A Sustainable Approach for Synthesizing (R)-4-Aminopentanoic Acid From Levulinic Acid Catalyzed by Structure-Guided Tailored Glutamate Dehydrogenase

In this study, a novel enzymatic approach to transform levulinic acid (LA), which can be obtained from biomass, into value-added (R)-4-aminopentanoic acid using an engineered glutamate dehydrogenase from Escherichia coli (EcGDH) was developed. Through crystal structure comparison, two residues (K116 and N348), especially residue 116, were identified to affect the substrate specificity of EcGDH. After targeted saturation mutagenesis, the mutant EcGDHK116C, which was active toward LA, was identified. Screening of the two-site combinatorial saturation mutagenesis library with EcGDHK116C as positive control, the kcat/Km of the obtained EcGDHK116Q/N348M for LA and NADPH were 42.0- and 7.9-fold higher, respectively, than that of EcGDHK116C. A molecular docking investigation was conducted to explain the catalytic activity of the mutants and stereoconfiguration of the product. Coupled with formate dehydrogenase, EcGDHK116Q/N348M was found to be able to convert 0.4 M LA by more than 97% in 11 h, generating (R)-4-aminopentanoic acid with >99% enantiomeric excess (ee). This dual-enzyme system used sustainable raw materials to synthesize (R)-4-aminopentanoic acid with high atom utilization as it utilizes cheap ammonia as the amino donor, and the inorganic carbonate is the sole by-product.

Effect of inorganic carbonate and organic matter in thermal treatment of mercury-contaminated soil

Thermal treatment of mercury (Hg)-contaminated soil was studied to investigate the desorption behavior of Hg at different temperatures. The soil samples were collected from two locations with different land uses around the mine and industrial site. The effect of soil properties such as inorganic carbonate minerals and organic matter content on Hg desorption was investigated to understand the thermal desorption process. The effect of soil composition on Hg desorption showed that behavior at 100 °C was similar, but a different behavior could be found at 300 °C. The thermal desorption efficiency at 300 °C is affected by the thermal properties of soils and the Hg desorption capacity of the soils. The Hg from both soil types was removed above 300 °C, and Hg was effectively removed from mine soil due to the partial decomposition of carbonate in the soil composition, while industrial soil showed that desorption would be restrained by Hg organic matter complexes due to organic matter content. Despite a relatively higher concentration of Hg in the mine soil, Hg removal efficiency was greater than that in the industrial soil. Sequential extraction results showed that only the Hg fractions (residual fractions, step 6) in mine soil changed, while the industrial soil was affected by changes in Hg fractions (step 3 to step 6) at 300 °C. Changes in soil pH during thermal desorption are also influenced by heating time and temperature. Therefore, the mechanisms of Hg desorption during thermal treatment were observed by soil properties. The volatilization of Hg in the soil is induced by organic carbon, while soil Hg release is controlled by organic matter complexes.

Effect of Inorganic Carbonate in Thermal Treatment of Mercury-contaminated Soil

Thermal treatment of mercury (Hg)-contaminated soil was studied to investigate the desorption behavior of Hg at different temperatures. The soil samples were collected from two locations with different land uses around the mine and industrial site. The effect of soil properties such as inorganic carbonate minerals and organic matter content on Hg desorption was investigated to understand the thermal desorption process. The effect of soil composition on Hg desorption showed that behavior at 100 °C was similar, but different behavior could be found at 300 °C. The thermal desorption efficiency at 300 °C is affected by the thermal properties of soils and the Hg desorption capacity of the soils. The Hg from both soil types was removed above 300 °C, and Hg was effectively removed from mine soil due to the partial decomposition of carbonate in the soil composition, while industrial soil showed that desorption would be restrained by Hg organic matter complexes due to organic matter content. Despite a relatively higher concentration of Hg in the mine soil, Hg removal efficiency was greater than that in the industrial soil. Sequential extraction results showed that only the Hg fractions (residual fractions, F6) in mine soil changed, while the industrial soil was affected by changes in Hg fractions (F3 to F6) at 300 °C. Changes in soil pH during thermal desorption are also influenced by heating time and temperature. Therefore, the mechanisms of Hg desorption during thermal treatment were observed by soil properties. The volatilization of Hg in the soil is induced by organic carbon, while soil Hg release is controlled by organic matter complexes.

INFLUENCES OF UPPER FLORIDAN AQUIFER WATERS ON RADIOCARBON IN THE OTOLITHS OF GRAY SNAPPER (Lutjanus griseus) IN THE GULF OF MEXICO

ABSTRACTThe otoliths (ear stones) of fishes are commonly used to describe the age and growth of marine and freshwater fishes. These non-skeletal structures are fortuitous in their utility by being composed of mostly inorganic carbonate that is inert through the life of the fish. This conserved record functions like an environmental chronometer and bomb-produced radiocarbon (14C)—a 14C signal created by atmospheric testing of thermonuclear devices—can be used as a time-specific marker in validating fish age. However, complications from the hydrogeology of nearshore marine environments can complicate 14C levels, as was the case with gray snapper (Lutjanus griseus) along the Gulf of Mexico coast of Florida. Radiocarbon of these nearshore waters is influenced by freshwater input from the karst topography of the Upper Floridan Aquifer—estuarine waters that are 14C-depleted from surface and groundwater inputs. Some gray snapper likely recruited to this kind of environment where 14C levels were depleted in the earliest otolith growth, although age was validated for individuals that were not exposed to 14C-depleted waters to an age of at least 25 years with support for a 30-year lifespan.

Recent Organic Transformations with Silver Carbonate as a Key External Base and Oxidant

Silver carbonate (Ag2CO3), a common transition metal-based inorganic carbonate, is widely utilized in palladium-catalyzed C–H activations as an oxidant in the redox cycle. Silver carbonate can also act as an external base in the reaction medium, especially in organic solvents with acidic protons. Its superior alkynophilicity and basicity make silver carbonate an ideal catalyst for organic reactions with alkynes, carboxylic acids, and related compounds. This review describes recent reports of silver carbonate-catalyzed and silver carbonate-mediated organic transformations, including cyclizations, cross-couplings, and decarboxylations.

Inorganic carbonate composites as potential high temperature CO2 sorbents with enhanced cycle stability

A Ca/Mg/Al oxide composite was synthesised and showed a high CO2 uptake of 0.537 g g−1 at 650 °C with high uptake even after 100 cycles.

Distribution of planktonic biogenic carbonate organisms in the Southern Ocean south of Australia: a baseline for ocean acidification impact assessment

The Southern Ocean provides a vital service by absorbing about one-sixth of humankind's annual emissions of CO2. This comes with a cost – an increase in ocean acidity that is expected to have negative impacts on ocean ecosystems. The reduced ability of phytoplankton and zooplankton to precipitate carbonate shells is a clearly identified risk. The impact depends on the significance of these organisms in Southern Ocean ecosystems, but there is very little information on their abundance or distribution. To quantify their presence, we used coulometric measurement of particulate inorganic carbonate (PIC) on particles filtered from surface seawater into two size fractions: 50–1000 µm to capture foraminifera (the most important biogenic carbonate-forming zooplankton) and 1–50 µm to capture coccolithophores (the most important biogenic carbonate-forming phytoplankton). Ancillary measurements of biogenic silica (BSi) and particulate organic carbon (POC) provided context, as estimates of the biomass of diatoms (the highest biomass phytoplankton in polar waters) and total microbial biomass, respectively. Results for nine transects from Australia to Antarctica in 2008–2015 showed low levels of PIC compared to Northern Hemisphere polar waters. Coccolithophores slightly exceeded the biomass of diatoms in subantarctic waters, but their abundance decreased more than 30-fold poleward, while diatom abundances increased, so that on a molar basis PIC was only 1 % of BSi in Antarctic waters. This limited importance of coccolithophores in the Southern Ocean is further emphasized in terms of their associated POC, representing less than 1 % of total POC in Antarctic waters and less than 10 % in subantarctic waters. NASA satellite ocean-colour-based PIC estimates were in reasonable agreement with the shipboard results in subantarctic waters but greatly overestimated PIC in Antarctic waters. Contrastingly, the NASA Ocean Biogeochemical Model (NOBM) shows coccolithophores as overly restricted to subtropical and northern subantarctic waters. The cause of the strong southward decrease in PIC abundance in the Southern Ocean is not yet clear. The poleward decrease in pH is small, and while calcite saturation decreases strongly southward, it remains well above saturation ( > 2). Nitrate and phosphate variations would predict a poleward increase. Temperature and competition with diatoms for limiting iron appear likely to be important. While the future trajectory of coccolithophore distributions remains uncertain, their current low abundances suggest small impacts on overall Southern Ocean pelagic ecology.