混合堆肥过程中自由空域(FAS)的层次效应及动态变化

城市污泥、猪粪混合堆肥试验表明:升温期和高温期FAS分别为42.3%、26.2%,在这2个堆肥期内堆体上部的FAS明显高于下部,堆体内的空气能满足微生物的需求;降温期FAS为52.4%,堆体上部的FAS高于中部,中部高于下部,FAS呈明显的层次效应;腐熟期FAS为54.7%,FAS的层次效应减弱,堆体上部和中部的通气性明显好于下部.不同堆肥期剖面上下部FAS的差异由大到小分别为:降温期>高温期>后熟期>升温期;堆体内FAS由高到低为:上部>中部>下部.FAS随时间的变化满足二级反应动力学方程.     

二羟基苯甲酸的硅烷化及其在气质联用测量气相OH自由基的应用

通过优化GC-MS参数有效分离了水杨酸(SA)及其羟基化产物2,3-DHBA和2,5-DHBA的硅烷化产物,检测限分别为10.2 fmol和9.9 fmol.采用浸渍膜捕集OH标准源发生体系产生的OH自由基,测得气相OH自由基与固相SA反应生成的2,3-DHBA 和2,5-DHBA的产率分别为52%和48%.因此,SA捕集-硅烷化衍生-气质联用测量方法研究大气OH自由基有很好的应用前景.     

澳门南湾湖钻孔沉积物中自由态和束缚态的多环芳烃

研究自然条件下沉积物中有机污染物沉积后的环境行为,考察澳门南湾湖钻孔沉积物中自由态和束缚态PAHs的含量与分布.研究表明,自由态PAHs以4-环、6,7-环和5-环为主,其质量百分贡献分别为28.7%～40.6%、17.6%～29.6%和13.2%～28.2%;而束缚态PAHs则以4-环、3-环和2-环为主,质量百分贡献分别为42.3%～55.8%、20.2%～35.8%和7.8%～18.8%.说明低分子量PAHs比高分子量PAHs更容易进入沉积有机质的孔隙中.自由态PAHs的垂直分布特征受区域经济发展及环境治理进程的影响,束缚态PAHs的含量一方面受控于PAHs的输入量,另一方面与沉积有机质的结构(特别是聚合程度)有关,随着沉积埋藏时间的延长有利于各化合物从自由态向束缚态转变.     

Free cupric ions in contaminated agricultural soils around a copper mine in eastern Nanjing City, China

To determine the environmental free metal ion activity was a recent hot issue. A method to measure low-level free cupric ion activity in soil solution extracted with 0.01 mol/L KNO3 was developed by using cupric ion-selective electrode （ISE） and calibrating with Cu-buffer solution. Three copper buffers including iminodiacetic acid （IDA）, ethylenediamine （EN）, and glycine （Gly） were compared for calibrating the Cu-ISE curves in the range of free cupric ions （pCu^2＋） 7-13. The Cu-EN buffer showed the best electrode response and thus was applied as the calibration buffer. The pCu^2＋ of 39 contaminated agricultural soils around a copper mine was measured, ranging from 5.03 to 9.20. Most Cu in the soil solutions was found to be complexed with dissolved soil organic matters, averaging 98.1%. The proportion of free Cu^2＋ ions in the soil solutions decreased with the increasing of solution pH. Soluble Cu and free Cu^2＋ ions concentrations were analyzed by multiple linear regressions to evaluate the effects of soil properties on metal levels and speciation. The results showed that soil solution pH was the most significant factor influencing pCu^2＋ （with R^2 value of 0.76）, while not important for the soluble Cu concentration.     

Removal of PCDD/Fs and PCBs from sediment by oxygen free pyrolysis

Few studies have dealt on the evaluation of volatilization and decomposition reactions of dioxins from sediment by oxygen free pyrolysis. In this study, the performance of pyrolysis on the removal of dioxins from sediment was investigated. Dioxin concentrations of the raw sediment and the solid residues after pyrolysis were analyzed at different conditions. Results showed a removal efficiency of 99.9999% for total dioxins at 800℃ and retention time of 30 min. All the polychlorinated dibenzo-furans （PCDFs） have been removed and were not formed in the solid residues at the retention time range of 30-90 min at 800℃. Close to 100% removal of polychlorinated dibenzo-p-dioxins （PCDDs） was also achieved. Only trace PCDDs were detected in the solid yields at a retention time of 60 min. The highest removal efficiency of polychlorinated biphenyls （PCBs） was more than 99.9994% at a retention time of 30 min. During cooling period following pyrolysis, however, the concentration of total dioxins in solid residues increased 130 times as compared to that of the raw sediment under air atmosphere. This confirmed that some complex reactions do occur to form PCDD/Fs and PCBs from 800 to 400℃ in the presence of oxygen. Oxygen-free atmosphere therefore can prevent formation of dioxin during thermal process thus generating clean solid residues.     

碱渣在公路工程应用中Cl-对环境的影响研究

在我国氨碱法生产纯碱的企业,每年都会排放大量的废碱渣,如把这些碱渣用于公路工程建设,其中所合的游离氯离子可能会对周围环境造成影响。通过对碱渣的化学成分,以及碱渣中游离Cl-与碱渣-石灰稳定土、外加固结剂之间的物理-化学作用机理的分析,并结合公路建设的工程实际,研究了游离氯离子对周围土壤和地下水质的影响。研究结果表明,工业碱渣作为公路路基的替代石灰的材料,符合国家公路建设标准和环保要求。     

丙烷扩散火焰燃烧光谱特性研究

为实现烃类火灾事故的光谱辨识,对丙烷火焰燃烧初期过程中的光谱特性进行实验研究,利用拉曼光谱仪等设备采集、提取丙烷扩散火焰光谱数据。分析燃烧初期OH~*,C₂~*,CH~*,H₂O分子谱带范围及特征峰值分布特性,揭示谱带光谱特征强弱的主要原因,阐述沿火焰轴向与径向C₂~*,CH~*以及H₂O分子光谱峰值强度的分布特性。研究结果表明：丙烷火焰特征光谱主要分布在可见光与近红外波段,250～380 nm的近紫外波段光谱强度较弱。C₂~*的509.4,512.8,810.5 nm特征谱带,CH~*的431.4 nm谱带以及H₂O分子的586.2,652.2 nm处振动-转动谱带可作为丙烷火焰燃烧的关键特征光谱,为烃类火灾的早期识别与防控提供光谱实验依据。     

考虑脉动压力相关性的自由体随机振动分析

目的 获得自由体在脉动压力载荷作用下的结构响应.方法 采用有限元方法 ,建立锥壳自由体结构的随机振动分析有限元模型,根据自由体的脉动压力载荷和随机振动分析理论,计算自由体在脉动压力下的加速度响应均方根值.结果 载荷为一定程度相关时的计算结果 在完全相关和不相关之间,最小相差约15％,最大相差约50％.结论 在进行自由体...     

Persistent free radicals in humin under redox conditions and their impact in transforming polycyclic aromatic hydrocarbons

• Regulation of redox conditions promotes the generation of free radicals on HM. • HM-PFRs can be fractionated into active and inactive types depending on stability. • The newly produced PFRs readily release electrons to oxygen and generate ROS. • PFR-induced ROS mediate the transformation of organic contaminants adsorbed on HM. The role of humic substance-associated persistent free radicals (PFRs) in the fate of organic contaminants under various redox conditions remains unknown. This study examined the characterization of original metal-free peat humin (HM), and HM treated with varying concentrations of H₂O₂ and L-ascorbic acid (VC) (assigned as H₂O₂-HM and VC-HM). The concentration of PFRs in HM increased with the addition of VC/H₂O₂ at concentrations less than 0.08 M. The evolution of PFRs in HM under different environmental conditions (e.g., oxic/anoxic and humidity) was investigated. Two types of PFRs were detected in HM: a relatively stable radical existed in the original sample, and the other type, which was generated by redox treatments, was relatively unstable. The spin densities of VC/H₂O₂-HM readily returned to the original value under relatively high humidity and oxic conditions. During this process, the HM-associated “unstable” free radicals released an electron to O₂, inducing the formation of reactive oxygen species (ROS, i.e., ^•OH and ^•O₂⁻). The generated ROS promoted the degradation of polycyclic aromatic hydrocarbons based on the radical quenching measurements. The transformation rates followed the order naphthalene>phenanthrene>anthracene>benzo[a]pyrene. Our results provide valuable insight into the HM-induced transformation of organic contaminants under natural conditions.     

Ca5（AsO4）3OH的溶解度与稳定性研究

通过在不同pH值,温度等条件下Ca5（AsO4）3OH的溶解,确定其稳定存在的pH值范围,得出它的溶度积和生成的自由能（ΔG0f）。结果表明,Ca5（AsO4）3OH在水中的溶解度和稳定范围与pH和温度有关,在酸性条件下（初始pH=2）它的溶解度较大,而且在水中的溶解度随着温度的升高而降低。利用PHREEQC程序计算确定Ca5（AsO4）3OH的溶度积为10-40.86,生成自由能ΔG0f为-5 063.53 kJ/mol。利用JADE5软件计算得到其晶格参数a=b=9.696,c=6.967和晶胞体积为567.304 3。