风化过程对船舶燃料油组分及其指纹特征的影响

以某船舶燃料油为研究对象,进行自然条件下的风化实验,研究燃料油中的正构烷烃、PAHs的风化规律及特征比值随风化时间的稳定性,了解风化与该油品的化学组成变化间的关系。结果表明:(1)自然风化60 d后,燃料油品低碳组分(小于nC13)的正构烷烃几乎完全消失,中碳数正构烷烃可能比高碳数正构烷烃更难于风化;(2)随着PAHs环数的增加,燃料油品PAHs组分的风化损失减少;菲与二苯并噻吩的损失表明烷基化程度大的化合物可能比未发生取代的PAHs损失程度更大。最后,通过将正构烷烃、甾萜烷类生物标志物和PAHs中的24个特征比值的相对标准偏差与5%进行比较,判断其稳定性,筛选出该油品中稳定性好的特征比值,为其风化溢油鉴别提供技术支持。     

短期风化条件下渤海中部原油中PAHs风化规律研究

以渤海中部某原油作为研究对象进行短期风化实验,探讨了原油中五大类PAHs组分的分布情况及其风化规律。结果表明:经过22d风化,渤海中部某原油PAHs中芳烃的分布已经发生了较大的改变:萘系列化合物损失最为严重,相对浓度的损失达到79.15%;菲系列所占的比例有所提高,二苯并噻吩、、芴系列则保持相对稳定;所选取新诊断比值中,菲和系列、烷基取代二苯并噻吩类、烷基取代芴类抗风化能力较强。     

基于诊断比值的Fisher判别法鉴定海上溢油

采用GC-FID检测分析了8种燃料油、8种中东原油、13种非中东原油的正构烷烃分布特征。以具有地球化学意义和较强的抗风化能力的诊断比值n-C₁₇/Pr、n-C₁₈/Ph、Pr/Ph、LMW/HMW、CPI和（n-C₁₉+n-C₂₀）/（n-C₁₉~n-C₂₂）为建模参数,对中东原油、非中东原油和燃料油进行Fisher判别。由于n-C₁₇/Pr和n-C₁₈/Ph间存在共线性,且燃料油的n-C₁₇/Pr受风化影响较大,所以将其不作为建模参数。所建模型的Wilks's lambda分布所对应的P值为0,表明判别模型是有效的,模型判别准确率达到93.1%。对短期风化30d后的油样的判别准确率也能够达到93.1%,说明模型也同样适用于风化溢油的鉴别。     

长江中下游典型硅酸盐岩流域自然风化与人类活动影响下的水化学特征-以抚河流域为例

抚河汇流于中国第一大淡水湖鄱阳湖,也是长江中下游的重要支流,其河流水化学组成代表了典型的硅酸盐岩地区河流风化特征.本研究于2019年1月对抚河流域进行了系统的采样分析,通过离子的主成分分析、离子比值分析等方法对流域河水水化学空间变化、控制因素和主要离子来源进行了研究.结果表明,K+、Na+和HCO3-为抚河流域水体的主...     

利用双金刚烷指标研究下古生界海相碳酸盐岩的热成熟度

金刚烷类化合物是一类具有重要地球化学意义的结构特殊的化合物。其中的双金刚烷系列化合物尤为重要，本文建立的双金刚烷成熟度指标X(MD)与镜质组反射率具有良好的相关关系，利用该成熟度指标可以解决高演化阶段判定烃源岩和原油成熟度等难题。对于缺乏镜质体的下古生界海相碳酸盐烃源岩，利用该指标判定成熟度就显得尤为重要。     

原油中芳烃及其碳稳定同位素组成特征

芳烃作为原油的主要组分之一,蕴含丰富的地球化学信息,常用原油中芳烃的分布及其碳稳定同位素组成来评价原油的有机质来源和热成熟度等指标。为了补充油品化学指纹的基础鉴别指标和数据,找出适用于油样鉴别的芳烃地球化学指标以及碳稳定同位素组成,本文主要测定了来自不同地区七种原油芳香烃组分的相对含量以及碳稳定同位素组成,并计算分析了甲基萘比值（MNR）、二甲基萘比值（DNR）、三甲基萘比值（TNR）、甲基菲比值（MPR）、甲基菲指数（MPI1）和甲基菲分馏系数（MPDF）等常见的芳烃特征比值。从原油中芳烃组分相对含量分布来看,七种原油均显示出了各自的特点;从原油芳烃的特征比值来看,成熟度参数（MNR、TNR1、TNR2、MPR、MPI1、MPDF1和MPDF2）均反映出所有原油的高成熟度,其它芳烃参数如DNR1、DNR2和TNR4等比值反映原油的母质来源及生物降解等信息,由芳烃特征比值的单因素方差分析（ANOVA）结果可知,与成熟度参数MNR和MPI1相比,DNR1、DNR2和TNR4在不同原油间的差异更加明显;从原油芳烃碳稳定同位素组成来看,不同地区原油间差别较大,其中巴西原油最富集13C,阿曼原油和委内瑞拉原油最亏损13C,二甲基萘和菲的碳稳定同位素组成在不同油样间的差异最明显。将显著性差异大的芳烃参数与芳烃δ13C值联用,结果表明,该方法可以更加有效区分七种原油。最后使用主成分分析方法分析原油芳烃碳稳定同位素组成,七种原油显示出各自不同的碳稳定同位素组成特征和明显的区分效果,利用不同油样芳烃的碳稳定同位素组成差异可实现对油样来源的鉴别。     

柴油和燃料油在风化模拟过程中物理化学特性的比较

溢油风化模拟实验是溢油预测和应急处理的重要基础.通过自制的溢油风化模拟系统在深圳进行室外溢油风化模拟实验,研究了我国南海产的柴油和燃料油风化过程中外部形态、运动粘度、密度、水分含量等方面的变化.结果表明,风化过程中,柴油颜色不断加深,并在液面形成"球状物",燃料油则形成稳定的"巧克力冻".柴油和燃料油的运动粘度、水分均...     

强化造粒条件下颗粒污泥中EPS不同组分的空间分布特征

采用多重荧光染色方法分析强化造粒条件下(不同时间段投加PAC)好氧颗粒污泥形成过程中胞外聚合物(extracellular polymeric substances,EPS)各组分的空间分布特征。研究发现:强化造粒条件下污泥完全颗粒化进程与对照组相比,所需时间明显缩短,粒径更大,含水率、比重、强度更优,且颗粒结构更规则紧密。EPS不同组分空间分布分析表明:α-呋喃葡萄糖、α-甘露糖主要分布在颗粒外侧,蛋白质在整个颗粒污泥断面均有分布,PAC投加对它们的分布影响较小,但对β-D-呋喃葡萄糖、脂类以及死细胞和活细胞在颗粒污泥中的分布有明显的影响;其中在1~7 d投加PAC,死细胞和β-D-呋喃葡萄糖主要集中在颗粒污泥外侧,活细胞和脂类主要分布在颗粒污泥内部,而8~14 d投加PAC,上述情况刚好相反;对照组(不投加PAC)颗粒污泥EPS各组分的空间分布与推迟PAC投加时间后的情况基本相似。     

不同产地原油的碳稳定同位素组成特征研究

本文应用GC/MS、GC/IRMS和EA/IRMS等方法对6种不同产地原油的特征比值, 全油和正构烷烃组分的碳稳定同位素组成进行分析, 研究不同产地原油的碳稳定同位素组成特征, 并探讨其原因。结果显示, 6种原油的C₁₉+C₂₀/(C₁₉~C₂₂)、OEP₁和CPI_13-22特征比值不存在显著性差异, 不能作为区分这6种原油的有效指标。原油全样的δ13C值差异明显, 阿曼δ13C值最轻为-33.4‰, 巴西最重为-24.5‰, 其余4种原油介于两者之间。GC/IRMS分析结果显示不同油种具有不同的碳稳定同位素组成特征, 6种原油的正构烷烃δ13C值和分布曲线明显不同。单因素方差分析结果显示除个别油样外, 不同原油两两之间全油δ13C值和nC₂₀的δ13C值差异性显著(P < 0.05)。实验结果表明, 特征比值和碳稳定同位素组成相结合能更加有效的区分不同种类原油, 油品中同位素组成特征差异可为原油种类鉴别和溯源提供一个有效的技术支撑。     

溢油长期风化的碳稳定同位素指纹变化规律

根据石油中的碳稳定同位素具有母质继承效应,利用稳定同位素手段对原油的油指纹进行鉴定。对于正构烷烃指标,在室内对380#燃料油进行了长期风化模拟实验,在长期风化中δ13C_Pr/C19、δ13C_Ph/C19、δ13C_Pr/C20和δ13C_Ph/C20其相对标准偏差（RSD,relative standard deviation）小于5%,表现出一定的稳定性,可作为诊断比值来进行油指纹鉴别。对于多环芳烃,对380#燃料油和科威特原油进行了室内长期风化模拟实验,燃料油和原油风化样的δ13C_flu和δ13C_ph分别分布于-27.476‰~-26.583‰和-26.482‰~-21.914‰,各自集中于一定范围内,利用δ13C_flu和δ13C_phe双指标可区分不同油品的风化样品。研究证明稳定同位素作为一种追踪油源的技术手段,可以用于风化后的油源鉴别。     

溢油风化过程研究进展

讨论了近１０ａ来国内外学都在溢油的组成和性质的变化养及蒸发，溶解，乳化等风化过程听研究进展。和过去相比，随着分析手段的提高和认识的加深，近１０ａ的研究已从经验方程的建立，深入到风化的机理研究上，促进预测模型向更合理，更准确的方向发展。     

短期风化对溢油组成的影响

采用实验室内的溢油模拟实验,从分子级水平揭示短期风化作用对溢油组成的影响。研究表明,该原油的风化损失主要发生在最初的24 h,且以饱和烃组分的损失为主;正构烷烃的分布形态中C数大于18的部分基本不受短期风化作用的影响;大多数的多环芳烃指标都明显受风化作用的影响;相对含量较低以及共溢出的存在是影响甾萜类生标化合物准确定量的两个主要因素。研究结果可为溢油源鉴定指标的选择提供实验依据。     

Emission of intermediate volatility organic compounds from a ship main engine burning heavy fuel oil

Intermediate volatility organic compounds (IVOCs) are crucial precursors of secondary organic aerosol (SOA). In this study, gaseous IVOCs emitted from a ship main engine burning heavy fuel oil (HFO) were investigated on a test bench, which could simulate the real-world operations and emissions of ocean-going ships. The chemical compositions, emission factors (EFs) and volatility distributions of IVOC emissions were investigated. The results showed that the main engine burning HFO emitted a large amount of IVOCs, with average IVOC EFs of 20.2–201?mg/kg-fuel. The IVOCs were mainly comprised of unspeciated compounds. The chemical compositions of exhaust IVOCs were different from that of HFO fuel, especially for polycyclic aromatic compounds and alkylcyclohexanes. The volatility distributions of IVOCs were also different between HFO exhausts and HFO fuel. The distinctions in IVOC emission characteristics between HFO exhausts and HFO fuel should be considered when assessing the IVOC emission and related SOA formation potentials from ocean-going ships burning HFO, especially when using fuel-surrogate models.     

Variation on leaching behavior of caustic compounds in bauxite residue during dealkalization process

Bauxite residue,a byproduct of alumina manufacture,is a serious environmental pollutant due to its high leaching contents of metals and caustic compounds.Four typical anions of CO₃^2-,HCO₃^-,Al(OH)₄^- and OH-(represented caustic compounds) and metal ions(As,B,Mo and V) were selected to assess their leaching behavior under dealkalization process with different conditions including liquid/solid ratio(L/S ratio),temperature and leaching...     

The dynamic development of bacterial community following long-term weathering of bauxite residue

Bauxite residue is the industrial waste generated from alumina production and commonly deposited in impoundments. These sites are bare of vegetation due to the extreme high salinity and alkalinity, as well as lack of nutrients. However, long term weathering processes could improve residue properties to support the plant establishment. Here we investigate the development of bacterial communities and the geochemical drivers in bauxite residue, using Illumina high-throughput sequencing technology. Long term weathering reduced the pH in bauxite residue and increased its nutrients content. The bacterial community also significantly developed during long term weathering processes. Taxonomic analysis revealed that natural weathering processes encouraged the populations of Proteobacteria, Chloroflexi, Acidobacteria and Planctomycetes, whereas reducing the populations of Firmicutes and Actinobacteria. Redundancy analysis (RDA) indicated that total organic carbon (TOC) was the dominant factors affecting microbial structure. The results have demonstrated that natural weathering processes improved the soil development on the abandoned bauxite residue disposal areas, which also increased our understanding of the correlation between microbial variation and residue properties during natural weathering processes in Bauxite residue disposal areas.     

海上溢油风化特性及化学分散效果的影响因素研究

以渤海埕北油田Ｂ平台外输原油为对象，在人工模拟波浪下，研究原油特性随风化时间的变化在伴随着的化学分散效果的变化。本文同时研究了化学分散剂处理海上溢油的影响因素。研究结果对于决策溢油事故时能否使用分散剂，在什么时间、条件下、使用保种分散剂具有指导意义。     

Fundamentals and systematics of the non-statistical distributions of isotopes in natural compounds

The intermolecular and intramolecular non-statistical distribution of the isotopes of the bio-elements in natural compounds must obviously be controlled by logical principles. However, a critical review of the available isotope patterns of natural compounds indicates that a previously discussed general thermodynamic order and its mechanistic foundation cannot satisfactorily explain all experimental data. In the present contribution it is shown that a partial thermodynamic order can eventually be attained for defined positions and compounds under steady-state conditions of metabolism. However, as biological systems are generally open and irreversible, many other in vivo isotope discriminations are dominated by kinetic isotope effects, even in context with reversible reactions. On the other hand, kinetic isotope effects can only become effective in vivo in combination with metabolic branching and the implied isotope shifts of the products are balanced by their relative yields. In vivo, the influences of thermodynamic and kinetic isotope effects are modulated by interferences of the actual metabolic conditions, such as the nature and kind of precursors, alternative metabolic pathways, metabolite pools and fluxes, and by reaction mechanisms. This is demonstrated by giving examples for the isotopes of hydrogen, carbon, nitrogen, oxygen and sulfur, while simultaneously the particularities of the individual elements are elaborated. The resulting general theory of the origin of non-statistical isotope distributions in biological systems permits the interpretation and prediction of isotope patterns and provides the scientific basis for the elucidation of biosyntheses and origin assignments of natural compounds.An erratum to this article can be found at