• 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.

• Economic and Environmental Geology
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• v.19 no.spc
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• pp.19-41
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• 1986

Structural, radioactive, petrological, petrochemical, mineralogical and stable isotopic study as well as the review of previous studies of the uranium-bearing slates in the Ogcheon sequence were carried out to examine the lithological and structural controls, and geochemical environment in the uranium deposition in the sequence. And the study was extended to the coal-bearing formation (Jangseong Series-Permian) to compare the geochemical and sedimentologic aspects of uranium chemistry between Ogcheon and Hambaegsan areas. The results obtained are as follows: 1. The uranium mineralization occurs in the carbonaceous black slates of the middle to lower Guryongsan formation and its equivalents in the Ogcheon sequence. In general, two or three uranium-bearing carbonaceous beds are found with about 1 to 1.5km stratigraphic interval and they extend from Chungju to Jinsan for 90km in distance, with intermittent igneous intrusions and structural Jisturbances. Average thickness of the beds ranges from 20 to 1,500m. 2. These carbonaceous slate beds were folded by a strong $F_1$-fold and were refolded by subsequent $F_1$-fold, nearly co-axial with the $F_1$, resulting in a repeated occurrence of similar slate. The carbonaceous beds were swelled in hing zones and were shrinked or thined out in limb by the these foldings. Minor faulting and brecciation of the carbonaceous beds were followed causing metamorphism of these beds and secondary migration and alteration of uranium minerals and their close associations. 3. Uranium-rich zones with high radioactive anomalies are found in Chungju, Deogpyong-Yongyuri, MiwonBoun, Daejeon-Geumsan areas in the range of 500~3,700 cps (corresponds to 0.017~0.087%U). These zones continue along strike of the beds for several tens to a few hundred meters but also discontinue with swelling and pinches at places that should be analogously developed toward underground in their vertical extentions. The drilling surveyings in those area, more than 120 holes, indicate that the depth-frequency to uranium rich bed ranging 40~160 meter is greater. 4. The features that higher radioactive anomalies occur particularly from the carbonaceous beds among the argillaceous lithologic units, are well demonstrated on the cross sections of the lithology and radioactive values of the major uranium deposits in the Ogcheon zone. However, one anomalous radioactive zone is found in a l:ornfels bed in Samgoe, near Daejeon city. This is interpreted as a thermal metamorphic effect by which original uranium contents in the underlying black slate were migrated into the hornfels bed. 5. Principal minerals of the uranium-bearing black slates are quartz, sericite, biotite and chlorite, and as to chemical composition of the black slates, $Al_2O_3$ contents appear to be much lower than the average values by its clarke suggesting that the Changri basin has rather proximal to its source area. 6. The uranium-bearing carbonaceous beds contain minor amounts of phosphorite minerals, pyrite, pyrrhotite and other sulfides but not contain iron oxides. Vanadium. Molybdenum, Barium, Nickel, Zirconium, Lead, Cromium and fixed Carbon, and some other heavy metals appear to be positive by correlative with uranium in their concentrations, suggesting a possibility of their genetic relationships. The estimated pH and Eh of the slate suggests an euxenic marine to organic-rich saline water environment during uranium was deposited in the middle part of Ogcheon zone. 7. The Carboniferous shale of Jangseong Series(Sadong Series) of Permian in Hambaegsan area having low radioactivity and in fluvial to beach deposits is entirely different in geochemical property and depositional environment from the middle part of Ogcheon zone, so-called "Pibanryong-Type Ogcheon Zone". 8. Synthesizing various data obtained by several aspects of research on uranium mineralization in the studied sequence, it is concluded that the processes of uranium deposition were incorporated with rich organic precipitation by which soluble uranyl ions, $U{_2}^{+{+}}$ were organochemically complexed and carried down to the pre-Ogcheon sea bottoms formed in transitional environment, from Red Sea type basin to Black Sea type basin. Decomposition of the organic matter under reducing conditions to hydrogen sulfide, which reduced the $UO{_2}^{+2}$ ions to the insoluble uranium dioxide($UO_2$), on the other side the heavy metals are precipitated as sulfides. 9. The EPMA study on the identification of uraninite and others and the genetic interpretation of uranium bearing slates by isotopic values of this work are given separately by Yun, S. in 1984.

• Applied Chemistry for Engineering
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• v.21 no.1
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• pp.52-57
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• 2010

Although chemical sedimentation and ion exchange are usually applied to the treatment of heavy metal ions and radioactive cations, they have some serious disadvantages like a great consumption of chemicals, the disposal of valuable metals, and the secondary pollution of soil by the solid-waste. The advanced countries recently have studied the electrochemical ion exchange, combined electrochemical reduction and ion exchange, for the development of the alternative technique. This study has been performed to investigate the optimum condition for the preparation of the nickel hexacyanoferrate (NiHCNFe) which is an electrochemical ion exchanger. NiHCNFe film was deposited on the surface of nickel plate by chemical method or electrochemical method. The morphology and composition of NiHCNFe were observed by SEM and EDS, respectively. The peak current density of NiHCNFe was measured from the cyclic voltammograms of the continuous oxidation-reduction reaction in a parallel plane ion exchange electrode reactor. It was found that the chemical preparation method was better than the electrochemical method. The concentrated NiHCNFe was apparently deposited on nickel plate when dipping in the preparing solution for 118 h, especially. It also had a best durable performance as an ion exchange electrode.

• Journal of the Korea Academia-Industrial cooperation Society
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• v.13 no.11
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• pp.5601-5609
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• 2012

The fine particulate matter($PM_{10}$) concentrations and contents were measured to check the health and environment influential factors in Pohang Iron and Steel Industrial Complex and its vicinities. In addition, the $PM_{10}$ distribution for each year and season was surveyed using the regional air quality monitoring stations. The measuring on the $PM_{10}$ inside the industrial complex showed $61.3{\pm}12.1{\mu}g/m^3$ for average concentration of $PM_{10}$ which was measured by Dongil Industry and $44.3{\pm}8.1{\mu}g/m^3$ measured by steel manufacturing industry complex management office. Both of them satisfied the environmental air quality standard. The percentage of $SO_4{^2}$, $NO_3{^-}$, $NH_4{^+}$ which are the secondary ions created out of the $PM_{10}$ in Dongil Industry and steel manufacturing industry complex management office was checked and it was revealed that the percentage of ${SO_4}^{2-}$ was high and it is considered that the pollution source related with the sulfides exist at the industrial complex. They were in order of ${SO_4}^{2-}$ > $Cl^-$ > $NO_3{^-}$ > $F^-$ > $NH_4{^+}$ in Dongil Industry and ${SO_4}^{2-}$ > $Cl^-$ > $NO_3{^-}$ > $NH_4{^+}$ > $F^-$ in steel manufacturing industry complex management office.

• Applied Chemistry for Engineering
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• v.31 no.1
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• pp.97-102
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• 2020

Recently, various degradation mechanisms of lithium secondary battery cathode materials have been revealed. As a result, many studies on overcoming the limitation of cathode materials and realizing new electrochemical properties by controlling the degradation mechanism have been reported. Li-rich layered oxide is one of the most promising cathode materials due to its high reversible capacity. However, the utilization of Li-rich layered oxide has been restricted, because it undergoes a unique atomic structure change during the cycle, in turn resulting in unwanted electrochemical degradations. To understand an atomic structure deterioration mechanism and suggest a research direction of Li-rich layered oxide, we deeply evaluated the atomic structure of 0.4Li₂MnO₃_0.6LiNi_1/3Co_1/3Mn_1/3O₂ Li-rich layered oxide during electrochemical cycles, by using an atomic-resolution analysis tool. During a charge process, Li-rich materials undergo a cation migration of transition metal ions from transition metal slab to lithium slab due to the structural instability from lithium vacancies. As a result, the partial structural degradation leads to discharge voltage drop, which is the biggest drawback of Li-rich materials.

• Journal of the Korean Magnetics Society
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• v.20 no.4
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• pp.134-142
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• 2010

Barium ferrite ($BaFe_{12}O_{19}$) powders were synthesized by the co-precipitation method. $Fe^{3+}:Ba^{2+}$ mole ratio was fixed 8 and relative amount of $Fe^{3+}$ and $Ba^{2+}$ was controlled. The effects of the pH (= 8, 9, 10), calcination temperature and time on the morphology, structure and magnetic properties of the barium ferrite particles are characterized using XRD, FESEM, and VSM respectively. Coercivity and magnetization value of powders were changed with calcination temperature and time, relative amount of $Fe^{3+}$ and $Ba^{2+}$ and pH. Single-phase barium ferrite was obtained when pH value was 9 in the investigated range of $Fe^{3+}:Ba^{2+}$ relative amount and secondary phases were appeared at $Fe^{3+}:Ba^{2+}$ relative amount of 14.4 : 1.8. The largest value of magnetization (65.7 emu/g) was obtained when $Fe^{3+}:Ba^{2+}$ mole ratio was 12.8 : 1.6 and calcination temperature was $900^{\circ}C$ with air calcination atmosphere. The largest value of coercivity (5280 Oe) was obtained with $O_2$ calcination atmosphere.

• The Journal of Engineering Geology
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• v.12 no.1
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• pp.95-109
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• 2002

A significant question is what role does newly-formed expansive mineral growth play in the premature deterioration of concrete. These minerals formed in cement paste as a result of chemical reactions involving cement paste and coarse/fine aggregate. Petrographic observations and SEM/EDAX analysis were conducted in order to determine chemical and mineralogical changes in the aggregate and cement paste of samples taken from lowa concrete highways that showed premature deterioration. Formation and expansive mechanisms involved in deterioration were Investigated. Brucite, Mg(OH)$_2$, is potentially expansive mineral that farms in cement paste of concretes containing reactive dolomite aggregate as a result of partial dedolomitization of the aggregate. No cracking was observed to be spatially associated with brucite, but most brucite was microscopic in size and widely disseminated in the cement paste of less durable concretes. Expansion stresses associated with its growth at innumerable microlocations may be retrieved by cracking at weaker locations in the concrete. Ettringite, 3CaO.Al$_2$O$_3$.3CaSO$_4$.32$H_2O$, completely fills many small voids and occurs as rims lining the margin of larger voids. Microscopic ettringite is common disseminated throughout the paste in many samples. Severe cracking of cement paste causing premature deterioration is often closely associated with ettringite locations, and strongly suggests that ettringite contributed to deterioration. Pyrite, FeS2, is commonly present in coarse/fine aggregates, and its oxidation products is observed in many concrete samples. Pyrite oxidation provides sulfate ions for ettringite formation.

• Atmosphere
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• v.29 no.4
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• pp.403-416
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• 2019

Precipitation samples were collected at the GAW Stations in Anmyeon-do and Gosan for 10 years (2008-2017) to analyze pH, electrical conductivity and NH₄⁺, Na⁺, K⁺, Mg²⁺, Ca²⁺, SO₄^2-, NO₃^-, Cl^-, and F^- ions. From the analysis, the correlation between pH and rainfall, the composition of precipitation and comparison with other regions, and the results of neutralization characteristics by seasonal and pH were determined. In the comparison of ion balance and conductivity for the validation of analytical data, the correlation coefficients were within the range of 0.996~0.999, implying good linear relationship. The volume-weighted pH of the Anmyeon-do and Gosan areas were 4.7 and 4.9, respectively. The pH of the rainfall was affected by washout and rainout in both areas. The ionic strength of precipitation at Anmyeondo and Gosan were 0.42 ± 0.63 mM and 0.37 ± 0.75 mM, indicating about 27.6% and 35.3% of the total precipitation as per a pure precipitation criterion (10^-4 M), respectively. The composition ratio of ionic species were 44.7% and 57.5% for marine sources (Na⁺, Mg²⁺, Cl^-), 40.6% and 22.2% for the secondary inorganic components (NH₄⁺, nss-SO₄^2-, NO₃^-), and 5.6% and 4.0% for the soil source (nss-Ca²⁺), respectively. The neutralization factor of Anmyeon-do and Gosan were 0.43~0.65 and 0.34~0.48, and the neutralization factors of calcium carbonate were 0.15~0.34 and 0.25~0.30, respectively. Thus, both regions have the highest rate of neutralization caused by ammonia. As pH increased in Anmyeon-do and Gosan, change in calcium carbonate became greater than that in ammonia.

• Journal of Korean Society for Atmospheric Environment
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• v.34 no.3
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• pp.393-405
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• 2018

Volatile organic compounds (VOCs) are representative air pollutants due to their detrimental effects on human health and their role in formation of secondary organic aerosols. Assessments and monitoring programs of VOCs using periodic grab sampling like Tedlar bags, canisters, and sorbent traps provide limited information, often with delay times of days or weeks. Selected ion flow tube mass spectrometry (SIFT-MS) is an emerging analytical technique for the real-time quantification of VOCs in air. It relies on chemical ionization of the VOCs molecules in air introduced into helium carrier gas using $H_3O^+$, $NO^+$, and $O_2{^+}$ precursor ions. Real-time monitoring method of 60 VOCs in the ambient air was developed using TO-15 standard gas mixture. Calibration curves, method detection limit, and quantitation reproducibility of the target compounds were tested. Dynamic dilution system was used to dilute standard gas from 0.174 ppbv to 100 ppbv, where calibration curves showed good linearity with $r^2$> 0.95 in all target analytes. Limit of detection (LOD) all compounds were sub ppbv, and some halogenated compounds showed pptv levels. Seven consecutive analyses of target compounds showed good repeatability with relative standard deviation of less than 10%. One day monitoring of VOCs in ambient air was conducted in Geoje. Average concentration of target VOCs in Geoje were relatively lower than other regions, among which formaldehyde showed the highest concentration ($15.4{\pm}5.78ppbv$). SIFT-MS provided good temporal resolution data (1 data per 3.2 minute), which can be used for identifying ephemeral short-term event. It is expected that SIFT-MS will be a versatile monitoring platform for VOCs in ambient air.

• Journal of Korean Society for Atmospheric Environment
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• v.29 no.1
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• pp.74-85
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• 2013

Since the underground transportation system is a closed environment, indoor air quality problems may seriously affect many passengers' health. The purpose of this study was to understand $PM_{10}$ characteristics in the underground air environment and further to quantitatively estimate $PM_{10}$ source contributions in a Seoul Metropolitan subway station. The $PM_{10}$ was intensively collected on various filters with $PM_{10}$ aerosol samplers to obtain sufficient samples for its chemical analysis. Sampling was carried out in the M station on the Line-4 from April 21 to 28, July 13 to 21, and October 11 to 19 in the year of 2010 and January 11 to 17 in the year of 2011. The aerosol filter samples were then analyzed for metals, water soluble ions, and carbon components. The 29 chemical species (OC1, OC2, OC3, OC4, CC, PC, EC, Ag, Al, Ba, Cd, Cr, Cu, Fe, Mn, Ni, Pb, Si, Ti, V, Zn, $Cl^-$, $NO_3{^-}$, $SO_4{^{2-}}$, $Na^+$, $NH_4{^+}$, $K^+$, $Mg^{2+}$, $Ca^{2+}$) were analyzed by using ICP-AES, IC, and TOR after proper pretreatments of each sample filter. Based on the chemical information, positive matrix factorization (PMF) model was applied to identify the $PM_{10}$ sources and then six sources such as biomass burning, outdoor, vehicle, soil and road dust, secondary aerosol, ferrous, and brakewear related source were classified. The contributions rate of their sources in tunnel are 4.0%, 5.8%, 1.6%, 17.9%, 13.8% and 56.9% in order.