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1. Comparison of powdered enamel sample pretreatment methods for strontium isotope analysis

   https://doi.org/10.3389/fenvc.2023.1114807  

   Crowley, Brooke Erin; Bruff Simpson, Emily Michelle; Hammer, Sarah Jayne; Smith, Joshua Michael; Johnson, Thomas Martin (March 2023, Frontiers in Environmental Chemistry)

   Most researchers assume minimal impact of pretreatment on strontium isotope ratios ( 87 Sr/ 86 Sr) for bones and teeth, and methods vary tremendously. We compared 14 pretreatment methods, including no prep other than powdering enamel, ashing, soaking in water, an oxidizing agent (bleach or hydrogen peroxide) or acetic acid (0.1 M, 1.0 M, and 1.0 M buffered with calcium acetate), and a combination of these steps. We prepared and analyzed aliquots of powdered molar enamel from three proboscideans (one modern captive Indian elephant, Elephas maximus indicus ; one Pleistocene mastodon, Mammut americanum ; and one Miocene gomphothere, Afrochoerodon kisumuensis ). Each pretreatment was performed in triplicate and we measured 87 Sr/ 86 Sr, Sr concentration, and uranium (U) concentration, using the same lab space and instrumentation for all samples. Variability in 87 Sr/ 86 Sr and Sr and U concentrations was considerable across pretreatments. Mean 87 Sr/ 86 Sr across methods ranged from 0.70999 to 0.71029 for the modern tooth, 0.71458 to 0.71502 for the Pleistocene tooth, and 0.70804 to 0.70817 for the Miocene tooth. The modern tooth contained the least Sr and negligible U. The Pleistocene tooth contained slightly more Sr and measurable amounts of U, and the Miocene tooth had approximately 5x more Sr and U than the Pleistocene tooth. For all three teeth, variance in 87 Sr/ 86 Sr, Sr concentrations, and U concentrations among replicates was statistically indistinguishable across pretreatments, but there were apparent differences among pretreatments for the modern and Pleistocene teeth. Both contained relatively little Sr, and it is possible that small amounts of exogenous Sr from reagents, building materials or dust affected some replicates for some pretreatments. For the modern tooth, median 87 Sr/ 86 Sr varied considerably (but statistically insignificantly) across pretreatments. For the Pleistocene tooth, variability in median 87 Sr/ 86 Sr was also considerable; some pretreatments were statistically distinct but there were no obvious patterns among methods. For the Miocene tooth, variability in median 87 Sr/ 86 Sr was much smaller, but there were significant differences among pretreatments. Most pretreatments yielded 87 Sr/ 86 Sr and Sr concentrations comparable to, or lower than, untreated powder, suggesting selective removal of exogenous material with high 87 Sr/ 86 Sr. Further evaluation of the mechanisms driving isotopic variability both within and among pretreatment methods is warranted. Researchers should clearly report their methods and avoid combining data obtained using different methods. Small differences in 87 Sr/ 86 Sr could impact data interpretations, especially in areas where isotopic variability is low. 

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2. Investigation of the Bimodal Leaching Response of RAM Chip Gold Fingers in Ammonia Thiosulfate Solution

   https://doi.org/10.3390/ma16144940  

   Lin, Peijia; Ali, Zulqarnain Ahmad; Werner, Joshua (July 2023, Materials)

   Oxidative thiosulfate leaching using Cu(II)-NH3 has been explored for both mining and recycling applications as a promising method for Au extraction. This study seeks to understand the dissolution behavior of Au from waste RAM chips using a Cu(II)-NH3-S2O3 solution. In the course of this work, bimodal leaching and Au loss were observed in a manner that we have not identified in the literature. Identification of the existence of a specific Au-Ni-Cu lamellar structure in the gold fingers from RAM chips by scanning electron microscopy and energy dispersive X-ray spectroscopy (SEM-EDS) revealed the possibility of interference between Au recovery and the existence of Cu and Ni. During leaching, the co-extraction of Ni was found to predict a negative impact on the Au recovery, as a result of chemical interactions from the Au-Ni-Cu interlayer. Decopperization as a pretreatment was found necessary to remove the pre-existing Cu and promote Au leaching. As part of the study parameters, such as Cu(II) concentration, aeration rates, thiosulfate and ammonia concentrations, particle sizes, and temperatures, were investigated. A satisfactory Au recovery of 98% was achieved using 50 mM Cu(II), 120 mL/min aeration rate, 0.5 M (NH3)2S2O3, and 0.75 M NH4OH (i.e., AT/AH ratio of 0.67) for 4 h residence time at room temperature (25 °C). However, there were several high recoveries prior to Au loss from the lixiviant. It was revealed that the main cause of lower Au recovery was due to a precipitation or cementation reaction that included a sulfur species formation. Because of the bimodal leaching, a composite response comprised of the time to Au loss and maximum recovery was developed, termed leaching proclivity, to facilitate statistical analysis. Furthermore, this study explores the interactions between Au-Ni-Cu and provides suggestions for improving Au thiosulfate leaching under the interference of co-existing metals from waste PCB materials. 

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3. Supercritical CO ₂ -induced alteration of polymer-metal matrix and selective extraction of valuable metals from waste printed circuit boards

   https://doi.org/10.1039/D0GC02521F  

   Peng, Peng; Park, Ah-Hyung Alissa (January 2020, Green Chemistry)

   The rapidly accumulating amounts of waste electrical and electronic equipment (WEEE) is one of the biggest environmental concerns in modern societies, and this problem will be further accelerated in the future. The use of supercritical CO2 (scCO2) mixed with acids has been proposed as a greener solvent system compared to conventional cyanide and aqua regia solvents, however, the mechanisms of scCO2 in metal extraction from WEEE are still poorly understood. Thus, this study focused on the physical, structural, and chemical interactions between scCO2/acid solvents and complex layered components in waste printed circuit boards (WPCBs), one of the common WEEEs. Our study showed that the use of scCO2-based pretreatment allows faster leaching of metals including copper (Cu) in the subsequent hydrometallurgical process using H2SO4 and H2O2, while allowing gold (Au) recovery as hydrometallurgically delaminated solids. This enhancement is due to the selective leaching of Ni and unique inner porous structures created by ScCO2/acid treatment via dissolving the Ca-silicate-bearing fiberglass within the WPCB. Thus, the scCO2-based pretreatment of WPCBs shows a multifaceted green chemistry potential relating to the reduction in solvent usage and targeted recovery of Au prior to shredding or grinding that would reduce any loss or dilution of Au in the subsequent waste stream. 

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4. Arctic Permafrost Thawing Enhances Sulfide Oxidation

   https://doi.org/10.1029/2022GB007644  

   Kemeny, Preston Cosslett; Li, Gen K.; Douglas, Madison; Berelson, William; Chadwick, Austin J.; Dalleska, Nathan F.; Lamb, Michael P.; Larsen, William; Magyar, John S.; Rollins, Nick E.; et al (November 2023, Global Biogeochemical Cycles)

   Abstract Permafrost degradation is altering biogeochemical processes throughout the Arctic. Thaw‐induced changes in organic matter transformations and mineral weathering reactions are impacting fluxes of inorganic carbon (IC) and alkalinity (ALK) in Arctic rivers. However, the net impact of these changing fluxes on the concentration of carbon dioxide in the atmosphere (pCO₂) is relatively unconstrained. Resolving this uncertainty is important as thaw‐driven changes in the fluxes of IC and ALK could produce feedbacks in the global carbon cycle. Enhanced production of sulfuric acid through sulfide oxidation is particularly poorly quantified despite its potential to remove ALK from the ocean‐atmosphere system and increasepCO₂, producing a positive feedback leading to more warming and permafrost degradation. In this work, we quantified weathering in the Koyukuk River, a major tributary of the Yukon River draining discontinuous permafrost in central Alaska, based on water and sediment samples collected near the village of Huslia in summer 2018. Using measurements of major ion abundances and sulfate () sulfur (³⁴S/³²S) and oxygen (¹⁸O/¹⁶O) isotope ratios, we employed the MEANDIR inversion model to quantify the relative importance of a suite of weathering processes and their net impact onpCO₂. Calculations found that approximately 80% of in mainstem samples derived from sulfide oxidation with the remainder from evaporite dissolution. Moreover,³⁴S/³²S ratios,¹³C/¹²C ratios of dissolved IC, and sulfur X‐ray absorption spectra of mainstem, secondary channel, and floodplain pore fluid and sediment samples revealed modest degrees of microbial sulfate reduction within the floodplain. Weathering fluxes of ALK and IC result in lower values ofpCO₂over timescales shorter than carbonate compensation (∼10⁴ yr) and, for mainstem samples, higher values ofpCO₂over timescales longer than carbonate compensation but shorter than the residence time of marine (∼10⁷ yr). Furthermore, the absolute concentrations of and Mg²⁺in the Koyukuk River, as well as the ratios of and Mg²⁺to other dissolved weathering products, have increased over the past 50 years. Through analogy to similar trends in the Yukon River, we interpret these changes as reflecting enhanced sulfide oxidation due to ongoing exposure of previously frozen sediment and changes in the contributions of shallow and deep flow paths to the active channel. Overall, these findings confirm that sulfide oxidation is a substantial outcome of permafrost degradation and that the sulfur cycle responds to permafrost thaw with a timescale‐dependent feedback on warming. 

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5. Understanding the effect of Deep Eutectic Solvent (DES) pretreatment on the utilization of corn stover

   Hsu, Elizabeth; Varghese, Athan; Ryu, Jiae; Leem, Alicia; Lin, Jialong (October 2024, Journal of high school science)

   Pretreatment is an important step to reduce the recalcitrance factors in biomass for effective biomass utilization. In particular, the choice of processing solvents in the pretreatment influences the quantity and quality of the final products. Although conventional organosolv pretreatments are effective, they are typically performed under harsh conditions. Compared to those approaches, recent studies have shown that the use of Deep Eutectic Solvents (DES) made up of a hydrogen bond donor and acceptor at the eutectic point can be a promising alternative as biomass processing solvents because of their good thermal stability and compatibility with natural components. In this study, DES pretreatment was applied to corn stover, which is the largest agricultural residue in the United States. The performance of the pretreatments was assessed by measuring the removal of xylan and lignin from the corn stover, as well as the production of glucose and xylose by subsequent enzymatic hydrolysis. The results indicated that the DES pretreatment resulted in significantly higher delignification rates (75%) than an organosolv pretreatment (35%) at the same processing temperature. The DES pretreatment also resulted in a more effective conversion of glucan (81%) and xylan (56%) than the organosolv pretreatment. The results indicated that DES pretreatment is a promising processing strategy for biomass utilization. 

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