海洋中液-固界面作用的分形研究Ⅰ.SAXS法测量固体交换剂的分维

本文将分形作为一个新概念,应用到海洋化学的液-固界面作用的一系列的研究上。根据用SAXS法测定一些常见的粘土矿物(高岭石,蒙脱石)和水合氧化物(水锰矿、δ-MnO_2、氧化铁凝胶、针铁矿、无定形氧化铁)的分维结果,可将这些结果划分成三类:(1)小尺度模量下具有表面分形;大尺度模量下具有质量分形。(2)只有一种分维值的表面分形。(3)在小尺度模量下和大尺度模量下分别具有不同分维值的表面分形。     

海洋中液-固界面作用的分形研究 Ⅱ.混合交换剂表面分维的加和性规律和非加和性规律研究

用SAXS方法验证了海洋化学液-固界面研究中一些混合交换剂体系的分维分别具有加和性和非加性规律。实验测得:针铁矿/蒙脱石、水锰矿/无定形氧化铁、δ-MnO_2/针铁矿、δ-MnO_2/无定形氧化铁等混合交换剂体系的表面分维对混合百分率具有线性加和性;而高岭石/无定形氧化铁、无定形氧化铁/蒙脱石、δ-MnO_2/蒙脱石、δ-MnO_2/氧化铁凝胶等混和交换剂具有非线性加和性。上述诸体系在海水介质中平衡一年后,SAXS测定的表面分维皆具有非线性加和性,或非线的程度有所增加。     

海水中液-固界面的台阶型动力学曲线 Ⅰ.动力学曲线之台阶的消长和变化规律

对海水中Zn(Ⅱ),Ca(Ⅱ),Cd(Ⅱ)与高岭石、伊利石和蒙脱石等粘土矿物;无定形水合氧化铁、α-FeOOH等铁的水合氧化物;δ-MaO_2,γ-MnOOH,水锰矿等锰的水合氧化物等30个左右实验体系的液-固界面台阶型动力学曲线进行了系统的实验测定和全面的条件研究。在实验测定上提出两种方法、互为校核。对动力学曲线之台阶的消长和变化规律作了系统研究,确定主要影响因素是:金属离子初始浓度、固体交换剂量、体系的pH值和温度,以及搅拌速度等。     

海水中液-固界面的台阶型动力学曲线

对海水中Zn（Ⅱ）,Ca（Ⅱ）,Cd（Ⅱ）与高岭石、伊利石和蒙脱石等粘土矿物;无定形水合氧化铁、α-FeOOH等铁的水合氧化物; δ-MaO₂, γ-MnOOH,水锰矿等锰的水合氧化物等30个左右实验体系的液-固界面台阶型动力学曲线进行了系统的实验测定和全面的条件研究。在实验测定上提出两种方法、互为校核。对动力学曲线之台阶的消长和变化规律作了系统研究,确定主要影响因素是:金属离子初始浓度、固体交换剂量、体系的pH值和温度,以及搅拌速度等。     

海水中液－固界面上负离子分级交换吸附研究──Ⅰ.E(%)－pH关系曲线和新的N－型曲线

本文研究了海水中钼(Ⅵ)与粘土矿物(高岭石、蒙脱石)、水合氧化铁(赤铁矿、无定形氧化铁)和水合氧化锰(水锰矿、δ-MnO₂)相互作用的交换百分率E(%)-pH曲线.钼在这三类固体粒子上的E(%)-pH曲线分别为新发现的N-型曲线,以及峰型和反S型曲线.其中N-型曲线在负离子交换吸附文献中尚未见报道,本文提出用“静电交换和分级离子/配位子交换共同作用”的观点作理论解释.峰型和反S型E(%)-pH曲线可用固-液界面上负离子交换吸附作用解释.钼(Ⅵ)在这三类粒子上的交换能力顺序为:水合氧化锰>水合氧化铁>粘土矿物.     

海水中液－固界面上负离子分级交换吸附的研究 Ⅱ.交换吸附等温线和新的N－型曲线

本文研究了海水中钼(Ⅵ)与粘土矿物(高岭石、蒙脱石)、水合氧化铁(赤铁矿、无定形氧化铁)和水合氧化锰(水锰矿、δ-MnO₂)相互作用等温线,钼(Ⅵ)-粘土矿物体系所得是一种具有极大值的N-型等温线,钼(Ⅵ)-水合氧化物体系所得是具有一个拐点和两个台阶的“台阶型”等温线.这两类等温线在负离子交换吸附文献上均尚未见报道.N-型等温线的产生是因溶液中钼(Ⅵ)的复杂存在形式和负离子交换机理复合作用的结果.“台阶型”等温线的形成则是氧化物表面存在着几类能量不同的羟基分级交换吸附的结果.     

太平洋多金属结核中铁锰矿物分析及成因研究

铁锰矿物是大详多金属结核的重要组成,了解不同类型结核中主要铁锰矿物种类、形态、分布特点和结晶程度等,不仅有助于对锰矿物乃至多金属结核成因的研究,而且对选矿冶炼和资源的综合利用也具有现实意义.本文通过透射电子显微镜等多种手段综合分析与鉴定,指出多金属结核中主要铁锰矿物有钙锰矿、水羟锰矿、水钠锰矿、方锰矿、锰铁矿和针铁矿等.结晶程度普遍较差,钙锰矿结晶相对好于其他矿物,并在粗糙型结核中含量高,外层至核心含量稳定,变化小.水羟锰矿广为分布,但结晶差.铁矿物含量东区低于西区,结核外壳铁含量高于内核.锰矿物分布在叠层石柱体和纹层内,呈束状、纤维状和树枝状,与建造多金属结核的超微生物菌丝体形态一致.粗糙型结核是选冶的主要对象.     

海水介质中钼酸根在针铁矿上的吸附(英文)

研究了ｐＨ 和总钼酸根浓度对海水中钼酸根在针铁矿上吸附的影响。钼酸根在针铁矿上的吸附等温线为Ｓ型。假设海水中钼酸根在针铁矿表面的吸附,是在双电层的内Ｈｅｌｍｈｏｌｔ 层中的能量相等的不同位置上进行的,并考虑到吸附的钼酸根之间存在着横向相互作用,由此推导得到的吸附等温式可描述钼酸根在针铁矿上的Ｓ型吸附等温线,并计算得到钼酸根在针铁矿上的最大吸附量为４ ．７６ ×１０－ ５ｍｏｌ／ｇ。钼酸根在针铁矿上的吸附受溶液ｐＨ影响,吸附密度随ｐＨ 的增加而降低。加入到海水中的钼约有２０ ％ 可被水合氧化铁的清除作用所转移。     

北部湾表层黏土矿物分布特征及物源研究

利用X射线衍射(XRD)对北部湾表层沉积物中黏土矿物组成和结晶学特征进行了详细研究,揭示了源区和洋流对该区沉积物搬运和分布的控制机制。结果表明,北部湾表层沉积物中黏土矿物组成以伊利石、蒙脱石和高岭石为主,含有少量的绿泥石。在空间分布上,蒙脱石含量表现为中部高近岸低;伊利石含量表现为西南高东北低,绿泥石组分含量与之类似;高岭石含量表现为东北高,西南低。伊利石结晶度指数和化学指数平均分别为0.25°(Δ2θ)和0.5,表明伊利石结晶程度极好,为富Al伊利石,来源于化学风化作用占主导的源区。黏土矿物物源分析表明,红河是北部湾伊利石、绿泥石和蒙脱石的主要物源,其中蒙脱石因受沉积分异作用影响而在研究区中部富集;高岭石受到了红河、珠江以及广西和海南岛沿岸河流物质输入的共同影响。本研究结果对理解北部湾沉积物"源-汇"过程和古环境有重要参考意义。     

富钴结壳中矿物组成对稀土元素分布的制约

为探讨富钴结壳中矿物组成对稀土元素分布的制约,对约翰斯顿岛富钴结壳中矿物组成及稀土元素特征进行了研究。依据主要矿物组成,富钴结壳可以分为3种类型,分别命名为A、B、C。由A到C,水羟锰矿含量逐渐降低,B类中磷灰石含量最高,C类中水钠锰矿和钙锰矿含量最高。A类结壳中富集REE3+、Ce,B类结壳中富集Ce和Y。A类富钴结壳中,REE3+、Y以专属吸附的方式富集在铁氧化物上,Ce3+氧化成Ce4+与其他REE分离,吸附在锰矿物上。B类结壳中,稀土元素主要以独立矿物的形式存在,另有部分Ce、LREE3+吸附于铁相中,部分Y存在于磷灰石中。C类结壳中,稀土元素主要赋存在锰矿物中,部分Y存在于磷灰石中。     

环境因子对菲在黄河口沉积物上吸附的影响

为研究多环芳烃从河口到近海的环境归趋行为与生态风险,考察了沉积物质量浓度、溶解性有机质、温度、盐度4种典型环境因子对菲在黄河口沉积物上吸附的影响,比较了黄河口与近海两种沉积物对菲的吸附性能。研究结果表明,沉积物质量浓度越低,单位质量颗粒物的菲吸附量越高;共存的溶解性有机质对菲的吸附具有增促作用,且腐殖酸比黄腐酸的作用更显著;温度的升高不利于菲的吸附,而盐度的增加有利于菲的吸附。菲在沉积物上的吸附是分配作用与表面吸附两种行为的耦合,其中黄河口沉积物以表面吸附为主,而近海沉积物以分配作用为主。近海沉积物菲吸附量显著高于黄河口沉积物菲吸附量。基于此,菲从河口到近海的迁移过程中,更易于在沉积物表面发生吸附沉降,从而可能降低水相中的生态危害,但对近海底栖生物具有潜在的健康生态风险。     

The role of organic matter in the sorption capacity of marine sediments

Past studies have suggested that desiccation enhances hydrophobicity of salt marsh sediment, and that drying and rewetting sediment can be used to investigate sorption mechanisms of amino acids and other organic compounds [Liu, Z., Lee, C., 2006. Drying effects on sorption capacity of coastal sediment: The importance of architecture and polarity of organic matter. Geochim. Cosmochim. Acta 70, 3313–3324]. Here we further develop this technique to study sorption of hydrophobic and hydrophilic organic compounds in a wide range of marine sediments. Our results show that hydrophilic compounds sorb strongly to wet coastal sediments; in dried sediments, sorption of hydrophilic compounds decreases, while sorption of hydrophobic compounds is greatly enhanced. Small compounds with aromatic rings sorb more in dried than wet coastal sediments, suggesting that aromatic groups have a stronger effect on sorption than polar groups like amino and carboxyl moieties. Sorption of lysine, glutamic acid and putrescine decreases greatly when sediment is pretreated with KCl, indicating the importance of cation ion exchange. However, α-amino acids sorb much more than corresponding β- or γ-amino acids, and l-alanine sorbs more than d-alanine, suggesting that amino group location and chiral selectivity play an important role in sorption. Comparison of lysine and tyrosine sorption in different sediments indicates that source and diagenetic state of organic matter are important factors determining sorption capacity. Lysine sorbs much more to organic detritus from salt marsh sediment than to fresh Spartina root materials, marine particles, lignin or humic acids, indicating the importance of structural integrity in sorption. Desorption hysteresis of glutamic acid, putrescine and lysine (in dried sediment) suggests the presence of enzyme-type sorption sites of high sorption energy or multiple binding mechanisms. Taken together, these findings suggest that organic matter plays the major role in amino acid sorption in organic-rich sediments.     

Interactions between dissolved petroleum hydrocarbons and pure and humic acid-coated mineral surfaces in artificial seawater

The adsorption of total petroleum hydrocarbons (TPHs) on suspended particles in the marine environment is an important process affecting the fate of oils spilled in the ocean. Adsorption kinetics and adsorption isotherms of the water-soluble fraction of Fuel Oil No. 6 were performed on pure and humic acid-modified montmorillonite, alumina and kaolinite. The rates of adsorption on all sorbents are very fast and a pseudo-equilibrium is reached within 0.5 h. Linear adsorption isotherms were obtained for TPH and individual aromatic hydrocarbons on all sorbents. Higher sorption coefficients (Kd) were obtained for the humic acid-coated clays compared to the pure clays. However, a great contribution of mineral surface to overall adsorption was found on humic acid-modified particles in this study. A linear relationship between the log K and log Kow was also found for individual compounds on both pure alumina (log Km) and humic acid-coated alumina (log Koc).     

The removal of dissolved humic acid during estuarine mixing

A simple method for the determination of dissolved humic acid based on carbon analysis is presented. This method was used to measure the distribution of dissolved humic acids in seven coastal plain estuaries located in the middle-Atlantic United States. Results indicate that 100% of the dissolved humic acid was removed during estuarine mixing, although concurrent measurements of dissolved organic carbon showed either production or conservative behavior in regions of the estuary where humic acid removal was observed. It is apparent from these observations that removal of dissolved humic acid is a minor part of the estuarine transport of dissolved organic carbon.Laboratory experiments carried out by mixing river water with sea water demonstrated that salt-induced removal of dissolved humic acid was insignificant in two of three estuaries studied. These results suggest in situ removal of dissolved humic acid may not be universally caused by increasing estuarine salinity.     

HUMIC SUBSTANCES IN SEDIMENTS

In this paper the chemical characteristics of humic substances (humic acid and fulvic acid) from East China Sea surficial sediment are studied through combination of chemical and physical methods. Results show that humic acids have less aromatic hydrocarbon and more alkane structure.The contents of amino acids from hydrolyzate of humic substances are different. The amount of various amino acids (such as acidic, neutral or basic amino aicd) of fulvic acid is higher than that of humic acid. The distribution order of amino acid abundance in various kinds of sediments is neutral amino acid>aromatic amino acid> basic amino acid.In addition, mathematical statistic method is also used to study their distribution. All samples show similar regularities, i. e., the contents of glycine, alanine, aspartic and glutamic are very high and those of cystine and methionine are very low or even disappear.The above results further confirm that humic acid and fulvic acid have similar composition and structure.     

Characterization of humic and fulvic acids isolated from marine sediments of Sagami and Suruga Bays with C-13 and proton nuclear magnetic resonance

The C-13 and proton NMR spectra of marine humic and fulvic acids isolated from sediments of Sagami and Suruga Bays and Aldrich humic acid were obtained using pulse Fourier transform mode. The C-13 and proton NMR spectra, which clarified the differences in chemical characteristics among the various humic substances, showed that the marine humic acids had more aliphatic and less aromatic character than the Aldrich humic acid, and the marine fulvic acids had polysaccharide-like character. The C-13 NMR spectra of the marine humic substances, in particular, had many relatively well-resolved peaks with significant intensities, indicating the presence of variously bonded carbon atoms in them.     

The occurrence of high molecular weight humic material in recent organic-rich sediment from the Namibian shelf

The molecular size distribution of humic substances has been investigated in two recent sediment samples of different ages taken from a single core sample collected off Walvis Bay, south-west Africa. Extractable humic acids were found to be by far the major form of organic carbon in both sediments, the near-surface younger sample containing predominantly high molecular weight (>100 000 molecular weight) humic acids and little fulvic acids whilst the deeper, older sample contained relatively less humic acid and relatively more fulvic acid of a range of molecular weights. A significant age difference was found between the >300 000 molecular weight and the <30 000 molecular weight fractions of the near-surface sample, the lower molecular weight fraction being older than the higher molecular weight fraction.The data suggest that in this rapidly accumulating, organic-rich sediment the first step en route from the planktonic matter to the humic complexes is direct and rapid incorporation of the biogenic material into high molecular weight humic acids.     

Molecular weight and trace metal distributions in fulvic and humic acid fractions of coastal marine sediments

Molecular weight and trace metal distributions of fulvic and humic acid fractions of marine sediments from the Seto Inland Sea were investigated by using a gel filtration technique in combination with atomic absorption and emission spectrometries. A binary molecular weight distribution was found both in the fulvic acid fraction and in the humic acid fraction. The fulvic acid fractions with molecular weights of less than 1.5×10³ and of 5×10³?10⁴ accounted for 38–57 % and 25–41 % of the total fulvic acids, respectively, and the humic acid fractions with molecular weights of 10²?10⁴ and of over 2×10⁵ accounted for 58–73 % and 16–27 % of the total humic acids, respectively. The components with molecular weights of over 1.5×10³ contained 54 %, on average, of the Fe, Zn and Cu in the fulvic acid fraction, and the components with molecular weights of over 10⁴ contained 58 %, on average, of these metals in the humic acid fraction.     

Studies in seawater and lake water on interactions of trace metals with humic substances isolated from marine and estuarine sediments: II. Voltammetric investigations on trace metal complex formation in the dissolved phase

In seawater and lake water the complexation of several heavy metals, present in the dissolved state at relevant trace levels, with humic substances isolated from two marine and an estuarine sediment has been studied by differential pulse anodic stripping voltammetry (DPASV) at a hanging mercury drop electrode (HMDE). Taking Zn(II) as an example, the aim of this study was to gain direct information on the general level of importance of humic substances for the speciation of certain heavy metals in fresh and saline waters.In seawater humic acids originating from different sediments have very similar complexing properties for Zn(II), decreasing slightly in the order HAN > HAL > HAM. In lake water HAL is most efficient for complexing Zn(II), followed by HAN and HAM.In both types of natural waters, the sedimentary fulvic acid is less efficient in complexing Zn(II) than the respective humic acid from the same site. In general, the complexing efficiency decreases in the order EDTA > NTA > humic acids > fulvic acid.The problem of humic acid adsorption at the electrode, which somewhat limits the investigation of Pb(II) and Cd(II), and the impact of pH on the amount of complexed Zn(II) are also discussed.The findings provide further direct evidence for the conclusion previously drawn from existing complexation data that because of the rather low levels of dissolved humics in large parts of the oceans, the complexation efficiency of humics for Cd, Pb and Zn is too low to affect the speciation pattern of these three heavy metals.     

Distribution of oxygen-containing functional groups and elements in humic acids from marine sediments

The elemental composition and oxygen-containing functional groups contents in the marine humic acids from the five sediment samples from Sagami Bay and Suruga Bay were determined. Kumada's method of classification of soil humic acids was applied to the marine humic acids. The carbon, nitrogen, hydrogen, oxygen and sulfur contents of the marine humic acids were, on average, 52.96, 5.12, 5.79, 34.99 and 1.13%, respectively, without wide variation. In comparison with terrestrial humic acids, the marine ones had relatively lower carbon content and higher hydrogen and nitrogen contents. It is suggested that the marine humic acids have more aliphatic and less aromatic character, as expected from their possible origins, e.g., phytoplankton. The total acidity, carboxyl, phenolic and alcoholic hydroxyl, carbonyl and methoxyl group contents in the marine humic acids were, on average, 5.80, 3.27, 2.53, 2.53, 3.09 and 0.41 milliequivalents per gram of dry ash-free humic acid (me g^–1), respectively. From quantitative data on the elemental composition and functional groups of the average marine humic acid, its empirical formula was calculated to be C₁₀₇H₁₃₈O₂₀(COOH)₉(OH)₇ ^phenolic (OH)₇ ^alcoholic (CO)₉(OCH)₃N₁₀S. The marine humic acids were similar to the so-called B type of soil humic acids with regard to the distribution of functional groups and spectroscopic properties.