Abstract There is limited information on how the nutrient and freshwater input affects water column carbonate chemistry in the estuaries along the northern Gulf of Mexico. In this study, we assess the seasonal and spatial variability in carbonate chemistry in the Barataria Basin, a eutrophic estuary adjacent to the mouth of the Mississippi River. Eleven stations were sampled along a salinity gradient during the winter (January), spring (April), summer (July), and fall (October) of 2021. Surface and bottom water samples were collected for the analyses of dissolved inorganic carbon (DIC); total alkalinity (TA); and nitrite plus nitrate (NO2 + NO3), phosphate (PO4), and dissolved silica (SiO4). Dissolved CO2(pCO2) was measured in the surface water. Seasonal surface DIC and TA values ranged from 1553 to 2582 μmol kg−1and 1217 to 2217 μmol kg−1, respectively. DIC and TA varied seasonally and showed an increasing trend from fresh stations to saline stations. The highest DIC and TA values were observed during the fall season, likely due to the increased contribution of DIC and TA from adjacent marshes as a result of enhanced porewater exchange. In contrast to DIC and TA, pCO2decreased with the increase of salinity. The seasonal and spatial patterns in carbonate chemistry could not be explained solely by physical mixing and reflected complex interactions between biogeochemical processes driven by nutrient supply and temperature as well as tidal flushing and material exchanges with adjacent marshes.
more »
« less
Synoptic assessment of coastal total alkalinity through community science
Abstract Comprehensive sampling of the carbonate system in estuaries and coastal waters can be difficult and expensive because of the complex and heterogeneous nature of near-shore environments. We show that sample collection by community science programs is a viable strategy for expanding estuarine carbonate system monitoring and prioritizing regions for more targeted assessment. ‘Shell Day’ was a single-day regional water monitoring event coordinating coastal carbonate chemistry observations by 59 community science programs and seven research institutions in the northeastern United States, in which 410 total alkalinity (TA) samples from 86 stations were collected. Field replicates collected at both low and high tides had a mean standard deviation between replicates of 3.6 ± 0.3 µ mol kg −1 ( σ mean ± SE, n = 145) or 0.20 ± 0.02%. This level of precision demonstrates that with adequate protocols for sample collection, handling, storage, and analysis, community science programs are able to collect TA samples leading to high-quality analyses and data. Despite correlations between salinity, temperature, and TA observed at multiple spatial scales, empirical predictions of TA had relatively high root mean square error >48 µ mol kg −1 . Additionally, ten stations displayed tidal variability in TA that was not likely driven by low TA freshwater inputs. As such, TA cannot be predicted accurately from salinity using a single relationship across the northeastern US region, though predictions may be viable at more localized scales where consistent freshwater and seawater endmembers can be defined. There was a high degree of geographic heterogeneity in both mean and tidal variability in TA, and this single-day snapshot sampling identified three patterns driving variation in TA, with certain locations exhibiting increased risk of acidification. The success of Shell Day implies that similar community science based events could be conducted in other regions to not only expand understanding of the coastal carbonate system, but also provide a way to inventory monitoring assets, build partnerships with stakeholders, and expand education and outreach to a broader constituency.
more »
« less
- PAR ID:
- 10318296
- Author(s) / Creator(s):
- ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; more »
- Date Published:
- Journal Name:
- Environmental Research Letters
- Volume:
- 16
- Issue:
- 2
- ISSN:
- 1748-9326
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Abstract Estuarine total alkalinity (TA), which buffers against acidification, is temporally and spatially variable and regulated by complex, interacting hydrologic and biogeochemical processes. During periods of net evaporation (drought), the Mission-Aransas Estuary (MAE) of the northwestern Gulf of Mexico experienced TA losses beyond what can be attributed to calcification. The contribution of sedimentary oxidation of reduced sulfur to the TA loss was examined in this study. Water column samples were collected from five stations within MAE and analyzed for salinity, TA, and calcium ion concentrations. Sediment samples from four of these monitoring stations and one additional station within MAE were collected and incubated between 2018 and 2021. TA, calcium, magnesium, and sulfate ion concentrations were analyzed for these incubations. Production of sulfate along with TA consumption (or production) beyond what can be attributed to calcification (or carbonate dissolution) was observed. These results suggest that oxidation of reduced sulfur consumed TA in MAE during droughts. We estimate that the upper limit of TA consumption due to reduced sulfur oxidation can be as much as 4.60 × 108 mol day−1in MAE. This biogeochemical TA sink may be present in other similar subtropical, freshwater-starved estuaries around the world.more » « less
-
null (Ed.)Spatial and temporal carbonate chemistry variability on coral reefs is influenced by a combination of seawater hydrodynamics, geomorphology, and biogeochemical processes, though their relative influence varies by site. It is often assumed that the water column above most reefs is well-mixed with small to no gradients outside of the benthic boundary layer. However, few studies to date have explored the processes and properties controlling these multi-dimensional gradients. Here, we investigated the lateral, vertical, and temporal variability of seawater carbonate chemistry on a Bermudan rim reef using a combination of spatial seawater chemistry surveys and autonomous in situ sensors. Instruments were deployed at Hog Reef measuring current flow, seawater temperature, salinity, pH T , p CO 2 , dissolved oxygen (DO), and total alkalinity (TA) on the benthos, and temperature, salinity, DO, and p CO 2 at the surface. Water samples from spatial surveys were collected from surface and bottom depths at 13 stations covering ∼3 km 2 across 4 days. High frequency temporal variability in carbonate chemistry was driven by a combination of diel light and mixed semi-diurnal tidal cycles on the reef. Daytime gradients in DO between the surface and the benthos suggested significant water column production contributing to distinct diel trends in pH T , p CO 2 , and DO, but not TA. We hypothesize these differences reflect the differential effect of biogeochemical processes important in both the water column and benthos (organic carbon production/respiration) vs. processes mainly occurring on the benthos (calcium carbonate production/dissolution). Locally at Hog Reef, the relative magnitude of the diel variability of organic carbon production/respiration was 1.4–4.6 times larger than that of calcium carbonate production/dissolution, though estimates of net organic carbon production and calcification based on inshore-offshore chemical gradients revealed net heterotrophy (−118 ± 51 mmol m –2 day –1 ) and net calcification (150 ± 37 mmol CaCO 3 m –2 day –1 ). These results reflect the important roles of time and space in assessing reef biogeochemical processes. The spatial variability in carbonate chemistry parameters was larger laterally than vertically and was generally observed in conjunction with depth gradients, but varied between sampling events, depending on time of day and modifications due to current flow.more » « less
-
Abstract Estuaries may be uniquely susceptible to the combined acidification pressures of atmospherically driven ocean acidification (OA), biologically driven CO 2 inputs from the estuary itself, and terrestrially derived freshwater inputs. This study utilized continuous measurements of total alkalinity (TA) and the partial pressure of carbon dioxide (pCO 2 ) from the mouth of Great Bay, a temperate northeastern U.S. estuary, to examine the potential influences of endmember mixing and biogeochemical transformation upon estuary buffering capacity ( β – H ). Observations were collected hourly over 28 months representing all seasons between May 2016 and December 2019. Results indicated that endmember mixing explained most of the observed variability in TA and dissolved inorganic carbon (DIC), concentrations of which varied strongly with season. For much of the year, mixing dictated the relative proportions of salinity‐normalized TA and DIC as well, but a fall season shift in these proportions indicated that aerobic respiration was observed, which would decrease β – H by decreasing TA and increasing DIC. However, fall was also the season of weakest statistical correspondence between salinity and both TA and DIC, as well as the overall highest salinity, TA and β – H . Potential biogeochemically driven β – H decreases were overshadowed by increased buffering capacity supplied by coastal ocean water. A simple modeling exercise showed that mixing processes controlled most monthly changes in TA and DIC, obscuring impacts from air–sea exchange or metabolic processes. Advective mixing contributions may be as important as biogeochemically driven changes to observe when evaluating local estuarine and coastal OA.more » « less
-
Abstract The capacity of aquatic systems to buffer acidification depends on the sum contributions of various chemical species to total alkalinity (TA). Major TA contributors are inorganic, with carbonate and bicarbonate considered the most important. However, growing evidence shows that many rivers, estuaries, and coastal waters contain dissolved organic molecules with charge sites that create organic alkalinity (OrgAlk). This study describes the first comparison of (1) OrgAlk distributions and (2) acid–base properties in contrasting estuary‐plume systems: the Pleasant (Maine, USA) and the St. John (New Brunswick, CA). The substantial concentrations of OrgAlk in each estuary were sometimes not conservative with salinity and typically associated with very low pH. Two approaches to OrgAlk measurement showed consistent differences, indicating acid–base characteristics inconsistent with the TA definition. The OrgAlk fraction of TA ranged from 78% at low salinity to less than 0.4% in the coastal ocean endmember. Modeling of titration data identified three groups of organic charge sites, with mean acid–base dissociation constants (pKa) of 4.2 (± 0.5), 5.9 (± 0.7) and 8.5 (± 0.2). These represented 21% (± 9%), 8% (± 5%), and 71% (± 11%) of titrated organic charge groups. Including OrgAlk, pKa, and titrated organic charge groups in carbonate system calculations improved estimates of pH. However, low and medium salinity, organic‐rich samples demonstrated persistent offsets in calculated pH, even using dissolved inorganic carbon and CO2partial pressure as inputs. These offsets show the ongoing challenge of carbonate system intercomparisons in organic rich systems whereby new techniques and further investigations are needed to fully account for OrgAlk in TA titrations.more » « less
An official website of the United States government

