Abstract. Coastal areas are impacted by multiple natural and anthropogenic processes and experience stronger pH fluctuations than the open ocean. These variations can weaken or intensify the ocean acidification signal induced by increasing atmospheric pCO2. The development of eutrophication-induced hypoxia intensifies coastal acidification, since the CO2 produced during respiration decreases the buffering capacity in any hypoxic bottom water. To assess the combined ecosystem impacts of acidification and hypoxia, we quantified the seasonal variation in pH and oxygen dynamics in the water column of a seasonally stratified coastal basin (Lake Grevelingen, the Netherlands). Monthly water-column chemistry measurements were complemented with estimates of primary production and respiration using O2 light–dark incubations, in addition to sediment–water fluxes of dissolved inorganic carbon (DIC) and total alkalinity (TA). The resulting data set was used to set up a proton budget on a seasonal scale. Temperature-induced seasonal stratification combined with a high community respiration was responsible for the depletion of oxygen in the bottom water in summer. The surface water showed strong seasonal variation in process rates (primary production, CO2 air–sea exchange), but relatively small seasonal pH fluctuations (0.46 units on the total hydrogen ion scale). In contrast, the bottom water showed less seasonality in biogeochemical rates (respiration, sediment–water exchange), but stronger pH fluctuations (0.60 units). This marked difference in pH dynamics could be attributed to a substantial reduction in the acid–base buffering capacity of the hypoxic bottom water in the summer period. Our results highlight the importance of acid–base buffering in the pH dynamics of coastal systems and illustrate the increasing vulnerability of hypoxic, CO2-rich waters to any acidifying process.

Alkalinity, the excess of proton acceptors over donors, plays a major role in ocean chemistry, in buffering and in calcium carbonate precipitation and dissolution. Understanding alkalinity dynamics is pivotal to quantify ocean carbon dioxide uptake during times of global change. Here we review ocean alkalinity and its role in ocean buffering as well as the biogeochemical processes governing alkalinity and pH in the ocean. We show that it is important to distinguish between measurable titration alkalinity and charge balance alkalinity that is used to quantify calcification and carbonate dissolution and needed to understand the impact of biogeochemical processes on components of the carbon dioxide system. A general treatment of ocean buffering and quantification via sensitivity factors is presented and used to link existing buffer and sensitivity factors. The impact of individual biogeochemical processes on ocean alkalinity and pH is discussed and quantified using these sensitivity factors. Processes governing ocean alkalinity on longer time scales such as carbonate compensation, (reversed) silicate weathering, and anaerobic mineralization are discussed and used to derive a close‐to‐balance ocean alkalinity budget for the modern ocean.

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Please cite this article as: Hagens, M., Middelburg, J.J., Generalised expressions for the response of pH to changes in ocean chemistry, Geochimica et Cosmochimica Acta (2016), doi: http://dx.doi.org/10. 1016/j.gca.2016.04.012 This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain. The extent to which oceans are capable of buffering chemical changes resulting from the 9 uptake of carbon dioxide (CO 2 ) or other acidifying processes can be quantified using buffer 10 factors. Here, we present general expressions describing the sensitivity of pH, CO 2 and other 11 acid-base species to a change in ocean chemistry. These expressions can include as many 12 acid-base systems as desirable, making them suitable for application to, e.g., upwelling 13 regions or nutrient-rich coastal waters. We show that these expressions are fully consistent 14 with previously derived expressions for the Revelle factor and other buffer factors, which 15 only included the carbonate and borate acid-base systems, and provide more accurate values. 16We apply our general expressions to contemporary global ocean surface water and possible 17 changes therein by the end of the 21 st century. These results show that most sensitivities 18 describing a change in pH are of greater magnitude in a warmer, high-CO 2 ocean, indicating 19 a decreased seawater buffering capacity. This trend is driven by the increase in CO 2 and 20 slightly moderated by the warming. Respiration-derived carbon dioxide may amplify or 21 attenuate ocean acidification due to rising atmospheric CO 2 , depending on their relative 22 importance. Our work highlights that, to gain further insight into current and future pH 23 dynamics, it is crucial to properly quantify the various concurrently acting buffering 24 mechanisms. 25 26

A multitracer approach is applied to assess the impact of boundary fluxes (e.g., benthic input from sediments or lateral inputs from the coastline) on the acid-base buffering capacity, and overall biogeochemistry, of the North Sea. Analyses of both basin-wide observations in the North Sea and transects through tidal basins at the North-Frisian coastline, reveal that surface distributions of the d 13 C signature of dissolved inorganic carbon (DIC) are predominantly controlled by a balance between biological production and respiration.In particular, variability in metabolic DIC throughout stations in the well-mixed southern North Sea indicates the presence of an external carbon source, which is traced to the European continental coastline using naturally occurring radium isotopes ( 224 Ra and 228 Ra). 228 Ra is also shown to be a highly effective tracer of North Sea total alkalinity (AT) compared to the more conventional use of salinity. Coastal inputs of metabolic DIC and AT are calculated on a basin-wide scale, and ratios of these inputs suggest denitrification as a primary metabolic pathway for their formation. The AT input paralleling the metabolic DIC release prevents a significant decline in pH as compared to aerobic (i.e., unbuffered) release of metabolic DIC. Finally, longterm pH trends mimic those of riverine nitrate loading, highlighting the importance of coastal AT production via denitrification in regulating pH in the southern North Sea.

Abstract. Phosphorus (P) concentrations in sediments are frequently used to reconstruct past environmental conditions in freshwater and marine systems, with high values thought to be indicative of a high biological productivity. Recent studies suggest that the post-depositional formation of vivianite, an iron(II)-phosphate mineral, might significantly alter trends in P with sediment depth. To assess its importance, we investigate a sediment record from the Bornholm Basin that was retrieved during the Integrated Ocean Drilling Program (IODP) Baltic Sea Paleoenvironment Expedition 347 in 2013, consisting of lake sediments overlain by brackish-marine deposits. Combining bulk sediment geochemistry with microanalysis using scanning electron microscope energy dispersive spectroscopy (SEM-EDS) and synchrotron-based X-ray absorption spectroscopy (XAS), we demonstrate that vivianite-type minerals rich in manganese and magnesium are present in the lake deposits just below the transition to the brackish-marine sediments (at 11.5 to 12 m sediment depth). In this depth interval, phosphate that diffuses down from the organic-rich, brackish-marine sediments meets porewaters rich in dissolved iron in the lake sediments, resulting in the precipitation of iron(II) phosphate. Results from a reactive transport model suggest that the peak in iron(II) phosphate originally occurred at the lake-marine transition (9 to 10 m) and moved downwards due to changes in the depth of a sulfidization front. However, its current position relative to the lake-marine transition is stable as the vivianite-type minerals and active sulfidization fronts have been spatially separated over time. Experiments in which vivianite was subjected to sulfidic conditions demonstrate that incorporation of manganese or magnesium in vivianite does not affect its susceptibility to sulfide-induced dissolution. Our work highlights that post-depositional formation of iron(II) phosphates such as vivianite has the potential to strongly alter sedimentary P records particularly in systems that are subject to environmental perturbation, such as a change in primary productivity, which can be associated with a lake-marine transition.

Abstract. Coastal areas are impacted by multiple natural and anthropogenic processes and experience stronger pH fluctuations than the open ocean. These variations can weaken or intensify the ocean acidification signal induced by increasing atmospheric pCO2. The development of eutrophication-induced hypoxia intensifies coastal acidification, since the CO2 produced during respiration decreases the buffering capacity of the hypoxic bottom water. To assess the combined ecosystem impacts of acidification and hypoxia, we quantified the seasonal variation in pH and oxygen dynamics in the water column of a seasonally stratified coastal basin (Lake Grevelingen, the Netherlands). Monthly water column chemistry measurements were complemented with estimates of primary production and respiration using O2 light-dark incubations, in addition to sediment-water fluxes of dissolved inorganic carbon (DIC) and total alkalinity (TA). The resulting dataset was used to set up a proton budget on a seasonal scale. Temperature-induced seasonal stratification combined with a high community respiration was responsible for the depletion of oxygen in the bottom water in summer. The surface water showed strong seasonal variation in process rates (primary production, CO2 air–sea exchange), but relatively small seasonal pH fluctuations (0.46 units on the total hydrogen ion scale). In contrast, the bottom water showed less seasonality in biogeochemical rates (respiration, sediment–water exchange), but stronger pH fluctuations (0.60 units). This marked difference in pH dynamics could be attributed to a substantial reduction in the acid-base buffering capacity of the hypoxic bottom water in the summer period. Our results highlight the importance of acid-base buffering in the pH dynamics of coastal systems and illustrate the increasing vulnerability of hypoxic, CO2-rich waters to any acidifying process.

On‐going ocean acidification and increasing availability of high‐frequency pH data have stimulated interest to understand seasonal pH dynamics in surface waters. Here we show that it is possible to accurately reproduce observed pH values by combining seasonal changes in temperature (T), dissolved inorganic carbon (DIC), and total alkalinity (TA) from three time series stations with novel pH sensitivity factors. Moreover, we quantify the separate contributions of T, DIC, and TA changes to winter‐to‐summertime differences in pH, which are in the ranges of −0.0334 to −0.1237, 0.0178 to 0.1169, and −0.0063 to 0.0234, respectively. The effects of DIC and temperature are therefore largely compensatory, and are slightly tempered by changes in TA. Whereas temperature principally drives pH seasonality in low‐latitude to midlatitude systems, winter‐to‐summer DIC changes are most important at high latitudes. This work highlights the potential of pH sensitivity factors as a tool for quantifying the driving mechanisms behind pH changes.