Temporal and spatial variations in the biogeochemical cycling of cobalt in two urban estuaries: Hudson River Estuary and San Francisco Bay

Despite the fact that Co is an essential trace element for the growth of marine phytoplankton, there is very limited information on the cycling of this trace metal in the marine environment. We report here the distribution of dissolved (<0.4 μm) and particulate (>0.4 μm) Co in surface waters of the Hudson River Estuary (HRE) and San Francisco Bay (SFB). Samples were collected during several cruises (from 1990 to 1995 in SFB and from 1995 to 1997 in the HRE) along the whole salinity gradient. Dissolved Co concentrations (mean±1 standard deviation) were nearly identical in magnitude in both estuaries despite differences in climate, hydrography, riverine-flow conditions and land-usage (HRE=0.91±0.61 nM; SFB=1.12±0.69 nM). Dissolved Co levels in each system showed non-conservative distributions when plotted as a function of salinity, with increasing concentrations downstream from the riverine end-members. Desorption from suspended particulates and sewage inputs, therefore, seems to be the major processes responsible for the non-conservative behavior of Co observed. Mass balance estimates also indicated that most of the estuarine Co is exported out of both estuaries, indicating that they and other estuarine systems are principal sources of this essential trace element to the open ocean.     

Importance of geochemical transformations in determining submarine groundwater discharge-derived trace metal and nutrient fluxes

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.     

Impact of submarine hydrothermal vents on the metal composition of krill and its excretion products

We have measured the metal composition and estimated the excretion rate of trace elements (Ag, Cd, Co, Cu, Ni, Pb, V and Zn) by Antarctic krill (Euphausia superba) in three locations (two located within a submarine hydrothermal vent field and one away from it) along the Antarctic Peninsula region of the Southern Ocean. Results indicated that krill excreted large amounts of Ag, Cu, Pb and Zn, (range: 1.9–41.2 pmol Ag g DW^? 1 h^? 1, 15.3–26.8 nmol Cu g DW^? 1 h^? 1, 308.7–1118.3 pmol Pb g DW^? 1 h^? 1 and 24.4–76.5 nmol Zn g DW^? 1 h^? 1), compared with the non-significant or undetectable release rates of Cd, Co, Ni and V. The metal composition of the excreted material from krill collected in the area of hydrothermal activity was similar to the metal composition reported for suspended particles emitted from those vents. Our results suggest that krill recycling of Ag, Cu, Pb and Zn could potentially influence trace metal concentrations in the water column of the Bransfield region of the Southern Ocean, and that the original source of metals to these waters may be hydrothermal vents.     

A new method for the quantification of different redox-species of molybdenum (V and VI) in seawater

A new method for the direct determination of reduced and oxidized Mo species (Mo (V) and Mo (VI)) in seawater was developed and used for the first time. The method includes the complexation of Mo (V) with tartrate, solid phase extraction of the Mo (V)–tartrate complex by a XAD 7HP resin, followed by elution with acidic acetone. In this study, the eluted Mo (V) was quantified by graphite furnace atomic absorption spectrometry. The detection limit of this protocol was on the order of 0.2 nM. The analytical precision was 10% of ~ 10 nM. This method was successfully applied to the determination of Mo (V) and Mo (VI) in surface and bottom waters at the head of Peconic River Estuary. Total Mo (Mo (V) + Mo (VI)) ranged from 100–120 nM in most bottom saline waters, and 2.5–15 nM for surface fresher waters. Concentrations of Mo (V) in these environments ranged from 0 nM to ~ 15 nM, accounting for 0%–15% of the total dissolved Mo pool. The time series experiments showed that the Mo speciation changed within 1 h after the water collection, and therefore it is strongly suggested that speciation analysis be carried out within the first 15 min. However, since these are the first Mo speciation data in concentration ranges typical of normal marine and coastal waters, additional research may be required to optimize the methodology and further explore Mo cycling mechanisms.     

Physico-chemical Speciation of Lead in South San Francisco Bay

The speciation of lead at a site in the South San Francisco Bay was determined using a combination of physical size fractionation and electrochemical analyses. The ‘ total dissolvable ’ Pb was 8·1 nM from analysis of an acidified unfiltered sample. The ‘ dissolved ’ Pb was equal to 0·20 nM (41 ng l⁻¹), only 2·5% of the ‘ total dissolvable ’ Pb. The difference yielded the ‘ particulate ’ Pb equal to 7·9 nM (1·6 μg l⁻¹). Results from crossflow ultrafiltration indicated that almost all (0·19 nM) of the dissolved Pb was ‘ in solution ’ [<10K nominal molecular weight (MW)] and that colloidal Pb (10K MW to 0·2 μm)accounted for onlyc. 1% of the dissolved Pb at this station. This small concentration (0·01 nM) of colloidal Pb may be attributed to the low amount of organic carbon associated with colloid size fraction as determined by dissolved organic carbon analyses.The chemical speciation of lead was determined in the dissolved sample and ultrafiltered sub-sample. Differential pulse anodic stripping voltammetry (DPASV) on a thin mercury film (TMF) rotating glassy carbon disk electrode (RGCDE) was used to distinguish the kinetically labile inorganic species (Pb′) from the Pb-chelated by organic ligands (PbL_i). Lead titration results were similar for both samples revealing that Pb′, PbL_iand excess unbound ligands were present primarily in the ultrafiltrate, rather than in the colloidal phase. The titration data can be interpreted as dissolved Pb being influenced by two classes of Pb-binding ligands. In the dissolved sample, the concentration of the stronger class of ligands was [L₁]=0·89±0·35 nM, with a conditional stability constant ofK^cond_L1,Pb′=3±1×10¹⁰M⁻¹. The weaker class was [L₂]=12·8±1·9 nM, withK^cond_L1,Pb′=4±1×10⁸ M⁻¹. The presence of these ligands, in excess of the dissolved Pb, resulted in [Pb′]=7±2 pM and [Pb²⁺]=0·3 pM (62 pg l⁻¹). While less than 2·4% of the ambient Pb was ‘ in solution ’, it existed chiefly in the form of organic complexes with [PbL₁]=0·15 nM and [PbL₂]=0·03 nM. More significantly, there were large concentrations of unchelated Pb-binding ligands, (L_i′), available to buffer the free Pb²⁺concentration in the event of perturbations in dissolved Pb.     

Dissolved trace element cycles in the San Francisco Bay estuary

Dissolved trace element (copper, nickel, cadmium, zinc, cobalt, and iron) concentrations were measured in surface water samples collected from 27 stations in the San Francisco Bay and Sacramento—San Joaquin Delta during April, August and December of 1989. The trace element distributions were relatively similar for all three sampling periods, and evidenced two distinct biogeochemical regimes within the estuarine system. The two regimes were comprised of relatively typical trace element gradients in the northern reach and anthropogenically perturbed gradients in the southern reach of the estuary. These dichotomous trace element distributions were consistent with previous reports on the distributions of nutrients and some other constituents within the estuary.In the northern reach, trace element and dissolved phosphate concentrations were non-conservative. Simple estuarine mixing models indicated substantial internal sources of dissolved copper (46–150%), nickel (250–500%) and cadmium (630–780%) relative to riverine inputs in April and August, and sizable internal sinks for dissolved cobalt (> 99%) and iron (> 70%) during the same periods. Dissolved zinc fluxes varied temporally, with a relatively large (135%) internal source in April and a relatively small (29%) internal sink in August.Concentrations of many trace elements (copper, nickel, cadmium, zinc, and cobalt) in the southern reach were anomalously high relative to concentrations at comparable salinities in the northern reach. Mass balance calculations indicated that those excesses were primarily due to anthropogenic inputs (waste-water discharges and urban runoff) and diagenetic remobilization from benthic sediments. The magnitude of these excesses was amplified by the long hydraulic residence time of dissolved constituents within the South Bay.The influence of other factors was evident throughout the system. Notably, upwelling appeared to elevate substantially dissolved cadmium concentrations at the mouth of the estuary and authigenic flocculation appeared to dominate the cycling of dissolved iron in both the northern and southern reaches of the system. Biological scavenging, geochemical scavenging and diagenic remobilization were also found to be important in different parts of the estuary. Additional complementary information is required to quantify accurately these processes.     

Distribution of colloidal trace metals in the San Francisco Bay estuary

The size distribution of trace metals (Al, Ag, Cd, Cu, Fe, Mn, Ni, Sr, and Zn) was examined in surface waters of the San Francisco Bay estuary. Water samples were collected in January 1994 across the whole salinity gradient and fractionated into total dissolved (<0.2 μm colloidal (10 KDa–0.2 μm) and < 10 kDa molecular weight phases. In the low salinity region of the estuary, concentrations of colloidal A1, Ag, and Fe accounted for ≥84% of the total dissolved fraction, and colloidal Cu and Mn accounted for 16–20% of the total. At high salinities, while colloidal Fe was still relatively high (40% of the dissolved), very little colloidal Al, Mn, and Cu (<10%) and no colloidal Ag was detectable. Colloidal Zn accounted for <3% of the total dissolved along the estuary, and colloidal Ni was only detectable (<2%) at the river endmember. All of the total dissolved Cd and Sr throughout the estuary consisted of relatively low molecular weight (<10 kDa) species. The relative affinity of metals for humic substances and their reactivity with particle surfaces appear to determine the amounts of metal associated with colloids. The mixing behavior of metals along the estuary appears to be determined by the relative contribution of the colloidal phase to the total dissolved pool. Metals with a small or undetectable colloidal fraction showed a nonconservative excess (Cd, Cu, Ni, and Mn) or conservative mixing (Sr) in the total dissolved fraction, relative to ideal dilution of river water and seawater along the estuary.

The salt-induced coagulation of colloidal A1, Fe, and Cu is indicated by their highly nonconservative removal along the salinity gradient. However, colloidal metals with low affinity for humic substances (Mn and Zn) showed conservative mixing behavior, indicating that some riverine colloids are not effectively aggregated during their transport to the sea. While colloidal metal concentrations correlated with dissolved organic carbon, they also covaried with colloidal Al, suggesting that colloids are a mixture of organic and inorganic components. Furthermore, the similarity between the colloidal metal:A1 ratios with the crustal ratios indicated that colloids could be the product of weathering processes or particle resuspension. Distribution coefficients for colloidal particles (K_c) and for large, filter-retained particles (K_d) were of the same magnitude, suggesting similar binding strength for the two types of particles. Also, the dependence of the distribution coefficients on the amount of suspended particulate matter (the so-called particle concentration effect) was still evident for the colloids-corrected distribution coefficient (K_p+c) and for metals (e.g., Ni) without affinity for colloidal particles.     

Spatial and temporal dynamics of dissolved trace metals, organic carbon, mineral nutrients, and phytoplankton in a coastal lagoon: Great South Bay, New York

Although marine lagoons are ubiquitous features along coastal margins, studies investigating the dynamics of metal, organic matter, and nutrient concentrations in such systems are rare. Here we present a comprehensive examination of the temporal and spatial gradients in dissolved trace metals (Ag, Cd, Cu, Mn, Pb), organic and inorganic nutrients (POC, PON, DOC, N0₃ ⁻, NH₄ ⁺, H₄SiO₄, PO₄ ⁻³, and urea), and algal biomass in a lagoon estuary, Great South Bay (GSB), New York, USA. While this estuary has experienced a series of environmental problems during recent decades (urbanization, loss of fisheries, harmful algal blooms), root causes are largely unknown, in part because levels of bioactive substances, such as trace metals, have never been measured. Sampling was undertaken within multiple estuarine, riverine, and groundwater sites during spring, summer, and fall. Trace metal tracers (e.g., Ag, Mn) and statistical analyses were used to differentiate the influences of natural and anthropogenic processes on the chemical composition of the lagoon. Our analyses revealed three clusters of biogeochemical constituents that behaved similarly in GSB: constituents under strong biological control such as POC, PON, DOC and chlorophyll,a; elements indicative of benthic remobilization processes such as Mn, Cd, and Cu; and constituents strongly influence by anthropogenic processes such as Ag, Pb, PO₄ ⁻³, NO₃ ⁻, and NH₄ ⁺. Although GSB is surrounded by a densely populated watershed (c. 1 million people), it does not appear to be significantly contaminated by trace metals compared to other urban estuaries. Levels of DOC (up to 760 μM) in GSB were well correlated with phytoplankton biomass and exceeded at least 98% of values reported in similar mid Atlantic estuaries at the same salinities. These high levels of DOC are likely to be an important source of carbon export to the coastal ocean and likely promote mixotrophic harmful algal blooms in this system.     

Dissolved iron distributions in the central region of the Gulf of California,México

We report dissolved iron (Fe_d) concentrations measured in the upper 600 m in the central region of the Gulf of California (GC) under spring conditions. Our results showed the complex nature of Fe cycling within the GC. In the northern region of the study area, surface waters were relatively enriched, with Fe_d concentrations >5.0 nM, which can be partially explained by an atmospheric source. These concentrations are 12 times higher than those found in the adjacent Pacific Ocean. In contrast, Fe_d depth profiles in the southern region did not show any Fe_d surface enrichment (concentrations <1.5 nM) because of particle scavenging and higher stratification of the water-column. The most southern station in our area of study was the most stratified and showed an excess Fe_d and PO₄ with respect to NO₃, conditions favorable for nitrogen fixation. This station also showed the least negative surface value of N* of all stations. However, despite the adequate levels of Fe_d and PO₄ at that location, the surface temperature (22.6 °C) was probably not high enough for diazotrophs to develop. A slight increase in Fe_d levels in intermediate waters at the southern region was associated with the oxygen minimum zone. Finally, our results suggest that remineralization of organic matter is probably the major source of Fe_d in subsurface waters of the GC.     

Distributions of dissolved vitamin B12 and Co in coastal and open-ocean environments

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.