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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. 

In the northwestern Gulf of Mexico (nwGOM), the coastal climate shifts abruptly from the humid northeast to the semiarid southwest within a narrow latitudinal range. The climate effect plays an important role in controlling freshwater discharge into the shallow estuaries in this region. In addition to diminishing freshwater runoff down the coast, evaporation also increases substantially. Hence, these estuaries show increasing salinity along the coastline due to the large difference in freshwater inflow balance (river runoff and precipitation minus evaporation and diversion). However, this spatial gradient can be disrupted by intense storm events as a copious amount of precipitation leads to river flooding, which can cause temporary freshening of these systems in extreme cases, in addition to freshwater-induced ephemeral stratification. We examined estuarine water aragonite saturation state (Ω arag ) data collected between 2014 and 2018, covering a period of contrasting hydrological conditions, from the initial drought to multiple flooding events, including a brief period that was influenced by a category 4 hurricane. Based on freshwater availability, these estuaries exhibited a diminishing Ω arag fluctuation from the most freshwater enriched Guadalupe Estuary to the most freshwater-starved Nueces Estuary. While Ω arag values were usually much higher than the threshold level (Ω arag = 1), brief freshwater discharge events and subsequent low oxygen levels in the lower water column led to episodic corrosive conditions. Based on previously obtained Ω arag temporal trends and Ω arag values obtained in this study, we estimated the time of emergence (ToE) for Ω arag . Not only did estuaries show decreasing ToE with diminishing freshwater availability but the sub-embayments of individual estuaries that had a less freshwater influence also had shorter ToE. This spatial pattern suggests that planning coastal restoration efforts, especially for shellfish organisms, should emphasize areas with longer ToE. 

Abstract Water quality parameters from 2000 to 2020 were used to identify the spatial and temporal sulfate variations in estuaries of the northwestern Gulf of Mexico. Sulfate enrichment relative to conservative mixing was found to be associated with a low river discharge period from 2012 to 2014 in all estuaries. Based on reaction stoichiometry, sedimentary sulfide oxidation holds significant potential for reducing the alkalinity in estuarine waters. However, during this extreme drought, alkalinity enrichment was also occasionally observed in some of the southern estuaries along with sulfate enrichment, and when alkalinity depletion occurred, the magnitude of depletion was usually much less than what would be expected based on sulfide oxidation alone. This discrepancy can be partially explained by carbonate dissolution and other proton removal pathways (e.g., Fe‐oxide dissolution), and by the uncertainties in the model used to estimate alkalinity enrichment/depletion. Under a changing climate, the close coupling between river discharge variation and estuarine sulfate dynamics will significantly impact estuarine carbonate chemistry.