SGD-OD: investigating the potential oxygen demand of submarine groundwater discharge in coastal systems.

Submarine groundwater discharge (SGD) supplies nutrients, carbon, metals, and radionuclide tracers to estuarine and coastal waters. One aspect of SGD that is poorly recognized is its direct effect on dissolved oxygen (DO) demand in receiving waters, denoted here as SGD-OD. Sulfate-mediated oxidation of organic matter in salty coastal aquifers produces numerous reduced byproducts including sulfide, ammonia, dissolved organic carbon and nitrogen, methane, and reduced metals. When these byproducts are introduced to estuarine and coastal systems by SGD and are oxidized, they may substantially reduce the DO concentration in receiving waters and impact organisms living there. We consider six estuarine and coastal sites where SGD derived fluxes of reduced byproducts are well documented. Using data from these sites we present a semiquantitative model to estimate the effect of these byproducts on DO in the receiving waters. Without continued aeration with atmospheric oxygen, the study sites would have experienced periodic hypoxic conditions due to SGD-OD. The presence of H2S supplied by SGD could also impact organisms. This process is likely prevalent in other systems worldwide.

Automated determination of gallium in seawater using seaFAST pre-concentration and high-resolution inductively-coupled plasma mass spectrometry.

There has been increased interest in dissolved gallium (Ga) in natural waters due to its long residence time and its usefulness in tracking water masses; however, current analytical approaches are time consuming and labor intensive (e.g., magnesium hydroxide co-precipitation method, (Mg(OH)2)) or have concerns such as carryover and sample recovery (automated resin column extraction). Ocean observing programs, such as GEOTRACES, recover hundreds of samples per expedition. There are both logistical (sample volume) and analytical (person-hour) demands to economically collect and analyze Ga. We present an automated isotope dilution method (using 99.8% enriched 71Ga) to determine Ga in seawater utilizing commercially available equipment while addressing the challenges of a) sample volume and sample pre-concentration factor, b) instrumental interferences, c) sample-sample carryover, d) sample recovery variability, and e) improving sample detection limits, accuracy and precision. A seaFAST SC-4DXS pico (Elemental Scientific, Inc.; ESI) was used to pre-concentrate 20 mL of sample on a Nobias PA1 resin column 67-fold before analysis in medium resolution on a ThermoFisher high-resolution inductively-coupled plasma mass spectrometer (HR-ICP-MS) equipped with an APEX Q FAST enabled spray chamber (ESI) to increase signal intensity and decrease instrument interferences. The new automated seaFAST method reproduced Ga concentrations determined by the Mg(OH)2 method, but with greater precision (RSD <4%) and a lower detection limit (0.10 pmol L-1). This method is ideal for high throughput applications and can be easily implemented using commercially available equipment.

Multiplexed printed sensors for in situ monitoring in bivalve aquaculture.

Non-intrusive sensors that can be attached to marine species offer opportunities to study the impacts of environmental changes on their behaviors and well-being. This work presents a thin, flexible sensor tag to monitor the effects of dissolved oxygen and salinity on bivalve gape movement. The measurement range studied was 0.5-6 ppm for the dissolved oxygen sensor and 4-40 g kg-1 for the salinity sensor. The curvature strain sensor based on electrodeposited semiconducting fibers enabled measurements of an oyster's gape down to sub-mm displacement. The multiplexed sensors were fabricated by low-cost techniques, offering an economical and convenient platform for aquaculture studies.

Strong Margin Influence on the Arctic Ocean Barium Cycle Revealed by Pan-Arctic Synthesis.

Early studies revealed relationships between barium (Ba), particulate organic carbon and silicate, suggesting applications for Ba as a paleoproductivity tracer and as a tracer of modern ocean circulation. But, what controls the distribution of barium (Ba) in the oceans? Here, we investigated the Arctic Ocean Ba cycle through a one-of-a-kind data set containing dissolved (dBa), particulate (pBa), and stable isotope Ba ratio (δ138Ba) data from four Arctic GEOTRACES expeditions conducted in 2015. We hypothesized that margins would be a substantial source of Ba to the Arctic Ocean water column. The dBa, pBa, and δ138Ba distributions all suggest significant modification of inflowing Pacific seawater over the shelves, and the dBa mass balance implies that ∼50% of the dBa inventory (upper 500 m of the Arctic water column) was supplied by nonconservative inputs. Calculated areal dBa fluxes are up to 10 µmol m-2 day-1 on the margin, which is comparable to fluxes described in other regions. Applying this approach to dBa data from the 1994 Arctic Ocean Survey yields similar results. The Canadian Arctic Archipelago did not appear to have a similar margin source; rather, the dBa distribution in this section is consistent with mixing of Arctic Ocean-derived waters and Baffin Bay-derived waters. Although we lack enough information to identify the specifics of the shelf sediment Ba source, we suspect that a sedimentary remineralization and terrigenous sources (e.g., submarine groundwater discharge or fluvial particles) are contributors.

Point-of-use printed nitrate sensor with desalination units.

Nitrate is an important marker of water quality that can be challenging to detect in seawater due to the presence of multiple chemical interferants and high background chloride. Here, we demonstrate a compact microfluidic device that incorporates electrochemical desalination to selectively remove the interfering chloride ions and improve the detection limit of the downstream potentiometric nitrate sensor. The microfluidic platform was fabricated by a low-cost cut-and-lamination approach, and the detection mechanism was based on potentiometric measurements at an Ag/AgCl electrode coated with a nitrate-selective membrane. The sensor system achieved a detection limit of 0.5 mM with a sensitivity of 11.3 mV/dec under continuous flow.

Impact of local rivers on coastal acidification.

Coastal ecosystems are highly dynamic areas for carbon cycling and are likely to be negatively impacted by increasing ocean acidification. This research focused on dissolved inorganic carbon (DIC) and total alkalinity (TA) in the Mississippi Sound to understand the influence of local rivers on coastal acidification. This area receives large fluxes of freshwater from local rivers, in addition to episodic inputs from the Mississippi River through a human-built diversion, the Bonnet Carré Spillway. Sites in the Sound were sampled monthly from August 2018 to November 2019 and weekly from June to August 2019 in response to an extended spillway opening. Prior to the 2019 spillway opening, the contribution of the local, lower alkalinity rivers to the Sound may have left the study area more susceptible to coastal acidification during winter months, with aragonite saturation states (Ωar) < 2. After the spillway opened, despite a large increase in TA throughout the Sound, aragonite saturation states remained low, likely due to hypoxia and increased CO2 concentrations in subsurface waters. Increased Mississippi River input could represent a new normal in the Sound's hydrography during spring and summer months. The spillway has been utilized more frequently over the last two decades due to increasing precipitation in the Mississippi River watershed, which is primarily associated with climate change. Future increases in freshwater discharge and the associated declines in salinity, dissolved oxygen, and Ωar in the Sound will likely be detrimental to oyster stocks and the resilience of similar ecosystems to coastal acidification.

Advection of Karenia brevis blooms from the Florida Panhandle towards Mississippi coastal waters.

Harmful Algal Blooms (HABs) of Karenia brevis have been documented along coastal waters of every state bordering the Gulf of Mexico (GoM). Some Gulf Coast locations, such as Florida and Texas, suffer from recurrent intense and spatially large blooms, while others such as Mississippi seem to rarely observe them. The main objective of this work is to understand the dynamics that led to the K. brevis bloom in Mississippi coastal waters in fall 2015. Blooms of K. brevis from the Florida Panhandle region are often advected westward towards the Mississippi-Alabama coast; however there is interannual variability in their presence and intensity in Mississippi coastal waters. The 2015 K. brevis bloom was compared to the 2007 Florida Panhandle K. brevis bloom, which showed a westward advection pattern, but did not intensify along the Mississippi coast. Cell counts and flow cytometry were obtained from the Mississippi Department of Marine Resources, Alabama Department of Public Health, Florida Fish and Wildlife Conservation Commission and The University of Southern Mississippi. Ocean color satellite imagery from the Moderate Resolution Imaging Spectroradiometer onboard the Aqua satellite was used to detect and delineate the blooms in 2007 and 2015. Two different regional applications of NCOM-Navy Coastal Ocean Model (1-km resolution NCOM-GoM/Gulf of Mexico and 6-km resolution NCOM-IASNFS/Intra Americas Sea Nowcast Forecast System) were used to understand the circulation and transport pathways. A Lagrangian particle tracking software was used to track the passive movement of particles released at different locations for both bloom events. Ancillary data (e.g., nutrients, wind, salinity, river discharge) from local buoys, monitoring stations and coincident oceanographic cruises were also included in the analysis. The blooms of K. brevis reached the Mississippi coast both years; however, the bloom in 2007 lasted only a few days and there is no evidence that it entered the Mississippi Sound. Two major differences were observed between both years. First, circulation patterns in 2015 resulting from an intense westward-northwestward that persisted until December allowed for continuous advection, whereas this pattern was not evident in 2007. Second, local river discharge was elevated throughout late fall 2015 while 2007 was below the average. Thus, elevated discharge may have provided sufficient nutrients for bloom intensification. These results illustrate the complex, but important interactions in coastal zones. Further, they emphasize the importance in establishing comprehensive HAB monitoring programs, which facilitate our understanding of nutrient and phytoplankton dynamics, and stress the importance for multi-agency cooperation across state boundaries.

Whether hurricane Katrina impacted trace metal and dioxin depositional histories in marshes of St. Louis Bay, Mississippi.

Salt marsh sediments generally undergo steady accumulation over time and thus are widely used to reconstruct the depositional histories of various anthropogenic contaminants derived from atmospheric and fluvial sources. Major hurricanes can significantly affect coastal landscapes by eroding and re-distributing sediment. Thus, each major hurricane can leave distinct signals in coastal wetland sediments. On the other hand, early-diagenetic remobilization of Fe and Mn in organic rich marsh sediment is a common phenomenon. However, remobilization of Fe and Mn across the redox boundary can induce remobilization of other trace elements and thus can disturb their depositional histories. Four short (~1m) sediment cores were collected from the fringing marshes of St. Louis Bay, Mississippi (located ~30km east of Hurricane Katrina's track) during 2010-2011 to investigate possible impacts of Hurricane Katrina (2005), and early-diagenetic remobilization of Fe and Mn, on trace metal and dioxin depositional histories in these sediments. Results from 210Pb, 137Cs, stable Cs, particulate organic carbon (POC), sediment bulk density and grain size indicate significant impact of hurricane event layers on anthropogenic stable Cs, while deposition profiles of V, Ni and Cr are impacted by Fe and Mn remobilization to a limited extent.

Roles of Copper and a Conserved Aspartic Acid in the Autocatalytic Hydroxylation of a Specific Tryptophan Residue during Cysteine Tryptophylquinone Biogenesis.

The first posttranslational modification step in the biosynthesis of the tryptophan-derived quinone cofactors is the autocatalytic hydroxylation of a specific Trp residue at position C-7 on the indole side chain. Subsequent modifications are catalyzed by modifying enzymes, but the mechanism by which this first step occurs is unknown. LodA possesses a cysteine tryptophylquinone (CTQ) cofactor. Metal analysis as well as spectroscopic and kinetic studies of the mature and precursor forms of a D512A LodA variant provides evidence that copper is required for the initial hydroxylation of the precursor protein and that if alternative metals are bound, the modification does not occur and the precursor is unstable. It is shown that the mature native LodA also contains loosely bound copper, which affects the visible absorbance spectrum and quenches the fluorescence spectrum that is attributed to the mature CTQ cofactor. When copper is removed, the fluorescence appears, and when it is added back to the protein, the fluorescence is quenched, indicating that copper reversibly binds in the proximity of CTQ. Removal of copper does not diminish the enzymatic activity of LodA. This distinguishes LodA from enzymes with protein-derived tyrosylquinone cofactors in which copper is present near the cofactor and is absolutely required for activity. Mechanisms are proposed for the role of copper in the hydroxylation of the unactivated Trp side chain. These results demonstrate that the reason that the highly conserved Asp512 is critical for LodA, and possibly all tryptophylquinone enzymes, is not because it is required for catalysis but because it is necessary for CTQ biosynthesis, more specifically to facilitate the initial copper-dependent hydroxylation of a specific Trp residue.

Aqueous Mesocosm Techniques Enabling the Real-Time Measurement of the Chemical and Isotopic Kinetics of Dissolved Methane and Carbon Dioxide.

Previous studies of microbially mediated methane oxidation in oceanic environments have examined the many different factors that control the rates of oxidation. However, there is debate on what factor(s) are limiting in these types of environments. These factors include the availability of methane, O2, trace metals, nutrients, the density of cell population, and the influence that CO2 production may have on pH. To look at this process in its entirety, we developed an automated mesocosm incubation system with a Dissolved Gas Analysis System (DGAS) coupled to a myriad of analytical tools to monitor chemical changes during methane oxidation. Here, we present new high temporal resolution techniques for investigating dissolved methane and carbon dioxide concentrations and stable isotopic dynamics during aqueous mesocosm and pure culture incubations. These techniques enable us to analyze the gases dissolved in solution and are nondestructive to both the liquid media and the analyzed gases enabling the investigation of a mesocosm or pure culture experiment in a completely closed system, if so desired.

Coastal ocean and shelf-sea biogeochemical cycling of trace elements and isotopes: lessons learned from GEOTRACES.

Continental shelves and shelf seas play a central role in the global carbon cycle. However, their importance with respect to trace element and isotope (TEI) inputs to ocean basins is less well understood. Here, we present major findings on shelf TEI biogeochemistry from the GEOTRACES programme as well as a proof of concept for a new method to estimate shelf TEI fluxes. The case studies focus on advances in our understanding of TEI cycling in the Arctic, transformations within a major river estuary (Amazon), shelf sediment micronutrient fluxes and basin-scale estimates of submarine groundwater discharge. The proposed shelf flux tracer is 228-radium (T1/2 = 5.75 yr), which is continuously supplied to the shelf from coastal aquifers, sediment porewater exchange and rivers. Model-derived shelf 228Ra fluxes are combined with TEI/ 228Ra ratios to quantify ocean TEI fluxes from the western North Atlantic margin. The results from this new approach agree well with previous estimates for shelf Co, Fe, Mn and Zn inputs and exceed published estimates of atmospheric deposition by factors of approximately 3-23. Lastly, recommendations are made for additional GEOTRACES process studies and coastal margin-focused section cruises that will help refine the model and provide better insight on the mechanisms driving shelf-derived TEI fluxes to the ocean.This article is part of the themed issue 'Biological and climatic impacts of ocean trace element chemistry'.

Determination of dissolved methane in natural waters using headspace analysis with cavity ring-down spectroscopy.

Methane (CH4) is the third most abundant greenhouse gas (GHG) but is vastly understudied in comparison to carbon dioxide. Sources and sinks to the atmosphere vary considerably in estimation, including sources such as fresh and marine water systems. A new method to determine dissolved methane concentrations in discrete water samples has been evaluated. By analyzing an equilibrated headspace using laser cavity ring-down spectroscopy (CRDS), low nanomolar dissolved methane concentrations can be determined with high reproducibility (i.e., 0.13 nM detection limit and typical 4% RSD). While CRDS instruments cost roughly twice that of gas chromatographs (GC) usually used for methane determination, the process presented herein is substantially simpler, faster, and requires fewer materials than GC methods. Typically, 70-mL water samples are equilibrated with an equivalent amount of zero air in plastic syringes. The equilibrated headspace is transferred to a clean, dry syringe and then drawn into a Picarro G2301 CRDS analyzer via the instrument's pump. We demonstrate that this instrument holds a linear calibration into the sub-ppmv methane concentration range and holds a stable calibration for at least two years. Application of the method to shipboard dissolved methane determination in the northern Gulf of Mexico as well as river water is shown. Concentrations spanning nearly six orders of magnitude have been determined with this method.

Trace element distributions in the water column near the Deepwater Horizon well blowout.

To understand the impact of the Deepwater Horizon well blowout on dissolved trace element concentrations, samples were collected from areas around the oil rig explosion site during four cruises in early and late May 2010, October 2010, and October 2011. In surface waters, Ba, Fe, Cu, Ni, Mn, and Co were relatively well correlated with salinity during all cruises, suggesting mixing with river water was the main influence on metal distributions in these waters. However, in deep oil/gas plumes (1000-1400 m depth), modestly elevated concentrations of Co and Ba were observed in late May, compared with postblowout conditions. Analysis of the oil itself along with leaching experiments confirm the oil as the source of the Co, whereas increased Ba was likely due to drilling mud used in the top kill attempt. Deep plume dissolved Mn largely reflected natural benthic input, though some samples showed slight elevation probably associated with the top kill. Dissolved Fe concentrations were low and also appeared largely topographically controlled and reflective of benthic input. Estimates suggest that microbial Fe demand may have affected the Fe distribution but probably not to the extent of Fe becoming a growth-limiting factor. Experiments showed that the dispersant can have some limited impact on dissolved-particulate metal partitioning.

Olefin metathesis catalysts bearing a pH-responsive NHC ligand: a feasible approach to catalyst separation from RCM products.

Two novel ruthenium-based olefin metathesis catalysts, H(2)ITap(PCy(3))Cl(2)Ru[double bond, length as m-dash]CH-Ph and H(2)ITapCl(2)Ru[double bond, length as m-dash]CH-(C(6)H(4)-O-iPr) (H(2)ITap = 1,3-bis(2',6'-dimethyl-4'-dimethylaminophenyl)-4,5-dihydroimidazol-2-ylidene), were synthesized bearing a pH-responsive NHC ligand with two aromatic NMe(2) groups. The crystal structures of complexes and were determined via X-ray crystallography. Both catalysts perform ring opening metathesis polymerization (ROMP) of cyclooctene (COE) at faster rates than their commercially available counterparts H(2)IMes(PCy(3))Cl(2)Ru[double bond, length as m-dash]CH-Ph and H(2)IMesCl(2)Ru[double bond, length as m-dash]CH-(C(6)H(4)-O-iPr) (H(2)IMes = 1,3-bis(2',4',6'-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene) and perform at similar rates during ring closing metathesis (RCM) of diethyldiallylmalonate (DEDAM). Upon addition of 2 equiv. of HCl, catalyst is converted into a mixture of several mono and diprotonated Ru-carbene species 12' which are soluble in methanol but degrade within a few hours at room temperature. Catalyst can be protonated with 2 equiv. of HCl and the resulting complex is moderately water-soluble. The complex is stable in aqueous solution in air for >4 h, but over prolonged periods of time shows degradation in acidic media due to hydrolysis of the NHC-Ru bond. Catalysts and perform RCM of diallylmalonic acid in acidic protic media with only moderate activity at 50 degrees C and do not produce polymer in the ROMP of cationic 7-oxanorbornene derivative under the same conditions. Catalyst was used for Ru-seperation studies when RCM of DEDAM or 3,3-diallypentadione (DAP) was conducted in low-polar organic solution and the Ru-species was subsequently precipitated by addition of strong acid. The Ru-species were removed by (1) filtration and (2) filtration and subsequent extraction with water. The residual Ru-levels could be reduced to as far as 11 ppm (method 2) and 24 ppm (method 1) without the use of chromatography or other scavenging methods.

Syringe filtration methods for examining dissolved and colloidal trace element distributions in remote field locations.

It is well-established that sampling and sample processing can easily introduce contamination into dissolved trace element samples if precautions are not taken. However, work in remote locations sometimes precludes bringing bulky clean lab equipment into the field and likewise may make timely transport of samples to the lab for processing impossible. Straightforward syringe filtration methods are described here for collecting small quantities (15 mL) of 0.45- and 0.02-microm filtered river water in an uncontaminated manner. These filtration methods take advantage of recent advances in analytical capabilities that require only small amounts of waterfor analysis of a suite of dissolved trace elements. Filter clogging and solute rejection artifacts appear to be minimal, although some adsorption of metals and organics does affect the first approximately 10 mL of water passing through the filters. Overall the methods are clean, easy to use, and provide reproducible representations of the dissolved and colloidal fractions of trace elements in river waters. Furthermore, sample processing materials can be prepared well in advance in a clean lab and transported cleanly and compactly to the field. Application of these methods is illustrated with data from remote locations in the Rocky Mountains and along the Yukon River. Evidence from field flow fractionation suggests that the 0.02-microm filters may provide a practical cutoff to distinguish metals associated with small inorganic and organic complexes from those associated with silicate and oxide colloids.