Equilibration Times of Dissolved Inorganic Carbon During pH Transitions

Equilibration times of dissolved inorganic carbon (DIC) depend on conversion reactions between CO2(aq) and the dissociation products of carbonic acid [S = (H2CO3) + (HCO3−) + (CO32−)]. Here, we develop analytical equations and a numerical model to calculate chemical equilibration times of DIC during pH transitions in buffered and unbuffered solutions. We approximate the equilibration degree of the DIC reservoir by the smaller of the CO2(aq) and S pools at the new pH, since the smaller pool is always farther from equilibrium during the chemical evolution. Both the amount of DIC converted and the rate of conversion differ between a pH increase and decrease, leading to distinct equilibration times for these general cases. Alkalinity perturbations in unbuffered solutions initially drive pH overshoots (increase or decrease) relative to the new equilibrium pH. The increased rates of DIC conversion associated with the pH overshoot yield shorter equilibration times compared to buffered solutions. Salinity has opposing effects on buffered and unbuffered solutions, decreasing and increasing equilibration times, respectively.

Decoupling of inorganic and organic carbon during slab mantle devolatilisation

Serpentinites are an important sink for both inorganic and organic carbon, and their behavior during subduction is thought to play a fundamental role in the global cycling of carbon. Here we show that fluid-derived veins are preserved within the Zermatt-Saas ultra-high pressure serpentinites providing key evidence for carbonate mobility during serpentinite devolatilisation. We show through the O, C, and Sr isotope analyses of vein minerals and the host serpentinites that about 90% of the meta-serpentinite inorganic carbon is remobilized during slab devolatilisation. In contrast, graphite-like carbonaceous compounds remain trapped within the host rock as inclusions within metamorphic olivine while the bulk elemental and isotope composition of organic carbon remains relatively unchanged during the subduction process. This shows a decoupling behavior of carbon during serpentinite dehydration in subduction zones. This process will therefore facilitate the transfer of inorganic carbon to the mantle wedge and the preferential slab sequestration of organic carbon en route to the deep mantle.

Vertical Distribution and Controlling Factors of Soil Inorganic Carbon in Poplar Plantations of Coastal Eastern China

Afforestation is a strategy to protect croplands and to sequestrate carbon in coastal areas. In addition, inorganic carbon is a considerable constitute of the coastal soil carbon pool. However, the vertical distribution and controlling factors of soil inorganic carbon (SIC) in plantations of coastal areas have been rarely studied. We analyzed the SIC content as well as physiochemical properties along soil profiles (0–100 cm) in young (YP) and mature (MP) poplar plantations in coastal eastern China. The soil profile was divided into six layers (0–10, 11–20, 21–40, 41–60, 61–80 and 81–100 cm) and a total of 36 soil samples were formed. The SIC content first increased from 0–10 cm (0.74%) to 11–20 cm (0.92%) and then fluctuated in the YP. In contrast, the SIC content increased with increasing soil depth until 40 cm and then leveled off, and the minimum and maximum appeared at 0–10 cm (0.54%) and 81–100 cm (0.98%) respectively in the MP. The soil inorganic carbon density was 12.05 and 12.93 kg m−2 within 0–100 cm in the YP and MP, respectively. Contrary to SIC, soil organic carbon (SOC) first decreased then levelled off within the soil profiles. Compared with the YP, the SIC content decreased 27.8% at 0–10 cm but increased 13.2% at 21–40 cm, meanwhile the SOC content in MP decreased 70.6% and 46.7% at 21–40 cm and 61–80 cm, respectively. The water-soluble Ca2+ and Mg2+ gradually decreased and increased, respectively within the soil profiles. The soil water-soluble Ca2+ increased 18.3% within 41–100 cm; however, the soil water-soluble Mg2+ decreased 32.7% within 21–100 cm in the MP when compared to the YP. Correlation analysis showed that SIC was negatively correlated with SOC, but positively correlated with soil pH and water-soluble Mg2+. Furthermore, structural equation modeling (SEM) indicated that SOC was the most important factor influencing the SIC content in the studied poplar plantations, indicating SOC sequestration promoted the dissolution of SIC. Therefore, our study highlights the trade-off between SIC and SOC in poplar plantations of coastal Eastern China.

The DIC carbon isotope evolutions during CO2 bubbling: implications for ocean acidification laboratory culture

Ocean acidification increases pCO2 and decreases pH of seawater and its impact on marine organisms has emerged as a key research focus. In addition to directly measured variables such as growth or calcification rate, stable isotopic tracers such as carbon isotopes have also been used to more completely understand the physiological processes contributing to the response of organisms to ocean acidification. To simulate ocean acidification in laboratory cultures, direct bubbling of seawater with CO2 has been a preferred method because it adjusts pCO2 and pH without altering total alkalinity. Unfortunately, the carbon isotope equilibrium between seawater and CO2 gas has been largely ignored so far. Frequently, the dissolved inorganic carbon (DIC) in the initial seawater culture has a distinct 13C/12C ratio which is far from the equilibrium expected with the isotopic composition of the bubbled CO2. To evaluate the consequences of this type of experiment for isotopic work, we measured the carbon isotope evolutions in two chemostats during CO2 bubbling and composed a numerical model to simulate this process. The isotopic model can predict well the carbon isotope ratio of dissolved inorganic carbon evolutions during bubbling. With help of this model, the carbon isotope evolution during a batch and continuous culture can be traced dynamically improving the accuracy of fractionation results from laboratory culture. Our simulations show that if not properly accounted for in experimental or sampling design, many typical culture configurations involving CO2 bubbling can lead to large errors in estimated carbon isotope fractionation between seawater and biomass or biominerals, consequently affecting interpretations and hampering comparisons among different experiments. Therefore, we describe the best practices on future studies working with isotope fingerprinting in the ocean acidification background.

A dissolved inorganic carbon measurement method featured self-calibration function via an electrodialytic generator

A simple dissolved inorganic carbon (DIC) measurment method featured self-calibration function via an electrodialytic bicarbonate eluent generator (cEDG) is described. It is based on gas diffusion flow analysis system that...

Implications of salinity normalization of seawater total alkalinity in coral reef metabolism studies

Salinity normalization of total alkalinity (TA) and dissolved inorganic carbon (DIC) data is commonly used to account for conservative mixing processes when inferring net metabolic modification of seawater by coral reefs. Salinity (S), TA, and DIC can be accurately and precisely measured, but salinity normalization of TA (nTA) and DIC (nDIC) can generate considerable and unrecognized uncertainties in coral reef metabolic rate estimates. While salinity normalization errors apply to nTA, nDIC, and other ions of interest in coral reefs, here, we focus on nTA due to its application as a proxy for net coral reef calcification and the importance for reefs to maintain calcium carbonate production under environmental change. We used global datasets of coral reef TA, S, and modeled groundwater discharge to assess the effect of different volumetric ratios of multiple freshwater TA inputs (i.e., groundwater, river, surface runoff, and precipitation) on nTA. Coral reef freshwater endmember TA ranged from -2 up to 3032 μmol/kg in hypothetical reef locations with freshwater inputs dominated by riverine, surface runoff, or precipitation mixing with groundwater. The upper bound of freshwater TA in these scenarios can result in an uncertainty in reef TA of up to 90 μmol/kg per unit S normalization if the freshwater endmember is erroneously assumed to have 0 μmol/kg alkalinity. The uncertainty associated with S normalization can, under some circumstances, even shift the interpretation of whether reefs are net calcifying to net dissolving, or vice versa. Moreover, the choice of reference salinity for normalization implicitly makes assumptions about whether biogeochemical processes occur before or after mixing between different water masses, which can add uncertainties of ±1.4% nTA per unit S normalization. Additional considerations in identifying potential freshwater sources of TA and their relative volumetric impact on seawater are required to reduce uncertainties associated with S normalization of coral reef carbonate chemistry data in some environments. However, at a minimum, researchers should minimize the range of salinities over which the normalization is applied, precisely measure salinity, and normalize TA values to a carefully selected reference salinity that takes local factors into account.

Effect of Different Cultivation Modes (Photoautotrophic, Mixotrophic, and Heterotrophic) on the Growth of Chlorella sp. and Biocompositions

In the past, biomass production using microalgae culture was dependent on inorganic carbon sources as microalgae are photosynthetic organisms. However, microalgae utilize both organic and inorganic carbon sources, such as glucose. Glucose is an excellent source of organic carbon that enhances biomass yield and the content of useful substances in microalgae. In this study, photoautotrophic, mixotrophic, and heterotrophic cultivation conditions were applied to three well-known strains of Chlorella (KNUA104, KNUA114, and KNUA122) to assess biomass productivity, and compositional changes (lipid, protein, and pigment) were evaluated in BG11 media under photoautotrophic, mixotrophic, and heterotrophic conditions utilizing different initial concentrations of glucose (5, 10, 15, 20, and 25 g L−1). Compared to the photoautotrophic condition (biomass yield: KNUA104, 0.35 ± 0.04 g/L/d; KNUA114, 0.40 ± 0.08 g/L/d; KNUA122, 0.38 ± 0.05 g/L/d) glucose was absent, and the biomass yield improved in the mixotrophic (glucose: 20 g L−1; biomass yield: KNUA104, 2.99 ± 0.10 g/L/d; KNUA114, 5.18 ± 0.81 g/L/d; KNUA122, 5.07 ± 0.22 g/L/d) and heterotrophic conditions (glucose: 20 g L−1; biomass yield: KNUA104, 1.72 ± 0.26 g/L/d; KNUA114, 4.26 ± 0.27 g/L/d; KNUA122, 4.32 ± 0.32 g/L/d). All strains under mixotrophic and heterotrophic conditions were optimally cultured when 15–20 g L−1 initial glucose was provided. Although bioresourse productivity improved under both mixotrophic and heterotrophic conditions where mixotrophic conditions were found to be optimal as the yields of lipid and pigment were also enhanced. Protein content was less affected by the presence of light or the concentration of glucose. Under mixotrophic conditions, the highest lipid content (glucose: 15 g L−1; lipid content: 68.80 ± 0.54%) was obtained with Chlorella vulgaris KNUA104, and enhanced pigment productivity of Chlorella sorokiniana KNUA114 and KNUA122 (additional pigment yield obtained with 15 g L−1 glucose: KNUA 114, 0.33 ± 0.01 g L−1; KNUA122, 0.21 ± 0.01 g L−1). Also, saturated fatty acid (SFA) content was enhanced in all strains (SFA: KNUA104, 29.76 ± 1.31%; KNUA114, 37.01 ± 0.98%; KNUA122, 33.37 ± 0.17%) under mixotrophic conditions. These results suggest that mixotrophic cultivation of Chlorella vulgaris and Chlorella sorokiniana could improve biomass yield and the raw material quality of biomass.