• Title/Summary/Keyword: Oxidation-Reduction Potential

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Sulfur Dioxide, Mineral Contents and Physicochemical Properties Generated during Manufacture of Bamboo Salt (죽염 제조공정에 따른 이산화황, 미네랄 함량 및 이화학적 특성)

  • Kim, Hag-Lyeol;Lee, Seong-Jae;Lee, Jung-Hee;Kim, In-Cheol
    • Journal of the Korean Society of Food Science and Nutrition
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    • v.43 no.8
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    • pp.1248-1256
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    • 2014
  • The purpose of this study was to investigate the mechanisms of behind $SO_2$ formation and elevated cause of reducing power in purple bamboo salt (PBS) along with an analysis of physicochemical properties, content of sulfur compounds, oxidation reduction potential (ORP), mineral contents of salt type (MSS, mudflat solar salt; BS, bamboo salt), and addition of raw bamboo (RB). $SO_2$ content of 630 ppm was detected in PBS. $SO_2$ was not detected in MSS, BS, or RB, whereas $SO_2$ (782 ppm) from $K_2SO_4$ was detected after heating a NaCl, KCl, $MgCl_2$, $MgSO_4$, MgO, $CaCl_2$, $K_2SO_4$, and $FeSO_4$ with RB. $SO_2$ content of BS increased with baking time, and it originated from BSRB1 (13.88 ppm) to BSRB4 (109.13 ppm). $SO_3{^{2-}}$ originated only from MSSRB4 and BSRB2~BSRB4. Sulfate ion content decreased along with increasing $SO_2$ and sulfite ion contents. ORP increased with baking time of MSS and BS, and it was present at higher levels in BSRB4 (-211.40 mV) of BS than MSS. Insoluble content was higher in BS than MSS. Further, Ca, K, and Mg ion contents decreased in MSS and increased in BS with baking time. BSRB4 had 1.4 fold higher levels of Ca, 1.5 fold higher levels of Mg, and 1.8 fold higher levels of K than BS. Li, Al, Mn, Fe, and Sr in MSS as well as Al, Fe, and Ni in BS increased with baking time. Anions (Cl, $NO_3$, and Br) and heavy metals (Pb, Cd, Hg, and As) between MSS and BS were not significantly different. These results suggest that the reducing power of BS was due to $SO_2$ and sulfite ion. To increase the amounts of these compounds and reducing power, higher melting temperature and longer baking time are necessary along with BS, which is created by the addition of RB to roasted salt.

Synthesis and Electrochemical Properties of Carbon Coated Li4Ti5O12 using PVC (PVC를 원료로 탄소코팅한 Li4Ti5O12의 합성 및 전기화학적 특성)

  • Hyun, Si-Cheol;Na, Byung-Ki
    • Clean Technology
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    • v.24 no.1
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    • pp.77-84
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    • 2018
  • In this study, $Li_4Ti_5O_{12}$ anode materials for lithium ion battery were synthesized by dry ball-mill method. Polyvinyl chloride (PVC) as a carbon source was added to improve electrochemical properties. When the PVC was added after $Li_4Ti_5O_{12}$ formation, the spinel structure was well synthesized and it was confirmed by X-ray diffraction (XRD) experiments. When the carbon material was added before the synthesis and the heat treatment was performed, it was confirmed that a material having a different crystal structure was synthesized even when a small amount of carbon material was added. In the case of $Li_4Ti_5O_{12}$ without the carbon material, the electrical conductivity value was about $10{\mu}S\;m^{-1}$, which was very small and similar to that of the nonconductor. As the carbon was added, the electrical conductivity was greatly improved and increased up to 10,000 times. Electrochemical impedance spectroscopy (EIS) analysis showed that the size of semicircle corresponding to the resistance decreased with the carbon addition. This indicates that the resistance inside the electrode is reduced. According to the Cyclic voltammetry (CV) analysis, the potential difference between the oxidation peak and the reduction peak was reduced with carbon addition. This means that the rate of lithium ion insertion and deinsertion was increased. $Li_4Ti_5O_{12}$ with 9.5 wt% PVC added sample showed the best properties in rate capabilities of $180mA\;h\;g^{-1}$ at 0.2 C-rate, $165mA\;h\;g^{-1}$ at 0.5 C-rate, and $95.8mA\;h\;g^{-1}$ at 5 C-rate.

Characteristics of Seepage Water and Groundwater in a Coastal LPG Storage Cavern of Jeonnam (전남 해안 LPG 저장공동 유출수와 주변 지하수의 수질특성)

  • Lee, Jin-Yong;Choi, Mi-Jung;Kim, Hyun-Jung;Cho, Byung-Wook
    • Journal of Soil and Groundwater Environment
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    • v.14 no.4
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    • pp.33-44
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    • 2009
  • Water curtain of an underground LPG storage cavern is a facility to prevent leakage of high pressure gases, for which groundwater should flow freely towards the cavern and groundwater level also must be stably maintained. In this study, in order to evaluate qualities of seepage water and surrounding groundwater of an underground LPG storage cavern in Yeosu, 4 rounds of samplings, field measurements and laboratory analyses (February, May, August, October of 2007) were conducted. According to field measurements, pH was weak acidic to neutral but it gradually increased with time. Electrical conductivity (EC) of groundwater near a salt stack showed very high values between 10.47 and 38.50 mS/cm. Dissolved oxygen (DO) showed a very wide range of 0.20~8.74 mg/L and a mean of oxidation-reduction potential (ORP) was 159 mV, which indicated an oxidized condition. Levels of $Fe^{2+}$ and $Mn^{2+}$ were mostly less than 3 mg/L. All of seepage waters showed a Na-Cl type while only groundwater near the salt stack showed a Na-Cl type with a high total dissolved solid. The other groundwaters exhibited typical $Ca-HCO_3$ types. Levels of aerobic bacteria were mostly very high (573-39,520 CFU/mL). Based on the analyses of these hydrochemistry and biological characteristics, it is concluded that there are no particular problems in groundwater and seepage water, which not causing a trouble in the cavern operation. However, both for control of bio-clogging and for sustainable operation of the water curtain system, a regular hydrochemical and microbiological monitoring is required for the seepage water and surrounding groundwater.

Origin and Reservoir Types of Abiotic Native Hydrogen in Continental Lithosphere (대륙 암석권에서 무기 자연 수소의 성인과 부존 형태)

  • Kim, Hyeong Soo
    • Korean Journal of Mineralogy and Petrology
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    • v.35 no.3
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    • pp.313-331
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    • 2022
  • Natural or native abiotic molecular hydrogen (H2) is a major component in natural gas, however yet its importance in the global energy sector's usage as clean and renewable energy is underestimated. Here we review the occurrence and geological settings of native hydrogen to demonstrate the much widesprease H2 occurrence in nature by comparison with previous estimations. Three main types of source rocks have been identified: (1) ultramafic rocks; (2) cratons comprising iron (Fe2+)-rich rocks; and (3) uranium-rich rocks. The rocks are closely associated with Precambrian crystalline basement and serpentinized ultramafic rocks from ophiolite and peridotite either at mid-ocean ridges or within continental margin(Zgonnik, 2020). Inorganic geological processes producing H2 in the source rocks include (a) the reduction of water during the oxidation of Fe2+ in minerals (e.g., olivine), (b) water splitting due to radioactive decay, (c) degassing of magma at low pressure, and (d) the reaction of water with surface radicals during mechanical breaking (e.g., fault) of silicate rocks. Native hydrogen are found as a free gas (51%), fluid inclusions in various rock types (29%), and dissolved gas in underground water (20%) (Zgonnik, 2020). Although research on H2 has not yet been carried out in Korea, the potential H2 reservoirs in the Gyeongsang Basin are highly probable based on geological and geochemical characteristics including occurrence of ultramafic rocks, inter-bedded basaltic layers and iron-copper deposits within thick sedimentary basin and igneous activities at an active continental margin during the Permian-Paleogene. The native hydrogen is expected to be clean and renewable energy source in the near future. Therefore it is clear that the origin and exploration of the native hydrogen, not yet been revealed by an integrated studies of rock-fluid interaction studies, are a field of special interest, regardless of the presence of economic native hydrogen reservoirs in Korea.

Effects of Adsorption and Decomposition on the Removal of Total Organic Carbon (TOC) in Oil Wastewater by Cellulose-based Pseudo Graphene and Persulfate (셀룰로오스 기반 유사-그래핀과 과황산염에 의한 압연류 폐수내 총유기탄소(TOC) 흡착 및 분해효과 연구)

  • Song-I Kim;Ji-Young Shin;Kyung-Chul Park;Jae-Kyu Yang;Dong-Su Kim
    • Journal of the Korea Organic Resources Recycling Association
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    • v.32 no.3
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    • pp.5-18
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    • 2024
  • Chemical oxygen demand (COD), an organic material measurement index, has a limit to the management of the total amount of all organic materials including non-degradable organic materials due to low oxidation rate. So total organic carbon (TOC) that can measure organic materials more accurately is introduced and used as a measurement index. Several environmental companies including company A in Gyeonggi-do dilute raw wastewater first and then treats it with chemicals. And an activated carbon is used at the rear stage to treat total organic carbon even though various treatment processes can be applied to reduce TOC in wastewater. There are some problems such as use of a lot of diluting water and generation of an excessive amount of sludge, so it is urgent to come up with an alternative plan. Therefore, in this study, an application experiment was conducted on two different methods for improving the TOC reduction efficiency of waste water from Company A. The first method is the evaluation of the substitution potential of powered activated carbon(PAC), an adsorbent currently used, by manufacturing cellulose-based graphene like carbon (CGLC). This first study showed that CGLC had about 10% higher TOC adsorption efficiency than commercial PAC, showing the possibility of being applied as an alternative adsorbent for PAC in water treatment sites. The second method relates to the removal of TOC by sulfate radials produced by persulfate (PS) activation. Two activation methods were applied: using CGLC and PAC as carbon-based catalyst and using the high temperature of wastewater for PS activation. As a result of using PAC and CGLC as PS activation materials, the TOC removal rate was lower than the adsorption amount of TOC by CGLC and PAC due to excessive chlorine ions present in the real wastewater. However, as a result of using the high water temperature (55~60℃) of the field wastewater for PS activation, it showed a much greater TOC removal efficiency than PAC alone, CGLC alone, and using a carbon-based catalyst for PS activation. When PS was injected more than 0.5%, it showed a TOC removal efficiency of 95% or more within 24 hr. In addition, when PS was injected more than 0.3%, the TOC concentration could be lowered to less than 75 ppm, which is the wastewater discharge standard applied to company A. When these results were summarized, raw wastewater of high temperature can be treated with a simple process of only adding of PS and discharged by treating TOC below the wastewater discharge standard applied to company A.

Field Studios of In-situ Aerobic Cometabolism of Chlorinated Aliphatic Hydrocarbons

  • Semprini, Lewts
    • Proceedings of the Korean Society of Soil and Groundwater Environment Conference
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    • 2004.04a
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    • pp.3-4
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    • 2004
  • Results will be presented from two field studies that evaluated the in-situ treatment of chlorinated aliphatic hydrocarbons (CAHs) using aerobic cometabolism. In the first study, a cometabolic air sparging (CAS) demonstration was conducted at McClellan Air Force Base (AFB), California, to treat chlorinated aliphatic hydrocarbons (CAHs) in groundwater using propane as the cometabolic substrate. A propane-biostimulated zone was sparged with a propane/air mixture and a control zone was sparged with air alone. Propane-utilizers were effectively stimulated in the saturated zone with repeated intermediate sparging of propane and air. Propane delivery, however, was not uniform, with propane mainly observed in down-gradient observation wells. Trichloroethene (TCE), cis-1, 2-dichloroethene (c-DCE), and dissolved oxygen (DO) concentration levels decreased in proportion with propane usage, with c-DCE decreasing more rapidly than TCE. The more rapid removal of c-DCE indicated biotransformation and not just physical removal by stripping. Propane utilization rates and rates of CAH removal slowed after three to four months of repeated propane additions, which coincided with tile depletion of nitrogen (as nitrate). Ammonia was then added to the propane/air mixture as a nitrogen source. After a six-month period between propane additions, rapid propane-utilization was observed. Nitrate was present due to groundwater flow into the treatment zone and/or by the oxidation of tile previously injected ammonia. In the propane-stimulated zone, c-DCE concentrations decreased below tile detection limit (1 $\mu$g/L), and TCE concentrations ranged from less than 5 $\mu$g/L to 30 $\mu$g/L, representing removals of 90 to 97%. In the air sparged control zone, TCE was removed at only two monitoring locations nearest the sparge-well, to concentrations of 15 $\mu$g/L and 60 $\mu$g/L. The responses indicate that stripping as well as biological treatment were responsible for the removal of contaminants in the biostimulated zone, with biostimulation enhancing removals to lower contaminant levels. As part of that study bacterial population shifts that occurred in the groundwater during CAS and air sparging control were evaluated by length heterogeneity polymerase chain reaction (LH-PCR) fragment analysis. The results showed that an organism(5) that had a fragment size of 385 base pairs (385 bp) was positively correlated with propane removal rates. The 385 bp fragment consisted of up to 83% of the total fragments in the analysis when propane removal rates peaked. A 16S rRNA clone library made from the bacteria sampled in propane sparged groundwater included clones of a TM7 division bacterium that had a 385bp LH-PCR fragment; no other bacterial species with this fragment size were detected. Both propane removal rates and the 385bp LH-PCR fragment decreased as nitrate levels in the groundwater decreased. In the second study the potential for bioaugmentation of a butane culture was evaluated in a series of field tests conducted at the Moffett Field Air Station in California. A butane-utilizing mixed culture that was effective in transforming 1, 1-dichloroethene (1, 1-DCE), 1, 1, 1-trichloroethane (1, 1, 1-TCA), and 1, 1-dichloroethane (1, 1-DCA) was added to the saturated zone at the test site. This mixture of contaminants was evaluated since they are often present as together as the result of 1, 1, 1-TCA contamination and the abiotic and biotic transformation of 1, 1, 1-TCA to 1, 1-DCE and 1, 1-DCA. Model simulations were performed prior to the initiation of the field study. The simulations were performed with a transport code that included processes for in-situ cometabolism, including microbial growth and decay, substrate and oxygen utilization, and the cometabolism of dual contaminants (1, 1-DCE and 1, 1, 1-TCA). Based on the results of detailed kinetic studies with the culture, cometabolic transformation kinetics were incorporated that butane mixed-inhibition on 1, 1-DCE and 1, 1, 1-TCA transformation, and competitive inhibition of 1, 1-DCE and 1, 1, 1-TCA on butane utilization. A transformation capacity term was also included in the model formation that results in cell loss due to contaminant transformation. Parameters for the model simulations were determined independently in kinetic studies with the butane-utilizing culture and through batch microcosm tests with groundwater and aquifer solids from the field test zone with the butane-utilizing culture added. In microcosm tests, the model simulated well the repetitive utilization of butane and cometabolism of 1.1, 1-TCA and 1, 1-DCE, as well as the transformation of 1, 1-DCE as it was repeatedly transformed at increased aqueous concentrations. Model simulations were then performed under the transport conditions of the field test to explore the effects of the bioaugmentation dose and the response of the system to tile biostimulation with alternating pulses of dissolved butane and oxygen in the presence of 1, 1-DCE (50 $\mu$g/L) and 1, 1, 1-TCA (250 $\mu$g/L). A uniform aquifer bioaugmentation dose of 0.5 mg/L of cells resulted in complete utilization of the butane 2-meters downgradient of the injection well within 200-hrs of bioaugmentation and butane addition. 1, 1-DCE was much more rapidly transformed than 1, 1, 1-TCA, and efficient 1, 1, 1-TCA removal occurred only after 1, 1-DCE and butane were decreased in concentration. The simulations demonstrated the strong inhibition of both 1, 1-DCE and butane on 1, 1, 1-TCA transformation, and the more rapid 1, 1-DCE transformation kinetics. Results of tile field demonstration indicated that bioaugmentation was successfully implemented; however it was difficult to maintain effective treatment for long periods of time (50 days or more). The demonstration showed that the bioaugmented experimental leg effectively transformed 1, 1-DCE and 1, 1-DCA, and was somewhat effective in transforming 1, 1, 1-TCA. The indigenous experimental leg treated in the same way as the bioaugmented leg was much less effective in treating the contaminant mixture. The best operating performance was achieved in the bioaugmented leg with about over 90%, 80%, 60 % removal for 1, 1-DCE, 1, 1-DCA, and 1, 1, 1-TCA, respectively. Molecular methods were used to track and enumerate the bioaugmented culture in the test zone. Real Time PCR analysis was used to on enumerate the bioaugmented culture. The results show higher numbers of the bioaugmented microorganisms were present in the treatment zone groundwater when the contaminants were being effective transformed. A decrease in these numbers was associated with a reduction in treatment performance. The results of the field tests indicated that although bioaugmentation can be successfully implemented, competition for the growth substrate (butane) by the indigenous microorganisms likely lead to the decrease in long-term performance.

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Sesquiterpenoids Bioconversion Analysis by Wood Rot Fungi

  • Lee, Su-Yeon;Ryu, Sun-Hwa;Choi, In-Gyu;Kim, Myungkil
    • 한국균학회소식:학술대회논문집
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    • 2016.05a
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    • pp.19-20
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    • 2016
  • Sesquiterpenoids are defined as $C_{15}$ compounds derived from farnesyl pyrophosphate (FPP), and their complex structures are found in the tissue of many diverse plants (Degenhardt et al. 2009). FPP's long chain length and additional double bond enables its conversion to a huge range of mono-, di-, and tri-cyclic structures. A number of cyclic sesquiterpenes with alcohol, aldehyde, and ketone derivatives have key biological and medicinal properties (Fraga 1999). Fungi, such as the wood-rotting Polyporus brumalis, are excellent sources of pharmaceutically interesting natural products such as sesquiterpenoids. In this study, we investigated the biosynthesis of P. brumalis sesquiterpenoids on modified medium. Fungal suspensions of 11 white rot species were inoculated in modified medium containing $C_6H_{12}O_6$, $C_4H_{12}N_2O_6$, $KH_2PO_4$, $MgSO_4$, and $CaCl_2$ for 20 days. Cultivation was stopped by solvent extraction via separation of the mycelium. The metabolites were identified as follows: propionic acid (1), mevalonic acid lactone (2), ${\beta}$-eudesmane (3), and ${\beta}$-eudesmol (4), respectively (Figure 1). The main peaks of ${\beta}$-eudesmane and ${\beta}$-eudesmol, which were indicative of sesquiterpene structures, were consistently detected for 5, 7, 12, and 15 days These results demonstrated the existence of terpene metabolism in the mycelium of P. brumalis. Polyporus spp. are known to generate flavor components such as methyl 2,4-dihydroxy-3,6-dimethyl benzoate; 2-hydroxy-4-methoxy-6-methyl benzoic acid; 3-hydroxy-5-methyl phenol; and 3-methoxy-2,5-dimethyl phenol in submerged cultures (Hoffmann and Esser 1978). Drimanes of sesquiterpenes were reported as metabolites from P. arcularius and shown to exhibit antimicrobial activity against Gram-positive bacteria such as Staphylococcus aureus (Fleck et al. 1996). The main metabolites of P. brumalis, ${\beta}$-Eudesmol and ${\beta}$-eudesmane, were categorized as eudesmane-type sesquiterpene structures. The eudesmane skeleton could be biosynthesized from FPP-derived IPP, and approximately 1,000 structures have been identified in plants as essential oils. The biosynthesis of eudesmol from P. brumalis may thus be an important tool for the production of useful natural compounds as presumed from its identified potent bioactivity in plants. Essential oils comprising eudesmane-type sesquiterpenoids have been previously and extensively researched (Wu et al. 2006). ${\beta}$-Eudesmol is a well-known and important eudesmane alcohol with an anticholinergic effect in the vascular endothelium (Tsuneki et al. 2005). Additionally, recent studies demonstrated that ${\beta}$-eudesmol acts as a channel blocker for nicotinic acetylcholine receptors at the neuromuscular junction, and it can inhibit angiogenesis in vitro and in vivo by blocking the mitogen-activated protein kinase (MAPK) signaling pathway (Seo et al. 2011). Variation of nutrients was conducted to determine an optimum condition for the biosynthesis of sesquiterpenes by P. brumalis. Genes encoding terpene synthases, which are crucial to the terpene synthesis pathway, generally respond to environmental factors such as pH, temperature, and available nutrients (Hoffmeister and Keller 2007, Yu and Keller 2005). Calvo et al. described the effect of major nutrients, carbon and nitrogen, on the synthesis of secondary metabolites (Calvo et al. 2002). P. brumalis did not prefer to synthesize sesquiterpenes under all growth conditions. Results of differences in metabolites observed in P. brumalis grown in PDB and modified medium highlighted the potential effect inorganic sources such as $C_4H_{12}N_2O_6$, $KH_2PO_4$, $MgSO_4$, and $CaCl_2$ on sesquiterpene synthesis. ${\beta}$-eudesmol was apparent during cultivation except for when P. brumalis was grown on $MgSO_4$-free medium. These results demonstrated that $MgSO_4$ can specifically control the biosynthesis of ${\beta}$-eudesmol. Magnesium has been reported as a cofactor that binds to sesquiterpene synthase (Agger et al. 2008). Specifically, the $Mg^{2+}$ ions bind to two conserved metal-binding motifs. These metal ions complex to the substrate pyrophosphate, thereby promoting the ionization of the leaving groups of FPP and resulting in the generation of a highly reactive allylic cation. Effect of magnesium source on the sesquiterpene biosynthesis was also identified via analysis of the concentration of total carbohydrates. Our current study offered further insight that fungal sesquiterpene biosynthesis can be controlled by nutrients. To profile the metabolites of P. brumalis, the cultures were extracted based on the growth curve. Despite metabolites produced during mycelia growth, there was difficulty in detecting significant changes in metabolite production, especially those at low concentrations. These compounds may be of interest in understanding their synthetic mechanisms in P. brumalis. The synthesis of terpene compounds began during the growth phase at day 9. Sesquiterpene synthesis occurred after growth was complete. At day 9, drimenol, farnesol, and mevalonic lactone (or mevalonic acid lactone) were identified. Mevalonic acid lactone is the precursor of the mevalonic pathway, and particularly, it is a precursor for a number of biologically important lipids, including cholesterol hormones (Buckley et al. 2002). Farnesol is the precursor of sesquiterpenoids. Drimenol compounds, bi-cyclic-sesquiterpene alcohols, can be synthesized from trans-trans farnesol via cyclization and rearrangement (Polovinka et al. 1994). They have also been identified in the basidiomycota Lentinus lepideus as secondary metabolites. After 12 days in the growth phase, ${\beta}$-elemene caryophyllene, ${\delta}$-cadiene, and eudesmane were detected with ${\beta}$-eudesmol. The data showed the synthesis of sesquiterpene hydrocarbons with bi-cyclic structures. These compounds can be synthesized from FPP by cyclization. Cyclic terpenoids are synthesized through the formation of a carbon skeleton from linear precursors by terpene cyclase, which is followed by chemical modification by oxidation, reduction, methylation, etc. Sesquiterpene cyclase is a key branch-point enzyme that catalyzes the complex intermolecular cyclization of the linear prenyl diphosphate into cyclic hydrocarbons (Toyomasu et al. 2007). After 20 days in stationary phase, the oxygenated structures eudesmol, elemol, and caryophyllene oxide were detected. Thus, after growth, sesquiterpenes were identified. Per these results, we showed that terpene metabolism in wood-rotting fungi occurs in the stationary phase. We also showed that such metabolism can be controlled by magnesium supplementation in the growth medium. In conclusion, we identified P. brumalis as a wood-rotting fungus that can produce sesquiterpenes. To mechanistically understand eudesmane-type sesquiterpene biosynthesis in P. brumalis, further research into the genes regulating the dynamics of such biosynthesis is warranted.

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