A biological process for the reclamation of flue gas desulfurization gypsum using mixed sulfate-reducing bacteria with inexpensive carbon sources

A combined chemical and biological process for the recycling of flue gas desulfurization (FGD) gypsum into calcium carbonate and elemental sulfur is demonstrated. In this process, a mixed culture of sulfate-reducing bacteria (SRB) utilizes inexpensive carbon sources, such as sewage digest or synthesis gas, to reduce FGD gypsum to hydrogen sulfide. The sulfide is then oxidized to elemental sulfur via reaction with ferric sulfate, and accumulating calcium ions are precipitated as calcium carbonate using carbon dioxide. Employing anaerobically digested municipal sewage sludge (AD-MSS) medium as a carbon source, SRBs in serum bottles demonstrated an FGD gypsum reduction rate of 8 mg/L/h (10⁹ cells)^-1. A chemostat with continuous addition of both AD-MSS media and gypsum exhibited sulfate reduction rates as high as 1.3 kg FGD gypsum/m³d. The increased biocatalyst density afforded by cell immobilization in a columnar reactor allowed a productivity of 152 mg SO₄ ^-2/Lh or 6.6 kg FGD gypsum/m³d. Both reactors demonstrated 100% conversion of sulfate, with 75–100% recovery of elemental sulfur and chemical oxygen demand utilization as high as 70%. Calcium carbonate was recovered from the reactor effluent on precipitation using carbon dioxide. It was demonstrated that SRBs may also use synthesis gas (CO, H₂, and CO₂ in the reduction of gypsum, further decreasing process costs. The formation of two marketable products—elemental sulfur and calcium carbonate—from FGD gypsum sludge, combined with the use of a low-cost carbon source and further improvements in reactor design, promises to offer an attractive alternative to the landfilling of FGD gypsum.

     

Noble Metal Ion-Directed Assembly of 2D Materials for Heterostructured Catalysts and Metallic Micro-Texturing

Assembling 2D-material (2DM) nanosheets into micro- and macro-architectures with augmented functionalities requires effective strategies to overcome nanosheet restacking. Conventional assembly approaches involve external binders and/or functionalization, which inevitably sacrifice 2DM's nanoscale properties. Noble metal ions (NMI) are promising ionic crosslinkers, which can simultaneously assemble 2DM nanosheets and induce synergistic properties. Herein, a collection of NMI–2DM complexes are screened and categorized into two sub-groups. Based on the zeta potentials, two assembly approaches are developed to obtain 1) NMI-crosslinked 2DM hydrogels/aerogels for heterostructured catalysts and 2) NMI–2DM inks for templated synthesis. First, tetraammineplatinum(II) nitrate (TPtN) serves as an efficient ionic crosslinker to agglomerate various 2DM dispersions. By utilizing micro-textured assembly platforms, various TPtN–2DM hydrogels are fabricated in a scalable fashion. Afterward, these hydrogels are lyophilized and thermally reduced to synthesize Pt-decorated 2DM aerogels (Pt@2DM). The Pt@2DM heterostructures demonstrate high, substrate-dependent catalytic activities and promote different reaction pathways in the hydrogenation of 3-nitrostyrene. Second, PtCl₄ can be incorporated into 2DM dispersions at high NMI molarities to prepare a series of PtCl₄–2DM inks with high colloidal stability. By adopting the PtCl₄–graphene oxide ink, various Pt micro-structures with replicated topographies are synthesized with accurate control of grain sizes and porosities.     

Molecular sensing of 3-chloro-1,2-propanediol by molecular imprinting

A covalent interaction-based molecularly imprinted polymer (MIP) material for 3-chloro-1,2-propanediol (3-MCPD), a post-testicular anti-fertility agent and possible carcinogen and mutagen in food products containing acid-hydrolyzed vegetable proteins, has been successfully fabricated using 4-vinylphenylboronic acid as the functional monomer. Rebinding assay revealed that the binding constant, K_B, for the receptor sites and non-specific sites are 1.93±0.1×10⁴ and 2.74±0.7×10² M⁻¹, respectively. The estimated number of receptor site, B_max, imprinted is 123.3±3 μmol/g of MIP. The MIP material is able to act as a potentiometric chemosensor for 3-MCPD via increase in Lewis acidity of the receptor sites upon reaction of the arylboronic acid with 3-MCPD to form the more acidic arylboronic acid esters. A simple pH glass electrode is sufficient to monitor the analyte-specific rebinding. In unbuffered aqueous media, linear potentiometric response from 0 to 350 ppm of 3-MCPD can be achieved. The MIP-based chemosensing in a soya sauce matrix has also been attempted. It is found that the dynamic range of the potentiometric chemosensing response of the MIP material is much reduced, probably due to the blocking or deactivation of receptor sites by interferents in soya sauces. Nevertheless, the present work demonstrated the feasibility of using MIP-based chemosensors as semi-quantitative analytical tools for screening purposes in quality control of food products.     

Biological generation of tritiated vitamin D3 metabolites and their purification by high-performance liquid chromatography

Summary A simple, reproducible method for the biological synthesis of tritiated 24,25-dihydroxycholecalciferol, 25,26-dihydroxycholecalciferol and 1,25-dihydroxycholecalciferol is described. Kidney homogenates from both vitamin D deficient and replete chicks were usedin vitro to generate these dihydroxylated metabolites using 25 (23,24-³H) hydroxycholecalciferol as the substrate. Tritiated products were purified by Sephadex LH 20 chromatography followed by high-performance liquid chromatography; the identity of each metabolite was established by chromatography with authentic crystalline preparations.Presented at the Symposium organised by the Chromatography Discussion Group, held at Hatfield Lodge on 29 November 1979.     

FT-Raman spectroscopy of lichens on dolomitic rocks: an assessment of metal oxalate formation

The FT-Raman spectra of five epilithic lichen taxa growing on dolomite and magnesium-rich carbonate rocks have been analysed and interpreted for the key molecular marker bands associated with calcium oxalate monohydrate (whewellite), calcium oxalate dihydrate (weddelite) and magnesium oxalate dihydrate. From the results, it can be concluded that the biomineral product of lichen biodeterioration involves the calcareous part of the substratum only; no trace of magnesium oxalate has been found in the Raman spectra. Two of the species, Lecanora sulfurea and Aspicilia calcarea, produce calcium oxalate monohydrate exclusively, but Dirina massiliensis f. sorediata, D. massiliensis f. massiliensis and Tephromela atra produce significant quantities of the dihydrate. An explanation is advanced for the exclusive accumulation of calcium oxalate into the lichen thallus despite the significant presence of magnesium ions.     

Synthesis of the aziridinomitosene skeleton by intramolecular Michael addition of alpha-lithioaziridines: an aromatic route featuring deuterium as a removable blocking group

A convergent synthetic route to the 1,2-aziridinopyrrolo(1,2-a)indole 34 has been developed. Key features of this route include the deuterium kinetic isotope effect to block undesired indole lithiation during tin-lithium exchange from 27a to 30a, the intramolecular Michael addition to generate the enolate 31a, and conversion into 34 by trapping with phenylselenenyl chloride. Reductive cleavage of the N-trityl group in 34 allows access to tetracyclic aziridinomitosenes containing the aziridine N-H subunit. Reduction of the C(9) ester in 34 with LAH gives the primary alcohol 35 with the correct C(9), C(9a), C(10) oxidation state corresponding to the aziridinomitosenes, and deprotection of 34 affords 37.