Eutrophication Induced CO₂‑Acidification of Subsurface Coastal Waters: Interactive Effects of Temperature, Salinity, and Atmospheric <i>P</i>_CO₂

Increasing atmospheric carbon dioxide (CO₂) is raising seawater CO₂ concentrations and thereby acidifying ocean water. But a second environmental problem, eutrophication, is also causing large CO₂ inputs into coastal waters. This occurs because anthropogenic inputs of nutrients have fueled massive algal blooms, which deplete bottom waters of oxygen (O₂) and release CO₂ when the organic matter from these blooms is respired by bacteria. On the basis of a biogeochemical model, these CO₂ inputs are predicted to decrease current pH values by 0.25 to 1.1 units, effects that increased with decreasing temperature and salinity. Our model predictions agreed well with pH data from hypoxic zones in the northern Gulf of Mexico and Baltic Sea, two eutrophic coastal systems with large temperature and salinity differences. The modeled and measured decreases in pH are well within the range shown to adversely impact marine fauna. Model calculations show that the acidification from respiratory CO₂ inputs interacts in a complex fashion with that from increasing atmospheric CO₂ and that these pH effects can be more than additive in seawater at intermediate to higher temperatures. These interactions have important biological implications in a future world with increasing atmospheric CO₂, increasing anthropogenic inputs of nutrients, and rising temperatures from CO₂-linked global warming

DataSheet_1_Rapid changes in the surface carbonate system under complex mixing schemes across the Bering Sea: a comparative study of a forward voyage in July and a return voyage in September 2018.pdf

Regulated by the rapid changes in temperature, mixing, and biological production during warm seasons, the surface carbonate system in the Bering Sea is subject to significant spatial-temporal variability. However, the seasonal evolution of the carbon cycle and its controls are less clear due to the lack of observations. Here, we present the carbonate data collected during a forward voyage in July and a return voyage in September 2018 across the Bering Sea. For both voyages, we show distinct dissolved inorganic carbon versus total alkalinity (DIC-TA) relationships and partial pressure of CO2 (pCO2) distribution patterns in the Southern Basin (54-57°N), the Northern Basin (57-59°N), the Slope (59-61°N), the Shelf (61-64°N), and the Bering Strait (>64°N). In the Southern Basin, the Northern Basin, and the Slope, surface water was a two end-member mixing of Rainwater and Bering Summer Water (BSW) during the forward voyage and a two end-member mixing of North Pacific Surface Water (NPSW) and BSW during the return voyage. As a result, the observed DIC was almost consistent with the conservative mixing line, with a slight DIC addition/removal of -8.6~5.8 µmol kg-1, suggesting low biological production/respiration during both voyages. Seasonally, the higher factions of NPSW featuring low pCO2 during the return voyage dominated the pCO2 drawdown from July to September in the Southern Basin and the Slope. On the Shelf, the surface water was a two end-member mixing of plume water from the Anadyr River and BSW during both voyages, but the decreased DIC consumption via biological production from 59.9 ± 25.8 µmol kg-1 to 34.8 ± 14.0 µmol kg-1 contributed to the pCO2 increase from July to September. In the Bering Strait, the coastal area was characterized by the influence of plume water from the Anadyr River in July and the coastal upwelling in September. The high biological production in plume water made a strong CO2 sink during the forward voyage, while the upwelling of carbon-enriched subsurface water with minor DIC consumption made the coastal ecosystem a strong CO2 source during the return voyage. In different geographical regions, the observed seawater pCO2 was much lower than the overlying atmospheric CO2, resulting in a net CO2 sink with fluxes of -2.1~-14.0 mmol m-2 d-1 and -2.5~-11.6 mmol m-2 d-1, respectively, during the forward and return voyages.</p

Photooxidation and Its Effects on the Carboxyl Content of Dissolved Organic Matter in Two Coastal Rivers in the Southeastern United States

Photodecarboxylation (often stoichiometrically expressed as RCOOH + 1/2O2 → ROH + CO2) has long been postulated to be principally responsible for generating CO2 from photooxidation of dissolved organic matter (DOM). In this study, the quantitative relationships were investigated among O2 consumption, CO2 production, and variation of carboxyl content resulting from photooxidation of DOM in natural water samples obtained from the freshwater reaches of the Satilla River and Altamaha River in the southeastern United States. In terms of loss of dissolved organic carbon (DOC), loss of optical absorbance, and production of CO2, the rate of photooxidation of DOM was increased in the presence of Fe redox chemistry and with increasing O2 content. The ratio of photochemical O2 consumption to CO2 photoproduction ranged from ∼0.8 to 2.5, depending on the O2 content, the extent of involvement of Fe, and probably the initial oxidation state of DOM as well. The absolute concentration of carboxyl groups ([-COOH]) on DOM only slightly decreased or increased over the course of irradiation, possibly depending on the stages of photooxidation, while the DOC-normalized carboxyl content substantially increased in the presence of Fe redox chemistry and sufficient O2. Both the initial [-COOH] and the apparent loss of this quantity over the course of irradiation was too small to account for the much larger production of CO2, suggesting that carboxyl groups were photochemically regenerated or that the major production pathway for CO2 did not involve photodecarboxylation. The results from this study can be chemically rationalized by a reaction scheme of (a) photodecarboxylation/regeneration of carboxyl:  CxHyOz(COOH)m + aO2 + (metals, hv) → bCO2 + cH2O2 + Cx-bHy‘Oz‘(COOH)m-b(COOH)b or of (b) nondecarboxylation photooxidation:  CxHyOz(COOH)m + aO2 + (metals, hv) → bCO2 + cH2O2 + Cx-bHy‘Oz‘(COOH)m

DataSheet_1_Seasonal and Spatial Production Patterns of Dissolved Inorganic Carbon and Total Alkalinity in a Shallow Beach Aquifer.docx

Dissolved inorganic carbon (DIC) and total alkalinity (AlkT) fluxes to the nearshore ocean can directly impact the rates of primary production, coral reef formation, coastal ocean acidification, and continental shelf ecology. Current understanding of the transformations that DIC and AlkT undergo as they move from land to sea are limited, leading to difficulties in estimating future DIC and AlkT export that may be altered under a changing climate. While much research has focused on carbon fluxes in carbon-rich mangroves and coastal wetlands, DIC and AlkT transformations and distributions in sandy beach aquifers, which are comparatively carbon-poor, have not been studied as extensively. We monitored DIC and AlkT concentrations in a sandy beach system over six sampling events spanning two years. Substantial changes to DIC and AlkT occurred along subsurface flowpaths due to aerobic respiration and anoxic reactions, resulting in an additional mean flux to the ocean of 191 and 134 mmol/d per meter length of shoreline, respectively. The chemical alterations occurred within the saltwater-freshwater mixing zone beneath the beach surface. Both aerobic and anaerobic reactions actively contributed to DIC and AlkT production within the system, as indicated by DIC: AlkT and dDIC:dAlkT ratios relative to the theoretical dilution line. The work indicates that beach aquifers support active transformation of inorganic carbon and highlights a potentially important and overlooked source of DIC and AlkT to coastal systems.</p

Treated Wastewater Changes the Export of Dissolved Inorganic Carbon and Its Isotopic Composition and Leads to Acidification in Coastal Oceans

Human-induced changes in carbon fluxes across the land–ocean interface can influence the global carbon cycle, yet the impacts of rapid urbanization and establishment of wastewater treatment plants (WWTPs) on coastal ocean carbon cycles are poorly known. This is unacceptable as at present ∼64% of global municipal wastewater is treated before discharge. Here, we report surface water dissolved inorganic carbon (DIC) and sedimentary organic carbon concentrations and their isotopic compositions in the rapidly urbanized Jiaozhou Bay in northeast China as well as carbonate parameters in effluents of three large WWTPs around the bay. Using DIC, δ¹³C_DIC and total alkalinity (TA) data and a tracer model, we determine the contributions to DIC from wastewater DIC input, net ecosystem production, calcium carbonate precipitation, and CO₂ outgassing. Our study shows that high-DIC and low-pH wastewater effluent represents an important source of DIC and acidification in coastal waters. In contrast to the traditional view of anthropogenic organic carbon export and degradation, we suggest that with the increase of wastewater discharge and treatment rates, wastewater DIC input may play an increasingly more important role in the coastal ocean carbon cycle

Hypoxic bottom waters as a carbon source to atmosphere during a typhoon passage over the East China Sea

The dataset is a time series mooring record (3–20 July, 2015), collected in the Changjiang Estuary (122.8°E, 30.6°N) . It includes surface salinity, sea surface temperature, bottom temperature, surface pCO2, dissolved oxygen, Chl a, and wind speed.The dataset shows the variations of pCO2 and other biogeochemical parameters during typhoon Chan-hom in the East China Sea shelf in 2015. All the data are daily-average values. The surface temperature, salinity, dissolved oxygen, and Chl a were obtained using Water Quality Monitor. The pCO2 data were collected using SAMI pCO2 (Sunburst sensor). The bottom temperature were measured using RBR. The wind speed data were obtained using Young

Table_2_The Development and Validation of a Profiling Glider Deep ISFET-Based pH Sensor for High Resolution Observations of Coastal and Ocean Acidification.DOCX

Coastal and ocean acidification can alter ocean biogeochemistry, with ecological consequences that may result in economic and cultural losses. Yet few time series and high resolution spatial and temporal measurements exist to track the existence and movement of water low in pH and/or carbonate saturation. Past acidification monitoring efforts have either low spatial resolution (mooring) or high cost and low temporal and spatial resolution (research cruises). We developed the first integrated glider platform and sensor system for sampling pH throughout the water column of the coastal ocean. A deep ISFET (Ion Sensitive Field Effect Transistor)-based pH sensor system was modified and integrated into a Slocum glider, tank tested in natural seawater to determine sensor conditioning time under different scenarios, and validated in situ during deployments in the U.S. Northeast Shelf (NES). Comparative results between glider pH and pH measured spectrophotometrically from discrete seawater samples indicate that the glider pH sensor is capable of accuracy of 0.011 pH units or better for several weeks throughout the water column in the coastal ocean, with a precision of 0.005 pH units or better. Furthermore, simultaneous measurements from multiple sensors on the same glider enabled salinity-based estimates of total alkalinity (AT) and aragonite saturation state (ΩArag). During the Spring 2018 Mid-Atlantic deployment, glider pH and derived AT/ΩArag data along the cross-shelf transect revealed higher pH and ΩArag associated with the depth of chlorophyll and oxygen maxima and a warmer, saltier water mass. Lowest pH and ΩArag occurred in bottom waters of the middle shelf and slope, and nearshore following a period of heavy precipitation. Biofouling was revealed to be the primary limitation of this sensor during a summer deployment, whereby offsets in pH and AT increased dramatically. Advances in anti-fouling coatings and the ability to routinely clean and swap out sensors can address this challenge. The data presented here demonstrate the ability for gliders to routinely provide high resolution water column data on regional scales that can be applied to acidification monitoring efforts in other coastal regions.</p

Table_1_The Development and Validation of a Profiling Glider Deep ISFET-Based pH Sensor for High Resolution Observations of Coastal and Ocean Acidification.DOCX

Coastal and ocean acidification can alter ocean biogeochemistry, with ecological consequences that may result in economic and cultural losses. Yet few time series and high resolution spatial and temporal measurements exist to track the existence and movement of water low in pH and/or carbonate saturation. Past acidification monitoring efforts have either low spatial resolution (mooring) or high cost and low temporal and spatial resolution (research cruises). We developed the first integrated glider platform and sensor system for sampling pH throughout the water column of the coastal ocean. A deep ISFET (Ion Sensitive Field Effect Transistor)-based pH sensor system was modified and integrated into a Slocum glider, tank tested in natural seawater to determine sensor conditioning time under different scenarios, and validated in situ during deployments in the U.S. Northeast Shelf (NES). Comparative results between glider pH and pH measured spectrophotometrically from discrete seawater samples indicate that the glider pH sensor is capable of accuracy of 0.011 pH units or better for several weeks throughout the water column in the coastal ocean, with a precision of 0.005 pH units or better. Furthermore, simultaneous measurements from multiple sensors on the same glider enabled salinity-based estimates of total alkalinity (AT) and aragonite saturation state (ΩArag). During the Spring 2018 Mid-Atlantic deployment, glider pH and derived AT/ΩArag data along the cross-shelf transect revealed higher pH and ΩArag associated with the depth of chlorophyll and oxygen maxima and a warmer, saltier water mass. Lowest pH and ΩArag occurred in bottom waters of the middle shelf and slope, and nearshore following a period of heavy precipitation. Biofouling was revealed to be the primary limitation of this sensor during a summer deployment, whereby offsets in pH and AT increased dramatically. Advances in anti-fouling coatings and the ability to routinely clean and swap out sensors can address this challenge. The data presented here demonstrate the ability for gliders to routinely provide high resolution water column data on regional scales that can be applied to acidification monitoring efforts in other coastal regions.</p

Table_3_The Development and Validation of a Profiling Glider Deep ISFET-Based pH Sensor for High Resolution Observations of Coastal and Ocean Acidification.DOCX

Coastal and ocean acidification can alter ocean biogeochemistry, with ecological consequences that may result in economic and cultural losses. Yet few time series and high resolution spatial and temporal measurements exist to track the existence and movement of water low in pH and/or carbonate saturation. Past acidification monitoring efforts have either low spatial resolution (mooring) or high cost and low temporal and spatial resolution (research cruises). We developed the first integrated glider platform and sensor system for sampling pH throughout the water column of the coastal ocean. A deep ISFET (Ion Sensitive Field Effect Transistor)-based pH sensor system was modified and integrated into a Slocum glider, tank tested in natural seawater to determine sensor conditioning time under different scenarios, and validated in situ during deployments in the U.S. Northeast Shelf (NES). Comparative results between glider pH and pH measured spectrophotometrically from discrete seawater samples indicate that the glider pH sensor is capable of accuracy of 0.011 pH units or better for several weeks throughout the water column in the coastal ocean, with a precision of 0.005 pH units or better. Furthermore, simultaneous measurements from multiple sensors on the same glider enabled salinity-based estimates of total alkalinity (AT) and aragonite saturation state (ΩArag). During the Spring 2018 Mid-Atlantic deployment, glider pH and derived AT/ΩArag data along the cross-shelf transect revealed higher pH and ΩArag associated with the depth of chlorophyll and oxygen maxima and a warmer, saltier water mass. Lowest pH and ΩArag occurred in bottom waters of the middle shelf and slope, and nearshore following a period of heavy precipitation. Biofouling was revealed to be the primary limitation of this sensor during a summer deployment, whereby offsets in pH and AT increased dramatically. Advances in anti-fouling coatings and the ability to routinely clean and swap out sensors can address this challenge. The data presented here demonstrate the ability for gliders to routinely provide high resolution water column data on regional scales that can be applied to acidification monitoring efforts in other coastal regions.</p

Monitoring Ocean Acidification within State Borders: Lessons from Washington State (USA)

The Washington State Department of Ecology conducted a large-scale ocean acidification (OA) study in greater Puget Sound to: (1) produce a marine carbon dioxide (CO2) system dataset capable of distinguishing between long-term anthropogenic changes and natural variability, (2) characterize how rivers and freshwater drive OA conditions in the region, and (3) understand the relative influence of cumulative anthropogenic forcing on regional OA conditions. Marine CO2 system data were collected monthly at 20 stations between October 2018 and February 2020. While additional data are still needed, the climate-level data collected thus far have uncovered novel insights into spatiotemporal distributions of and variability in the regional marine CO2 system, especially at low salinities in shallow, river-forced shelf regions. The data provide a strong foundation with which to continue monitoring OA conditions across the region. More importantly, this work represents the first successful long-term OA monitoring program undertaken at the state-level by a regulatory agency. Therefore, we offer the work described herein as a blueprint to help state and local scientists and environmental and natural resource managers develop, implement, and conduct long-term OA monitoring programs and studies in their own contexts and jurisdictions.</p