Description: The effect of phototrophic biofilm activity on advective transport of cadmium (Cd), copper (Cu), nickel (Ni), and lead (Pb) in sandy sediments was examined using percolated columns. Cd and Ni in the effluent exhibited clear diel cycles in biofilm-containing columns, with concentrations at the end of dark periods exceeding those during illumination by up to 4.5- and 10-fold for Ni and Cd, respectively. Similar cycles were not observed for Pb or Cu. Breakthrough of the latter metals was greatly retarded and incomplete relative to Cd and Ni, and trends in biofilm treatments did not differ greatly from those in control columns. Inhibition of photosystem II by DCMU (3-(3,4-dichlorophenyl)-1,1-dimethylurea) proved that diel cycles of Cd and Ni were controlled by oxygenic photosynthesis, and microsensor measurements showed that metal cycles closely matched metabolic activity-driven pH variations. The sorption edge pH for the sand/biofilm substrate followed the order Ni 〉 Cd 〉 Cu 〉 Pb, and for Ni and Cd, was within the pH 7–10 range observed in the biofilm-containing column. Adsorption dynamics over the light periods matched pH increases, but desorption during dark periods was incomplete and slower than the rate of change of pH. Over a diel cycle, desorption was less than adsorption, resulting in net binding of dissolved metals due to the biofilm metabolic activity. Extraction with selective reagents indicated that the adsorbed metals were readily exchangeable, and potentially bioavailable. Thus, phototrophic benthic biofilms can control the transport of some metals across the sand–water interface, and processes in this very thin surficial layer should be considered when evaluating chemical fluxes in permeable sediments.

Description: Diel cycles of dissolved cationic metal concentrations commonly occur in freshwater streams in apparent response to coincident cycles in water quality parameters (pH, O2, temperature). Hourly sampling of the Cd-contaminated Riou Mort (France) revealed large diel cycles in “total” dissolved Cd (232−357 nM; 〈0.45 μm) and “truly” dissolved Cd (56−297 nM; 〈0.02 μm) which were strongly correlated with changes in water pH. Using measured fluxes, a dissolved O2 model was constructed that indicated that benthic metabolic activities, respiration and photosynthesis, were responsible for the diel O2 (and thus, CO2 and pH) variation in the stream. However, microsensor measurements also showed that the pH changes occurred at the biofilm interface earlier than in the bulk water column. This difference in timing was reflected in the Cd dynamics, where pH-controlled sorption effects caused Cd partitioning from the truly dissolved pool onto the biofilm in the morning, and from the truly dissolved pool onto large colloids (0.02−0.45 μm) later in the day. Because this process causes large changes in the bioavailable Cd fraction, it has significant implications for Cd toxicity in freshwater streams. This study demonstrates the profound control of benthic microbiological processes on the cycling of heavy metals in aquatic systems.

Description: Author Posting. © The Author(s), 2013. This is the author's version of the work. It is posted here by permission of Elsevier B.V. for personal use, not for redistribution. The definitive version was published in Geochimica et Cosmochimica Acta 117 (2013): 33-52, doi:10.1016/j.gca.2013.03.021.

Description: Submarine groundwater discharge (SGD) to the ocean supplies Sr with less radiogenic 87Sr/86Sr than seawater, and thus constitutes an important term in the Sr isotope budget in the modern ocean. However, few data exist for Sr in coastal groundwater or in the geochemically dynamic subterranean estuary (STE). We examined Sr concentrations and isotope ratios from nine globally-distributed coastal sites and characterized the behavior of Sr in the STE. Dissolved Sr generally mixed conservatively in the STE, although large differences were observed in the meteoric groundwater end-member Sr concentrations among sites (0.1 – 24 μM Sr). Strontium isotope exchange was observed in the STE at five of the sites studied, and invariably favored the meteoric groundwater end-member signature. Most of the observed isotope exchange occurred in the salinity range 5-15, and reached up to 40% exchange at salinity 10. Differences in fresh groundwater Sr concentrations and isotope ratios (87Sr/86Sr = 0.707-0.710) reflected aquifer lithology. The SGD end-member 87Sr/86Sr must be lower than modern seawater (i.e., less than 0.70916) in part because groundwater Sr concentrations are orders of magnitude higher in less-carbonate and volcanic island aquifers. A simple lithological model and groundwater Sr data compiled from the literature were used to estimate a global average groundwater end-member of 2.9 μM Sr with 87Sr/86Sr = 0.7089. This represents a meteoric-SGD-driven Sr input to the ocean of 0.7-2.8 × 1010 mol Sr y-1. Meteoric SGD therefore accounts for 2-8% of the oceanic Sr isotope budget, comparable to other known source terms, but is insufficient to balance the remainder of the budget. Using reported estimates for brackish SGD, the estimated volume discharge at salinity 10 (7-11 × 1015 L y-1) was used to evaluate the impact of isotope exchange in the STE on the brackish SGD Sr flux. A moderate estimate of 25% isotope exchange in the STE gives an SGD Sr end-member 87Sr/86Sr of 0.7091. The brackish SGD Sr flux thus accounts for 11-23% of the marine Sr isotope budget, but does not appear sufficient to balance the ~40% remaining after other known sources are included. Substantial uncertainties remain for estimating the SGD source of Sr to the global ocean, especially in the determination of the volume flux of meteoric SGD, and in the paucity of measurements of groundwater Sr isotope composition in major SGD regions such as Papua New Guinea, the South America west coast, and West Africa. Consequently, our global estimate should be viewed with some caution. Nevertheless, we show that the combined sources of meteoric SGD and brackish SGD coupled with isotope exchange in the STE may constitute a substantial component (~13-30%) of the modern oceanic 87Sr/86Sr budget, likely exceeding less radiogenic Sr inputs by sedimentary diagenesis and hydrothermal circulation through the mid-ocean ridge system. Temporal variation in SGD Sr fluxes and isotope composition may have contributed to fluctuations in the oceanic 87Sr/86Sr ratio over geologic time.

Description: This project was supported by funding from the WHOI Coastal Ocean 670 Institute and the Tropical Research Initiative, and NSF OCE-0751525 to MAC. BPE acknowledges financial support from NSF ETBC-85101500 and a WHOI Coastal Ocean Institute Fellowship.

Description: Trace metals in the ocean act as both essential micro-nutrients and as toxins. There are relatively few multi-element studies of dissolved trace metals in the ocean, and none from the Gulf of Aqaba, Red Sea. This semi-enclosed basin surrounded by desert is a natural laboratory for studying the impact of atmospheric dry deposition of trace metals on the ocean surface. We have combined measurement of dissolved metals in seawater with measurements of the flux of metals associated with dry deposition. The total dissolved trace metal concentrations in Gulf of Aqaba water are generally higher (Fe, Cu, Zn, Co, Mn, Pb) or similar (Ni, Al, Cd, Mo) to those measured in the open North Atlantic Ocean. The concentrations of elements that are highly enriched in aerosols relative to Al (e.g. Cd, Pb, Zn and Cu) are not necessarily proportionally enriched in surface seawater when compared to Al, indicative of the high reactivity of these elements in seawater. Iron concentrations in the Gulf of Aqaba are high relative to Al, despite the fact that the aerosols are not more enriched in Fe relative to Al. There may be additional sources of dissolved iron to the Gulf of Aqaba, not associated with Al. Alternatively, intense photochemically-driven redox cycling may act to enhance Fe dissolution from aerosols, or may otherwise increase the lifetime of Fe in the water column, relative to Al. Copper concentrations in the Gulf of Aqaba are close to the value found to be a threshold for Cu toxicity in this region. A surface maximum in Cd:P is found in the Gulf of Aqaba, in contrast to the more typical surface minimum in this ratio observed in other locations. The surface maximum appears to be driven by atypically low uptake of Cd relative to P. A low Cd:P uptake ratio for this region is consistent with known environmental determinants of low Cd:P uptake, such as high concentrations of dissolved Zn and Fe, and a predominance of small phytoplankton including cyanobacteria. Highlights ► We measured dissolved trace metal concentrations in the Gulf of Aqaba four times. ► Iron concentrations are high relative to Al concentrations. ► Cu concentrations are close to the threshold for Cu toxicity in this region. ► A surface maximum in Cd:P is driven by unusually low uptake of Cd relative to PO4. ► This is consistent with the dominance of small phytoplankton and high Fe levels.

Description: This article reports the results of a study of submarine groundwater discharge (SGD) to coastal waters of Majorca (NW Mediterranean). The overall aim is to evaluate the relevance of SGD of the island and chemically characterize the components that are supplied to the coastal waters through this pathway. Although other discharge areas are identified, we particularly focus on SGD in bays and areas of increased sea water residence time where effects of the discharges are expected to be most notable. Analysis at four selected embayments with different land-use characteristics indicated a link between human activities (mainly agriculture and urban) and compounds arriving to the coast. A pathway for these elements is the diffuse discharge along the shoreline, as suggested by the inverse relationship between salinity and nutrients in nearshore porewaters. A general survey was conducted at 46 sites around the island, and used dissolved radium as a qualitative indicator of SGD. Measurements of nutrients (P and N), pCO2 and TOC were performed to characterize the elements delivered to the coastal environment. Most nearshore samples showed 224Ra enrichment (mean ± SE, 7.0 ± 0.6 dpm 100 l−1) with respect to offshore waters (1.1 ± 0.2 dpm 100 l−1); however, 224Ra measurements along the coast were highly variable (1.0–38.1 dpm 100 l−1). Coastal samples with enhanced radium levels showed elevated pCO2 with respect to atmospheric concentrations, which together with high pCO2 in groundwater (〉5,000 ppm) indicates that SGD is an important vector of CO2 to coastal waters. Moreover, a relationship between 224Ra and phytoplankton biomass was established, suggesting an important impact of SGD on coastal productivity. The results presented here provide a first approximation of the SGD effect in the coastal waters of Majorca, and indicate that SGD could be an important source of nutrients and CO2 to the coast, strongly influencing the productivity and biogeochemical cycling of the coastal waters of Majorca.

Description: Evaluating the effects of diagenesis on the isotopic compositions of Sr, O, and C in marine carbonates is critical to their use as proxies in reconstructing information on the salinity, temperature and dissolved inorganic carbon of ancient oceans. We have analyzed a series of samples of mollusk shells from the Baculites compressus zone (late Campanian) of the Pierre Shale of South Dakota. Samples included outer shell material and septa of cephalopods collected inside and outside concretions. Preservation was evaluated using light microscopy, scanning electron microscopy (SEM), trace element analysis and X-ray diffraction. All of the material consists of aragonite based on X-ray diffraction. An SEM preservation index (PI) was established based on comparison of the microstructure of the fossil material with that of modern Nautilus. Excellent preservation (PI = 5) was characterized by well-defined nacreous plates with discrete, angular boundaries. In contrast, samples showing fused nacreous plates with indistinct boundaries were rated poor (PI = 1). 87Sr/86Sr ratios vary with preservation and average 0.707648 ± .000021 (n = 10) for excellent preservation (PI ≈ 5), 0.707615 ± .000028 (n = 5) for good preservation (PI ≈ 3), 0.707404 ± .000074 (n=7) for fair preservation (PI ≈ 2), and 0.707261 ± .000053 (n=8) for poor preservation (PI ≈ 1). These data suggest that as the quality of the preservation declines, the mean 87Sr/86Sr ratio decreases and the standard error of the mean increases. Oxygen and carbon isotope analyses of the same specimens also show decreases with preservation, and δ18O, δ13C and 87Sr/86Sr are well correlated, suggesting that these tracers are all altered as the PI decreases. The Sr/Ca ratio increases as preservation decreases, indicating that Sr is added to the shell material during diagenesis. In contrast, Mg/Ca shows no trend with preservation. If the increasing Sr concentration (and decreasing 87Sr/86Sr) of the shell material with decreasing preservation represents the addition of Sr to the shell during diagenesis, we calculate that the added Sr had 87Sr/86Sr ranging from 0.707582 to 0.707032. Potential sources of the added Sr include older marine carbonates and weathering of volcanic ash layers present in the shale. The mechanisms of alteration likely include epitaxial growth of strontianite on the original shell aragonite and isotopic exchange of C and O between alteration fluids and shell carbonate. We conclude that SEM preservation criteria are effective in screening shell material that records original isotopic values and that variations in Sr, O and C isotope composition in well-preserved material can be used to assess paleoenvironmental parameters, such as salinity and temperature. Our results also indicate that assessing preservation is a critical prerequisite to the determination of numerical ages of shell material using strontium isotope stratigraphy.

Description: Submarine groundwater discharge represents a major but poorly constrained component of coastal marine chemical budgets. In the current study, the geochemical behavior of 224Ra, inorganic nitrogen species, and Fe in shallow coastal groundwater was characterized to improve estimates of chemical flux via submarine groundwater discharge (SGD) at a site in the York River estuary, VA (USA). Directly measured SGD rates varied between 3.9 ± 1.2 cm day−1 offshore, and 8.9 ± 2.6 cm day−1 close to shore. A clear inverse relationship was observed between SGD and tidal height, reflecting the hydraulic gradient between groundwater and surface water. Discharge rates varied spatially in conjunction with the subterranean estuary location, and there was a strong inverse correlation between seepage rates and seepage salinity. Dissolved 224Ra activity in the mixing zone reached levels up to 6 dpm L−1 and co-varied with salinity in the groundwater but not in the surface water or seepage water. Instead, a consistent sigmoidal trend of Ra with pH was observed, which matched previous laboratory experiment results. Dissolved NH4 + reached concentrations up to 120 μM in the groundwater and appeared to mix conservatively with respect to salinity in the subterranean estuary. In contrast, NOx (NO2 − + NO3 −) was low in both fresh groundwater and surface water and showed non-conservative enrichment (up to 23 μM) within the subterranean estuary. Dissolved Fe also showed non-conservative excess in the subterranean estuary, reaching concentrations up to 50 μM. SGD-derived chemical fluxes were estimated using several different commonly used approaches: average groundwater concentrations, pore water constituent-salinity trends coupled with directly collected seepage salinity, constituent concentrations in directly collected seepage, and concentrations in shallowest groundwater samples. Different flux estimates were compared with a “variable endmember” approach based on the observed geochemical distribution and inferred behavior.

Description: Submarine groundwater discharge (SGD) is an important component of chemical fluxes in the coastal ocean. The composition of SGD is influenced by biogeochemical reactions that take place within the subterranean estuary (STE), the subsurface mixing zone of fresh and saline groundwaters. The STE is characterized by redox gradients that affect the speciation and mobility of redox-sensitive elements (RSEs). We examined the distributions and behavior of the RSEs Mo, U, V, and Cr within the larger redox framework of a shallow STE and evaluated the source-sink function of the STE for these elements. We found that the advection of water through the STE and the apparent respiration of organic matter drives the formation of a “classic” redox sequence typically observed in diffusion-dominated fine-grained sediments. High concentrations of dissolved organic matter (up to 2.9 mM) lead to extensive sulfide production (up to 1.8 mM) within 3 m of the surface. Both Mo and U are quantitatively removed as oxic surface waters mix into ferruginous and sulfidic zones. Molybdenum removal appears to occur where sulfide concentrations exceed ~ 11 μM, a previously reported threshold for quantitative formation of highly particle-reactive thiomolybdate species. Uranium removal apparently occurs via reduction and formation of insoluble phases or sorption to sediments. It is not clear how readily sequestered metals may be returned to solution, but SGD may be an important sink in the marine budget for both Mo and U. In contrast, both V and Cr show non-conservative addition across the salinity mixing gradient. Increases in pH appear to promote dissolution of V from minerals within the shallow aquifer, and mobilization may also be associated with dissolved organic matter. Chromium enrichment is associated with higher dissolved organic matter and is likely due to the formation of soluble Cr-organic complexes. Fluxes of these elements were constrained using SGD volume fluxes, determined using radium isotopes as well as direct discharge measurements by Lee-type seepage meters, and concentrations in directly-sampled seepage (Mo: − 0.21 to − 7.7 μmol m− 2 day− 1; U: − 0.02 to − 0.6 μmol m− 2 day− 1; V: 0.05 to 2.0 μmol m− 2 day− 1; Cr: 0.12 to 4.4 μmol m− 2 day− 1).

Description: Oil derived from photosynthetic microalgae is a potential major source of renewable energy, but while industrial-scale efforts to grow algal biomass are underway, it remains an expensive process. The cost of biomass production may be offset by using the algae to simultaneously remediate chemical contaminants from wastewater or natural surface waters. This work examines trace metal accumulation and cycling in algae grown for biofuel use, and evaluates the potential of this approach for remediation purposes. In the system studied, a natural, mixed-species algal community was allowed to develop on a shallow floway fed with water from the York River estuary (VA, USA). Accumulation of metals ranged widely in the algal biomass (Fe 〉 Mn 〉 〉Pb 〉 Cu 〉 V 〉 Cd) and represented removal from the dissolved phase of between 1 and 87% (for Cd and Pb, respectively). These metals were selected for analysis because of their differing geochemical behavior, as well as their importance as micronutrients (Fe, Mn, Cu, V) and toxicants (Pb, Cu, Cd). Most of the algal metal inventory was partitioned in the intracellular fraction (∼30% for Mn, 50–90% for other metals; operationally defined using a chemical wash technique), indicating accumulation due to biochemical demand, not adsorption to cell surfaces. Although algal community composition was similar on the upstream and downstream ends of the floway, the metal inventory was two-fold higher on the downstream end. Differences in metal accumulation may have been related to algal physiology or to pronounced cycles of water pH and dissolved oxygen driven by algal photosynthesis and respiration. Differences in metal removal efficiency and biomass inventory indicate that algal floway systems may be manipulated to optimize remediation of metal-contaminated water.

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.