Noble metal catalyst detection in rocks using machine-learning: The future to low-cost, green energy materials?

Carbon capture and catalytic conversion to methane is promising for carbon-neutral energy production. Precious metals catalysts are highly efficient; yet they have several significant drawbacks including high cost, scarcity, environmental impact from the mining and intense processing requirements. Previous experimental studies and the current analytical work show that refractory grade chromitites (chromium rich rocks with Al2O3 > 20% and Cr2O3 + Al2O3 > 60%) with certain noble metal concentrations (i.e., Ir: 17-45 ppb, Ru: 73-178 ppb) catalyse Sabatier reactions and produce abiotic methane; a process which has not been investigated at the industrial scale. Thus, a natural source (chromitites) hosting noble metals might be used instead of concentrating noble metals for catalysis. Stochastic machine-learning algorithms show that among the various phases, the noble metal alloys are natural methanation catalysts. Such alloys form when pre-existing platinum group minerals (PGM) are chemically destructed. Chemical destruction of existing PGM results to mass loss forming locally a nano-porous surface. The chromium-rich spinel phases, hosting the PGM inclusions, are subsequently a second-tier support. The current work is the first multi-disciplinary research showing that noble metal alloys within chromium-rich rocks are double-supported, Sabatier catalysts. Thus, such sources could be a promising material in the search of low-cost, sustainable materials for green energy production.

How quality and quantity of organic matter affect polycyclic aromatic hydrocarbon desorption from Norwegian harbor sediments.

The desorption behavior of phenanthrene, pyrene, and benzo[a]pyrene was investigated for three Norwegian harbor sediments and their respective particle size fractions using the Tenax desorption method. Rate constants for rapidly, slowly, and very slowly desorbing fractions were on the order of 10(-1), 10(-2) to 10(-4), and 10(-4) to 10(-6)/h, respectively. Relatively small amounts were present in the rapidly desorbing fractions (F(rapid): < 6% for phenanthrene, 3-19% for pyrene, and 1-12% for benzo[a]pyrene). With the exception of benzo[a]pyrene, these F(rapid) values were generally lower than median F(rapid) values obtained from more than 100 literature values for native polycyclic aromatic hydrocarbons (PAHs) (22% for phenanthrene, 29% for pyrene, and 8% for benzo[a]pyrene). To understand which parameters influence PAH desorption, relations between desorption behavior and the sediment characteristics were investigated. A significant positive correlation was found between the extent of slow and very slow desorption and the ratios of black carbon to total organic carbon, as well as the temperature at which 50 and 90%, respectively, of the organic matter was oxidized, as obtained from oxidation-only Rock Eval analysis. Thus, black carbon-bound PAHs probably desorb slowly and very slowly. Furthermore, significant positive correlations between desorption behavior and the average particle size were observed, which could be explained by retarded intraparticle diffusion.

Influence of historical industrial epochs on pore water and partitioning profiles of polycyclic aromatic hydrocarbons and polychlorinated biphenyls in Oslo Harbor, Norway, sediment cores.

Contaminant levels in urban harbor sediments vary with contaminant emission levels, sedimentation rates, and sediment resuspension processes such as propeller wash. Levels of polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) are decreasing in many urban harbors, as heavily contaminated sediments that accumulated during past decades are being buried by less-contaminated sediments. However, PAHs and PCBs remain a concern in areas where burial is slow or resuspension processes re-expose heavily contaminated older layers. Chronostratigraphic sediment core studies typically characterize contaminant level histories by using total sediment concentrations, C(sed) , and do not determine the freely dissolved porewater concentrations, C(pw) , which provide a better measure of bioavailability. Here both C(sed) and C(pw) profiles were established for PAHs and PCBs in dated sediment cores from diverse areas of Oslo Harbor, Norway. Sediment-porewater partitioning profiles were established alongside profiles of various sorbing carbonaceous phases, including total organic carbon (TOC), black carbon, and diverse carbonaceous geosorbents identified by petrographic analysis. Stratigraphic trends in carbonaceous phases and C(sed) could be associated with different industrial epochs: hydropower (post-1960, approximately), manufactured gas (∼1925-1960), coal (∼1910-1925), and early industry (∼1860-1910). Partitioning was highly variable and correlated best with the TOC. Hydropower-epoch sediments exhibit decreasing C(sed) with time and a relatively strong sorption capacity compared with the manufactured-gas epoch. Sediments from the manufactured-gas epoch exhibit substantial PAH and metal contamination, large amounts of coke and char, and a low sorption capacity. Reexposure of sediments of this epoch increases risks to local benthic species. Implications on natural recovery as a sediment management strategy are discussed.

Strong sorption of native PAHs to pyrogenic and unburned carbonaceous geosorbents in sediments.

It has recently been shown that the presence of carbonaceous geosorbents (CG, including black carbon (BC), unburned coal, and kerogen) can cause strong sorption of polycyclic aromatic hydrocarbons (PAHs) in sediments. We studied sorption of native PAHs in four Norwegian harbor sediments of which high fractions (21-56%) of the total organic carbon (TOC) consisted of CG carbon (CGC), as shown by organic petrography. PAH sorption coefficients were 1-2 orders of magnitude above predictions based on amorphous organic carbon partitioning alone. In recent studies, such strong sorption was attributed solely to BC sorption under the implicit assumption that sorption is linear for coal and kerogen. The most important result of the present study is that total sorption is better explained by considering all three nonlinearly sorbing CGC materials than by only considering BC. In addition, it was evaluated whether activated carbon (AC) amendments could be effective in reducing the freely dissolved pore-water concentrations (CW) and thus the environmental risks of the PAHs in such strongly sorbing sediments. The results indicated that an addition of 2 weight % AC reduced the Cw by factors of 21-153 for the four sediments (average values for all PAHs). Itwas shown that phenanthrene sorption to AC was, on average, reduced by a factor of 6 in sediment-AC mixtures compared to pure AC.

Relations between environmental black carbon sorption and geochemical sorbent characteristics.

Pyrogenic carbon particles in sediments (soot and charcoal, collectively termed "black carbon" or BC) appear to be efficient sorbents of many hydrophobic organic compounds, so they may play an important role in the fate and toxicity of these substances. To properly model toxicant sorption behavior, it is important to (i) quantify the magnitude of the role of BC in sorption and (ii) elucidate which geochemical BC characteristics determine the strength of environmental BC sorption. Sorption isotherms of d10-phenanthrene (d10-PHE) were determined over a wide concentration range (0.0003-20 microg/L), for five sediments with widely varying characteristics. From the sorption isotherms, we determined Freundlich coefficients of environmental BC sorption, K(F,BCenv. These varied from 10(4.7) to 10(5.5). From the data, it could be deduced that BC was responsible for 49-85% of the total d10-PHE sorption at a concentration of 1 ng/L. At higher concentrations, the importance of BC for the sorption process diminished to <20% at 1 microg/L and 0-1% at 1 mg/L. There were no significant relationships between BC sorption strength and the tested geochemical BC characteristics [the fraction of small (<38 microm) BC particles, the BC resistance to high-temperature oxidation, the fraction of biomass-derived BC, the native polycyclic aromatic hydrocarbon and total organic carbon contents]. Because of the limited variation in BC sorption strength with widely varying BC characteristics, the presented BC sorption coefficients may putatively be used as generic starting points for environmental modeling purposes.