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Archive for pH

Chemical thermodynamic models of artificial seawater and the Tris buffers used to define the ‘total’ pH scale

Posted by mmaheigan

· Thursday, August 25th, 2022

The total pH scale used by oceanographers (for salinities 20 – 40, and temperatures 0 to 45°C) is calibrated from a combination of electromotive force measurements of artificial seawaters containing either added HCl of various molalities, or equimolal Tris and its protonated form TrisH⁺. In both cases, the added H⁺ or TrisH⁺ is substituted for Na⁺ on a mole-for-mole-basis, so as to change the properties of the artificial seawater medium as little as possible. The artificial seawater itself consists of the major ions of seawater (those present in constant ratios to one another in natural seawater), with substitutions for the inorganic acid-base species present in natural seawater (principally carbonate and borate). Figure 1 shows the composition of a typical Tris buffer.

Figure 1. The composition of a buffer solution containing 0.04 mol kg-1 of Tris and TrisH+ in artificial seawater of salinity 35. The TrisH+ is substituted for an equal amount of Na+, so that the buffer has the same ionic strength as a pure artificial seawater of the same nominal salinity.

The operational definition of the total pH scale in use today involves a number of assumptions associated with the small differences between pure artificial seawater, and artificial seawater containing the buffer substance. These cannot be determined experimentally. However, a chemical thermodynamic model of the ion activities and concentrations in the buffer solutions can be used to calculate these quantities and to link measured total pH to the conventional thermodynamic total of H⁺ and HSO₄^–. Such a model can also address a series of important future applications and uses of the total pH scale:

The measurement of the total pH of natural waters whose compositions differ from seawater stoichiometry, and the extension of the scale to low salinity waters
Conversion between total pH, a measure of [H⁺] + [HSO₄^–], and ‘free’ pH (a measure of [H⁺])
Calibration of electrode pairs such as H⁺/Cl^– or H⁺/Na⁺ for the potentiometric measurement of pH

Figure 2 shows a model simulation of the operationally defined total pH and the conventional thermodynamic sum [H⁺] + [HSO₄^–] in a buffer solution of salinity 35. The linear extrapolation to zero buffer molality yields a hypothetical total pH that is used by oceanographers and is shown to be the same for both cases, demonstrating that they are the same.

Figure 2. Modelled values of the operational total pH (dashed blue line) and the conventional thermodynamic total pH (solid red line) plotted against buffer molality (mBuffer) for a salinity 35 artificial seawater at 25°C. The fine dotted lines are extrapolations of linear fits to the two groups of points. The vertical distance between marked points A and B (about 0.0045 pH units) represents the effect of differences between the two solutions – hitherto assumed out of necessity to be zero, and here calculated for the first time. The two extrapolations (fine dotted lines) intercept at point C, for which mBuffer is equal to zero and the two definitions are numerically the same.

In these two papers, we describe the development of the model of solutions containing the ions of artificial seawater plus Tris buffer. The models include uncertainty propagation (a first, for models of this type). We assess the needs for further measurements to both improve the accuracy of the model and extend it over the full range of temperatures of interest to oceanographers. We have an ongoing programme of measurements to support this work involving colleagues at the National Institute of Standards and Technology and its equivalents in Germany and Japan. In late 2022, we will be releasing for public use the software that implements two models, and also one of seawater electrolyte. If interested, please contact Heather Benway to be added to our email list, and check the website of SCOR Working Group 145 (marchemspec.org).

Read the papers about the pH buffer and artificial seawater in Marine Chemistry.

Authors:
Simon L. Clegg (School of Environmental Sciences, University of East Anglia, United Kingdom)
Matthew P. Humphreys (NIOZ Royal Netherlands Institute for Sea Research, Netherlands)
Jason F. Waters (National Institute of Standards and Technology, Gaithersburg, USA
David R. Turner (University of Gothenburg, Sweden)
Andrew G. Dickson (Scripps Institution of Oceanography, La Jolla, USA)

pH: the secrets that you keep

Posted by mmaheigan

· Monday, September 20th, 2021

The Intergovernmental Panel on Climate Change (IPCC) defines ocean acidification as “a reduction in pH of the ocean over an extended period, typically decades or longer, caused primarily by the uptake of carbon dioxide (CO₂) from the atmosphere” (Rhein et al., 2013, p. 295). Does this mean that a greater change in pH at the ocean surface relative to the subsurface, or at one location relative to another, always indicates greater acidification? Based on this IPCC definition of ocean acidification, the answer is yes. But does that make sense?

Seawater pH is the negative base 10 logarithm of the seawater’s hydrogen ion concentration ([H⁺]) and is a useful way to display a wide range of [H⁺] in a compact form. A change in pH reflects a relative change in [H⁺]. Thus, anytime we speak of pH changes, we are really referring to a relative change in the chemical species of interest ([H⁺]). On the other hand, changes in all the other carbonate system variables that we measure are usually absolute. This characteristic of pH can lead to ambiguity in the interpretation and presentation of rates and patterns of change. Improved understanding comes from also studying changes in [H⁺], which can reveal aspects that studying changes in pH alone may conceal or overemphasize.

A recent Biogeosciences article reviewed the history leading to this unintuitive relationship between changes in pH and changes in [H⁺]. The article provides three real-world examples to display how examining pH changes alone can hide the ocean acidification signals of interest (Figure 1). These examples highlight potential challenges associated with comparing surface and subsurface pH changes across ocean domains without accounting for differences in the initial pH values. The authors recommend reporting both pH and [H⁺] in studies that assess changes in ocean chemistry to improve the clarity of ocean acidification research.

Figure Caption: Data used in this figure come from the GFDL ESM2M model for the combined historical and RCP8.5 experiments. Top: the 1950s surface ocean (left) pH and (right) [H+]. Bottom: the 1950s to 2090s change (Δ) in surface ocean (left) pH and (right) [H+]. The color bar for ΔpH is reversed to ease comparison with patterns of Δ[H+]

Authors:
Andrea J. Fassbender (NOAA Pacific Marine Environmental Laboratory)
Andrew G. Dickson (Scripps Institution of Oceanography, University of California, San Diego)
James C. Orr (LSCE/IPSL, Laboratoire des Sciences du Climat et de l’Environnement)

Acidity across the interface from the ocean surface to sea spray aerosol

Posted by mmaheigan

· Wednesday, March 31st, 2021

The pH of aerosols controls their impact on climate and human health. Sea spray aerosols are one of the largest sources of aerosols globally by mass, yet it has been challenging to measure the pH of fresh sea spray aerosols in the past. A recent study published in PNAS measured sea spray aerosols under controlled conditions, during a sampling intensive called SeaSCAPE, and optimized a pH paper-based technique to measure the aerosol acidity. The authors found that fresh sea spray aerosols can be rapidly acidified by 4 to 6 orders of magnitude relative to the ocean. This acidification is caused by interaction with surrounding acidic gases, changes in relative humidity, and enhanced dissociation of organic acids within the aerosols. This is a critical finding since the pH of aerosols controls key atmospheric chemical reactions including sulfur dioxide oxidation to form particulate sulfate. The results are also important in light of the fact that enzyme activity has been observed in sea spray aerosols, and enzyme activity is pH dependent.

Figure 1. Acidity of nascent sea spray aerosols (SSA) compared to bulk ocean water measured during the 2019 SeaSCAPE sampling intensive. Background artwork by Nigella Hillgarth.

Authors
Kyle Angle (University of California, San Diego)
Daniel Crocker (University of California, San Diego)
Rebecca Simpson (University of California, San Diego)
Kathryn Mayer (University of California, San Diego)
Lauren Garofalo (Colorado State University, Fort Collins)
Alexia Moore (University of California, San Diego)
Stephanie Mora Garcia (University of California, San Diego)
Victor Or (University of California, San Diego)
Sudarshan Srinivasan (University of California, San Diego)
Mahum Farhan (University of California, San Diego)
Jonathan Sauer (University of California, San Diego)
Christopher Lee (University of California, San Diego)
Matson Pothier (Colorado State University, Fort Collins)
Delphine Farmer (Colorado State University, Fort Collins)
Todd Martz (University of California, San Diego)
Timothy Bertram (University of Wisconsin, Madison)
Christopher Cappa (University of California, Davis)
Kimberly Prather (University of California, San Diego)
Vicki Grassian (University of California, San Diego)

Joint post with Surface Ocean – Lower Atmosphere Study (SOLAS)

Chesapeake Bay acidification partially offset by submerged aquatic vegetation

Posted by mmaheigan

· Wednesday, September 30th, 2020

Ocean acidification is often enhanced by eutrophication and subsequent hypoxia and anoxia in coastal waters, which collectively threaten marine organisms and ecosystems. Acidification is particularly of concern for organisms that form shells and skeletons from calcium carbonate (CaCO₃) such as commercially important shellfish species. Given that CaCO₃ mineral dissolution can increase the total alkalinity of water and neutralize anthropogenic and metabolic CO₂, it is important to include CaCO₃ cycle in the coastal water acidification study. However, very few studies have linked CaCO₃ dissolution to the timing and location of its formation in coastal waters. A recent study from the Chesapeake Bay published in Nature Geoscience reveals the occurrence of a bay-wide pH-buffering mechanism resulting from spatially decoupled CaCO₃ mineral cycling (Figure 1). Photosynthesis by submerged aquatic vegetation at the head of the Bay and in other shallow, nearshore waters can remove nutrient pollution from the Bay, generate very high pH, and elevate the carbonate mineral saturation state (Figure 1). This facilitates the formation of CaCO₃ minerals, which are then transported downstream along with other biologically produced carbonate shells into acidic subsurface waters, where they dissolve. This dissolution of carbonate minerals helps “buffer” the water against pH decreases and even drive pH increases. This finding has great ecological and natural resource management significance, in that coastal nutrient management and reduction via the resurgence of submerged aquatic vegetation can help mitigate low oxygen and acidification stress for these environments and organisms.

Figure 1: Conceptual model of the self-regulated pH-buffering mechanism in the Chesapeake Bay. Calcium carbonate is formed within the high-pH submerged aquatic vegetation beds in shallow waters (top left and upper part of diagram, all Shoals with SAV), where it could be subsequently transported longitudinally and/or laterally into the deep main channel of the mid and lower bay (center) and upon dissolution, increase pH buffering capacity and alleviate coastal acidification (lower section).

Authors:
Jianzhong Su (University of Delaware, Xiamen University)
Wei-Jun Cai (University of Delaware)
Jean Brodeur (University of Delaware)
Baoshan Chen (University of Delaware)
Najid Hussain (University of Delaware)
Yichen Yao (University of Delaware)
Chaoying Ni (University of Delaware)
Jeremy Testa (University of Maryland Center for Environmental Science)
Ming Li (University of Maryland Center for Environmental Science)
Xiaohui Xie (University of Maryland Center for Environmental Science, Second Institute of Oceanography)
Wenfei Ni (University of Maryland Center for Environmental Science)
K. Michael Scaboo (University of Delaware)
Yuanyuan Xu (University of Delaware)
Jeffrey Cornwell (University of Maryland Center for Environmental Science)
Cassie Gurbisz (St. Mary’s College of Maryland)
Michael S. Owens (University of Maryland Center for Environmental Science)
George G. Waldbusser (Oregon State University)
Minhan Dai (Xiamen University)
W. Michael Kemp (University of Maryland Center for Environmental Science)

The past, present, and future of the ocean carbon cycle: A global data product with regional insights

Posted by mmaheigan

· Tuesday, January 21st, 2020

A new study published in Scientific Reports debuts a global data product of ocean acidification (OA) and buffer capacity from the beginning of the Industrial Revolution to the end of the century (1750-2100 C.E.). To develop this product, the authors linked one of the richest observational carbon dioxide (CO₂) data products (6^th version of the Surface Ocean CO₂ Atlas, 1991-2018, ~23 million observations) with temporal trends modeled at individual locations in the global ocean. By linking the modeled pH trends to the observed modern pH distribution, the climatology benefits from recent improvements in both model design and observational data coverage, and is likely to provide more accurate regional OA trajectories than the model output alone. The authors also show that air-sea CO₂ disequilibrium is the dominant mode of spatial variability for surface pH, and discuss why pH and calcium carbonate mineral saturation states (Omega), two important metrics for OA, show contrasting spatial variability. They discover that sea surface temperature (SST) imposes two large but cancelling effects on surface ocean pH and Omega, i.e., the effects of SST on (a) chemical speciation of the carbonic system; and (b) air-sea exchange of CO₂ and the subsequent DIC/TA ratio of the seawater. These two processes act in concert for Omega but oppose each other for pH. As a result, while Omega is markedly lower in the colder polar regions than in the warmer subtropical and tropical regions, surface ocean pH shows little latitudinal variation.

Figure 1. Spatial distribution of global surface ocean pH_T (total hydrogen scale, annually averaged) in past (1770), present (2000) and future (2100) under the IPCC RCP8.5 scenario.

This data product, which extends from the pre-Industrial era (1750 C.E.) to the end of this century under historical atmospheric CO₂ concentrations (pre-2005) and the Representative Concentrations Pathways (post-2005) of the Intergovernmental Panel on Climate Change (IPCC)’s 5^th Assessment Report, may be helpful to policy-makers and managers who are developing regional adaptation strategies for ocean acidification.

The published paper is available here: https://www.nature.com/articles/s41598-019-55039-4

The data product is available here: https://www.nodc.noaa.gov/oads/data/0206289.xml

Authors:
Li-Qing Jiang (University of Maryland and NOAA NCEI)
Brendan Carter (NOAA PMEL and University of Washington JISAO)
Richard Feely (NOAA PMEL)
Siv Lauvset, Are Olsen (University of Bergen and Bjerknes Centre for Climate Research, Norway)

What really controls deep-seafloor calcite dissolution?

Posted by mmaheigan

· Monday, December 16th, 2019

On time scales of tens to millions of years, seawater acidity is primarily controlled by biogenic calcite (CaCO₃) dissolution on the seafloor. Our quantitative understanding of future oceanic pH and carbonate system chemistry requires knowledge of what controls this dissolution. Past experiments on the dissolution rate of suspended calcite grains have consistently suggested a high-order, nonlinear dependence on undersaturation that is independent of fluid flow rate. This form of kinetics has been extensively adopted in models of deep-sea calcite dissolution and pH of benthic sediments. However, stirred-chamber and rotating-disc dissolution experiments have consistently demonstrated linear kinetics of dissolution and a strong dependence on fluid flow velocity. This experimental discrepancy surrounding the kinetic control of seafloor calcite dissolution precludes robust predictions of oceanic response to anthropogenic acidification.

In a recent study published in Geochimica et Cosmochimica Acta, authors have reconciled these divergent experimental results through an equation for the mass balance of the carbonate ion at the sediment-water interface (SWI), which equates the rate of production of that ion via dissolution and its diffusion in sediment porewaters to the transport across the diffusive sublayer (DBL) at the SWI. If the rate constant derived from suspended-grain experiments is inserted into this balance equation, the rate of carbonate ion supply to the SWI from the sediment (sediment-side control) is much greater in the oceans than the rate of transfer across the DBL (water-side control). Thus, calcite dissolution at the seafloor, while technically under mixed control, is strongly water-side dominated. Consequently, a model that neglects boundary-layer transport (sediment-side control alone) invariably predicts CaCO₃-versus-depth profiles that are too shallow compared to available data (Figure 1). These new findings will inform future attempts to model the ocean’s response to acidification.

Figure 1: Plots of the calcite (CaCO₃) content of deep-sea sediments as a function of oceanic depth. Left panel: data from the Northwestern Atlantic Ocean. Right panel: data from the Southwest Pacific Ocean. The blue line represents predicted CaCO₃ content assuming no boundary-layer effects (pure sediment-side control). The red line is the prediction that includes both sediment and water effects (mixed control), and the green line is the prediction with pure water-side control. The agreement between the red and green lines signifies that calcite dissolution is essentially water-side controlled at the seafloor. These results are duplicated for all tested regions of the oceans.

Authors:
Bernard P. Boudreau (Dalhousie University)
Olivier Sulpis (University of Utrecht)
Alfonso Mucci (McGill University)

Long-term coastal data sets reveal unifying relationship between oxygen and pH fluctuations

Posted by mmaheigan

· Thursday, June 7th, 2018

Coastal habitats are critically important to humans, but without consistent and reliable observations we cannot understand the direction and magnitude of unfolding changes in these habitats. Environmental monitoring is therefore a prescient—yet still undervalued—societal service, and no effort better exemplifies this than the work conducted within the National Estuarine Research Reserve System (NERRS). NERRS is a network of 29 U.S. estuarine sites operated as a partnership between NOAA and the coastal states. NERRS has established a system-wide monitoring program with standardized instrumentation, protocols, and data reporting to guide consistent and comparable data collection across all NERRS sites. This has resulted in high-quality, comparable data on short- to long-term changes in water quality and biological systems to inform effective coastal zone management.

Figure 1: Using dissolved oxygen and salinity, monthly mean pH can be predicted within and across coastal systems due to the unifying metabolic coupling of oxygen and pH.

In a recent study published in Estuaries and Coasts, Baumann and Smith (2017) used a subset of this unique data set to analyze short- and long-term variability in pH and dissolved oxygen (DO) at 16 NERRS sites across the U.S. Atlantic, Caribbean, Gulf of Mexico, and Pacific coasts (> 5 million data points). They observed that large, metabolically driven fluctuations of pH and DO are indeed a unifying feature of nearshore habitats. Furthermore, mean pH or mean diel pH fluctuations can be predicted across habitats simply from salinity and oxygen levels/fluctuations (Fig.1). These results provide strong empirical evidence that common metabolic principles drive diel to seasonal pH and DO variations within and across a diversity of estuarine environments. As expected, the study did not yield interannual, monotonic trends in nearshore pH conditions; rather, interannual fluctuations were of similar magnitude to the pH decrease predicted for the average surface ocean over the next three centuries (Fig.2). Correlations of weekly anomalies of pH, oxygen, and temperature yielded strong empirical support for the hypothesis that coastal acidification—in addition to being driven by eutrophication and atmospheric CO₂ increases—is exacerbated by warming, likely via increased community respiration.

Figure 2: Interannual variations in temperature, pH, and dissolved oxygen (DO) anomalies in 16 NERRS sites across the US Atlantic, Gulf of Mexico, Caribbean, and Pacific coasts.

Analyses of these long-term data sets have provided important insights on biogeochemical variability and underlying drivers in nearshore environments, highlighting the value and utility of long-term monitoring efforts like NERRS. Sustained, high-quality data sets in these nearshore environments are essential for the study of environmental change and should be prioritized by funding agencies. The observed metabolically driven pH and DO fluctuations suggest that local measures to reduce nutrient pollution can be an effective management tool in support of healthy coastal environments, a boon for both the habitats and humans.

Authors:
Hannes Baumann (University of Connecticut)
Erik M. Smith (North Inlet-Winyah Bay National Estuarine Research Reserve, University of South Carolina)

Volcanic carbon dioxide drove ancient global warming event

Posted by mmaheigan

· Thursday, March 29th, 2018

A study recently published in Nature suggests that an extreme global warming event 56 million years ago known as the Palaeocene-Eocene Thermal Maximum (PETM) was driven by massive CO₂ emissions from volcanoes during the formation of the North Atlantic Ocean. Using a combination of new geochemical measurements and novel global climate modelling, the study revealed that atmospheric CO₂ more than doubled in less than 25,000 years during the PETM.

The PETM lasted ~150,000 years and is the most rapid and extreme natural global warming event of the last 66 million years. During the PETM, global temperatures increased by at least 5^°C, comparable to temperatures projected in the next century and beyond. While it has long been suggested that the PETM event was caused by the injection of carbon into the ocean and atmosphere, the source and total amount of carbon, as well as the underlying mechanism have thus far remained elusive. The PETM roughly coincided with the formation of massive flood basalts resulting from of a series of eruptions that occurred as Greenland and North America started separating from Europe, thereby creating the North Atlantic Ocean. What was missing is evidence linking the volcanic activity to the carbon release and warming that marks the PETM.

To identify the source of carbon, the authors measured changes in the balance of isotopes of the element boron in ancient sediment-bound marine fossils called foraminifera to generate a new record of ocean pH throughout the PETM. Ocean pH tells us about the amount of carbon absorbed by ancient seawater, but we can get even more information by also considering changes in the isotopes of carbon, which provide information about the carbon source. When forced with these ocean pH and carbon isotope data, a numerical global climate model implicates large-scale volcanism associated with the opening of the North Atlantic as the primary driver of the PETM.

North Atlantic microfossil-derived isotope records from extinct planktonic foraminiferal species M. subbotinae relative to the onset of the PETM carbon isotope excursion (CIE). The negative trend in carbon isotope composition (A) during the carbon emission phase is accompanied by decreasing pH (decreasing δ¹¹B, panel B) and increasing temperature (decreasing δ¹⁸O, panel C). Panels D and E zoom in on the PETM CIE, showing microfossil δ¹³C (D) and δ¹¹B-based pH (E) reconstructions. Also included in E are data from Penman et al. (2014) on their original age model, with recalculated (lab-based) pH values.

These new results suggest that the PETM was associated with a total input of >12,000 petagrams of carbon from a predominantly volcanic source. This is a vast amount of carbon—30 times larger than all of the fossil fuels burned to date and equivalent to all current conventional and unconventional fossil fuel reserves. In the following Earth System Model simulations, it resulted in the concentration of atmospheric CO₂ increasing from ~850 parts per million to >2000 ppm. The Earth’s mantle contains more than enough carbon to explain this dramatic rise, and it would have been released as magma poured from volcanic rifts at the Earth’s surface.

How the ancient Earth system responded to this carbon injection at the PETM can tell us a great deal about how it might respond in the future to man-made climate change. Earth’s warming at the PETM was about what we would expect given the CO₂ emitted and what we know about the sensitivity of the climate system based on Intergovernmental Panel on Climate Change (IPCC) reports. However, the rate of carbon addition during the PETM was about twenty times slower than today’s human-made carbon emissions.

In the model outputs, carbon cycle feedbacks such as methane release from gas hydrates—once the favoured explanation of the PETM—did not play a major role in driving the event. Additionally, one unexpected result was that enhanced organic matter burial was important in ultimately drawing down the released carbon out of the atmosphere and ocean and thereby accelerating the recovery of the Earth system.

Authors:
Marcus Gutjahr (National Oceanography Centre Southamption, GEOMAR)
Andy Ridgwell (Bristol University, University of California Riverside)
Philip F. Sexton (The Open University, UK)
Eleni Anagnostou (National Oceanography Centre Southamption)
Paul N. Pearson (Cardiff University)
Heiko Pälike (University of Bremen)
Richard D. Norris (Scripps Institution of Oceanography)
Ellen Thomas (Yale University, Wesleyan University)
Gavin L. Foster (National Oceanography Centre Southamption)

Funding for the Ocean Carbon & Biogeochemistry Project Office is provided by the National Science Foundation (NSF) and the National Aeronautics and Space Administration (NASA). The OCB Project Office is housed at the Woods Hole Oceanographic Institution.

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