skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.

Attention:

The NSF Public Access Repository (NSF-PAR) system and access will be unavailable from 10:00 PM ET on Thursday, March 12 until 2:00 AM ET on Friday, March 13 due to maintenance. We apologize for the inconvenience.


Title: A Biogeochemical Alkalinity Sink in a Shallow, Semiarid Estuary of the Northwestern Gulf of Mexico
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 × 10 8  mol day −1 in MAE. This biogeochemical TA sink may be present in other similar subtropical, freshwater-starved estuaries around the world.  more » « less
Award ID(s):
1654232
PAR ID:
10409129
Author(s) / Creator(s):
; ;
Date Published:
Journal Name:
Aquatic Geochemistry
Volume:
29
Issue:
1
ISSN:
1380-6165
Page Range / eLocation ID:
49 to 71
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. 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
  2. Browman, Howard (Ed.)
    Abstract Coral calcification is essential to provide the structural foundation for coral reefs and is integral in supporting marine biodiversity reliant on reef ecosystems. The drivers for calcification in corals are undoubtedly highly complex and require several perspectives to identify vulnerabilities in the context of environmental change. Specifically, ocean acidification (OA) resulting from the rise of anthropogenic carbon dioxide (CO2) emissions poses a potential threat to the physiological mechanisms that drive calcification in corals. Therefore, this report goes beyond environmental seawater chemistry to examine the physiological mechanism of calcium ion homeostasis. Calcium's role in calcification physiology is well established, but how calcium homeostasis could shift under acidification has little been considered a significant driver in reduced calcification. Calcium is potentially the most actively transported substrate in coral calcification, though in high chemical abundance in seawater, corals are likely utilizing the most energy to concentrate calcium at the site of calcification. We argue for increased consideration of the calcium ion in the context of OA when identifying sensitivities. The concepts proposed here are justified through a combination of results from novel RAMAN spectroscopy and molecular work that provides insight into shifts in calcium homeostasis when exposed to acidification. We speculate that future work incorporating methodologies considering calcium dynamics in OA could benefit by narrowing in on what physiological mechanisms are potentially vulnerable. It is imperative that we identify what drives lower calcification in corals under OA to inform efficient directives in identifying species sensitivities to future climate change. 
    more » « less
  3. The sulfur over calcium ratio (S/Ca) in foraminiferal shells was recently proposed as a new and independent proxy for reconstructing marine inorganic carbon chemistry. This new approach assumes that sulfur is incorporated into CaCO3 predominantly in the form of sulfate (SO42−) through lattice substitution for carbonate ions (CO32–), and that S/Ca thus reflects seawater [CO32–]. Although foraminiferal growth experiments validated this approach, field studies showed controversial results suggesting that the potential impact of [CO32–] may be overwritten by one or more parameters. Hence, to better understand the inorganic processes involved, we here investigate S/Ca values in inorganically precipitated CaCO3 (S/Ca(cc)) grown in solutions of CaCl2 − Na2CO3 − Na2SO4 − B(OH)3 − MgCl2. Experimental results indicate the dependence of sulfate partitioning in CaCO3 on the carbon chemistry via changing pH and suggest that faster precipitation rates increase the partition coefficient for sulfur. The S/Ca ratios of our inorganic calcite samples show positive correlation with modelled [CaSO40](aq), but not with the concentration of free SO42− ions. This challenges the traditional model for sulfate incorporation in calcite and implies that the uptake of sulfate potentially occurs via ion-ion pairs rather than being incorporated as single anions. Based on the [Ca2+] dependence via speciation, we here suggest a critical evaluation of this potential proxy. As sulfate complexation seems to control sulfate uptake in inorganic calcite, application as a proxy using foraminiferal calcite may be limited to periods for which seawater chemistry is well-constrained. As foraminiferal calcite growth is modulated by inward Ca2+ flow to the site of calcification coupled to outward H+ pumping, sulfate incorporation as CaSO40 ion-pair in the foraminifer’s shell also provides a mechanistic link for the observed relationship between S/Ca(cc) and [CO32–]. 
    more » « less
  4. The Ecosystem Science and Modeling lab has been collecting water samples from five stations in the Mission-Aransas Estuary (MAE, Northwest Gulf of Mexico, Texas coast) for carbonate system characterization on a monthly to twice monthly basis since May 2014. This dataset includes temperature, salinity, dissolved inorganic carbon (DIC), total alkalinity (TA), calcium, and pH measurements from surface and bottom water samples in MAE from May 2014 – Feb 2017 and Dec 2018 – Feb 2020. Additional data for this estuary to fill in the Feb 2017 – Dec 2018 gap are also archived with BCO-DMO (http://www.bco-dmo.org/dataset/784673, doi:10.1575/1912/bco-dmo.784673.1). 
    more » « less
  5. Organosulfates (OSs) are the most abundant class of organosulfur compounds (OrgS) in atmospheric fine particulate matter (PM2.5). Globally, isoprene‐derived OSs (iOSs) are the most abundantly reported OSs. The methyltetrol sulfates (MTSs), formed from multiphase chemical reactions of isoprene‐derived epoxidiols (IEPOX) with acidic sulfate aerosols, are the predominant iOSs. A recent study revealed that the heterogeneous hydroxyl radical (•OH) oxidation of fine particulate MTSs yields several highly oxygenated and functionalized OSs previously attributed to non‐IEPOX pathways. By using hydrophilic interaction liquid chromatography interfaced to electrospray ionization high‐resolution quadrupole time‐of‐flight mass spectrometry (HILIC/ESI‐HRQTOFMS), iOSs were quantitatively characterized in PM2.5 collected from 20 ground sites within the Interagency Monitoring of Protected Visual Environments (IMPROVE) network during the 2016 summer and winter seasons. Total water‐soluble sulfur (TWS‐S) and sulfur in the form of inorganic sulfate (Sinorg) were determined by inductively coupled plasmaoptical emission spectroscopy (ICP‐OES) and ion chromatography (IC), respectively. The difference between TWS‐S and Sinorg was used as an upper bound estimate of water‐soluble OrgS concentration. Significantly higher OrgS concentrations, coincident with elevated iOS concentrations, were observed only in summer. On average, iOSs (130 ± 60, up to 240 ng m‐3) explained 29% (± 7%) of OrgS and 5% (± 2%) of organic matter (OM = 1.8*OC) in summertime PM2.5 collected from the eastern U.S. For the western U.S., iOSs (11 ± 6 ng m‐3) account for 6% (± 5%) of OrgS and 0.7% (± 0.4%) of OM. This study provides critical insights into the abundance, prevalence, spatial variability of iOSs across the U.S. 
    more » « less