鼎湖山主要森林土壤CO_2排放和CH_4吸收特征

研究了鼎湖山生物圈保护区马尾松林、混交林和季风常绿阔叶林(季风林)在2000~2001年期间土壤CO2排放和CH4吸收特征。季风林、混交林和马尾松林土壤CO2排放速率在研究期间的平均值分别为(kgCO2-C·hm-2·d-1):18.6±2.6,20.5±3.7和17.8±3.8,土壤CH4吸收速率则分别为(gCH4-C·hm-2·d-1):-5.5±1.8,-3.3±1.6和-7.7±1.8。土壤CO2排放速率和土壤CH4吸收速率在三种森林类型中均表现明显的季节性变化,且其季节性变化根据森林类型和年份不同而异。总的来说,土壤CO2排放速率在所有森林中均呈现夏季最高而冬季最低的变化,土壤CH4吸收速率的季节性变化则相反,基本上表现为冬季最高而夏季最低的变化。三种森林土壤的CO2排放速率和CH4吸收速率在两观测年间的差异均不显著。土壤CO2排放速率在不同森林类型间的差异也不显著,但土壤CH4吸收速率在马尾松林显著高于混交林。在两观测年中,土壤CO2排放速率与土壤CH4吸收速率之间在季风林呈现显著的负相关关系,在混交林和马尾松林中它们之间也趋向呈负相关关系,但未达显著水平。土壤CO2排放速率与土壤温度之间在季风林呈现显著的指数正相关关系,但在其余森林(混交林和马尾松林)中它们之间的关系则不明显。     

氮、磷添加对不同林型土壤磷酸酶活性的影响

研究了鼎湖山3种森林类型(南亚热带季风常绿阔叶林、马尾松人工林和针叶阔叶混交林)的土壤酸性磷酸单酯酶活性(APA)对施肥的响应情况。在3种林型中分别设置对照、加氮(150 kg N hm-2a-1)、加磷(150 kg P hm-2a-1)以及N和P同时添加(150 kg N hm-2a-1+150 kg P hm-2a-1)4种不同处理。结果表明,季风林土壤APA((15.83±2.46)μmol g-1h-1)显著高于混交林((10.71±0.78)μmol g-1h-1)和马尾松林((9.12±0.38)μmol g-1h-1),且3种林型土壤APA与土壤有效磷含量均呈显著负相关。施加N肥显著提高了季风林土壤APA,而对混交林和马尾松林的作用不显著。施加P肥显著降低了混交林和马尾松林土壤APA,但对季风林的影响不明显。N和P同时添加仅显著降低了马尾松林土壤APA,但在季风林中存在交互作用。因此,N沉降会加剧亚热带成熟林土壤P的限制,可以考虑施加P肥作为森林管理的一种方式来缓解这种限制作用。     

模拟氮沉降对鼎湖山森林土壤酸性磷酸单酯酶活性和有效磷含量的影响

采用野外原位试验模拟氮(N)沉降,研究了其对鼎湖山马尾松林、混交林和季风林3种森林类型土壤酸性磷酸单酯酶活性(APA)和有效磷(AP)含量的影响.在季风林中设置对照(0 kg N·hm-2·a-1)、低N(50 kg N·hm-2·a-1)、中N(100 kg N·hm-2·a-1)和高N(150 kg N·hm-2·a-1)处理,在马尾松林和混交林中只设置对照、低N和中N处理.结果表明:随着土层加深,土壤APA和AP含量降低.土壤APA在季风林中最高,而AP含量在3种林型中没有显著差异.N沉降增加对土壤APA的作用与林型有关.季风林中适度N沉降可使APA升高,且低N处理的APA(19.52 μmol·g-1·h-1)最高;马尾松林和混交林中,中N处理的APA最高,分别为12.74和11.02 μmol·g-1·h-1.3种林型的AP含量均在低N处理下最高,但各N处理之间的差异并不显著.土壤APA与AP含量之间呈显著正相关关系.     

南亚热带森林土壤微生物量碳对氮沉降的响应

研究了鼎湖山自然保护区3种森林生态系统土壤微生物量碳对氮沉降增加的响应.选取南亚热带代表性森林类型马尾松林、混交林和季风常绿阔叶林(季风林)建立野外模拟氮沉降试验样地.2003年7月开始每月进行氮处理.这些处理分别为对照、低氮处理、中氮处理和高氮处理,即0、50、100 kg N hm-2 a-1 和150 kg N hm-2 a-1.在2004年11月和2006年6月用氯仿熏蒸浸提法分别测定土壤微生物量碳和土壤可浸提有机碳.土壤微生物量碳和可浸提有机碳含量均表现为2006年6月高于2004年11月;季风林高于马尾松林和混交林.随着氮沉降增加季风林土壤微生物量碳减少,但可浸提有机碳含量则增加,且此趋势在高氮处理下表现明显.然而,氮沉降增加对马尾松林和混交林土壤微生物量碳和可浸提有机碳含量的影响不显著.以上结果表明,氮沉降增加可能提高季风林土壤有机碳的固持能力.     

华南丘陵区2种土地利用方式下地表CH4和N2O通量研究

采用静态箱-气相色谱法对华南丘陵区马尾松林和果园地表CH4和N2O通量及其主要影响因子进行了观测(马尾松Pinus massoniana林为期16个月,果园15个月),比较和分析了不同土地利用方式下地表CH4,和N2O通量的季节变化,地表CH4和N2O通量与温度和土壤含水量的关系以及凋落物对地表CH4和N2O通量的影响.结果表明,在有凋落物覆盖下,马尾松林和果园年均地表CH4通量分别为-3.41±0.3和-3.24±0.44 kg CH,hm-2a-1;年均地表N2O通量分别为4.57±0.50和11.99±0.67 kg N2O-N hm-2a-1;去除凋落物情况下,马尾松林和果园年均地表CH4通量分别为-2.98±0.44和-1.93±0.53 kg CH4 hm-2a-1;年均地表N2O通量分别为3.12±0.28和9.42±0.56 kg N2O-N hm-2a-1.2种土地利用方式对地表CH4影响较小,对N2O通鼍的影响较大,果园地表N2O通量显著大于马尾松林(P<0.01).马尾松林和果园土壤对CH4的吸收在旱季(10～3月)高而雨季(4～9月)低,N2O排放雨季较高而旱季较低.土壤含水量对地表CH4和N2O通量的影响比温度要大.凋落物对地表CH4通量的影响较小,对N2O通量的影响较大,凋落物对马尾松林和果园N2O排放的贡献率分别为31.71%和21.40%.研究还表明,地表N2O)通量存在明显的降雨驱动效应.     

施氮对桉树人工林生长季和非生长季土壤温室气体通量的影响

森林在调控温室气体排放方面有重要作用,随着人工林的迅速发展,其温室气体通量和对施肥的响应逐渐引起广泛关注。为了解施氮对桉树人工林生长季和非生长季土壤温室气体通量的影响,在广西东门林场尾巨桉人工林样地设置低(84.2 kg N·hm-2)、中(166.8 kg N·hm-2)、高(333.7 kg N·hm-2)3个施氮水平和不施氮对照,采用静态箱-气相色谱法监测土壤CO2、N2O和CH4通量。结果表明:(1)不同施氮处理的桉树人工林土壤CO2、CH4和N2O年均排放通量分别为214~271 mg CO2·m-2·h-1、-47~-37 kg CH4·m-2·h-1和16~203 kg N2O·m-2·h-1;土壤CO2排放通量在生长季高于非生长季,CH4和N2O通量未表现出明显季节变化。(2)施氮显著增加了土壤CO2和N2O年均排放通量,其促进效应主要集中在生长季(施氮后的4个月,即6—9月),且随时间增加,效应减弱。(3)施氮显著降低了土壤CH4年均吸收通量。因此,在维持桉树人工林生产力的基础上,结合季节变化,合理调控施氮量将有助于减少桉树林土壤温室气体排放。     

干旱年份三江平原沼泽甲烷(CH4)排放及影响因子

为了研究淡水沼泽CH4排放的影响因子及其机制,在中国东北部的三江平原样地观测了CH4排放通量以及部分影响因子.结果表明,在2003年4～10月生长季内,毛果苔草沼泽CH4通量平均值为3.30 mg·m-2·h-1(最小值为0.65 mg·m-2·h-1,最大值为13.47 mg·m-2·h-1),低于小叶章沼泽化草甸CH4通量平均值4.91 mg·m-2·h-1(最小值为-0.12 mg·m-2·h-1,最大值为16.25 mg·m-2·h-1).在不同阶段,两种类型沼泽CH4通量有明显的变化,控制因子也不一样.4月份低温限制了CH4通量,两种类型沼泽差异很小.5～7月下旬,小叶章沼泽化草甸CH4通量显著高于毛果苔草沼泽CH4通量(P＜0.01),这种差异是由融冻作用造成的.8月份,植株密度和剖面中活性有机碳的浓度成为主要的影响因子,毛果苔草沼泽CH4通量比小叶章沼泽化草甸高.     

中国南方双季稻田转菜地对CO2和CH4通量的影响

采用静态箱-气相色谱法观测了我国南方亚热带水稻田转为旱作蔬菜地后第1年的CO2和CH4通量变化,旨在探索稻田转菜地初期对CO2和CH4通量的影响.结果表明:CO2通量因蔬菜种类、生长状况及生长季节的不同而不同.种植豇豆菜地CO2通量显著高于稻田,种植辣椒菜地CO2通量则显著低于稻田.稻田转菜地CH4通量从6.96 mg C·m-2·h-1显著下降到-0.004 mg C·m-2·h-1(P<0.001).转菜地后CO2和CH4的净累积碳吸收为543kg C·hm-2,显著低于稻田的3641 kg C·hm-2,但由净CO2和CH4排放造成的增温效应无显著差异.转成菜地1年后的土壤有机碳含量有所升高,且10~20 cm土层显著高于对照水稻田.     

鼎湖山南亚热带森林细根生产力与周转

 报道了鼎湖山季风常绿阔叶林和针阔叶混交林群落0～40cm土层中细根(≤2mm和2～5mm)的现存量、死亡量、生产力和周转率,并比较了用“连续钻取土芯法”和“埋无根土柱法”来估算表层土(0～20cm)细根生产力的差异。结果表明：在0～40cm土层中,季风常绿阔叶林≤2mm和2～5mm细根现存量分别为6.59t·hm-2和4.81t·hm-2,死根比率各为29.9％和22.9％;针阔叶混交林≤2mm和2～5mm细根现存量分别为5.35t·hm-2和4.24t·hm-2,死根比率各为34.4％和24.0％。细根现存量的季节性变化不显著。季风常绿阔叶林细根年分解量、年死亡量和年净生产力分别为0.90,1.59,2.65t·hm-2·a-1 (≤2mm)和0.41,0.63,1.25t·hm-2·a-1(2～5mm),针阔叶混交林的相应数值各为0.80,1.4l,2.42t·hm-2·a-1(≤2mm)和0.37,0.62,1.21t·hm-2·a-1(2～5mm)。季风常绿阔叶林细根年周转率为0.57 (≤2mm)和0.34次·a-1(2～5mm),针阔叶混交林分别为0.69(≤2mm)和0.38次·a-1(2～5mm)。     

温带针阔混交林土壤碳氮气体通量的主控因子与耦合关系

中高纬度森林地区由于气候条件变化剧烈,土壤温室气体排放量的估算存在很大的不确定性,并且不同碳氮气体通量的主控因子与耦合关系尚不明确。以长白山温带针阔混交林为研究对象,采用静态箱-气相色谱法连续4a(2005—2009年)测定土壤二氧化碳(CO2)、甲烷(CH4)和氧化亚氮(N2O)净交换通量以及温度、水分等相关环境因子。研究结果表明:温带针阔混交林土壤整体上表现为CO2和N2O的排放源和CH4的吸收汇。土壤CH4、CO2和N2O通量的年均值分别为-1.3 kg CH4hm-2a-1、15102.2 kg CO2hm-2a-1和6.13 kg N2O hm-2a-1。土壤CO2通量呈现明显的季节性规律,主要受土壤温度的影响,水分次之;土壤CH4通量的季节变化不明显,与土壤水分显著正相关;土壤N2O通量季节变化与土壤CO2通量相似,与土壤水分、温度显著正相关。土壤CO2通量和CH4通量不存在任何类型的耦合关系,与N2O通量也不存在耦合关系;土壤CH4和N2O通量之间表现为消长型耦合关系。这项研究显示温带针阔混交林土壤碳氮气体通量主要受环境因子驱动,不同气体通量产生与消耗之间存在复杂的耦合关系,下一步研究需要深入探讨环境变化对其耦合关系的影响以及内在的生物驱动机制。     

Crystal structures of MoCl2(O)(O2)(OPMePh2)2 and mixtures of MoCl2(O2)(OPPh3)2 and MoCl2(O)(O2)(OPPh3)2: allylic alcohol isomerization studies using MoCl2(O)(O2)(OPMePh2)2

Adding one equivalent of H₂O₂ to compounds of stoichiometry MoCl₂(O)₂(OPR₃)₂, OPR₃ = OPMePh₂ or OPPh₃, leads to the formation of oxo-peroxo compounds MoCl₂(O)(O₂)(OPR₃)₂. The compound MoCl₂(O)(O₂)(OPMePh₂)₂ crystallized with an unequal disorder, 63%:37%, between the oxo and peroxo ligands, as verified by single-crystal X-ray diffractometry, and can be isolated in reasonable yields. MoCl₂(O)(O₂)(OPPh₃)₂, was not isolated in pure form, co-crystallized with MoCl₂(O)₂(OPPh₃)₂ in two ratios, 18%:82% and 12%:88%, respectively, and did not contain any disorder in the arrangement of the oxo and peroxo groups. These complexes accomplish the isomerization of various allylic alcohols. A mechanism of this reaction has been constructed based on ¹⁸O isotopic studies and involves exchange between the alcohol and metal bonded O atoms.     

Solution-mediated syntheses and characterizations of two new zincophosphites [C6H14N2]0.5[Zn(H2PO3)2] and [C4H12N2]0.5[(CH3)2NH2][Zn2(HPO3)3]

Two new zincophosphites [C₆H₁₄N₂]_0.5[Zn(H₂PO₃)₂] 1 and [C₄H₁₂N₂]_0.5[(CH₃)₂NH₂][Zn₂(HPO₃)₃] 2 have been solvothermally synthesized in mixed solvents of N,N-dimethylformamide (DMF) and 1,4-dioxane (DOA), respectively. Single-crystal X-ray diffraction analysis reveals that compound 1 exhibits a neutral inorganic chain formed by ZnO₄ and HPO₂(OH) units. Interestingly, the left- and right-handed hydrogen-bonded helical chains are alternately formed via the hydrogen-bonds between two adjacent chains. Compound 2 exhibits a layer structure with 4- and 12-MRs formed by ZnO₄ and HPO₃ units, in which two kinds of organic amine molecules both act as countercations to compensate the overall negative electrostatic charge of the anionic network.     

Synthesis, structure and properties of TTF-carboxylate bridged paddlewheel dirhodium complexes, Rh2(BuCO2)3(TTFCO2) and Rh2(BuCO2)2(TTFCO2)2

Reaction of tetrathiafulvalene carboxylic acid (TTFCO₂H) with paddlewheel dirhodium complex Rh₂(Bu^tCO₂)₄ yielded TTFCO₂-bridged complexes Rh₂(Bu^tCO₂)₃(TTFCO₂) (1) and cis- and trans-Rh₂(Bu^tCO₂)₂(TTFCO₂)₂ (cis- and trans-2). Their triethylamine adducts [1(NEt₃)₂] and cis-[2(NEt₃)₂] were purified and isolated with chromatographic separation, and characterized with single crystal X-ray analysis. Trans-[2(NEt₃)₂] is not completely separated from a mixture of cis- and trans-[2(NEt₃)₂], but its single crystals were obtained from a solution of the mixture. A three-step quasi-reversible oxidation process was observed for 1 in MeCN. The first two steps correspond to the oxidation of the TTFCO₂ moiety and the last one is the oxidation of the Rh₂ core. The oxidation of cis-2 is observed as a two-step process with very similar E_1/2 values to those of the first two processes for 1. Both 1⁺ and cis-2²⁺ in MeCN at room temperature show isotropic ESR spectra with a g value of 2.008 and a_H = 0.135 mT for two equivalent H atoms and a_H = 0.068 mT for one H atom. The redox and ESR data of cis-2 suggest that the intramolecular interaction between the TTF moieties is very small.     

Syntheses and characterization of the W(II) and W(III) N2 complexes, [WCl2(PMe3)3]2N2 and [WCl3(PMe3)2]2N2

Refluxing WCl₄(PMe₃)₃ under a nitrogen atmosphere in the presence of two equivalents of sodium amalgam leads to a reduction to the W(II) complex [cis,mer-WCl₂(PMe₃)₃]₂N₂ (1), which can be converted to [mer,trans-WCl₃(PMe₃)₂]₂N₂ (2) via appropriate oxidation/chlorination. Structural data have been obtained for both complexes, and demonstrate significantly increased steric crowding in 1 due to PMe₃/PMe₃ interactions. The N-N bond distances in the two compounds are similar, at 1.279(4) and 1.243(18) Å, respectively.     

Comparative study of three magnetic nano-particles (FeSO4, FeSO4/SiO2, FeSO4/SiO2/TiO2) in plasmid DNA extraction

Recent updates on Magnetic Nano-Particles (MNPs) based separation of nucleic acids have received more attention due to their easy manipulation, simplicity, ease of automation and cost-effectiveness. It has been indicated that DNA molecules absorb on solid surfaces via hydrogen-bonding, and hydrophobic and electrostatic interactions. These properties highly depend on the surface condition of the solid support. Therefore, surface modification of MNPs may enhance their functionality and specification. In the present study, we functionalized Fe₃O₄ nano-particle surface utilizing SiO₂ and TiO₂ layer as Fe₃O₄/SiO₂ and Fe₃O₄/SiO₂/TiO₂ and then compare their functionality in the adsorption of plasmid DNA molecules with the naked Fe₃O₄ nano-particles. The result obtained showed that the purity and amount of DNA extracted by Fe₃O₄ coated by SiO₂ or SiO₂/TiO₂ were higher than the naked Fe₃O₄ nano-particles. Furthermore, we obtained pH 8 and 1.5 M NaCl as an optimal condition for desorption of DNA from MNPs. The result further showed that, 0.2 mg nano-particle and 10 min at 55 °C are the optimal conditions for DNA desorption from nano-particles. In conclusion, we recommended Fe₃O₄/SiO₂/TiO₂ as a new MNP for separation of DNA molecules from biological sources.     

New preparations and molecular structures of cis-MCl2(Ph2PCH2PPh2)2, M = Ru,Os and trans-RuCl2(Ph2PCH2PPh2)2

The title compounds were made by reacting bis(diphenylphosphino)methane (dppm) with reduced solutions of OsCl₆^4? and Ru₂OCl₁₀^4?. The crystal and molecular structures of these compounds have been determined form three-dimensional X-ray study. The cis-isomers crystallize with one CHCl₃ per molecule of the complex. All three compounds crystallize in the monoclinic space group P2₁/n with unit cell dimensions as follows: Cis-OsCl₂(dppm)₂·CHCl₃: a = 13.415(4) Å, b = 22.859(4) Å, c = 16.693(3) Å, β = 105.77(3)°, V = 4926(3) ų, Z = 4. cis-RuCl₂(dppm)₂·CHCl₃: a = 13.442(3) Å, b = 22.833(7) Å, c = 16.750(4) Å, β = 105.53(2)°, V = 4953(3) ų, Z = 4. trans-RuCl₂(dppm)₂: a = 11.368(7) Å, b = 10.656(6) Å, c = 18.832(12) Å; β = 103.90(6)°, V = 2213(7) ų; Z = 2. The structures were refined to R = 0.044 (R_w = 0.055) for cis-OsCl₂(dppm)₂·CHCl₃; R = 0.065 (R_w = 0.079) for cis-RuCl₂(dppm)₂·CHCl₃ and R = 0.028 (R_w = 0.038) for trans-RuCl₂(dppm)₂. The complexes are six coordinate with stable four-membered chelate rings. The PMP angle in the chelate rings is ca. 71° in each case.     

Photophysical properties of Eu(SiW11O39)2 and Eu(BW11O39)2

The photophysical properties (absorption, emission, and excitation spectra; luminescence quantum yields; luminescence decay lifetimes ) of K₁₃[Eu(SiW₁₁O₃₉)₂] and K₁₅[Eu(BW₁₁O₃₉)₂] in aqueous solution and in the solid state are reported. Both complexes exhibit broad and very intense O → W charge transfer bands in the U.V. region and weak and narrow f → f Eu₃₊ bands in the visible. At 77 K the luminescence emission of both complexes, which consists of ⁵D_O → ⁷F_J bands split by the local crystal field, can be pumped very efficiently via both the O → W CT and the f → f Eu³⁺ levels, whereas at 298 K only pumping via the f → f Eu³⁺ is efficient. The values of the luminescence decay lifetimes in H₂O and D₂O solution are quite similar, showing that no water molecule is coordinated to the central Eu₃₊ ion. The high resolution emission spectra are discussed in an attempt to define the coordination symmetry of Eu₃₊.     

Immunoaffinity column clean-up for the high-performance liquid chromatographic determination of aflatoxins B1, B2, G1, G2, M1 and Q1 in urine

A method for the determination of aflatoxins B₁, B₂, G₁, G₂, M₁ and Q₁ in human urine has been developed. The 10-ml urine samples were automatically cleaned up on immunoaffinity columns and analysed by high-performance liquid chromatography (HPLC), including post-column derivatization with bromine and fluorescence detection. Average aflatoxin recoveries were: B₁ 103%, B₂ 106%, G₁ 98% and G₂ 96% in the range 6.8–73 pg/ml of urine and M₁ 103% and Q₁ 100% in the range 18–97 pg/ml of urine. The relative standard deviations were all between 1% and 21%. The determination limits of aflatoxins in urine were 6.8 pg/ml for B₁, B₂, G₁ and G₂ and 18 pg/ml for M₁ and Q₁.     

Hydrothermal synthesis and structure of an open framework Co0.7Zn1.3(PO4)2(NH3-CH2CH2NH3) and Co6.2(OH)4(PO4)4Zn1.80, a new adamite type phase

The hydrothermal reaction of cobalt(II)oxalate di-hydrate, zinc oxide, and triethyl-orthophosphate, using 1,2-diaminoethane as structure directing template in water, produced two major crystal phases in almost equal amount: the purple crystals of [NH₃-CH₂CH₂NH₃][Co_0.7Zn_1.3(PO₄)₂] (1) and the red burgundy crystals of Co_6.2(OH)₄(PO₄)₄Zn_1.80 (2), a new adamite type phase. The structure of [NH₃-CH₂CH₂NH₃] [Co_0.7Zn_1.3(PO₄)₂] (1) exhibits a 3D open framework built from PO₄ and (Co/Zn)O₄ tetrahedra, and (Co/Zn)O₅ trigonal bipyramids, forming two major channels, an 8-membered ring channel and a 16-membered ring channel, that host the ethanediammonium ions. The Co_6.2(OH)₄(PO₄)₄Zn_1.80 (2) is isomorphous with adamite-type M₂(OH)XO₄ structure, with a condensed vertex and edge sharing network of (Co/Zn)O₅, and distorted CoO₆, and PO₄ subunits. The cobalt preference for higher coordination numbers is displayed in this structure, where the octahedral sites are wholly occupied by cobalt. Thermal analysis confirmed that these compounds display high thermal stability.     

Synthesis and characterization of isopropylamine complexes of lanthanide(II) diiodides: Molecular structure of TmI2(PrNH2)4 and EuI2(PrNH2)4

It was found that the lanthanide diiodides LnI₂ (1) (Ln = Nd, Sm, Eu, Dy, Tm, Yb) are dissolved in isopropylamine (IPA) without redox transformations. Stability of the formed solutions decreases in a row Eu ≈ Yb > Sm > Tm > Dy > Nd. Removing of a solvent in vacuum leaves complexes LnI₂(IPA)_x (2) (Nd, x = 5; Sm, Eu, Dy, Tm, Yb, x = 4) as crystalline colored solids. Stability of 2-Nd,Dy,Tm is higher than that of known THF or DME coordinated salts. Divalent state of metal in the products is confirmed by data of UV-Vis spectroscopy, magnetic measurements and their chemical behavior. Structure of 2-Eu and 2-Tm was established by X-ray diffraction analysis. Oxidation of 2-Nd,Dy in IPA affords amine-amides (PrⁱNH)Ln(IPA)_y (3) (Nd, y = 4; Dy, x = 3). n-Propylamine also dissolves the iodides 1-Sm,Eu,Dy,Tm,Yb but stability of the solutions is significantly lower. 1-Nd vigorously reacts with PrⁿNH₂ even at −30 °C which hampers the formation of the solution.