Persistent spatial structuring of coastal ocean acidification in the California Current System.

The near-term progression of ocean acidification (OA) is projected to bring about sharp changes in the chemistry of coastal upwelling ecosystems. The distribution of OA exposure across these early-impact systems, however, is highly uncertain and limits our understanding of whether and how spatial management actions can be deployed to ameliorate future impacts. Through a novel coastal OA observing network, we have uncovered a remarkably persistent spatial mosaic in the penetration of acidified waters into ecologically-important nearshore habitats across 1,000 km of the California Current Large Marine Ecosystem. In the most severe exposure hotspots, suboptimal conditions for calcifying organisms encompassed up to 56% of the summer season, and were accompanied by some of the lowest and most variable pH environments known for the surface ocean. Persistent refuge areas were also found, highlighting new opportunities for local adaptation to address the global challenge of OA in productive coastal systems.

Calibration of membrane inlet mass spectrometric measurements of dissolved gases: differences in the responses of polymer and nano-composite membranes to variations in ionic strength.

This work examines the transmission behavior of aqueous dissolved methane, nitrogen, argon and carbon dioxide through two types of membranes: a polysiloxane nano-composite (PNC) membrane and a conventional polydimethylsiloxane (PDMS) membrane. Transmission properties at 30 °C were examined by membrane introduction mass spectrometry (MIMS) at nearly constant gas partial pressures in NaCl solutions over a range of ionic strength (0-1 molal). Gas flow rates were examined as a function of dissolved gas concentrations using the Setschenow equation. Although MIMS measurements with PDMS and PNC membranes produced signal responses that were directly proportional to aqueous dissolved gas concentrations, the proportionalities varied with ionic strength and were distinctly different for the two types of membranes. With the exception of carbon dioxide, the PNC membrane had membrane salting coefficients quite similar to Setschenow coefficients reported for gases in aqueous solution. In contrast, the PDMS membrane had membrane salting coefficients that were generally smaller than the corresponding Setschenow gas coefficient for each gas. Differences between Setschenow coefficients and membrane salting coefficients lead to MIMS calibrations (gas-flow vs. gas-concentration proportionalities) that vary with ionic strength. Accordingly, gas-flow vs. gas-concentration relationships for MIMS measurements with PDMS membranes are significantly dependent on ionic strength. In contrast, for PNC membranes, flow vs. concentration relationships are independent (argon, methane, nitrogen) or weakly dependent (CO2) on ionic strength. Comparisons of gas Setschenow and membrane salting coefficients can be used to quantitatively describe the dependence of membrane gas-flow on gas-concentrations and ionic strength for both PDMS and PNC membranes.

Underwater mass spectrometers for in situ chemical analysis of the hydrosphere.

Underwater mass spectrometry systems can be used for direct in situ detection of volatile organic compounds and dissolved gases in oceans, lakes, rivers and waste-water streams. In this work we describe the design and operation of (1) a linear quadrupole mass filter and (2) a quadrupole ion trap mass spectrometer interfaced, in each case, with a membrane introduction/fluid control system and packaged for underwater operation. These mass spectrometry systems can operate autonomously, or under user control via a wireless rf link. Detection limits for each system were determined in the laboratory using pure solutions. The quadrupole mass filter system provides detection limits in the 1-5 ppb range with an upper mass limit of 100 amu. Its power requirement is approximately 95 Watts. The ion trap system has detection limits well below 1 ppb, an upper mass limit of 650 amu and MS/MS capability. Its power consumption is on the order of 150 Watts. The present membrane limits analysis to non-polar compounds (<300 amu) with analysis cycles of 5-15 minutes. Deployments of both types of instruments are described, along with a discussion of the challenges associated with in-water mass spectrometry and descriptions of alternative in-water mass spectrometer configurations.

Spectrophotometric determination of freshwater pH using bromocresol purple and phenol red.

The dissociation constants (KI = [H+][I2-]/[HI-]) of two sulfonephthalein indicators (bromocresol purple and phenol red) were determined as function of temperature (10-30 degrees C) at zero ionic strength. Freshwater pH, on the free hydrogen ion concentration scale (molal units), can be precisely calculated from measurements of indicator absorbance ratios (lambda2A/lambda1A) using the following equations: pH = pKI + log((R - e1)/(e2 - Re3)) and pKI = pKI(degrees) - AdeltaZ2(mu1/2 /(1 + mu1/2) - 0.3 mu), where R = lambda2A/lambda1A, pKI = -log KI, mu is the ionic strength, deltaZ2 = 4, and values of A for 283 < or = T < or = 303 can be estimated from the equation: A = 0.5092 + (T-298.15) x 8.5 x 10(-4). For bromocresol purple (lambda1 = 432 nm, lambda2 = 589 nm), pKI(degrees) = 5.226 + 378.1/T, e1 = 0.00387, e2 = 2.858, and e3 = 0.0181. For phenol red (lambda1 = 433 nm, lambda2 = 558 nm), pKI(degrees) = 5.798 + 666.7/T, e1 = 0.00244, e2= 2.734, and e3 = 0.1075. These two indicators can be used to make accurate pH measurements of freshwaters (river water, lake water, groundwater, rainwater, etc) within the range 4.5 < or =pH < or =8.5. The precision of pH measurements using phenol red in well-buffered freshwaters is on the order of +/-0.001 or better.

Construction of a compact spectrofluorometer/spectrophotometer system using a flexible liquid core waveguide.

A liquid-core waveguide made of Teflon AF-2400 has been used to construct a simple, sensitive and robust instrument capable of performing fluorimetric and spectrophotometric analyses on aqueous solutions. The instrument, which uses a CCD array detection system, is unique in that high performance is achieved for both measurement techniques with minimal changes in instrument configuration. The fluorimetric detection limits for quinine sulfate and chlorophyll-a are 0.06 nanomolar and 0.03 nanomolar, respectively. Absorbance measurements using the same instrument demonstrate nanomolar detection capacities for hydrogen sulfide and subnanomolar detection limits for methylene blue.

Determination of trace chromium(VI) and molybdenum(VI) in natural and bottled mineral waters using long pathlength absorbance spectroscopy (LPAS).

A liquid core waveguide (LCW) has been used to extend the sensitivity of conventional absorbance spectroscopy for chromium(VI) and molybdenum(VI). Analysis of Cr(VI) and Mo(VI) concentrations in water samples with a 5.0 m pathlength LCW made of Teflon AF-2400 provides 0.2 and 0.6 nM detection limits, respectively. No preconcentration is required in this analysis. The proposed procedures were applied to the determination of chromium(VI) and molybdenum(VI) in natural waters and commercial drinking water. The analytical apparatus is very simple and robust and is amenable to miniaturization and autonomous operation.

Acantharian fluxes and strontium to chlorinity ratios in the north pacific ocean.

Data on particulate strontium sulfate fluxes and strontium to chlorinity ratios were compared to provide insights into the strontium cycle of the North Pacific. Freedrifting sediment traps were used to derive large particle fluxes between depths of 100 and 3500 meters in the eastern and western North Pacific Ocean. Flux data revealed substantial quantities of acantharian skeletons and cysts (both made of strontium sulfate) settling through the upper kilometer of the water column. The greatest fluxes of celestite were detected at 400 meters. Minimal to nondetectable fluxes noted at and below 900 meters provide evidence that by this horizon, the majority of acantharian specimens had dissolved, thereby contributing to the pool of dissolved strontium. Growth and subsequent dissolution of acantharians in the upper kilometer are qualitatively consistent with the well-developed minimum and maximum strontium to chlorinity ratios that are consistently noted in these waters. These fluxes of particulate strontium and model calculations for fluxes of dissolved strontium indicate that acantharians play an important role in the ocean's strontium budget.

The oceanic carbonate system: a reassessment of biogenic controls.

Fluxes of biogenic carbonates moving out of the euphotic zone and into deeper undersaturated waters of the North Pacific were estimated with free-drifting sediment traps. Short-duration (1 to 1.5 day) sampling between 100 and 2200 meters points to a major involvement in the oceanic carbonate system by a class of organisms which had been relegated to a secondary role-aragonitic pteropods. Pteropod fluxes through the base of the euphotic zone are almost large enough to balance the alkalinity budget for the Pacific Ocean. Dissolution experiments with freshly collected materials shed considerable light on a mystery surrounding these labile organisms: although plankton collections from net tows almost always contain large numbers of pteropods, these organisms are never a major component of biogenic materials in long-duration sediment trap collections. Their low abundance in long-duration collections results from dissolution subsequent to collection. Shortduration sampling showed significant increases in the ratio of calcitic foraminifera to aragonitic pteropods in undersaturated waters, indicating the more stable mineralogic form, calcite, was preserved relative to aragonite. Approximately 90 percent of the aragonite flux is remineralized in the upper 2.2 kilometers of the water column.

Radiuin-226 and radon-222 in the coastal waters of west Florida: high concentrations and atmospheric degassing.

On the central portion of the west Florida continental shelf, radionuclide activities show unusually wide variations: radium-226 activities up to 350 disintegrations per minute per 100 liters, radon-222 activities up to 1300 disintegrations per minute per 100 liters, and deficiencies of radon-222 as low as -10 disintegrations per minute per 100 liters. Florida's phosphate-rich strata seerm to be the principal source of the radionuclides, with the transfer occurring directly from sediments or indirectly in streams, ground-water flow, and geothermal springs. Winter storm fronts may enhance radon degassing in the shelf waters.