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

20 Molybdenum (Mo) enrichments in marine sediments are a common indicator of the presence 21 of sulphide near the sediment-water interface and can thereby record historic bottom-water 22 oxygen depletion. Here, we assess the impact of temporal changes in manganese (Mn) cycling 23 and bottom-water oxygen on sedimentary Mo dynamics in a seasonally-hypoxic coastal marine 24 basin (Lake Grevelingen, the Netherlands). High resolution line scans obtained with LA-ICP-25 MS and discrete sample analyses reveal distinct oscillations in Mo with depth in the sediment. 26 These oscillations and high sediment Mo concentrations (up to ~130 ppm) are attributed to 27 deposition of Mo-bearing Mn-oxide-rich particles from the overlying water, the release of 28 molybdate (MoO4 2-) to the pore water upon reduction of these Mn-oxides, and subsequent 29 sequestration of Mo. The latter process only occurs in summer when sulphide concentrations 30 near the sediment-water interface are elevated. We hypothesise that cable bacteria enhance the 31 seasonality in sediment Mo records by contributing to remobilisation of Mo as MoO4 2during 32 oxic periods and by enhancing the pool of Mn-oxides in the system by dissolving Mn-33 carbonates. A sediment record that spans the past ~45 years indicates that sediment Mo 34 concentrations have increased over the past decades, despite less frequent occurrences of anoxia 35in the bottom waters based on oxygen measurements from water column monitoring. We 36 suggest that the elevated Mo in recent sediments reflects both enhanced rates of sulphate 37 reduction and sulphide production in the surface sediment as a result of increased input of 38 organic matter into the basin from the adjacent North Sea since 1999, and an associated 39 enhanced "Mn refluxing" in the marine lake in summer. 40 93 refluxing" is thought to contribute to the high Mo burial fluxes in environments with weakly 94 sulphidic bottom waters (Algeo and Lyons, 2006). To our knowledge, there are no detailed 95 seasonal studies of the dynamics of Mo and Mn in both pore waters and sediments of hypoxic 96 systems to confirm the suggested seasonality in coupled Mn-Mo cycling. 97 Recently, it was discovered that sulphide-oxidising cable bacteria (Nielsen et al., 2010; 98 Pfeffer et al., 2012) may dissolve Fe-sulphides and Mn-carbonates in surface sediments of 99 seasonally-hypoxic systems. Consequently, these bacteria actively contribute to the formation 100 of an oxidised, Fe-and Mn-oxide rich surface layer in winter and spring (Seitaj et al., 2015; 101 Sulu-Gambari et al., 2016b; Sulu-Gambari et al., 2016a). In contrast, sulphur oxidising 102 Beggiatoaceae, present in autumn, had a more limited effect on the formation of Fe-and Mn-103 oxides in the surface sediment (Seitaj et al., 2015; Sulu-Gambari et al., 2016b; Sulu-Gambari 104 et al., 2016a). Due to the coupling of Mn, Fe, S and Mo cycles in hypoxic systems, we 105 hypothesise that the activity of cable bacteria may also be of relevance to the sedimentary 106 dynamics of Mo. More specifical...

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.