Application of molybdenum and thallium isotopes as indicators of paleoredox conditions and genesis of hyper-enriched black shale deposits, Peel River, Yukon, Canada

ABSTRACT Hyper-enriched black shale (HEBS) deposits in northern Yukon, consist of thin (<10 cm), laterally extensive (tens of thousands of km2) stratiform sulfide mineralization layer(s) that are hyper-enriched in Ni, Mo, Zn, platinum group elements, Re, and Au. The genesis of HEBS deposits and the ambient paleoenvironment in which they formed are the subject of vigorous debate. Non-traditional stable isotopes, particularly molybdenum and thallium, are robust paleoredox indicators and we have employed these isotope systems in this study of Yukon HEBS. Systematic sampling and Mo and Tl isotopic analysis of a continuous 200 m stratigraphic section through the Yukon HEBS mineralization and footwall and hanging-wall strata at the Peel River north and south bank showings (spaced five km apart) give δ98Mo –1.24 to –0.53‰ and –8.1 to –5.2 ε-units for the mineralization and –0.70 to 0.60‰ and –6.5 to –2.0 ε-units for the unmineralized strata. These values preclude a hydrothermal origin and strongly suggest that redox processes were responsible for the Yukon HEBS mineralization. The isotopic compositions, together with rare earth element (REE) systematics (REE profile, Y positive anomalies, Ce negative anomalies, and Y/Ho values) and other bulk geochemical redox indicators (Mo, V, Re/Mo, Ni/Co, U/Th, and V/Cr) indicate that the Peel River HEBS mineralization formed because of metal scavenging from seawater in a quiescent, euxinic basinal paleoenvironment.

Tunable Band Gaps in MUV-10(M): A Family of Photoredox-Active MOFs with Earth-Abundant Open Metal Sites

<div> <div> <p>Titanium-based metal—organic frameworks (Ti-MOFs) attract intense research attention because they can store charges in the form of Ti3+ and they serve as photosensitizers for co-catalysts through heterogeneous photoredox reactions at the MOF-liquid interface. Both charge storage and charge transfer depend on redox potentials of the MOF and the molecular substrate, but the factors controlling these energetic aspects are not well understood. Additionally, photocatalysis involving Ti-MOFs relies on co-catalysts rather than the intrinsic Ti reactivity in part because Ti-MOFs with open metal sites are rare. Here, we report that the class of Ti-MOFs known as MUV-10 can be synthetically modified to include a range of redox-inactive ions with flexible coordination environments that control the energies of the photoactive orbitals. Lewis acidic cations installed in the MOF cluster (Cd, Sr , and Ba ) or introduced to the pores (H, Li, Na, K) tune the electronic structure and band gaps of the MOFs. Through use of optical redox indicators, we report the first direct measurement of the Fermi levels (redox potentials) of photoexcited MOFs in situ. Taken together, these results explain the ability of Ti-MOFs to store charges and provide design principles for achieving heterogeneous photoredox chemistry with electrostatic control.</p> </div> </div>

Tunable Band Gaps in MUV-10(M): A Family of Photoredox-Active MOFs with Earth-Abundant Open Metal Sites

<div> <div> <p>Titanium-based metal—organic frameworks (Ti-MOFs) attract intense research attention because they can store charges in the form of Ti3+ and they serve as photosensitizers for co-catalysts through heterogeneous photoredox reactions at the MOF-liquid interface. Both charge storage and charge transfer depend on redox potentials of the MOF and the molecular substrate, but the factors controlling these energetic aspects are not well understood. Additionally, photocatalysis involving Ti-MOFs relies on co-catalysts rather than the intrinsic Ti reactivity in part because Ti-MOFs with open metal sites are rare. Here, we report that the class of Ti-MOFs known as MUV-10 can be synthetically modified to include a range of redox-inactive ions with flexible coordination environments that control the energies of the photoactive orbitals. Lewis acidic cations installed in the MOF cluster (Cd, Sr , and Ba ) or introduced to the pores (H, Li, Na, K) tune the electronic structure and band gaps of the MOFs. Through use of optical redox indicators, we report the first direct measurement of the Fermi levels (redox potentials) of photoexcited MOFs in situ. Taken together, these results explain the ability of Ti-MOFs to store charges and provide design principles for achieving heterogeneous photoredox chemistry with electrostatic control.</p> </div> </div>

Tunable Band Gaps in MUV-10(M): A Family of Photoredox-Active MOFs with Earth-Abundant Open Metal Sites

<div> <div> <div> <p>Titanium-based metal—organic frameworks (Ti-MOFs) attract intense research attention because they can store charges in the form of Ti3+ and they serve as photosensitizers for co-catalysts through heterogeneous photoredox reactions at the MOF-liquid interface. Both charge storage and charge transfer depend on redox potentials of the MOF and the molecular substrate, but the factors controlling these energetic aspects are not well understood. Additionally, photocatalysis involving Ti-MOFs relies on co-catalysts rather than the intrinsic Ti reactivity in part because Ti-MOFs with open metal sites are rare. Here, we report that the class of Ti-MOFs known as MUV-10 can be synthetically modified to include a range of redox-inactive ions with flexible coordination environments that control the energies of the photoactive orbitals. Lewis </p> <p>acidic cations installed in the MOF cluster (Cd, Sr , and Ba ) or introduced to the pores (H, Li, Na, K) tune the electronic structure and band gaps of the MOFs. Through use of optical redox indicators, we report the first direct measurement of the Fermi levels (redox potentials) of photoexcited MOFs in situ. Taken together, these results explain the ability of Ti-MOFs to store charges and provide design principles for achieving heterogeneous photoredox chemistry with electrostatic control.</p> </div> </div> </div>

4,15-Dimethyl-7,12-diazoniatricyclo[10.4.0.02,7]hexadeca-1(12),2,4,6,13,15-hexaene dibromide monohydrate

The title compound, C16H20N2 2+·2Br−·H2O (1) is a member of the class of compounds called viologens. Viologens are quaternary salts of dipyridyls and are especially useful as redox indicators as a result of their large negative one-electron reduction potentials. Compound 1 consists of a dication composed of a pair of 4-methylpyridine rings mutually joined at the 2-position, with a dihedral angle between the pyridine rings of 62.35 (4)°. In addition, the rings are tethered via the pyridine nitrogen atoms by a tetramethylene bridge. Charge balance is provided by a pair of bromide anions, which are hydrogen bonded to a single water molecule [D O...Br = 3.3670 (15) and 3.3856 (15) Å]. The crystal structure of 1, details of an improved synthesis, and a full analysis of its NMR spectra are presented.

SIGNATURES OF PYRITIZATION OF TRANZITION ZONES FORM THE BAZHENOV FORMATION TO ENCLOSED DEPOSITS IN THE UPPER JURASSIC-LOWER CRETACEOUS WESTERN SIBERIAN BASIN

In the transitional zones from the Bazhenov Formation and to the enclosing deposits the complex of litological-geochemical researches, including the analysis of sections structure, distributions of C/S ratio and redox indicators (degree pyritization, authigenous uranium, Mn/Al) were made. It is defined that rocks on the borders with the Bazhenov Formation at the enclosing deposits are low carbonaceous with rather high content of pyrite; in the Bazhenov Formation near its roof in many cases rocks are characterized by approximately equal high contents of pyrite and kerogen. It is established that the pyritization of rocks on these intervals resulted by thermochemical sedimentation of iron from solutions on redox geochemical barriers without participation of bacterial activity.

Combining cross-reactivity of an electrode array with the selective thiol reporting process of redox indicators: targeted sensing of biothiols

Combining the cross-reactivity of the voltammetric sensor array with the selective thiol reporting process of redox indicators (RIs) enables the targeted sensing of biothiols.