Description: The distribution of dissolved aluminium (dAl) in the water column of the North Atlantic and Labrador Sea was studied along GEOTRACES section GA01 to unravel the sources and sinks of this element. Surface water dAl concentrations were low (median of 2.5 nM) due to low aerosol deposition and removal by phytoplankton. However, surface water dAl concentrations were enhanced on the Iberian and Greenland shelves (up to 30.9 nM) due to continental inputs (rivers, glacial flour and ice melt). A negative correlation was observed between dAl in surface waters and primary production, phytoplankton community structure and biogenic opal production. The abundance of diatoms exerted a significant (p 〈 0.01) control on the surface particulate Al (pAl) to dAl ratios by decreasing dAl levels and increasing pAl levels. Dissolved Al concentrations generally increased with depth and correlated strongly with silicate (R2 〉 0.76) west of the Iberian Basin, suggesting net release of dAl at depth during remineralization of sinking biogenic opal containing particles. Enrichment of dAl at near-bottom depths was observed due to resuspension of sediments near the sediment-water interface. The highest dAl (up to 38.7 nM) concentrations were observed in Mediterranean Overflow Waters which act as a major source of dAl to mid depth waters of the eastern North Atlantic. This study clearly shows that the vertical and lateral distribution of dAl in the North Atlantic differs when compared to other regions of the North Atlantic and global ocean due to the large spatial differences both in the main source of Al, atmospheric deposition, and the main sink for Al, particle scavenging, between different oceanic regions.

Description: The speciation of dissolved iron (DFe) in the ocean is widely assumed to consist almost exclusively of Fe(III)-ligand complexes. Yet in most aqueous environments a poorly defined fraction of DFe also exists as Fe(II), the speciation of which is uncertain. Here we deploy flow injection analysis to measure in situ Fe(II) concentrations during a series of mesocosm/microcosm/multistressor experiments in coastal environments in addition to the decay rate of this Fe(II) when moved into the dark. During five mesocosm/microcosm/multistressor experiments in Svalbard and Patagonia, where dissolved (0.2 µm) Fe and Fe(II) were quantified simultaneously, Fe(II) constituted 24 %–65 % of DFe, suggesting that Fe(II) was a large fraction of the DFe pool. When this Fe(II) was allowed to decay in the dark, the vast majority of measured oxidation rate constants were less than calculated constants derived from ambient temperature, salinity, pH, and dissolved O2. The oxidation rates of Fe(II) spikes added to Atlantic seawater more closely matched calculated rate constants. The difference between observed and theoretical decay rates in Svalbard and Patagonia was most pronounced at Fe(II) concentrations 〈2 nM, suggesting that the effect may have arisen from organic Fe(II) ligands. This apparent enhancement of Fe(II) stability under post-bloom conditions and the existence of such a high fraction of DFe as Fe(II) challenge the assumption that DFe speciation in coastal seawater is dominated by ligand bound-Fe(III) species.

Description: Due to its accurate and precise character, spectrophotometric pH detection is a common technique applied in measurement methods for carbonate system parameters. However, impurities in the used pH indicator dyes can influence the measurements quality. During our work described here, we focused on impacts of impurities in the pH indicator dye bromocresol green (BCG) on spectrophotometric seawater total alkalinity (AT) measurements. In order to evaluate the extent of such influences, purified BCG served as a reference. First, a high-performance liquid chromatography (HPLC) purification method for BCG was developed as such a method did not exist at the time of this study. An analysis of BCG dye from four different vendors with this method revealed different types and quantities of impurities. After successful purification, AT measurements with purified and unpurified BCG were carried out using the novel autonomous analyzer CONTROS HydroFIA® TA. Long-term measurements in the laboratory revealed a direct influence of impurity types and quantities on the drift behavior of the analyzer. The purer the BCG, the smaller was the AT increase per measurement. The observed drift is generally caused by deposits in the optical pathway mainly generated by the impurities. However, the analyzers drift behavior could not be fully overcome. Furthermore, we could show that a certain impurity type in some indicator dyes changed the drift pattern from linear to nonlinear, which can impair long-term deployments of the system. Consequently, such indicators are impractical for these applications. Laboratory performance characterization experiments revealed no improvement of the measurement quality (precision and bias) by using purified BCG as long as the impurities of the unpurified dye do not exceed a quantity of 2 % (relationship of peak areas in the chromatogram). However, BCG with impurity quantities higher than 6 % provided AT values which failed fundamental quality requirements. In conclusion, to gain optimal AT measurements especially during long-term deployments, an indicator purification is not necessarily required as long as the purchased dye has a purity level of at least 98 % and is free of the named impurity type. Consequently, high-quality AT measurements do not require pure but the purest BCG that is purchasable.

Description: Atmospheric deposition is an important source of micronutrients to the ocean, but atmospheric deposition fluxes remain poorly constrained in most ocean regions due to the limited number of field observations of wet and dry atmospheric inputs. Here we present the distribution of dissolved aluminium (dAl), as a tracer of atmospheric inputs, in surface waters of the Atlantic Ocean along GEOTRACES sections GA01, GA06, GA08, and GA10. We used the surface mixed layer concentrations of dAl to calculate atmospheric deposition fluxes using a simple steady state model. We have optimized the aerosol Al fractional solubility, dAl residence time within the surface mixed layer and depth of the surface mixed layer for each separate cruise to calculate the atmospheric deposition fluxes. We calculated the lowest deposition fluxes of 0.15 ± 0.1 and 0.27 ± 0.13 g m−2 yr−1 for the South and North Atlantic Ocean (〉 40° S and 〉 40° N), respectively, and highest fluxes of 2.67 ± 1.96 and 3.82 ± 2.72 g m−2 yr−1 for the South East Atlantic and tropical Atlantic Ocean, respectively. Overall, our estimations are comparable to atmospheric dust deposition model estimates and reported field-based atmospheric deposition estimates. We note that our estimates diverge from atmospheric dust deposition model flux estimates in regions influenced by riverine Al inputs and in upwelling regions. As dAl is a key trace element in the GEOTRACES Programme, the approach presented in this study allows calculations of atmospheric deposition fluxes at high spatial resolution for remote ocean regions.

Description: Underwater munitions containing millions of tons of toxic explosives are present worldwide in coastal marine waters as a result of unexploded ordnance and intentional dumping. Dissolution flux of solid explosives following corrosion of metal munition housings controls exposure of biological receptors to toxic munition compounds (MC; including TNT: 2,4,6-Trinitrotoluene, RDX: 1,3,5-Trinitro-1,3,5-triazinane, and DNB: 1,3-Dinitrobenzene). Very little is known about the dissolution behavior of MC in the marine environment. In this work, we exploit a unique marine study site in the Baltic Sea with exposed solid explosives to quantify in situ MC dissolution fluxes using dissolved MC gradients near the exposed explosive surface, as well as benthic chamber incubations. The gradient method gave dissolution fluxes that ranged between 0.001 and 3.2, 0.0001 and 0.04, and 0.003 and 1.7 mg cm-2 d-1 for TNT, RDX, and DNB, respectively. Benthic chamber incubations indicated dissolution fluxes of 0.0047-0.277, 0-0.11, and 0.00047-1.45 mg cm-2 d-1 for TNT, RDX, and DNB, respectively. In situ dissolution fluxes estimated in the current study were lower than most dissolution rates reported for laboratory experiments, but clearly demonstrated that MC are released from underwater munitions to the water column in the Baltic Sea.

Description: The availability of the micronutrient iron (Fe) in surface waters determines primary production, N2 fixation, and microbial community structure in large parts of the world's ocean, and thus it plays an important role in ocean carbon and nitrogen cycles. Eastern boundary upwelling systems and the connected oxygen minimum zones (OMZs) are typically associated with elevated concentrations of redox-sensitive trace metals (e.g., Fe, manganese (Mn), and cobalt (Co)), with shelf sediments typically forming a key source. Over the last 5 decades, an expansion and intensification of OMZs has been observed and this trend is likely to proceed. However, it is unclear how trace-metal (TM) distributions and transport are influenced by decreasing oxygen (O2) concentrations. Here we present dissolved (d; 〈0.2 µm) and leachable particulate (Lp; 〉0.2 µm) TM data collected at seven stations along a 50 km transect in the Mauritanian shelf region. We observed enhanced concentrations of Fe, Co, and Mn corresponding with low O2 concentrations (〈50 µmol kg−1), which were decoupled from major nutrients and nutrient-like and scavenged TMs (cadmium (Cd), lead (Pb), nickel (Ni), and copper (Cu)). Additionally, data from repeated station occupations indicated a direct link between dissolved and leachable particulate Fe, Co, Mn, and O2. An observed dFe (dissolved iron) decrease from 10 to 5 nmol L−1 coincided with an O2 increase from 30 to 50 µmol kg−1 and with a concomitant decrease in turbidity. The changes in Fe (Co and Mn) were likely driven by variations in their release from sediment pore water, facilitated by lower O2 concentrations and longer residence time of the water mass on the shelf. Variations in organic matter remineralization and lithogenic inputs (atmospheric deposition or sediment resuspension; assessed using Al as indicator for lithogenic inputs) only played a minor role in redox-sensitive TM variability. Vertical dFe fluxes from O2-depleted subsurface-to-surface waters (0.08–13.5 µmol m−2 d−1) driven by turbulent mixing and vertical advection were an order of magnitude larger than atmospheric deposition fluxes (0.63–1.43 µmol m−2 d−1; estimated using dAl inventories in the surface mixed layer) in the continental slope and shelf region. Benthic fluxes are therefore the dominant dFe supply to surface waters on the continental margins of the Mauritanian upwelling region. Overall, our results indicated that the projected future decrease in O2 concentrations in OMZs may result in increases in Fe, Mn, and Co concentrations.

Description: Based on an international workshop (Gothenburg, 14–16 May 2008), this review article aims to combine interdisciplinary knowledge from coastal and open ocean research on iron biogeochemistry. The major scientific findings of the past decade are structured into sections on natural and artificial iron fertilization, iron inputs into coastal and estuarine systems, colloidal iron and organic matter, and biological processes. Potential effects of global climate change, particularly ocean acidification, on iron biogeochemistry are discussed. The findings are synthesized into recommendations for future research areas.

Description: The physicochemical characteristics of dissolved organic matter (DOM) strongly influence its interactions with inorganic species such as protons and trace elements in natural waters. We collected water samples at Boknis Eck, a time series station in the Baltic Sea with a low exposure to freshwater inputs, to investigate how seasonal fluctuations impact the proton binding properties of the isolated DOM. We used potentiometric titrations to assess the binding properties of solid-phase extracted DOM (SPE–DOM) over a seasonal cycle. We report and critically analyze the first NICA parameters estimates of carboxylic-like and phenolic-like sites for brackish water SPE–DOM. The total amount of functional groups (QmaxH,tot) showed no seasonal fluctuations and an average value of 136 ± 5.2 mmol·mol C–1. The average proton affinity (logKH) and binding site heterogeneity (m) showed a relatively minor variability for samples obtained between April and September, when the water remained stratified. These results contribute to a better understanding of the ion binding characteristics of DOM in natural brackish waters.

Description: The chemical speciation of iron (Fe) in oceans is influenced by ambient pH, dissolved oxygen, and the concentrations and strengths of the binding sites of dissolved organic matter (DOM). Here, we derived new nonideal competitive adsorption (NICA) constants for Fe(III) binding to marine DOM via pH-Fe titrations. We used the constants to calculate Fe(III) speciation and derive the apparent Fe(III) solubility (SFe(III)app) in the ambient water column across the Peruvian shelf and slope region. We define SFe(III)app as the sum of aqueous inorganic Fe(III) species and Fe(III) bound to DOM at a free Fe (Fe3+) concentration equal to the limiting solubility of Fe hydroxide (Fe(OH)3(s)). A ca. twofold increase in SFe(III)app in the oxygen minimum zone (OMZ) compared to surface waters is predicted. The increase results from a one order of magnitude decrease in H+ concentration which impacts both Fe(III) hydroxide solubility and organic complexation. A correlation matrix suggests that changes in pH have a larger impact on SFe(III)app and Fe(III) speciation than DOM in this region. Using Fe(II) measurements, we calculated ambient DFe(III) and compared the value with the predicted SFe(III)app. The underlying distribution of ambient DFe(III) largely reflected the predicted SFe(III)app, indicating that decreased pH as a result of OMZ intensification and ocean acidification may increase SFe(III)app with potential impacts on surface DFe inventories.

Description: Marine dissolved organic matter (DOM) presents key thermodynamic properties that are not yet fully constrained. Here, we report the distribution of binding sites occupied by protons (i.e., proton affinity spectra) and parametrize the median intrinsic proton binding affinities (log K̅H) and heterogeneities (m), for DOM samples extracted from the North Atlantic. We estimate that 11.4 ± 0.6% of C atoms in the extracted marine DOM have a functional group with a binding site for ionic species. The log K̅H of the most acidic groups was larger (4.01–4.02 ± 0.02) than that observed in DOM from coastal waters (3.82 ± 0.02), while the chemical binding heterogeneity parameter increased with depth to values (m1= 0.666 ± 0.009) ca. 10% higher than those observed in surface open ocean or coastal samples. On the contrary, the log K̅H for the less acidic groups shows a difference between the surface (10.01 ± 0.08) and deep (9.22 ± 0.35) samples. The latter chemical groups were more heterogeneous for marine than for terrestrial DOM, and m2 decreased with depth to values of 0.28 ± 0.03. Binding heterogeneity reflects aromatic carbon compounds’ persistence and accumulation in diverse, low-abundance chemical forms, while easily degradable low-affinity groups accumulate more uniformly in the deep ocean.