Description: MedFlux sampling was carried out at the French JGOFS DYFAMED (DYnamique des Flux Atmospheriques en MEDiterranee) site in the Ligurian Sea (northwestern Mediterranean), 52km off Nice (431200N, 71400E) in 2300m water depth. In 2003, a mooring with sediment trap arrays was deployed 6 March (day of year, DOY 65) and recovered 6 May (DOY 126); this trap deployment will be referred to as Period 1 (P1). The array was redeployed a week later on 14 May (DOY 134) and recovered again on 30 June (DOY 181); this trap deployment will be referred to as Period 2 (P2). Indented-rotating sphere (IRS) valve traps were fitted with TS carousels to determine temporal variability of particulate matter flux. TS traps were fitted with ''dimpled'' spheres. Vertical flux at 200m depth is considered to be equivalent to new or export production, and traps sampled at 238 and 117m during P1 and P2, respectively. We also collected TS material at 711m during P1 and at 1918m during P2. Upon recovery, samples were split using a McLaneTM WSD splitter to allow multiple chemical analyses. Here we report 2003 data on TS particulate mass, and the contributions of organic carbon (OC), opal, lithogenic material and calcium carbonate to mass. In 2005, traps were deployed as described above for 55 d during a single period from 4 March (DOY 63) to 1 May (DOY 121). TS traps were fitted with ''dimpled'' spheres. TS particulate matter was collected from 313 to 924 m.

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: 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: 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: 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: Submarine groundwater discharge (SGD) into a shallow lagoon on the west coast of Mauritius Island (Flic-en-Flac) was investigated using radioactive (3H, 222Rn, 223Ra, 224Ra, 226Ra, 228Ra) and stable (2H, 18O) isotopes and nutrients. SGD intercomparison exercises were carried out to validate the various approaches used to measure SGD including radium and radon measurements, seepage rate measurements using manual and automated meters, sediment bulk conductivity and salinity surveys. SGD measurements using benthic chambers placed on the floor of the Flic-en-Flac Lagoon showed discharge rates up to 500 cm/day. Large variability in SGD was observed over distances of a few meters, which were attributed to different geomorphological features. Deployments of automated seepage meters captured the spatial and temporal variability of SGD with a mean seepage rate of 10 cm/day. The stable isotopic composition of submarine waters was characterized by significant variability and heavy isotope enrichment and was used to predict the contribution of fresh terrestrially derived groundwater to SGD (range from a few % to almost 100%). The integrated SGD flux, estimated from seepage meters placed parallel to the shoreline, was 35 m3/m day, which was in reasonable agreement with results obtained from a hydrologic water balance calculation (26 m3/m day). SGD calculated from the radon inventory method using in situ radon measurements were between 5 and 56 m3/m per day. Low concentrations of radium isotopes observed in the lagoon water reflected the low abundance of U and Th in the basalt that makes up the island. High SGD rates contribute to high nutrients loading to the lagoon, potentially leading to eutrophication. Each of the applied methods yielded unique information about the character and magnitude of SGD. The results of the intercomparison studies have resulted a better understanding of groundwater–seawater interactions in coastal regions. Such information is an important pre-requisite for the protection and management of coastal freshwater resources. Highlights ► Large fluctuations in SGD fluxes from 0 to 360 cm/day were observed. ► The integrated shoreline SGD fluxes were between 5 and 56 m3/m day. ► The groundwater contribution in SGD varied from a few % to almost 100%. ► The observed high SGD rates contributed to high nutrients loading to the lagoon.