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McLaughlin, K, Dickson A, Weisberg SB, Coale K, Elrod V, Hunter C, Johnson KS, Kram S, Kudela R, Martz T, Negrey K, Passow U, Shaughnessy F, Smith JE, Tadesse D, Washburn L, Weis KR.  2017.  An evaluation of ISFET sensors for coastal pH monitoring applications. Regional Studies in Marine Science. 12:11-18.   10.1016/j.rsma.2017.02.008   AbstractWebsite

The accuracy and precision of ion sensitive field effect transistor (ISFET) pH sensors have been well documented, but primarily by ocean chemistry specialists employing the technology at single locations. Here we examine their performance in a network context through comparison to discrete measurements of pH, using different configurations of the Honeywell DuraFET pH sensor deployed in six coastal settings by operators with a range of experience. Experience of the operator had the largest effect on performance. The average difference between discrete and ISFET pH was 0.005 pH units, but ranged from -0.030 to 0.083 among operators, with more experienced operators within +/- 0.02 pH units of the discrete measurement. In addition, experienced operators achieved a narrower range of variance in difference between discrete bottle measurements and ISFET sensor readings compared to novice operators and novice operators had a higher proportion of data failing quality control screening. There were no statistically significant differences in data uncertainty associated with sensor manufacturer or deployment environment (pier-mounted, flowthrough system, and buoy-mounted). The variation we observed among operators highlights the necessity of best practices and training when instruments are to be used in a network where comparison across data streams is desired. However, while opportunities remain for improving the performance of the ISFET sensors when deployed by less experienced operators, the uncertainty associated with their deployment and validation was several-fold less than the observed natural temporal variability in pH, demonstrating the utility of these sensors in tracking local changes in acidification. (C) 2017 Elsevier B.V. All rights reserved.

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Nam, S, Takeshita Y, Frieder CA, Martz T, Ballard J.  2015.  Seasonal advection of Pacific Equatorial Water alters oxygen and pH in the Southern California Bight. Journal of Geophysical Research-Oceans. 120:5387-5399.   10.1002/2015jc010859   AbstractWebsite

Chemical properties of the California Undercurrent (CU) have been changing over the past several decades, yet the mechanisms responsible for the trend are still not fully understood. We present a survey of temperature, salinity, O-2, pH, and currents at intermediate depths (defined here as 50-500 m) in the summer (30 June to 10 July) and winter (8-15 December) of 2012 in the southern region of the Southern California Bight. Observations of temperature, salinity, and currents reveal that local bathymetry and small gyres play an important role in the flow path of the California Undercurrent (CU). Using spiciness (p) as a tracer, we observe a 10% increase of Pacific Equatorial Water (PEW) in the core of the CU during the summer versus the winter. This is associated with an increase in p of 0.2, and a decrease in O-2 and pH of 30 mu mol kg(-1) and 0.022, respectively; the change in pH is driven by increased CO2, while total alkalinity remains unchanged. The high-p, low-O-2, and low-pH waters during the summer are not distributed uniformly in the study region. Moreover, mooring observations at the edge of the continental shelf reveal intermittent intrusions of PEW onto the shelf with concomitant decreases in O-2 and pH. We estimate that increased advection of PEW in the CU could account for approximately 50% of the observed decrease in O-2, and between 49 and 73% of the decrease in pH, over the past three decades.

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Ohman, MD, Rudnick DL, Chekalyuk A, Davis RE, Feely RA, Kahru M, Kim HJ, Landry MR, Martz TR, Sabine CL, Send U.  2013.  Autonomous ocean measurements in the California Current ecosystem. Oceanography. 26:18-25. AbstractWebsite

Event-scale phenomena, of limited temporal duration or restricted spatial extent, often play a disproportionately large role in ecological processes occurring in the ocean water column. Nutrient and gas fluxes, upwelling and downwelling, transport of biogeochemically important elements, predator-prey interactions, and other processes may be markedly influenced by such events, which are inadequately resolved from infrequent ship surveys. The advent of autonomous instrumentation, including underwater gliders, profiling floats, surface drifters, enhanced moorings, coastal high-frequency radars, and satellite remote sensing, now provides the capability to resolve such phenomena and assess their role in structuring pelagic ecosystems. These methods are especially valuable when integrated together, and with shipboard calibration measurements and experimental programs.

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Price, NN, Martz TR, Brainard RE, Smith JE.  2012.  Diel Variability in Seawater pH Relates to Calcification and Benthic Community Structure on Coral Reefs. Plos One. 7:e43843.: Public Library of Science   10.1371/journal.pone.0043843   AbstractWebsite

Community structure and assembly are determined in part by environmental heterogeneity. While reef-building corals respond negatively to warming (i.e. bleaching events) and ocean acidification (OA), the extent of present-day natural variability in pH on shallow reefs and ecological consequences for benthic assemblages is unknown. We documented high resolution temporal patterns in temperature and pH from three reefs in the central Pacific and examined how these data relate to community development and net accretion rates of early successional benthic organisms. These reefs experienced substantial diel fluctuations in temperature (0.78°C) and pH (>0.2) similar to the magnitude of ‘warming’ and ‘acidification’ expected over the next century. Where daily pH within the benthic boundary layer failed to exceed pelagic climatological seasonal lows, net accretion was slower and fleshy, non-calcifying benthic organisms dominated space. Thus, key aspects of coral reef ecosystem structure and function are presently related to natural diurnal variability in pH.

S
Strutton, PG, Martz TR, DeGrandpre MD, McGillis WR, Drennan WM, Boss E.  2011.  Bio-optical observations of the 2004 Labrador Sea phytoplankton bloom. Journal of Geophysical Research-Oceans. 116   10.1029/2010jc006872   AbstractWebsite

A unique time series of moored bio-optical measurements documented the 2004 spring-summer bloom in the southern Labrador Sea. In situ and satellite chlorophyll data show that chlorophyll levels in the 2004 bloom were at the upper end of those typically observed in this region. Satellite chlorophyll and profiling float temperature/salinity data show that the main bloom, which typically peaks in June/July, is often preceded by ephemeral mixed layer shoaling and a lesser, short-lived bloom in May; this was the case ;in 2004. The particulate backscatter to beam attenuation ratio (b(bp)[470 nm]/C(p)[660 nm]) showed peaks in the relative abundance of small particles at bloom initiation and during the decline of the bloom, while larger particles dominated during the bloom. Chlorophyll/C(p) and b(bp)/chlorophyll were correlated with carbon export and dominated by changes in the pigment per cell associated with lower light levels due to enhanced attenuation of solar radiation during the bloom. An NPZ (nutrients, phytoplankton, zooplankton) model captured the phytoplankton bloom and an early July peak in zooplankton. Moored acoustic Doppler current profiler (ADCP) data showed an additional mid-June peak in zooplankton biomass which was attributed to egg-laying copepods. The data reported here represent one of the few moored time series of C(p), b(bp) and chlorophyll extending over several months in an open ocean region. Interpretation of data sets such as this will become increasingly important as these deployments become more commonplace via ocean observing systems. Moreover, these data contribute to the understanding of biological-physical coupling in a biogeochemically important, yet poorly studied region.

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Takeshita, Y, Martz TR, Johnson KS, Plant JN, Gilbert D, Riser SC, Neill C, Tilbrook B.  2013.  A climatology-based quality control procedure for profiling float oxygen data. Journal of Geophysical Research-Oceans. 118:5640-5650.   10.1002/jgrc.20399   AbstractWebsite

Over 450 Argo profiling floats equipped with oxygen sensors have been deployed, but no quality control (QC) protocols have been adopted by the oceanographic community for use by Argo data centers. As a consequence, the growing float oxygen data set as a whole is not readily utilized for many types of biogeochemical studies. Here we present a simple procedure that can be used to correct first-order errors (offset and drift) in profiling float oxygen data by comparing float data to a monthly climatology (World Ocean Atlas 2009). Float specific correction terms for the entire array were calculated. This QC procedure was evaluated by (1) comparing the climatology-derived correction coefficients to those derived from discrete samples for 14 floats and (2) comparing correction coefficients for seven floats that had been calibrated twice prior to deployment (once in the factory and once in-house), with the second calibration ostensibly more accurate than the first. The corrections presented here constrain most float oxygen measurements to better than 3% at the surface.

Takeshita, Y, Martz TR, Johnson KS, Dickson AG.  2014.  Characterization of an Ion Sensitive Field Effect Transistor and Chloride Ion Selective Electrodes for pH Measurements in Seawater. Analytical Chemistry. 86:11189-11195.: American Chemical Society   10.1021/ac502631z   AbstractWebsite
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Takeshita, Y, Johnson KS, Martz TR, Plant JN, Sarmiento JL.  2018.  Assessment of autonomous pH measurements for determining surface seawater partial pressure of CO2. Journal of Geophysical Research-Oceans. 123:4003-4013.   10.1029/2017jc013387   AbstractWebsite

The Southern Ocean Carbon and Climate Observations and Modeling (SOCCOM) program currently operates >80 profiling floats equipped with pH sensors in the Southern Ocean. Theoretically, these floats have the potential to provide unique year-around estimates of pCO(2) derived from pH measurements. Here, we evaluate this approach in the field by comparing pCO(2) estimates from pH sensors to directly measured pCO(2). We first discuss data from a ship's underway system which covered a large range in temperature (2-30 degrees C) and salinity (33.6-36.5) over 43 days. This pH sensor utilizes the same sensing technology but with different packaging than those on SOCCOM floats. The mean residual varied between -4.64.1 and 8.64.0 (1 sigma) atm, depending on how the sensor was calibrated. However, the standard deviation of the residual, interpreted as the ability to track spatiotemporal variability, was consistently <5 atm and was independent of the calibration method. Second, we assessed the temporal stability of this approach by comparing pCO(2) estimated from four floats over 3 years to the Hawaii Ocean Time-series. Good agreement of -2.110.4 (1 sigma) mu atm was observed, with coherent seasonal cycles. These results demonstrate that pCO(2) estimates derived from profiling float pH measurements appear capable of reproducing spatiotemporal variations in surface pCO(2) measurements and should provide a powerful observational tool to complement current efforts to understand the seasonal to interannual variability of surface pCO(2) in underobserved regions of the open ocean.

Takeshita, Y, McGillis W, Briggs EM, Carter A, Donham E, Martz TR, Price NN, Smith JE.  2016.  Assessment of net community production and calcification of a coral reef using a boundary layer approach. Journal of Geophysical Research: Oceans.   10.1002/2016JC011886   Abstract
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Takeshita, Y, Frieder CA, Martz TR, Ballard JR, Feely RA, Kram S, Nam S, Navarro MO, Price NN, Smith JE.  2015.  Including high-frequency variability in coastal ocean acidification projections. Biogeosciences. 12:5853-5870.   10.5194/bg-12-5853-2015   AbstractWebsite

Assessing the impacts of anthropogenic ocean acidification requires knowledge of present-day and future environmental conditions. Here, we present a simple model for upwelling margins that projects anthropogenic acidification trajectories by combining high-temporal-resolution sensor data, hydrographic surveys for source water characterization, empirical relationships of the CO2 system, and the atmospheric CO2 record. This model characterizes CO2 variability on timescales ranging from hours (e. g., tidal) to months (e. g., seasonal), bridging a critical knowledge gap in ocean acidification research. The amount of anthropogenic carbon in a given water mass is dependent on the age; therefore a density-age relationship was derived for the study region and then combined with the 2013 Intergovernmental Panel on Climate Change CO2 emission scenarios to add density-dependent anthropogenic carbon to the sensor time series. The model was applied to time series from autonomous pH sensors deployed in the surf zone, kelp forest, submarine canyon edge, and shelf break in the upper 100m of the Southern California Bight. All habitats were within 5 km of one another, and exhibited unique, habitat-specific CO2 variability signatures and acidification trajectories, demonstrating the importance of making projections in the context of habitat-specific CO2 signatures. In general, both the mean and range of pCO(2) increase in the future, with the greatest increase in both magnitude and range occurring in the deeper habitats due to reduced buffering capacity. On the other hand, the saturation state of aragonite (Omega(Ar)) decreased in both magnitude and range. This approach can be applied to the entire California Current System, and upwelling margins in general, where sensor and complementary hydrographic data are available.

Takeshita, Y, Martz TR, Coletti LJ, Dickson AG, Jannasch HW, Johnson KS.  2017.  The effects of pressure on pH of Tris buffer in synthetic seawater. Marine Chemistry. 188:1-5.   10.1016/j.marchem.2016.11.002   AbstractWebsite

Equimolar Tris (2-amino-2-hydroxymethyl-propane-1,3-diol) buffer prepared in artificial seawater media is a widely accepted pH standard for oceanographic pH measurements, though its change in pH over pressure is largely unknown. The change in volume (Delta V) of dissociation reactions can be used to estimate the effects of pressure on the dissociation constant of weak acid and bases. The Delta V of Tris in seawater media of salinity 35 (Delta V-Tris*) was determined between 10 and 30 degrees C using potentiometry. The potentiometric cell consisted of a modified high pressure tolerant Ion Sensitive Field Effect Transistor pH sensor and a Chloride-Ion Selective Electrode directly exposed to solution. The effects of pressure on the potentiometric cell were quantified in aqueous HCl solution prior to measurements in Tris buffer. The experimentally determined Delta V-Tris* were fitted to the equation Delta V-Tris*= 4528 +0.04912t where t is temperature in Celsius; the resultant fit agreed to experimental data within uncertainty of the measurements, which was estimated to be 0.9 cm(-3) mol(-1). Using the results presented here, change in pH of Tris buffer due to pressure can be constrained to better than 0.003 at 200 bar, and can be expressed as: DpH(Tris) = -(4.528 + 0.04912t)p/ln(10)RT. where T is temperature in Kelvin, R is the universal gas constant (83.145 cm(3) bar K-1 mol(-1)), and Pis gauge pressure in bar. On average, pH of Tris buffer changes by approximately -0.02 at 200 bar. (C) 2016 Elsevier B.V. All rights reserved.

Takeshita, Y, Cyronak T, Martz TR, Kindeberg T, Andersson AJ.  2018.  Coral reef carbonate chemistry variability at different functional scales. Frontiers in Marine Science. 5   10.3389/fmars.2018.00175   AbstractWebsite

There is a growing recognition for the need to understand how seawater carbonate chemistry over coral reef environments will change in a high-CO2 world to better assess the impacts of ocean acidification on these valuable ecosystems. Coral reefs modify overlying water column chemistry through biogeochemical processes such as net community organic carbon production (NCR) and calcification (NCC). However, the relative importance and influence of these processes on seawater carbonate chemistry vary across multiple functional scales (defined here as space, time, and benthic community composition), and have not been fully constrained. Here, we use Bermuda as a case study to assess (1) spatiotemporal variability in physical and chemical parameters along a depth gradient at a rim reef location, (2) the spatial variability of total alkalinity (TA) and dissolved inorganic carbon (DIC) over distinct benthic habitats to infer NCC:NCP ratios [< several km(2); rim reef vs. seagrass and calcium carbonate (CaCO3) sediments] on diel timescales, and (3) compare how TA-DIC relationships and NCC:NCP vary as we expand functional scales from local habitats to the entire reef platform (10's of km(2)) on seasonal to interannual timescales. Our results demonstrate that TA-DIC relationships were strongly driven by local benthic metabolism and community composition over diel cycles. However, as the spatial scale expanded to the reef platform, the TA-DIC relationship reflected processes that were integrated over larger spatiotemporal scales, with effects of NCC becoming increasingly more important over NCR. This study demonstrates the importance of considering drivers across multiple functional scales to constrain carbonate chemistry variability over coral reefs.

Y
Yu, PC, Matson PG, Martz TR, Hofmann GE.  2011.  The ocean acidification seascape and its relationship to the performance of calcifying marine invertebrates: Laboratory experiments on the development of urchin larvae framed by environmentally-relevant pCO(2)/pH. Journal of Experimental Marine Biology and Ecology. 400:288-295.   10.1016/j.jembe.2011.02.016   AbstractWebsite

Variation in ocean pH is a dynamic process occurring naturally in the upwelling zone of the California Current Large Marine Ecosystem. The nearshore carbonate chemistry is under-characterized and the physiology of local organisms may be under constant challenge from cyclical changes in pH and carbonate ion concentration of unexpectedly high magnitude. We looked to environmental pH conditions of coastal upwelling and used those values to examine effects of low pH on 4-arm larvae of purple sea urchin Strongylocentrotus purpuratus. We deployed a pH sensor at a nearshore shallow benthic site for 3 weeks during summer 2010 to assess the changes in pH in the Santa Barbara Channel, a region considered to have relatively less intense upwelling along the US Pacific Coast. Large fluctuations in pH of up to 0.67 pH units were observed over short time scales of several days. Daily pH fluctuations on a tidal pattern followed temperature fluctuations over short time scales, but not over scales greater than a day. The lowest pH values recorded (similar to 7.70) are lower than some of those pH values predicted to occur in surface oceans at the end of the century. In the context of this dynamic pH exposure, larvae were raised at elevated pCO(2) levels of 1000 ppm and 1450 ppm CO(2) (pH 7.7 and 7.5 respectively) and measured for total larval length (from the spicule tip of the postoral arm to the spicule tip of the aboral point) along the spicules, to assess effects of low pH upwelling water on morphology. Larvae in all treatments maintained normal development and developmental schedule to day 6, and did not exhibit significant differences in larval asymmetry between treatments. At day 3 and day 6, larvae in the 1450 ppm CO(2) treatment were significantly smaller (p<0.001) than the control larvae by only 7-13%. The observation of smaller larvae raised under high pCO(2) has an as yet undetermined physiological mechanism, but has implications for locomotion and feeding. These effects of small magnitude in these urchin larvae are indicative of a potential resilience to near-future levels of ocean acidification. Using environmental monitoring of pH to inform experimental parameters provides a means to improve our understanding of acclimatization of organisms in a dynamic ecosystem. (C) 2011 Elsevier B.V. All rights reserved.