An official website of the United States government
Abstract Ion‐sensitive field effect transistor‐based pH sensors have been shown to perform well in high frequency and long‐term ocean sampling regimes. The Honeywell Durafet is widely used due to its stability, fast response, and characterization over a large range of oceanic conditions. However, potentiometric pH monitoring is inherently complicated by the fact that the sensors require careful calibration. Offsets in calibration coefficients have been observed when comparing laboratory to field‐based calibrations and prior work has led to the recommendation that an in situ calibration be performed based on comparison to discrete samples. Here, we describe our work toward a self‐calibration apparatus integrated into a SeapHOx pH, dissolved oxygen, and CTD sensor package. This Self‐Calibrating SeapHOx is capable of autonomously recording calibration values from a high quality, traceable, primary reference standard: equimolar tris buffer. The Self‐Calibrating SeapHOx's functionality was demonstrated in a 6‐d test in a seawater tank at Scripps Institution of Oceanography (La Jolla, California, U.S.A.) and was successfully deployed for 2 weeks on a shallow, coral reef flat (Lizard Island, Australia). During the latter deployment, the tris‐based self‐calibration using 15 on‐board samples exhibited superior reproducibility to the standard spectrophotometric pH‐based calibration using > 100 discrete samples. Standard deviations of calibration pH using tris ranged from 0.002 to 0.005 whereas they ranged from 0.006 to 0.009 for the standard spectrophotometric pH‐based method; the two independent calibration methods resulted in a mean pH difference of 0.008. We anticipate that the Self‐Calibrating SeapHOx will be capable of autonomously providing climate quality pH data, directly linked to a primary seawater pH standard, and with improvements over standard calibration techniques.
more »
« less
Preparation of 2‐amino‐2‐hydroxymethyl‐1,3‐propanediol ( TRIS ) pHT buffers in synthetic seawater
Abstract Buffers of known quality for the calibration of seawater pHTmeasurements are not widely or commercially available. Although there exist published compositions for the 0.04 mol kg‐H2O−1equimolar buffer 2‐amino‐2‐hydroxymethyl‐1,3‐propanediol (TRIS)‐TRIS · H+in synthetic seawater, there are no explicit procedures that describe preparing this buffer to achieve a particular pHTwith a known uncertainty. Such a procedure is described here which makes use of easily acquired laboratory equipment and techniques to produce a buffer with a pHTwithin 0.006 of the published pHTvalue originally assigned by DelValls and Dickson (1998), 8.094 at 25°C. Such a buffer will be suitable for the calibration of pH measurements expected to fulfil the “weather” uncertainty goal of the Global Ocean Acidification Observation Network of 0.02 in pHT, an uncertainty goal appropriate to “identify relative spatial patterns and short‐term variation.”
more »
« less
- Award ID(s):
- 1657799
- PAR ID:
- 10455172
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Limnology and Oceanography: Methods
- Volume:
- 18
- Issue:
- 9
- ISSN:
- 1541-5856
- Page Range / eLocation ID:
- p. 504-515
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
null (Ed.)Abstract. Equimolal tris (2-amino-2-hydroxymethyl-propane-1,3-diol) buffer in artificialseawater is a well characterized and commonly used standard for oceanographic pH measurements. We evaluated the stability of tris pH when stored in purportedly gas-impermeable bags across a variety of experimental conditions, including bag type and storage in air vs. seawater over300 d. Bench-top spectrophotometric pH analysis revealed that the pH of tris stored in bags decreased at a rate of 0.0058±0.0011 yr−1 (mean slope ±95 % confidence interval of slope). The upper and lower bounds of expected pH change att=365 d, calculated using the averages and confidence intervals of slope and intercept of measured pH change vs. time data, were −0.0042 and −0.0076 from initial pH. Analyses of total dissolved inorganic carbonconfirmed that a combination of CO2 infiltration and/or microbialrespiration led to the observed decrease in pH. Eliminating the change in pH of bagged tris remains a goal, yet the rate of pH change is lower than many processes of interest and demonstrates the potential of bagged tris for sensor calibration and validation of autonomous in situ pH measurements.more » « less
-
Electrocatalytic generation of H2is challenging in neutral pH water, where high catalytic currents for the hydrogen evolution reaction (HER) are particularly sensitive to the proton source and solution characteristics. A tris(hydroxymethyl)aminomethane (TRIS) solution at pH 7 with a [2Fe-2S]-metallopolymer electrocatalyst gave catalytic current densities around two orders of magnitude greater than either a more conventional sodium phosphate solution or a potassium chloride (KCl) electrolyte solution. For a planar polycrystalline Pt disk electrode, a TRIS solution at pH 7 increased the catalytic current densities for H2generation by 50 mA/cm2at current densities over 100 mA/cm2compared to a sodium phosphate solution. As a special feature of this study, TRIS is acting not only as the primary source of protons and the buffer of the pH, but the protonated TRIS ([TRIS-H]+) is also the sole cation of the electrolyte. A species that is simultaneously the proton source, buffer, and sole electrolyte is termed a protic buffer electrolyte (PBE). The structure–activity relationships of the TRIS PBE that increase the HER rate of the metallopolymer and platinum catalysts are discussed. These results suggest that appropriately designed PBEs can improve HER rates of any homogeneous or heterogeneous electrocatalyst system. General guidelines for selecting a PBE to improve the catalytic current density of HER systems are offered.more » « less
-
Abstract The implications of ocean acidification are acute for calcifying organisms, notably tropical reef corals, for which accretion generally is depressed and dissolution enhanced at reduced seawater pH. We describe year‐long experiments in which back reef and fore reef (17‐m depth) communities from Moorea, French Polynesia, were incubated outdoors under pCO2regimes reflecting endpoints of representative concentration pathways (RCPs) expected by the end the century. Incubations were completed in three to four flumes (5.0 × 0.3 m, 500 L) in which seawater was refreshed and circulated at 0.1 m s−1, and the response of the communities was evaluated monthly by measurements of net community calcification (NCC) and net community productivity (NCP). For both communities, NCC (but not NCP) was affected by treatments and time, with NCC declining with increasing pCO2, and for the fore reef, becoming negative (i.e., dissolution was occurring) at the highest pCO2(1067–1433μatm, RCP8.5). There was scant evidence of community adjustment to reduce the negative effects of ocean acidification, and inhibition of NCC intensified in the back reef as the abundance of massivePoritesspp. declined. These results highlight the risks of dissolution under ocean acidification for coral reefs and suggest these effects will be most acute in fore reef habitats. Without signs of amelioration of the negative effects of ocean acidification during year‐long experiments, it is reasonable to expect that the future of coral reefs in acidic seas can be predicted from their current known susceptibility to ocean acidification.more » « less
-
Abstract Measurements of riverine dissolved inorganic carbon, total alkalinity (AT), pH, and the partial pressure of carbon dioxide (pCO2) can provide insights into the biogeochemical function of rivers, including the processes that control biological production, chemical speciation, and air‐water CO2fluxes. The complexity created by these combined processes dictates that studies of inorganic carbon be made over broad spatial and temporal scales. Time‐series data like these are relatively rare, however, because sampling and measurements are labor intensive and, for some variables, good measurement quality is difficult to achieve (e.g., pH). In this study, spectrophotometric pH and ATwere quantified with high precision and accuracy at biweekly to monthly intervals over a four‐year period (2018–2021) along 216 km of the Upper Clark Fork River (UCFR) in the northern Rocky Mountains, USA. We use these and other time‐series data to provide insights into the processes that control river inorganic carbon, with a focus onpCO2and air‐water CO2fluxes. We found that seasonal snowmelt runoff increasedpCO2and that expected increase and decrease ofpCO2due to seasonal heating and cooling were likely offset by an increase and loss of algal biomass, respectively. Overall, the UCFR was a small net source (0.08 ± 0.14 mol m−2 d−1) of CO2to the atmosphere over the four‐year study period with highly variable annual averages (0.0–0.10 mol m−2 d−1). The seasonally correlated, offsetting mechanisms highlight the challenges in predictingpCO2and air‐water CO2fluxes in rivers.more » « less
