, and a weak class (L_w) ranging from 1.4 to 9.8 nM with an average K_HgLs of 10²³. The range of conditional stability constants between mercury and natural ligands suggested that sulfides and thiolates are important binding sites for dissolved mercury in estuarine waters. A positive correlation between the estuarine distribution of dissolved glutathione and that of mercury-complexing ligands supported this suggestion. Thermodynamic equilibrium modeling using stability constants for HgL, HgCl_x, Hg(OH)_x, and HgCl(OH) and concentrations of each ligand demonstrated that almost all of the dissolved mercury (> 99%) in Galveston Bay was complexed by natural ligands associated with dissolved organic matter. The importance of low concentrations of high-affinity ligands that may originate in the biological system (i.e., glutathione and phytochelatin) suggests that the greater portion of bulk dissolved organic matter may not be important for mercury complexation in estuarine surface waters.     

Molecular masses and chromophoric properties of dissolved organic ligands for copper(II) in oceanic water

The distribution of molecular masses of organic ligands for copper(II) in oceanic water was investigated. The bulk dissolved organic matter (DOM) was fractionated by ultrafiltration and organic ligands were extracted from the resultant fractions by using immobilized metal ion affinity chromatography (IMAC). Contributions of total organic ligands were 2.0–4.4% of the bulk DOM in surface waters, as determined by the UV absorbance. In the distribution of molecular masses of organic ligands, relative contribution of the fraction with low molecular masses (<1000 Da) was dominant (49–62%), while 26–33% of the total organic ligands was in the 1000–10,000 Da fraction, leaving 10–19% in the >10,000 Da fraction. The distribution of molecular masses of organic ligands shifted to higher molecular masses, as compared with that of the bulk DOM. The fluorescence intensities of organic ligands were shown to be associated with carboxyl contents, based on peak excitation/emission wavelengths and the pH-dependence of fluorescence. Two ligand classes with different conditional stability constants (log K_CuL′≈7 and 9) were determined from fluorescence quenching of ligand fractions during copper(II) titration. Organic ligands in low molecular mass fractions were relatively weak and strong ligands occurred in higher molecular mass fractions. It is suggested that the weaker ligand sites would consist of two or more carboxyl groups (log K_HL′=4), whereas carboxyl groups (log =2), which are protonated at lower pH, and primary amine may additionally contribute to the formation of more stable copper(II) complexes of the stronger ligand.     

Determination of copper complexation with natural organic ligands in seawater by equilibration with MnO2 II. Experimental procedures and application to surface seawater

The MnO₂ adsorption method combined with voltammetry is proposed for the direct determination of metal complexation in seawater of various salinities as a more satisfactory alternative to direct voltammetric measurements and bioassay methods. A small quantity of MnO₂ is equilibrated with copper ions in filtered seawater. Natural organic ligands in the seawater compete for copper with the MnO₂. Total dissolved copper is measured by differential pulse anodic stripping voltammetry after filtration and acidification of the sample. Preconcentration of natural water samples is unnecessary and measurement is performed at the natural equilibrium pH of the aerated sample. The analytical limit of detection of the method depends on contamination from the filtration step, and for copper complexation a ligand concentration of 5 × 10^?8 M was obtained. The sensitivity can be increased by use of radioisotopes as tracers. The method is very versatile in that complexation of various metals may be determined by any analytical method that measures total dissolved metal concentrations. Neither organic ligands nor their complexes with copper adsorb on the MnO₂ at pH8, but at pH 1.8 MnO₂ is an efficient scavenger for electroactive organic material.Samples of surface water from the Irish Sea and the Atlantic Ocean were found to contain ligand concentrations of 1.7 × 10^?7 and 1.1 × 10^?7 M, with conditional stability constants (log values) of 9.84 ± 0.13 and 9.86 ± 0.23, respectively, at pH 8.0.     

An evaluation of a C-18 solid phase extraction technique for isolating metal-organic complexes from central North Pacific Ocean waters

This paper presents results from an investigation using a C-18 solid phase extraction (SPE) method for isolating dissolved metal-organic complexes from seawater. The vertical distribution of dissolved organically complexed copper isolated by this technique in the intermediate and deep waters of the central North Pacific is similar to that observed in the North Atlantic. Copper isolated by C-18 SPE from 125 to 5000 m in the North Pacific ranged from 11 to 30% of the total dissolved copper, whereas published concentrations for similar depths in the North Atlantic ranged from 22 to 36% of the total dissolved copper. Evidence from voltammetric studies suggests that the C-18 SPE technique may isolate the major portion of the organically complexed copper from deep waters.In oceanic surface waters, however, a major discrepancy exists — recent voltammetric and equilibration studies indicate that essentially all of the dissolved copper and zinc is associated with organic complexes, while the C-18 SPE method isolates <10% of the total dissolved copper and zinc in the North Pacific and <40% of the total dissolved copper in the North Atlantic. Thus, in surface waters, it appears that the major fraction of organically complexed copper and zinc is not isolated by the C-18 SPE approach.The fractions of total dissolved cadmium, iron, manganese, and nickel isolated by the C-18 SPE technique were also studied. The degree to which each of these metals is complexed with the fraction of the dissolved organic matter isolated by this method is smaller and not as significant as that observed for copper. These results do not imply, however, that organic complexation of these metals is not significant, only that the organic—metal complexes are not isolated by the C-18 SPE method.     

Importance of organic Fe complexing ligands in the Mississippi River plume

As part of a larger program focused on understanding the biogeochemistry of large river plumes, we participated in two expeditions during 2000 to sample the Mississippi River plume. Surface water samples were collected using a trace metal clean towed fish and analyzed for total dissolved Fe, organic Fe complexing ligands and their associated conditional stability constants. The ligands in the river plume have conditional stability constants (log K′_FeL between 10.5 and 12.3 with an average of 11.2 and standard deviation of 0.6) very similar to ligands found in the open ocean. Comparison of high flow and low flow regimes indicates that variability in flow may be the main cause of the variability in Fe concentrations in the plume. The organic Fe complexing ligands are in greatest excess during a time of higher flow. These ligands are responsible for maintaining very high (5 nM) Fe concentrations throughout the plume. Due to complexation with these organic ligands, the concentration of Fe remains above the Fe-hydroxide solubility level until a salinity above 35 is reached where there appears to be a sink for Fe in the less productive waters. Therefore, Fe is transported a great distance from the river source and is available for biological utilization in the coastal zone.     

Organic complexation and its control of the dissolved concentrations of copper and zinc in the Scheldt estuary

Cathodic stripping voltammetry (CSV) is used to determine total (after UV-irradiation) and labile dissolved metal concentrations as well as complexing ligand concentrations in samples from the river Scheldt estuary. It was found that even at high added concentrations of catechol (1 m for copper and 0·4 m for iron) and of APDC (1 m for zinc) only part of the dissolved metal was labile (5–58% for copper, 34–69% for zinc, 10–38% for iron); this discrepancy could be explained by the low solubility of iron which is largely present as colloidal material, and by competition for dissolved copper and zinc by organic complexing ligands. Ligand concentrations varied between 28 and 206 n for copper and between 22 and 220 n for zinc; part of the copper complexing ligands could be sub-divided into strong complexing sites with concentrations between 23 and 121 n and weaker sites with concentrations between 44 and 131 n . Values for conditional stability constants varied between (logK′ values) 13·0 and 14·8 for strong and between 11·5 and 12·1 for weaker copper complexing ligands, whereas for zinc the values were between 8·6 and 10·6. The average products of ligand concentrations and conditional stability constants (a-coefficients) were 6 × 10² for zinc and 6 × 10⁶ for copper.The dissolved zinc concentration was found to co-vary with the zinc complexing ligand concentration throughout the estuary. It is argued that the zinc concentration is regulated, in this estuary at least, by interactions with dissolved organic complexing ligands. A similar relationship was apparent between the dissolved copper and the strong copper complexing ligand concentration. The total copper complexing ligand concentrations were much greater than the dissolved copper concentrations, suggesting that only strongly complexed copper is kept in solution.These results provide evidence for the first time that interactions of copper and zinc with dissolved organic complexing ligands determine the geochemical pathway of these metals.     

Iron availability and the release of iron-complexing ligands by Emiliania huxleyi

The ubiquitous algal species, Emiliania huxleyi, was incubated in sea water supplemented only with nitrate and phosphate (N and P) without chelating agents to control metal speciation. Growth was slow in a “low-iron” culture containing 1.3 nM iron and was found to be iron-limited, growth-accelerating when a 1-nM iron addition was made. The growth rate in a “high-iron” culture (5.4 nM iron) was greater, reaching 0.4 div day⁻¹ but this culture too was found to have become iron-limited when a 9-nM iron addition was made on day 17 of the incubation. Both cultures were found to release iron-complexing ligands in excess of the iron concentration, 6 nM in the low-iron culture, and 10 nM in the high-iron culture. More ligands were produced after the iron addition taking the ligand concentration to 11 nM in the low-iron culture. The data show that the ligands are released in response to the iron addition, when at least some of the iron had already been taken up. This type of release is contrary to the concept of a siderophore, which is supposed to be released in periods of lack of iron; however the increase in the ligand concentration is similar to that released by the natural community in response to the iron addition in the IRON-EX II experiment [Rue, E.L., Bruland, K.W., 1997. The role of organic complexation on ambient iron chemistry in the equatorial Pacific Ocean and the response of a mesoscale iron addition experiment. Limnol. Oceanogr. 42, 901–910]. The enhanced growth in the cultures when more iron was added indicated that the organically complexed iron present in the cultures was not immediately available to the organisms (or at least not at sufficiently high rate), and that the organisms responded to freshly added, inorganic, iron.     

Kinetic and equilibrium studies of copper-dissolved organic matter complexation in water column of the stratified Krka River estuary (Croatia)

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 (K_i^equ), total ligands concentration (L_iT) and association/dissociation rate constants (k_i¹,k_i^- 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 K₁^equ: 11.2–13.0, log K₂^equ: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 µM_C, i.e. 1 mg_CL^− 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).     

Seasonal variations of alkenones and U37 in the Chesapeake Bay water column

Alkenone unsaturation indices (U^K₃₇ and U^K′₃₇) have long been used as proxies for surface water temperature in the open ocean. Recent studies have suggested that in other marine environments, variables other than temperature may affect both the production of alkenones and the values of the indices. Here, we present the results of a reconnaissance field study in which alkenones were extracted from particulate matter filtered from the water column in Chesapeake Bay during 2000 and 2001. A multivariate analysis shows a strong positive correlation between U^K₃₇ (and U^K′₃₇) values and temperature, and a significant negative correlation between U^K₃₇ (and U^K′₃₇) values and nitrate concentrations. However, temperature and nitrate concentrations also co-vary significantly. The temperature vs. U^K₃₇ relationships (U^K₃₇=0.018 (T)−0.162, R²=0.84, U^K′₃₇=0.013 (T)−0.04, R²=0.80) have lower slopes than the open-ocean equations of Prahl et al. [1988. Further evaluation of long-chain alkenones as indicators of paleoceanographic conditions. Geochimica et Cosmochimica Acta 52, 2303–2310] and Müller et al. [1998. Calibration of the alkenone paleotemperature index U^K′₃₇ based on core-tops from the eastern South Atlantic and the global ocean (60°N–60°S). Geochimica et Cosmochimica Acta 62, 1757–1772], but are similar to the relationships found in controlled studies with elevated nutrient levels and higher nitrate:phosphate (N:P) ratios. This implies that high nutrient levels in Chesapeake Bay have either lowered the U^K₃₇ vs. temperature slope, or nutrient levels are the main controller of the U^K₃₇ index. In addition, particularly high abundances (>5% of total C₃₇ alkenones) of the tetra-unsaturated ketone, C_37:4, were found when water temperatures reached 25 °C or higher, thus posing further questions about the controls on alkenone production as well as the biochemical roles of alkenones.     

Chemical fractionation of zinc versus cadmium among other metals nickel, copper and lead in the northern North Sea

Concentrations of dissolved Ni, Cu, Zn, Cd and Pb were measured in water samples collected during a cruise with R.V Pelagia (29-6/14-7-1993) in the northern North Sea and N.E. Atlantic Ocean. At least six depths (0–90 m) were sampled with modified Go-Flo samplers from a rubber zodiac. In the study area, the first 25 m were well mixed and stratification occurred below this depth. The local bloom of Emiliania huxleyi hardly affected the trace metals concentration, except for some removal of Cd as seen from its correlation with nitrate. The mean dissolved concentrations were for Ni (3.66 nM), Cu (1.61 nM), Zn (4.5 nM), Cd (48 pM) and Pb (108 pM). These concentrations are among the lowest reported for the North Sea and are of similar magnitude to those found in the eastern North Atlantic at the same latitude. Zn was the only exception with values 10 times higher compared to those in the Atlantic Ocean, suggesting external inputs, mainly atmospheric and possibly from surrounding land masses. The observed ratio Zn:Cd in the North Sea and estuaries is in between the high ratio 600–900 for continental sources and the low ratio 5–10 for oceanic waters. Latter low ratio is consistent with the 21-fold stronger inorganic complexation of Cd in seawater which, in combination with the preferential biological uptake of Zn, may lead to the observed about hundredfold fractionation of Zn versus Cd in the marine system. Other processes may play a role but would need further investigation. The dissolved Pb values tend to be lower than found before in the North Sea, indicating decreasing inventories due to reduced anthropogenic emissions.     

Variability in the speciation of iron in the northern North Sea

Variations in the speciation of iron in the northern North Sea were investigated in an area covering at least two different water masses and an algal bloom, using a combination of techniques. Catalytic cathodic stripping voltammetry was used to measure the concentrations of reactive iron (Fe_R) and total iron (Fe_T) in unfiltered samples, while dissolved iron (Fe_D) was measured by GFAAS after extraction of filtered sea water. Fe_R was defined by the amount of iron that complexed with 20 μM 1-nitroso-2-napthol (NN) at pH 6.9. Fe_T was determined after UV-digestion at pH 2.4. Concentrations of natural organic iron complexing ligands and values for conditional stability constants, were determined in unfiltered samples by titration. Mean concentrations of 1.3 nM for Fe_R, 10.0 nM for Fe_T and 1.7 nM for Fe_D were obtained for the area sampled. Fe_R concentrations increased towards the south of the area investigated, as a result of the increased influence of continental run off. Fe_R concentrations were found to be enhanced below the nutricline (below 40 m) as a result of the remineralisation of organic material. Enhanced levels of Fe_T were observed in some surface samples and in samples collected below 30 m at stations in the south of the area studied, thought to be a result of high concentrations of biogenic particulate material and the resuspended sediments respectively. Fe_D concentrations varied between values similar to those of Fe_T in samples from the north of the area to values similar to those of Fe_R in the south. The bloom was thought to have influenced the distribution of both Fe_R and Fe_T, but less evidence was observed for any influence on Fe_R and Fe_D. The concentration of organic complexing ligands, which could possibly include a contribution from adsorption sites on particulate material, increased slightly in the bloom area and in North Sea waters. Iron was found to be fully (99.9%) complexed by the organic complexing ligands at a pH of 6.9 and largely complexed (82–96%) at pH 8. The ligands were almost saturated with iron suggesting that the ligand concentration could limit the concentration of iron occurring as dissolved species.