Measuring Protons with Photons: A Hand-Held, Spectrophotometric pH Analyzer for Ocean Acidification Research, Community Science and Education.

Ocean Acidification (OA) is negatively affecting the physiological processes of marine organisms, altering biogeochemical cycles, and changing chemical equilibria throughout the world's oceans. It is difficult to measure pH broadly, in large part because accurate pH measurement technology is expensive, bulky, and requires technical training. Here, we present the development and evaluation of a hand-held, affordable, field-durable, and easy-to-use pH instrument, named the pHyter, which is controlled through a smartphone app. We determine the accuracy of pH measurements using the pHyter by comparison with benchtop spectrophotometric seawater pH measurements, measurement of a certified pH standard, and comparison with a proven in situ instrument, the iSAMI-pH. These results show a pHyter pH measurement accuracy of ±0.046 pH or better, which is on par with interlaboratory seawater pH measurement comparison experiments. We also demonstrate the pHyter's ability to conduct both temporal and spatial studies of coastal ecosystems by presenting data from a coral reef and a bay, in which the pHyter was used from a kayak. These studies showcase the instrument's portability, applicability, and potential to be used for community science, STEM education, and outreach, with the goal of empowering people around the world to measure pH in their own backyards.

Changes in the Arctic Ocean Carbon Cycle With Diminishing Ice Cover.

Less than three decades ago only a small fraction of the Arctic Ocean (AO) was ice free and then only for short periods. The ice cover kept sea surface pCO2 at levels lower relative to other ocean basins that have been exposed year round to ever increasing atmospheric levels. In this study, we evaluate sea surface pCO2 measurements collected over a 6-year period along a fixed cruise track in the Canada Basin. The measurements show that mean pCO2 levels are significantly higher during low ice years. The pCO2 increase is likely driven by ocean surface heating and uptake of atmospheric CO2 with large interannual variability in the contributions of these processes. These findings suggest that increased ice-free periods will further increase sea surface pCO2, reducing the Canada Basin's current role as a net sink of atmospheric CO2.

Autonomous in situ measurements of seawater alkalinity.

Total alkalinity (AT) is an important parameter for describing the marine inorganic carbon system and understanding the effects of atmospheric CO2 on the oceans. Measurements of AT are limited, however, because of the laborious process of collecting and analyzing samples. In this work we evaluate the performance of an autonomous instrument for high temporal resolution measurements of seawater AT. The Submersible Autonomous Moored Instrument for alkalinity (SAMI-alk) uses a novel tracer monitored titration method where a colorimetric pH indicator quantifies both pH and relative volumes of sample and titrant, circumventing the need for gravimetric or volumetric measurements. The SAMI-alk performance was validated in the laboratory and in situ during two field studies. Overall in situ accuracy was -2.2 ± 13.1 µmol kg(-1) (n = 86), on the basis of comparison to discrete samples. Precision on duplicate analyses of a carbonate standard was ±4.7 µmol kg(-1) (n = 22). This prototype instrument can measure in situ AT hourly for one month, limited by consumption of reagent and standard solutions.

Universal tracer monitored titrations.

Titrations, while primarily known as the chemical rite of passage for fledgling science students, are still widely used for chemical analysis. With its many years of existence and improvement, the method would seem an unlikely candidate for innovation, yet it is desirable, in this age of autonomous sensing where analyzers may be sent into space or to the bottom of the ocean, to have a simplified titrimetric method that does not rely upon volumetric or gravimetric measurement of sample and titrant. In previous work on the measurement of seawater alkalinity, we found that use of a tracer in the titrant eliminates the need to measure mass or volume. Here, we show the versatility of the method for diverse types of titrations and tracers. The results suggest that tracers may be employed in all types of titrations, opening the door for greatly simplified laboratory and field-based chemical analysis.

Evaluation of indicator-based pH measurements for freshwater over a wide range of buffer intensities.

Two different sulfonephthalein indicators, cresol red (CR) with a pKa of approximately 8.3 and bromothymol blue (BTB) with pKa of approximately 7.4, were tested for an analysis of freshwater over a broad range of pH and total alkalinity values. Measurements from an autonomous sensor system using a 1 cm optical path length were compared to those using a 10 cm path length on a benchtop spectrophotometer. The indicator pH perturbation was quantified with a thermodynamic model and nonlinear least-squares analysis. The laboratory study found that the perturbation-corrected pH differed between the 1 cm (large indicator perturbation) and 10 cm (small indicator perturbation) optical path length measurements from -0.017 to +0.15 with a median of +0.0041 pH units for CR and from -0.015 to +0.026 with a median of -0.0008 pH units for BTB. Precision was +0.0005-0.013 and +0.0001-0.0027 pH units for the 1 and 10-cm-path-length measurements, respectively. The autonomous sensor was deployed for 14 days in a local creek. Simultaneous glass pH electrode measurements had a large negative and drifting offset (-0.15 to -0.40 pH units) compared to the indicator-based measurements. This study is the first in situ comparison between potentiometric and spectrophotometric pH methods in a freshwater system.

Comparison between two detection systems for fiber-optic chemical sensor applications.

Two optical detection system designs are compared for fiber-optic chemical sensor applications. A single grating spectrograph with fiber-optic input and photodiodes at three different wavelengths is compared to 1x3 fiber-optic splitters and photodiode detectors with integrated interference filters. The splitters are used to direct the optical power to the filter photodiodes. Three types of 1x3 commercially available splitters were tested: a 400 microm fused glass fiber-optic coupler, a 1000 microm fused plastic fiber-optic coupler, and a 1000 microm glass fiber-optic bundle. This study finds that the fiber-splitter-based detection systems have similar stray light, signal-to-noise ratio, and long-term absorbance stability compared to the spectrograph detection system with a modest improvement in spectral resolution (from approximately 12 nm to approximately 6 nm). It is also much smaller in size and lower in cost. Applications of the two systems in a colorimetric CO2 partial pressure sensor are compared and similar accuracy and precision are achieved.

Tracer monitored titrations: measurement of total alkalinity.

We introduce a new titration methodology, tracer monitored titration (TMT), in which analyses are free of volumetric and gravimetric measurements and insensitive to pump precision and reproducibility. Spectrophotometric monitoring of titrant dilution, rather than volume increment, lays the burden of analytical performance solely on the spectrophotometer. In the method described here, the titrant is a standardized mixture of acid-base indicator and strong acid. Dilution of a pulse of titrant in a titration vessel is tracked using the total indicator concentration measured spectrophotometrically. The concentrations of reacted and unreacted indicator species, derived from Beer's law, are used to calculate the relative proportions of titrant and sample in addition to the equilibrium position (pH) of the titration mixture. Because the method does not require volumetric or gravimetric additions of titrant, simple low-precision pumps can be used. Here, we demonstrate application of TMT for analysis of total alkalinity (A(T)). High-precision, high-accuracy seawater A(T) measurements are crucial for understanding, for example, the marine CaCO3 budget and saturation state, anthropogenic CO2 penetration into the oceans, calcareous phytoplankton blooms, and coral reef dynamics. We present data from 286 titrations on three types of total alkalinity standards: Na2CO3 in 0.7 mol kg x soln(-1) NaCl, NaOH in 0.7 mol kg x soln(-1) NaCl, and a seawater Certified Reference Material (CRM). Based on Na2CO3 standards, the accuracy and precision are +/-0.2 and +/-0.1% (4 and 2 micromol kg x soln(-1) for A(T) approximately 2100-2500 micromol kg x soln(-1), n = 242), using low-precision solenoid pumps to introduce sample and titrant. Similar accuracy and precision were found for analyses run 42 days after the initial experiments. Excellent performance is achieved by optimizing the spectrophotometric detection system and relying upon basic chemical thermodynamics for calculating the equivalence point. Although applied to acid-base titrations in this paper, the approach should be generally applicable to other types of titrations.

Biogeochemical controls on Diel cycling of stable isotopes of dissolved O2 and dissolved inorganic carbon in the Big Hole River, Montana.

Rivers with high biological productivity typically show substantial increases in pH and dissolved oxygen (DO) concentration during the day and decreases at night, in response to changes in the relative rates of aquatic photosynthesis and respiration. These changes, coupled with temperature variations, may impart diel (24-h) fluctuations in the concentration of trace metals, nutrients, and other chemical species. A better understanding of diel processes in rivers is needed and will lead to improved methods of data collection for both monitoring and research purposes. Previous studies have used stable isotopes of dissolved oxygen (DO) and dissolved inorganic carbon (DIC) as tracers of geochemical and biological processes in streams, lakes, and marine systems. Although seasonal variation in 6180 of DO in rivers and lakes has been documented, no study has investigated diel changes in this parameter. Here, we demonstrate large (up to 13%o) cycles in delta18O-DO for two late summer sampling periods in the Big Hole River of southwest Montana and illustrate that these changes are correlated to variations in the DO concentration, the C-isotopic composition of DIC, and the primary productivity of the system. The magnitude of the diel cycle in delta18O-DO was greater in August versus September because of the longer photoperiod and warmer water temperatures. This study provides another biogeochemical tool for investigating the O2 and C budgets in rivers and may also be applicable to lake and groundwater systems.

A submersible autonomous sensor for spectrophotometric pH measurements of natural waters.

An autonomous sensor for long-term in situ measurements of the pH of natural waters is described. The system is based upon spectrophotometric measurements of a mixture of sample and sulfonephthalein indicator. A simple plumbing design, using a small, low-power solenoid pump and valve, avoids the need for quantitative addition of indicator. A approximately 50-microL slug of indicator is pulled into the sample stream by the pump, and subsequent pumping and mixing results in a section of indicator and sample where absorbance measurements can be made. The design also permits direct determination of the indicator pH perturbation. Absorbances are recorded at three wavelengths (439, 579, and 735 nm) using a custom-built 1.7-cm path length fiber-optic flow cell. Solution blanks are obtained by periodically flushing the cell with sample. Field tests were performed in a local river over an 8-day period. The in situ accuracy, based on comparison with laboratory spectrophotometric pH measurements, was -0.003 pH unit (n = 16), similar to the measurement precision. No drift was observed during the 8-day period. The absorbance ratio used to calculate pH, in combination with a simple and robust optical design, imparts an inherent stability not achievable with conventional potentiometric methods, making the design feasible for long-term autonomous pH measurements.