Description: Seasonal (Spring and Summer 2002) concentrations of dissolved (〈0.22 μm) trace metals (Ag, Al, Co, Cu, Mn, Ni, Pb), inorganic nutrients (NO3, PO4, Si), and DOC were determined in groundwater samples from 5 wells aligned along a 30 m shore-normal transect in West Neck Bay, Long Island, NY. Results show that significant, systematic changes in groundwater trace metal and nutrient composition occur along the flowpath from land to sea. While conservative mixing between West Neck Bay water and the groundwaters explains the behavior of Si and DOC, non-conservative inputs for Co and Ni were observed (concentration increases of 10- and 2-fold, respectively) and removal of PO4 and NO3 (decreases to about half) along the transport pathway. Groundwater-associated chemical fluxes from the aquifer to the embayment calculated for constituents not exhibiting conservative behavior can vary by orders of magnitude depending on sampling location and season (e.g. Co, 3.4 × 102– 8.2 × 103 μmol d−1). Using measured values from different wells as being representative of the true groundwater endmember chemical composition also results in calculation of very different fluxes (e.g., Cu, 6.3 × 103 μmol d−1 (inland, freshwater well) vs. 2.1 × 105 μmol d−1(seaward well, S = 17 ppt)). This study suggests that seasonal variability and chemical changes occurring within the subterranean estuary must be taken into account when determining the groundwater flux of dissolved trace metals and nutrients to the coastal ocean.

Description: Geochemical cycles occurring at the interface between terrestrial and marine groundwaters, in the so-called subterranean estuary (STE), are not well understood for most elements. This is particularly true of the transition metals, many of which have particular ecological relevance as micronutrients or toxicants. To gain a first approximation of trace metal geochemistry in the mixing zone, we examined the distribution of nine dissolved metals (Fe, Mn, Mo, V, Co, Ni, Cu, Pb, and Al) through a shallow STE in Great South Bay, New York, USA. We also performed a simple kinetic and chemical separation of labile and organic-complexed metal species in the STE. Dissolved Mn showed marked subsurface enrichment (up to 755 µM at 15 cm depth) that was suggestive of diagenetic remobilization. Dissolved Fe, however, was higher by more than three orders-of-magnitude in fresh groundwater (90 µM) as compared to marine groundwater (0.02 µM), and pH-mediated removal was evident as slightly acidic fresh groundwater (pH 6.8) mixed with marine groundwater (pH ∼ 8.0). Dissolved Mo, Co, and Ni were primarily cycled with Mn, and highly elevated concentrations relative to bay surface waters (up to 300, 75, and 44 nM, respectively) were observed in the STE. High levels of dissolved Pb (up to 4250 pM) observed in the fresh groundwater were nearly quantitatively removed within the salinity mixing zone, in conjunction with marked reduction of dissolved Al. Dissolved Cu exhibited non-conservative removal throughout the STE, and was correlated with the redox potential of the porewaters. Substantial percentages (〉 15%) of organic-metal species were only observed for Cu and Ni, suggesting that these complexes were not generally very important for metal cycling in the STE. Kinetically labile species were observed for all metals examined except Cu and Pb, and represented an approximately constant proportion (between 10% and 70%) of the total dissolved pool for each metal, indicating equilibrium between labile and non-labile species throughout the mixing zone. The non-conservative behavior observed for all metals examined in this study suggests that reactions occurring in the STE are vastly important to the source/sink function of permeable sediments, and studies seeking to quantify SGD-derived trace metal fluxes must take into account biogeochemical processes occurring in the subterranean estuary.

Description: We examined the physiological responses of steady-state iron (Fe)-replete and Fe-limited cultures of the biogeochemically critical marine unicellular diazotrophic cyanobacterium Crocosphaera at glacial (19 Pa; 190 ppm), current (39 Pa; 380 ppm), and projected year 2100 (76 Pa; 750 ppm) CO2 levels. Rates of N2 and CO2 fixation and growth increased in step with increasing partial pressure of CO2 (pCO2), but only under Fe-replete conditions. N2 and carbon fixation rates at 75 Pa CO2 were 1.4-1.8-fold and 1.2-2.0-fold higher, respectively, relative to those at present day and glacial pCO2 levels. In Fe-replete cultures, cellular Fe and molybdenum quotas varied threefold and were linearly related to N2 fixation rates and to external pCO2. However, N2 fixation and trace metal quotas were decoupled from pCO2 in Fe-limited Crocosphaera. Higher CO2 and Fe concentrations both resulted in increased cellular pigment contents and affected photosynthesis vs. irradiance parameters. If these results also apply to natural Crocosphaera populations, anthropogenic CO2 enrichment could substantially increase global oceanic N2 and CO2 fixation, but this effect may be tempered by Fe availability. Possible biogeochemical consequences may include elevated inputs of new nitrogen to the ocean and increased potential for Fe and/or phosphorus limitation in the future high-CO2 ocean, and feedbacks to atmospheric pCO2 in both the near future and over glacial to interglacial timescales.

Description: The late stage of the North East Atlantic (NEA) spring bloom was investigated during June 2005 along a transect section from 45 to 66° N between 15 and 20° W in order to characterize the contribution of siliceous and calcareous phytoplankton groups and describe their distribution in relation to environmental factors. We measured several biogeochemical parameters such as nutrients, surface trace metals, algal pigments, biogenic silica (BSi), particulate inorganic carbon (PIC) or calcium carbonate, particulate organic carbon, nitrogen and phosphorus (POC, PON and POP, respectively), as well as transparent exopolymer particles (TEP). Results were compared with other studies undertaken in this area since the JGOFS NABE program. Characteristics of the spring bloom generally agreed well with the accepted scenario for the development of the autotrophic community. The NEA seasonal diatom bloom was in the late stages when we sampled the area and diatoms were constrained to the northern part of our transect, over the Icelandic Basin (IB) and Icelandic Shelf (IS). Coccolithophores dominated the phytoplankton community, with a large distribution over the Rockall-Hatton Plateau (RHP) and IB. The Porcupine Abyssal Plain (PAP) region at the southern end of our transect was the region with the lowest biomass, as demonstrated by very low Chla concentrations and a community dominated by picophytoplankton. Early depletion of dissolved silicic acid (DSi) and increased stratification of the surface layer most likely triggered the end of the diatom bloom, leading to coccolithophore dominance. The chronic Si deficiency observed in the NEA could be linked to moderate Fe limitation, which increases the efficiency of the Si pump. TEP closely mirrored the distribution of both biogenic silica at depth and prymnesiophytes in the surface layer suggesting the sedimentation of the diatom bloom in the form of aggregates, but the relative contribution of diatoms and coccolithophores to carbon export in this area still needs to be resolved.

Description: [1] While recent studies have confirmed the ecological importance of vitamin B12, it is unclear whether the production of this vitamin could be limited by dissolved Co, a trace metal required for B12 biosynthesis, but found at only subnanomolar concentrations in the open ocean. Herein, we demonstrate that the spatial distribution of dissolved B12 (range: 0.13–5 pmol L−1) in the North Atlantic Ocean follows the abundance of total dissolved Co (range: 15–81 pmol L−1). Similar patterns were observed for bacterial productivity (range: 20–103 pmol 3H leucine L−1 hr−1) and algal biomass (range: 0.4–3.9 μg L−1). In contrast, vitamin B1 concentrations (range: 0.7–30 pM) were decoupled from both Co and B12 concentrations. Cobalt amendment experiments carried out in low-dissolved Co waters (∼20 pmol L−1) enhanced B12 production two-fold over unamended controls. This study provides evidence that B12 synthesis could be limited by the availability of Co in some regions of the world ocean.

Description: An increasing body of evidence suggests that much of the trace metal contamination observed in coastal waters is no longer derived from point-source inputs, but instead originates from diffuse, non-point sources. Previous research has shown that water temperature and dissolved oxygen regulate non-point source processes such as sediment diagenesis; however, limited information is available regarding the effect of these variables on toxic trace metal cycling and speciation in natural waters. Here, we present data on the seasonal variation of dissolved Cu cycling in the Long Island Sound, an urban estuary adjacent to New York City. An operationally defined chemical speciation technique based on kinetic lability and organic complexation has been applied to examine the most ecologically relevant metal fraction. In contrast to the decrease from spring to summer observed in the total dissolved Cu pool (average ± SD:  15.1 ± 4.4 nM in spring and 11.8 ± 3.5 nM in summer), our results revealed that in the highly impacted western LIS, levels of labile Cu reached higher levels in summer (range 3.6−7.7 nM) than in spring (range 1.5− 3.9 nM). Labile Cu in surface waters of the western Sound appeared to have a wastewater source during spring high flow conditions, coinciding with elevated levels of sewage-derived Ag. Labile Cu elsewhere in the LIS during spring apparently resulted from fluvial input and mixing. During summer, labile Cu increased in bottom waters (at one site, bottom water labile Cu increased from 1.5 nM in spring to 7.7 nM in summer), and covariance with tracers of diagenetic remobilization (e.g., Mn) revealed a sedimentary source. Although total dissolved Cu showed no consistent trends with water quality parameters, labile Cu in bottom waters showed an inverse correlation with dissolved oxygen and a positive, exponential correlation with water temperature. These results suggest that future increases in coastal water temperatures may cause the benthic source of labile Cu to become proportionally more significant.

Description: In order to identify the biogeochemical parameters controlling pCO2, total chlorophyll a, and dimethyl sulfide (DMS) concentrations during the North East Atlantic Spring Bloom (NASB), we used previously unpublished particulate and dissolved elemental concentrations to construct several linear regression models; first by hypothesis-testing, and then with exhaustive stepwise linear regression followed by leave-one-out cross-validation. The field data was obtained along a latitudinal transect from the Azores Islands to the North Atlantic, and best-fit models (determined by lowest predictive error) of up to three variables are presented. Total chlorophyll a is predicted best by biomass (POC, PON) parameters and by pigments characteristic of picophytoplankton for the southern section of the sampling transect (from the Azores to the Rockhall-Hatton Plateau) and coccolithophores in the northern portion (from the Rockhall-Hatton Plateau to the Denmark Strait). Both the pCO2 and DMS models included variables traditionally associated with the development of the NASB such as mixed-layer depth and with Fe, Si, and P-deplete conditions (dissolved Fe, dissolved and biogenic silica, dissolved PO3−4). However, the regressions for pCO2 and DMS also include intracellular V and Mo concentrations, respectively. Mo is involved in DMS production as a cofactor in dimethylsulfoxide reductase. No significant biological role for V has yet been determined, although intracellular V is significantly correlated (p-value 〈0.05) with biogenic silica (R2 = 0.72) and total chlorophyll a (R2 = 0.49) while the same is not true for its biogeochemical analogue Mo, suggesting active uptake of V by phytoplankton. Our statistical analysis suggests these two lesser-studied metals may play more important roles in bloom dynamics than previously thought, and highlights a need for studies focused on determining their potential biological requirements and cell quotas.

Description: Distributions of dissolved vitamin B12 and total dissolved Co were measured to gain an understanding of the cycling of these interdependent micronutrients in six marine settings including; an upwelling location, a semi-enclosed bay, two urban coastal systems, and two open ocean locations. Along the coast of Baja California, Mexico, concentrations of B12 and dissolved Co varied from 0.2 to 11 pM and 180 to 990 pM, respectively. At a nearby upwelling station, vitamin B12 and Co concentrations ranged from 0.3 to 7.0 pM and 22 to 145 pM, and concentrations did not correlate with upwelling intensity. Concentrations of B12 were highest within Todos Santos Bay, a semi-enclosed bay off the coast of Baja California, Mexico, during a dinoflagellate bloom, ranging from 2 to 61 pM, while Co concentrations varied between 61 and 194 pM. In the anthropogenically impacted Long Island Sound, NY, U.S.A., B12 levels were between 0.1 and 23 pM and Co concentrations varied from 60 to 1900 pM. However, anthropogenic inputs were not evident in B12 levels in the San Pedro Basin, located outside Los Angeles, Ca, U.S.A., where concentrations of B12 were 0.2–1.8 pM, approximating observed open ocean B12 concentrations. In the Southern Ocean and North Atlantic Ocean, B12 levels were 0.4–4 pM and 0.2–2 pM, respectively. Total Co concentrations in the Southern Ocean and North Atlantic tended to be low; measuring 26–59 pM and 15–80 pM, respectively. These low Co concentrations may limit B12 synthesis and its availability to B12-requiring phytoplankton because the total dissolved Co pool is not necessarily entirely bioavailable.

Description: We present the first comprehensive investigation of the concentrations, fluxes and sources of aerosol trace elements over the Gulf of Aqaba. We found that the mean atmospheric concentrations of crustally derived elements such as Al, Fe and Mn (1081, 683, and 16.7 ng m�3) are about 2–3 times higher than those reported for the neighboring Mediterranean area. This is indicative of the dominance of the mineral dust component in aerosols over the Gulf. Anthropogenic impact was lower in comparison to the more heavily populated areas of the Mediterranean. During the majority of time (69%) the air masses over the Gulf originated from Europe or Mediterranean Sea areas delivering anthropogenic components such as Cu, Cd, Ni, Zn, and P. Airflows derived from North Africa in contrast contained the highest concentrations of Al, Fe, and Sr but generally lower Cu, Cd, Ni, Zn, and P. Relatively high Pb, Ni, and V were found in the local and Arabian airflows suggesting a greater influence of local emission of fuel burning. We used the data and the measured trace metal seawater concentrations to calculate residence times of dissolved trace elements in the upper 50 m surface water of the Gulf (with respect to atmospheric input) and found that the residence times for most elements are in the range of 5–37 years while Cd and V residence times are longer.

Description: Jamaica Bay, NY, is a highly urbanized estuary within the boroughs of New York City conspicuously lacking published information on dissolved trace metal concentrations. The current study examines the distribution and cycling of trace metals in that embayment with data gathered during cruises in November 2004, April 2005, and June 2006. Most of the metal distributions (Fe, Zn, Co, Ag, Cu, Pb, Ni) in the water column are explained by the input of substantial volumes of treated wastewater effluent. However, several lines of evidence suggest that submarine groundwater discharge (SGD) is also an important source of dissolved Fe, Zn, Co, Ni, and isotopically distinct stable Pb ratios (206Pb, 207Pb, 208Pb) in the Bay. Conversely, the recirculated seawater component of SGD is an apparent sink for dissolved Mo. This study provides the first measurements of dissolved trace metals in the Jamaica Bay water column and subterranean estuary and provides evidence for trace metal input due to SGD.