Mercury in the Black Sea: New Insights From Measurements and Numerical Modeling.

Redox conditions and organic matter control marine methylmercury (MeHg) production. The Black Sea is the world's largest and deepest anoxic basin and is thus ideal to study Hg species along the extended redox gradient. Here we present new dissolved Hg and MeHg data from the 2013 GEOTRACES MEDBlack cruise (GN04_leg2) that we integrated into a numerical 1-D model, to track the fate and dynamics of Hg and MeHg. Contrary to a previous study, our new data show highest MeHg concentrations in the permanently anoxic waters. Observed MeHg/Hg percentage (range 9-57%) in the anoxic waters is comparable to other subsurface maxima in oxic open-ocean waters. With the modeling we tested for various Hg methylation and demethylation scenarios along the redox gradient. The results show that Hg methylation must occur in the anoxic waters. The model was then used to simulate the time evolution (1850-2050) of Hg species in the Black Sea. Our findings quantify (1) inputs and outputs of HgT (~31 and ~28 kmol yr-1) and MeHgT (~5 and ~4 kmol yr-1) to the basin, (2) the extent of net demethylation occurring in oxic (~1 kmol yr-1) and suboxic water (~6 kmol yr-1), (3) and the net Hg methylation in the anoxic waters of the Black Sea (~11 kmol yr-1). The model was also used to estimate the amount of anthropogenic Hg (85-93%) in the Black Sea.

Mesoscale iron enrichment experiments 1993-2005: synthesis and future directions.

Since the mid-1980s, our understanding of nutrient limitation of oceanic primary production has radically changed. Mesoscale iron addition experiments (FeAXs) have unequivocally shown that iron supply limits production in one-third of the world ocean, where surface macronutrient concentrations are perennially high. The findings of these 12 FeAXs also reveal that iron supply exerts controls on the dynamics of plankton blooms, which in turn affect the biogeochemical cycles of carbon, nitrogen, silicon, and sulfur and ultimately influence the Earth climate system. However, extrapolation of the key results of FeAXs to regional and seasonal scales in some cases is limited because of differing modes of iron supply in FeAXs and in the modern and paleo-oceans. New research directions include quantification of the coupling of oceanic iron and carbon biogeochemistry.

Shipboard techniques based on flow injection analysis for measuring dissolved Fe, Mn and Al in seawater.

An overview is presented of sampling techniques and flow injection analysis (FIA) methods for low concentrations of Fe, Mn and Al in filtered seawater. On the basis of sampling procedures, filtration techniques, accuracy, blanks, detection limits, intercalibration results and oceanographic consistency, the feasibility of these FIA methods was evaluated. It was found that these metals could be measured on board with a minimum risk of contamination and with good accuracy even at low subnanomolar levels (<0.5 nM). Results for reference seawater were in the case of Fe-FIA and Mn-FIA in excellent agreement with the certified values. Data from samples analyzed by Fe-FIA and by cathodic stripping voltametry (CSV) compared well, as did Mn-FIA and GFAAS. All three methods gave results that were mostly in good agreement with data from the same ocean regions published by other research groups. Two different types of surface water sampling were also tested and compared, namely conventional hand filling of a sample bottle from a rubber dinghy away from the ship, and underway pumping of seawater using a 'tow fish'. The latter method gave the best results. Also, conventional membrane filtration and cartridge filtration for large volume filtration were compared using Fe and Al data from water column samples. Good agreement was found for both filter types, although for defining dissolved metal species the latter filter type was preferred.

The determination and distribution of Zn in surface water samples collected in the northeast Atlantic Ocean.

Dissolved Zn concentrations were determined in surface water samples collected on-line along transects in the eastern North Atlantic in spring (March 1998). Two frontal zones could be identified in the research area by a change in salinity, temperature and nutrient concentrations. One zone was identified at 42 degrees N, separating the North Atlantic central water (NACW) and the Atlantic surface water (ASW) from each other, and another one crossing the continental slope at 12 degrees and 8 degrees E, respectively. Variability in Zn concentrations was observed near these zones, not only as a result of a change of water mass, but also due to external Zn sources. Surface Zn concentrations were 0.5-1 nM and 2 nM in the NACW and ASW, respectively, increasing to 4 nM over the continental shelf and finally 5-6 nM in the English Channel. Contributions of Zn derived from shelf sediments appear to be the major source for the enriched surface values in the continental zone.