This paper documents that the principal mode of Pan-Asian monsoon summer precipitation experienced a prominent interdecadal shift around 1992/1993 in terms of spatial pattern and major driving factors. During 1979-19...This paper documents that the principal mode of Pan-Asian monsoon summer precipitation experienced a prominent interdecadal shift around 1992/1993 in terms of spatial pattern and major driving factors. During 1979-1992 （Period 1, P1）, Pan-Asian monsoon summer precipitation anomalies mainly display a meridional dipole pattern from north to south, whereas in the period 1993-2016 （Period 2, P2）, it shows a meridional tripole pattern instead. The summer precipitation in P1 is primarily associated with a combination of the developing phase （central-eastern Pacific type） and decaying phase （eastern Pacific type） of El Nino-Southem Oscillation （ENSO）; while in P2, it is mainly associated with the decaying phase of central-eastern-Pacific-type ENSO.展开更多
Dissociation of methyl nitrite is the first step during CO catalytic coupling to dimethyl oxalate followed by hydrogenation to ethyl glycol in a typical coal to liquid process. In this work, the first-principle calcul...Dissociation of methyl nitrite is the first step during CO catalytic coupling to dimethyl oxalate followed by hydrogenation to ethyl glycol in a typical coal to liquid process. In this work, the first-principle calculations based on density functional theory were performed to explore the reaction mechanism for the non-catalytic dissociation of methyl nitrite in the gas phase and the catalytic dissociation of methyl nitrite on Pd(111) surface since palladium supported on alpha-alumina is the most effective catalyst for the coupling. For the non-catalytic case, the calculated results show that the CH_3O–NO bond will break with a bond energy of 1.91 eV, and the produced CH_3O radicals easily decompose to formaldehyde, while the further dissociation of formaldehyde in the gas phase is difficult due to the strong C–H bond. On the other hand, the catalytic dissociation of methyl nitrite on Pd(111) to the adsorbed CH_3O and NO takes place with a small energy barrier of 0.03 eV. The calculated activation energies along the proposed reaction pathways indicate that(i) at low coverage, a successive dehydrogenation of the adsorbed CH_3O to CO and H is favored while(ii) at high coverage, hydrogenation of CH_3O to methanol and carbonylation of CH_3O to methyl formate are more preferred. On the basis of the proposed reaction mechanism,two meaningful ways are proposed to suppress the dissociation of methyl nitrate during the CO catalytic coupling to dimethyl oxalate.展开更多
The distribution of iron monosulfide (quantified as acid volatile sulfur: SAV) was compared with geo- chemical properties that are known to affect its formation and accumulation in three coastal Holocene acid sulfate ...The distribution of iron monosulfide (quantified as acid volatile sulfur: SAV) was compared with geo- chemical properties that are known to affect its formation and accumulation in three coastal Holocene acid sulfate soils (ASS) at Tuckean Swamp, McLeods Creek and Bungawalbyn Swamp respectively. These properties included PH, reactive iron (FeR), pore-water sulfate (SO:42-) and organic carbon (OC). Iron monosulfide was concentrated at the oxic/anoxic boundary. The Tuckean Swamp and McLeods Creek sites are Holocene sediments, whereas the Bungawalbyn Swamp is a Holocene peat. The concentration of SAV averaged 0.2 g kg-l in a 0.5 m thick soil layer at the Tuckean Swamp, but was an order of magnitude lower in the oxic/anoxic transition layers at McLeods Creek and Bungawalbyn Swamp. The SAV mineral greigite (Fe3S4) was identified in the Tuckean Swamp by X-ray diffraction and scanning electron microscopy with quantitative energy dispersive X-ray analysis (SEM-EDX). Very small concentrations of greigite were also observed in the McLeods Creek, based on crystal morphology and elemental composition. The concentration of SAV was a small fraction of the total reduced sulfur, representing at most 3% of the Pyrite sulfur. However, the presence of this highly reactive sulfide mineral, distributed within pores where oxygen diffusion is most rapid, has important implications to the potential rate of acid production from these sediments.展开更多
基金supported by the National Natural Science Foundation of China[grant number 41505070]the Development Program of China[grant number 2016YFA0600703]the Chinese Academy of Sciences-Peking University Joint Research Program
文摘This paper documents that the principal mode of Pan-Asian monsoon summer precipitation experienced a prominent interdecadal shift around 1992/1993 in terms of spatial pattern and major driving factors. During 1979-1992 （Period 1, P1）, Pan-Asian monsoon summer precipitation anomalies mainly display a meridional dipole pattern from north to south, whereas in the period 1993-2016 （Period 2, P2）, it shows a meridional tripole pattern instead. The summer precipitation in P1 is primarily associated with a combination of the developing phase （central-eastern Pacific type） and decaying phase （eastern Pacific type） of El Nino-Southem Oscillation （ENSO）; while in P2, it is mainly associated with the decaying phase of central-eastern-Pacific-type ENSO.
基金Supported by the National Natural Science Foundation of China(21303102)China Postdoctoral Science Foundation funded project(2012M520900 and 2013T60449)
文摘Dissociation of methyl nitrite is the first step during CO catalytic coupling to dimethyl oxalate followed by hydrogenation to ethyl glycol in a typical coal to liquid process. In this work, the first-principle calculations based on density functional theory were performed to explore the reaction mechanism for the non-catalytic dissociation of methyl nitrite in the gas phase and the catalytic dissociation of methyl nitrite on Pd(111) surface since palladium supported on alpha-alumina is the most effective catalyst for the coupling. For the non-catalytic case, the calculated results show that the CH_3O–NO bond will break with a bond energy of 1.91 eV, and the produced CH_3O radicals easily decompose to formaldehyde, while the further dissociation of formaldehyde in the gas phase is difficult due to the strong C–H bond. On the other hand, the catalytic dissociation of methyl nitrite on Pd(111) to the adsorbed CH_3O and NO takes place with a small energy barrier of 0.03 eV. The calculated activation energies along the proposed reaction pathways indicate that(i) at low coverage, a successive dehydrogenation of the adsorbed CH_3O to CO and H is favored while(ii) at high coverage, hydrogenation of CH_3O to methanol and carbonylation of CH_3O to methyl formate are more preferred. On the basis of the proposed reaction mechanism,two meaningful ways are proposed to suppress the dissociation of methyl nitrate during the CO catalytic coupling to dimethyl oxalate.
基金Project (No. 41004) supported by the Cooperative Research Center for Sustainable Tourism, Australia.
文摘The distribution of iron monosulfide (quantified as acid volatile sulfur: SAV) was compared with geo- chemical properties that are known to affect its formation and accumulation in three coastal Holocene acid sulfate soils (ASS) at Tuckean Swamp, McLeods Creek and Bungawalbyn Swamp respectively. These properties included PH, reactive iron (FeR), pore-water sulfate (SO:42-) and organic carbon (OC). Iron monosulfide was concentrated at the oxic/anoxic boundary. The Tuckean Swamp and McLeods Creek sites are Holocene sediments, whereas the Bungawalbyn Swamp is a Holocene peat. The concentration of SAV averaged 0.2 g kg-l in a 0.5 m thick soil layer at the Tuckean Swamp, but was an order of magnitude lower in the oxic/anoxic transition layers at McLeods Creek and Bungawalbyn Swamp. The SAV mineral greigite (Fe3S4) was identified in the Tuckean Swamp by X-ray diffraction and scanning electron microscopy with quantitative energy dispersive X-ray analysis (SEM-EDX). Very small concentrations of greigite were also observed in the McLeods Creek, based on crystal morphology and elemental composition. The concentration of SAV was a small fraction of the total reduced sulfur, representing at most 3% of the Pyrite sulfur. However, the presence of this highly reactive sulfide mineral, distributed within pores where oxygen diffusion is most rapid, has important implications to the potential rate of acid production from these sediments.
