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Four species of shellfish, blue mussel (Mytilus galloprovincialis), Pacific abalone (Haliotis discus hannai), zhikong scallops (Chlamys farreri), and Pacific oyster (Crassostrea gigas), were exposed to decoupled carbonate system variables to investigate the impacts of different seawater carbonate parameters on the CO2 excretion process of mariculture shellfish. Six experimental groups with two levels of seawater pH (pH 8.1 and pH 7.7) and three levels of total alkalinity (TA = 1000, 2300, and 3600 μmol/kg, respectively) were established, while pH 8.1 and TA = 2300 μmol/kg was taken as control. Results showed that the CO2 excretion rates of these tested shellfish were significantly affected by the change in carbonate chemistry (P < 0.05). At the same TA level, animals incubated in the acidified group (pH 7.7) had a lower CO2 excretion rate than those in the control group (pH 8.1). In comparison, at the same pH level, the CO2 excretion rate increased when seawater TA level was elevated. No significant correlation between the CO2 excretion rate and seawater pCO2 levels (P > 0.05) was found; however, a significant correlation (P < 0.05) between CO2 excretion rate and TA-DIC (the difference between total alkalinity and dissolved inorganic carbon) was observed. Blue mussel has a significantly higher CO2 excretion rate than the other three species in the CO2 excretions per unit mass of soft parts, with no significant difference observed among these three species. However, in terms of CO2 excretion rate per unit mass of gills, abalone has the highest CO2 excretion rate, while significant differences were found between each species. Our studies indicate that the CO2 buffering capacity impacts the CO2 excretion rate of four shellfish species largely independent of pCO2. Since CO2 excretion is related to acid–base balancing, the results imply that the effects of other carbonate parameters, particularly the CO2 buffering capacity, should be studied to fully understand the mechanism of how acidification affects shellfish. Besides, the species difference in gill to soft parts proportion may contribute to the species difference in responding to ocean acidification. [ABSTRACT FROM AUTHOR]

There is growing concern about the effects of ocean acidification (OA) on coral reefs, with many studies indicating decreasing calcium carbonate production and reef growth. However, to accurately predict how coral reefs will respond to OA, it is necessary to characterize natural carbonate chemistry conditions, including the spatiotemporal mean and variability and the physical and biogeochemical drivers across different environments. In this study, spatial and temporal physiochemical variability was characterized at two contrasting reef locations in Bocas del Toro, Panama, that differed in their benthic community composition, reef morphology, and exposure to open ocean conditions, using a combination of approaches including autonomous sensors and spatial surveys during November 2015. Mean and diurnal temporal variability in both physical and chemical seawater parameters were similar between sites and sampling depths, but with occasional differences in extreme values. The magnitude of spatial variability was different between the two sites, which reflected the cumulative effect from terrestrial runoff and benthic metabolism. Based on graphical vector analysis of TA–DIC data, reef metabolism was dominated by organic over inorganic carbon cycling at both sites, with net heterotrophy and net calcium carbonate dissolution dominating the majority of observations. The results also highlight the potentially strong influence of terrestrial freshwater runoff on surface seawater conditions, and the challenges associated with evaluating and characterizing this influence on benthic habitats. The Bocas del Toro reef is a unique system that deserves attention to better understand the mechanisms that allow corals and coral reefs to persist under increasingly challenging environmental conditions. [ABSTRACT FROM AUTHOR]

Infaunal invertebrates are affected by the overlying water and the sediment in which they live. Therefore, understanding how these environmental conditions impact infauna is critical for evaluating how they may respond to future changes in these conditions due to climate change. Here, we considered which abiotic variables, for example, salinity, sediment characteristics (i.e. mean grain size, sorting), and water column and sediment carbonate chemistry, influence infaunal invertebrate communities and juvenile bivalve abundance at intertidal sites. We used data from sites in two regions in New Brunswick, Canada with contrasting tidal regimes and oceanographic conditions, the Bay of Fundy and the Southern Gulf of St. Lawrence. We were particularly interested in bivalve recruitment due to the importance of bivalves in ecosystem services and predicted sensitivity to climate change impacts. Using data collected in 2020 and 2021, statistical modeling was done to determine which abiotic variables were potential drivers of multivariate community composition as well as species richness, total abundance, and juvenile bivalve abundance. We found that carbonate chemistry variables, both sediment and water, explained a large amount of variation (~ 7–44%) in infaunal invertebrate communities in the two regions in both our multivariate and univariate analyses. Sediment pH explained the most variation (16.9%) in the multivariate analyses for the Bay of Fundy sites. However, in the Southern Gulf of St. Lawrence, salinity explained the most variation (9.8%) in the multivariate community composition. In the univariate modeling, alkalinity, either water column or sediment, was included in all top models for all four dependent variables, suggesting the importance of this carbonate chemistry variable for bivalves and infaunal communities. Climate change is expected to have large impacts on carbonate chemistry conditions in the oceans, specifically pH, carbonate availability, and alkalinity. The influence of carbonate chemistry parameters on infaunal invertebrate communities in these regions shows the potential sensitivity these animals have to future oceanic conditions. [ABSTRACT FROM AUTHOR]

In coastal regions and marginal bodies of water, the increase in partial pressure of carbon dioxide (pCO2) in many instances is greater than that of the open ocean due to terrestrial (river, estuarine, and wetland) influences, decreasing buffering capacity and/or increasing water temperatures. Coastal oceans receive freshwater from rivers and groundwater as well as terrestrial-derived organic matter, both of which have a direct influence on coastal carbonate chemistry. The objective of this research is to determine if coastal marshes in Georgia, USA, may be "hot-spots" for acidification due to enhanced inorganic carbon sources and if there is terrestrial influence on offshore acidification in the South Atlantic Bight (SAB). The results of this study show that dissolved inorganic carbon (DIC) and total alkalinity (TA) are elevated in the marshes compared to predictions from conservative mixing of the freshwater and oceanic end-members, with accompanying pH around 7.2 to 7.6 within the marshes and aragonite saturation states (ΩAr) <1. In the marshes, there is a strong relationship between the terrestrial/estuarine-derived organic and inorganic carbon and acidification. Comparisons of pH, TA, and DIC to terrestrial organic material markers, however, show that there is little influence of terrestrial-derived organic matter on shelf acidification during this period in 2014. In addition, ΩAr increases rapidly offshore, especially in drier months (July). River stream flow during 2014 was anomalously low compared to climatological means; therefore, offshore influences from terrestrial carbon could also be decreased. The SAB shelf may not be strongly influenced by terrestrial inputs to acidification during drier than normal periods; conversely, shelf waters that are well-buffered against acidification may not play a significant role in mitigating acidification within the Georgia marshes. [ABSTRACT FROM AUTHOR]

To accurately predict the impacts of ocean acidification on shallow-water ecosystems, we must account for the biogeochemical impact of local benthic communities, as well as the connectivity between offshore and onshore water masses. Estimation of residence time can help quantify this connectivity and determine the degree to which the benthos can influence the chemistry of the overlying water column. We present estimates of nearshore residence time for Guam and utilize these estimates to model the effects of benthic ecosystem metabolism on the coral reef carbonate system. Control volume and particle tracking approaches were used to estimate nearshore residence time. These estimates were paired with observed patterns in the reef carbonate system around Guam using water samples collected by NOAA's National Coral Reef Monitoring Program. Model performance results suggest that when considering the effects of benthic metabolism on the carbonate system, it is paramount to represent the contact time of the water volume with the benthos. Even coarse estimates of residence time significantly increase model skill. We observed the highest predictive skill in models including control volume derived estimates of residence time, but only when those estimates were included as an interaction with benthic composition. This work shows that not only is residence time critically important to better predict biogeochemical variability in coral reef environments, but that even coarse hydrodynamic models can provide useful residence time estimates at management relevant, whole-ecosystem scales. [ABSTRACT FROM AUTHOR]

Carbonate minerals are ubiquitous in most sediment-hosted mineral deposits. These deposits can contain a variety of carbonate types with complex paragenetic relationships. When normalized to chondritic values (CN), rare-earth elements and yttrium (REE+YCN) can be used to constrain fluid chemistry and fluid-rock interaction processes in both low- and high-temperature settings. Unlike other phases (e.g., pyrite), the application of in situ laser ablation-inductively coupled plasma-mass spectroscopy (LA-ICP-MS) data to the differentiation of pre-ore and hydrothermal carbonates remains relatively untested. To assess the potential applicability of carbonate in situ REE+Y data, we combined transmitted light and cathodoluminescence (CL) petrography with LA-ICP-MS analysis of carbonate mineral phases from (1) the Proterozoic George Fisher clastic dominated (CD-type) massive sulfide deposit and from (2) correlative, barren host rock lithologies (Urquhart Shale Formation). The REE+YCN composition of pre-ore calcite suggests it formed during diagenesis from diagenetic pore fluids derived from ferruginous, anoxic seawater. Hydrothermal and hydrothermally altered calcite and dolomite from George Fisher is generally more LREE depleted than the pre-ore calcite, whole-rock REE concentrations, and shale reference values. We suggest this is the result of hydrothermal alteration by saline Cl--rich mineralizing fluids. Furthermore, the presence of both positive and negative Eu/Eu* values in calcite and dolomite indicates that the mineralizing fluids were relatively hot (>250°C) and cooled below 200–250°C during ore formation. This study confirms the hypothesis that in situ REE+Y data can be used to differentiate between pre-ore and hydrothermal carbonate and provide important constraints on the conditions of ore formation. [ABSTRACT FROM AUTHOR]

Globally, coral reefs are threatened by ocean warming and acidification. The degree to which acidification will impact reefs is dependent on the local hydrodynamics, benthic community composition, and biogeochemical processes, all of which vary on different temporal and spatial scales. Characterizing the natural spatiotemporal variability of seawater carbonate chemistry across different reefs is critical for elucidating future impacts on coral reefs. To date, most studies have focused on select habitats, whereas fewer studies have focused on reef scale variability. Here, we investigate the temporal and spatial seawater physicochemical variability across the entire Heron Island coral reef platform, Great Barrier Reef, Australia, for a limited duration of six days. Autonomous sensor measurements at three sites across the platform were complemented by reef-wide boat surveys and discrete sampling of seawater carbonate chemistry during the morning and evening. Variability in both temporal and spatial physicochemical properties were predominantly driven by solar irradiance (and its effect on biological activity) and the semidiurnal tidal cycles but were influenced by the local geomorphology resulting in isolation of the platform during low tide and rapid flooding during rising tides. As a result, seawater from previous tidal cycles was sometimes trapped in different parts of the reef leading to unexpected biogeochemical trends in space and time. This study illustrates the differences and limitations of data obtained from high-frequency measurements in a few locations compared to low-frequency measurements at high spatial resolution and coverage, showing the need for a combined approach to develop predictive capability of seawater physicochemical properties on coral reefs. [ABSTRACT FROM AUTHOR]

The carbonate chemistry was investigated in the semiarid eutrophic Araruama Lagoon (Brazil), one of the largest hypersaline coastal lagoons in the world. Spatial surveys during winter and summer periods were performed, in addition to a diurnal sampling in summer. The hypersaline waters have higher concentrations of total alkalinity (TA) and dissolved inorganic carbon (DIC) than the seawater that feed the lagoon, due to evaporation. However, TA and DIC concentrations were lower than those expected from evaporation. Calcium carbonate (CaCO3) precipitation partially explained these deficits. The negative correlation between the partial pressure of CO2 (pCO2) and chlorophyll a (Chl a) indicated that DIC was also consumed by primary producers. The uptake by photosynthesis contributes to 57–63% of DIC deviation from evaporation, the remaining credited to CaCO3 precipitation. Marked pCO2 undersaturation was prevalent at the innermost region with shallow, confined, and phytoplankton-dominated waters, with a strong enrichment of heavier carbon isotope (δ13C-DIC up to 5.55‰), and highest pH (locally counter-acting the process of ocean acidification). Oversaturation was restricted to an urbanized region, and during night-time. The lagoon behaved as a marked CO2 sink during winter (− 15.32 to − 10.15 mmolC m−2 day−1), a moderate sink during summer (− 5.50 to − 4.67 mmolC m−2 day−1), with a net community production (NCP) of 93.7 mmolC m−2 day−1 and prevalence of net autotrophic metabolism. A decoupling between CO2 and O2 exchange rate at the air–water interface was attributed to differences in gas solubility, and high buffering capacity. The carbonate chemistry reveals simultaneous and antagonistic actions of CaCO3 precipitation and autotrophic metabolism on CO2 fluxes, and could reflect future conditions in populated and semiarid coastal ecosystems worldwide. [ABSTRACT FROM AUTHOR]

Increasing eutrophication of coastal waters generates disturbances in greenhouse gas (GHG) concentrations and emissions to the atmosphere that are still poorly documented, particularly in the tropics. Here, we investigated the concentrations and diffusive fluxes of carbon dioxide (CO2) and methane (CH4) in the urban-dominated Jacarepagua Lagoon Complex (JLC) in Southeastern Brazil. This lagoonal complex receives highly polluted freshwater and shows frequent occurrences of anoxia and hypoxia and dense phytoplankton blooms. Between 2017 and 2018, four spatial surveys were performed (dry and wet conditions), with sampling in the river waters that drain the urban watershed and in the lagoon waters with increasing salinities. Strong oxygen depletion was found in the rivers, associated with extremely high values of partial pressure of CO2 (pCO2; up to 20,417 ppmv) and CH4 concentrations (up to 288,572 nmol L−1). These high GHG concentrations are attributed to organic matter degradation from untreated domestic effluents mediated by aerobic and anaerobic processes, with concomitant production of total alkalinity (TA) and dissolved inorganic carbon (DIC). In the lagoon, GHG concentrations decreased mainly due to dilution with seawater and degassing. In addition, the phytoplankton growth and CH4 oxidation apparently consumed some CO2 and CH4, respectively. TA concentrations showed a marked minimum at salinity of ~20 compared to the two freshwater and marine end members, indicating processes of re-oxidation of inorganic reduced species from the low-salinity region, such as ammonia, iron, and/or sulfides. Diffusive emissions of gases from the entire lagoon ranged from 22 to 48 mmol C m−2 d−1 for CO2 and from 2.2 to 16.5 mmol C m−2 d−1 for CH4. This later value is among the highest documented in coastal waters. In terms of global warming potential (GWP) and CO2 equivalent emissions (CO2-eq), the diffusive emissions of CH4 were higher than those of CO2. These results highlight that highly polluted coastal ecosystems are hotspots of GHG emissions to the atmosphere, which may become increasingly significant in future global carbon budgets. [ABSTRACT FROM AUTHOR]

Seagrass systems are integral components of both local and global carbon cycles and can substantially modify seawater biogeochemistry, which has ecological ramifications. However, the influence of seagrass on porewater biogeochemistry has not been fully described, and the exact role of this marine macrophyte and associated microbial communities in the modification of porewater chemistry remains equivocal. In the present study, carbonate chemistry in the water column and porewater was investigated over diel timescales in contrasting, tidally influenced seagrass systems in Southern California and Bermuda, including vegetated (Zostera marina) and unvegetated biomes (0–16 cm) in Mission Bay, San Diego, USA and a vegetated system (Thallasia testudinium) in Mangrove Bay, Ferry Reach, Bermuda. In Mission Bay, dissolved inorganic carbon (DIC) and total alkalinity (TA) exhibited strong increasing gradients with sediment depth. Vertical porewater profiles differed between the sites, with almost twice as high concentrations of DIC and TA observed in the vegetated compared to the unvegetated sediments. In Mangrove Bay, both the range and vertical profiles of porewater carbonate parameters such as DIC and TA were much lower and, in contrast to Mission Bay where no distinct temporal signal was observed, biogeochemical parameters followed the semi-diurnal tidal signal in the water column. The observed differences between the study sites most likely reflect a differential influence of biological (biomass, detritus and infauna) and physical processes (e.g., sediment permeability, residence time and mixing) on porewater carbonate chemistry in the different settings. [ABSTRACT FROM AUTHOR]

Organic alkalinity is a poorly understood component of total titration alkalinity in aquatic environments. Using a numerical method, the effects of organic acid (HOA) and its conjugate base (OA−) on seawater carbonate chemistry and buffer behaviors, as well as those in a hypothetical estuarine mixing zone, are explored under both closed- and open-system conditions. The simulation results show that HOA addition leads to pCO2 increase and pH decrease in a closed system when total dissolved inorganic carbon (DIC) remains the same. If opened to the atmosphere (pCO2 = 400 µatm), CO2 degassing and re-equilibration would cause depressed pH compared to the unperturbed seawater, but the seawater buffer to pH change β DIC = ∂ ln H + ∂ DIC - 1 indicates that weaker organic acid (i.e., higher pKa) results in higher buffer capacity (greater βDIC) than the unperturbed seawater. In comparison, OA− (with accompanying cations) in the form of net alkalinity addition leads to pCO2 decrease in a closed system. After re-equilibrating with the atmosphere, the resulting perturbed seawater has higher pH and βDIC than the unperturbed seawater. If river water has organic alkalinity, pH in the estuarine mixing zone is always lower than those caused by a mixing between organic alkalinity-free river (at constant total alkalinity) and ocean waters, regardless of the pKa values. On the other hand, organic alkalinity with higher pKa provides slightly greater βDIC in the mixing zone, and that with lower pKa either results in large CO2 oversaturation (closed system) or reduced βDIC (in mid to high salinity in the closed system or the entire mixing zone in the open system). Finally, despite the various effects on seawater buffer through either HOA or OA− addition, destruction of organic molecules including organic alkalinity via biogeochemical reactions should result in a net CO2 loss from seawater. Nevertheless, the significance of this organic alkalinity, especially that comes from organic acids that are not accounted for under the currently recognized "zero proton level" (Dickson in Deep Sea Res 28:609–623, 1981), remains unknown thus a potentially interesting and relevant research topic in studying oceanic alkalinity cycle. [ABSTRACT FROM AUTHOR]

The B/Ca ratio of planktonic foraminifer shells has been used as a proxy for reconstructing past ocean carbonate chemistry. However, recent studies have revealed significant uncertainties associated with this proxy, such as whether seawater temperature or [CO32−] is the dominant control on the partition coefficient (KD) of planktonic foraminiferal B/Ca. To address these uncertainties and thus improve our understanding of the planktonic foraminiferal B/Ca proxy, we analysed B/Ca ratios in the tests of Neogloboquadrina dutertrei (300–355 urn) and Pulleniatina obliquiloculata (355–400 μm) in surface sediment samples from the tropical western Pacific and South China Sea. The relationship between these B/Ca ratios and bottom water calcite saturation states (Δ[CO32−]) is weak, thus suggesting only a small dissolution effect on the B/Ca of the two species. The correlation coefficients (R2) between the B/Ca ratios of N. dutertrei and P. obliquiloculata and environmental parameters (e.g., temperature, salinity, phosphate, DIC and ALK) in the tropical western Pacific and South China Sea are not high enough to justify using B/Ca ratios as a palaeoenvironmental proxy in the study areas. The significant correlation between KD values of N. dutertrei and P. obliquiloculata and carbonate system parameters (e.g., [CO32−], DIC, ALK, pH and [HCO3−]) in the study area reflect chemical links between the KD denominator and these variables. Based on our surface sediment calibration, an empirical relationship between the KD of N. dutertrei and temperature is proposed in the tropical western Pacific. We also generated a record of B/Ca ratios in N. dutertrei (300–355 μm) from Core MD06-3052 in the tropical western Pacific over the past 24 ka to evaluate the application of the revised B/Ca proxy method. Based on the reconstructed empirical relationship for B/Ca and subsurface seawater ALK, we estimated subsurface seawater carbonate system parameters in the tropical western Pacific since 24 ka. In general, the estimated subsurface seawater pH and [CO32−] show an increase with time, and the record of subsurface seawater pCO2 shows a decrease with time, in the tropical western Pacific over the past 24 ka. The consistent trends in subsurface seawater pCO2 and opal flux during deglaciation may imply that the reported increase in subsurface water pCO2 in the study area was promoted by enhanced upwelling in the Southern Ocean. [ABSTRACT FROM AUTHOR]

It has been hypothesized that highly productive coastal ecosystems, such as seagrass meadows, could lead to the establishment of ocean acidification (OA) refugia, or areas of elevated pH and aragonite saturation state (Ωa) compared to source seawater. However, seagrass ecosystems experience extreme variability in carbonate chemistry across short temporal and small spatial scales, which could impact the pH buffering capacity of these potential refugia. Herein, short-term (hourly to diel) and small-scale (across 0.01-0.14 km2) spatiotemporal carbonate chemistry variability was assessed within two seagrass meadows in order to determine their short-term potential to elevate seawater pH relative to source seawater. Two locations at similar latitudes were chosen in order to compare systems dominated by coarse calcium carbonate (Bailey’s Bay, Bermuda) and muddy silicate (Mission Bay, CA, USA) sediments. In both systems, spatial variability of pH across the seagrass meadow at any given time was often greater than diel variability (e.g., the average range over 24 h) at any one site, with greater spatial variability occurring at low tide in Mission Bay. Mission Bay (spatial ΔpH = 0.08 ± 0.08; diel ΔpH = 0.12 ± 0.01; mean ± SD) had a greater average range in both temporal and spatial seawater chemistry than Bailey’s Bay (spatial ΔpH = 0.02 ± 0.01; diel ΔpH = 0.03 ± 0.00; mean ± SD). These differences were most likely due to a combination of slower currents, a larger tidal range, and more favorable weather conditions for photosynthesis (e.g., sunny with no rain) in Mission Bay. In both systems, there was a substantial amount of time (usually at night) when seawater pH within the seagrass beds was lower relative to the source seawater. Future studies aimed at assessing the potential of seagrass ecosystems to act as OA refugia for marine organisms need to account for the small-scale, high-frequency carbonate chemistry variability in both space and time, as this variability will impact where and when OA will be buffered or intensified. [ABSTRACT FROM AUTHOR]

Significant diurnal variation in seawater carbonate chemistry occurs naturally in many coral reef environments, yet little is known of its effect on coral calcification. Laboratory studies on the response of corals to ocean acidification have manipulated the carbonate chemistry of experimental seawater to compare calcification rate changes under present-day and predicted future mean pH/Ω conditions. These experiments, however, have focused exclusively on differences in mean chemistry and have not considered diurnal variation. The aim of this study was to compare calcification responses of branching coral Acropora formosa under conditions with and without diurnal variation in seawater carbonate chemistry. To achieve this aim, we explored (1) a method to recreate natural diurnal variation in a laboratory experiment using the biological activities of a coral-reef mesocosm, and (2) a multi-laser 3D scanning method to accurately measure coral surface areas, essential to normalize their calcification rates. We present a cost- and time-efficient method of coral surface area estimation that is reproducible within 2% of the mean of triplicate measurements. Calcification rates were compared among corals subjected to a diurnal range in pH (total scale) from 7.8 to 8.2, relative to those at constant pH values of 7.8, 8.0 or 8.2. Mean calcification rates of the corals at the pH 7.8-8.2 (diurnal variation) treatment were not statistically different from the pH 8.2 treatment and were 34% higher than the pH 8.0 treatment despite similar mean seawater pH and Ω. Our results suggest that calcification of adult coral colonies may benefit from diurnal variation in seawater carbonate chemistry. Experiments that compare calcification rates at different constant pH without considering diurnal variation may have limitations. [ABSTRACT FROM AUTHOR]

Evidence of ocean acidification (OA) throughout the global ocean has galvanized some coastal communities to evaluate carbonate chemistry variations closer to home. An impediment to doing this effectively is that, often, only one carbonate system parameter is measured at a time, while two are required to fully constrain the inorganic carbon chemistry of seawater. In order to leverage the abundant single-carbonate-parameter datasets in Washington State for more rigorous OA research, we have characterized an empirical relationship between total alkalinity (TA) and salinity (TA = 47.7 × S + 647; 1 σ = ±17 μmol kg) for regional surface waters (≤25 m) that is robust in the salinity range from 20 to 35 for all seasons. The relationship was evaluated using 5 years of 3-h contemporaneous observations of salinity, carbon dioxide partial pressure ( pCO), and pH from a surface mooring on the outer coast of Washington. In situ pCO observations and salinity-based estimates of TA were used to calculate pH for comparison with in situ pH measurements. On average, the calculated pH values were 0.02 units lower than the measured pH values across multiple pH sensor deployments and showed extremely high fidelity in tracking the measured high-frequency pH variations. Our results indicate that the TA-salinity relationship will be a useful tool for expanding single-carbonate-parameter datasets in Washington State and quality controlling dual pCO-pH time series. [ABSTRACT FROM AUTHOR]

The structure, mineralogy, and accretion processes of the modern and subfossil cyanobacterial microbialites from the alkaline crater lake Alchichica (Puebla, Mexico) were studied, along the lake's bathymetry and hydrochemistry. The recent lowering of the lake level had exposed microbialitic carbonate mounds and crusts, which emerged up to 2 m above the water surface, while accreting cyanobacterial microbialites were present down to a depth of ~15 m. Morphological and molecular analysis found that the living cyanobacterial mats were composed of diverse filamentous and coccoid cyanobacteria (Nostocales, Chroococcales, Oscillatoriales, and Pleurocapsales). The emerged subfossil microbialites comprised two generations: 'white' (domes and crusts composed mainly of hydromagnesite with an admixture of huntite and calcite, U/Th age of ~2.8 ka BP), and 'brown' (chimneys, columns and laminated crusts composed of aragonite with an admixture of Mg-calcite, U/Th age of ~1.1 ka BP). The significant age, structural, mineralogical, and isotopic differences suggest that the two generations were formed in different environmental conditions: the 'white' during a dry period, and the 'brown' in wet climate associated with high water level and intense inflow of ground water, which lowered the Mg/Ca ratio resulting in formation of aragonite instead of hydromagnesite. The hydromagnesite, replacing the primary aragonite precipitated in the living cyanobacterial biofilm, frequently undergoes silicification, which obliterates both the primary structure of the carbonate and the enclosed remains of cyanobacterial microbiota. This process helps to explain the abundant formation of dolomites and cherts in an allegedly highly alkaline Early Precambrian ocean. Thus, Lake Alchichica represents a modern alkaline environment where biosedimentary structures resembling Precambrian deposits are generated. [ABSTRACT FROM AUTHOR]