吉林金川西大甸子泥炭沉积中火山物质的发现及其意义附：泥炭中胡敏酸的稳定碳同位素值（δ<'13>C）作为古气候代用指标可行性研究

泥炭以发育广泛、连续沉积好、沉积速率大（可达1mm/a甚至更大）、记录丰富等特点,正成为过去全球变化研究的良好综合地质档案.参考冰芯、黄土、深海沉积物等中矿物固体的研究思路和方法,希望能对泥炭中可能存在的火山物质和其它风粉尘进行研究.在对吉林金川西大甸子泥炭样品的处理过程中,摸索出一套泥炭样品中固体物质（如火山物质）初步的处理、分析方法;并对金川西大甸子干玛珥泥炭沉积中部一段泥砂状物质进行鉴定,首次发现火山玻璃,判断这些泥砂物为火山灰砂.目前研究表明,泥炭纤维素的δ<'13>C序列能较好地反映古气候变化,那么泥炭中胡敏酸的δ<'13>C序列可否也能反映古气候变化,该文对此作了初步研究.用碱溶酸沉淀方法从泥炭中提取出所谓的胡敏酸,用燃烧法将胡敏酸、纤维素中的碳转化为CO<,2>气体,测定它们的稳定碳同位素组成（δ<'13>C）.与能较好地反映气候变化的纤维素δ<'13>C序列相比,胡敏酸的δ<'13>C序列反映气候变化不明显.

溶液介质条件和腐殖影响下REE在水/粘土界面分配和分馏的实验研究

过去几十年，由于REE具有重要的物源和过程示踪的地球化学意义，又与核放射性元素（钢系元素）的地球化学结构类似，因此，稀土元素的表生地球化学分配和行为研究便成为微量元素地球化学研究的一个重要部分。目前"通过水体悬浮物吸附态REE组成变化分析研究水／微粒界面作用REE分异现象．的工作不少，但至今进行的胶体或其他微粒吸附REE的实验研究不多，且已有的实验未能对溶液介质条件（如pH、离子强度、阴离子、固／液比），尤其是天然有机物的控制机理进行系统研究，对所观察到的水体中REE及其他微量元素分布变化多样性的解释仍缺乏实验依据。本文用结晶良好且粘土矿物含量高的苏州高岭土、美国粘土协会高岭土（Kga-1b）和蒙脱土（Wwy-2）作为吸附剂，采用系列吸附实验定量研究了不同理化条件（如pH值、离子强度、固／液比）下，受溶液阴离子（Cl-、C1O4-、SO42-、HCO3-）和Fluka胡敏酸（HA）影响，REE在粘土／水界面的分配和分馏，并讨论了HA和粘土的相互作用及胡敏酸存在与不存在时的REE形态分布。得到以下几点重要认识，为合理解释地表水体中既E和其他微量元素分布变化的多样性提供了实验依据：1、REE在苏州高岭土／水界面的重现性实验结果为：稀土配分系数D的相对标准偏差最大值为Eu8.4％，其他大多介于5．0％和6．6％间。而稀土吸附率Rd的相对标准偏差最大值为D2.2％，其他大多＜2％。较小误差表明本次研究所用实验方法是可行的。2、REE在苏州高岭土／水界面的动力学实验结果表明：短时间内（几分钟）稀土快速吸附在高岭土：接着因为粘土的层状结构，在20h内粘土层间金属与REE发生交换，稀土分配系数变化较大；20h以后能达到稳定的吸附／解吸平衡。因此本次研究采用的平衡时间为24h。3、pH分别为4.5和6.5时REE在苏州高岭土冰界面的分配能用Langmuir吸附等温线模拟和MINEQL＋软件表达。与静电吸附相对应，pH值越高REE最大吸附量越大。同时REE浓度的差异造成了REE分馏，总的趋势是REE含量越高，分馏越不明显。4、近中性（pH＝6.5）条件下不同阴离子的存在对REE在苏州高岭土／水界面分配和分馏的影响表明：随阴离子（Cl-、ClO4-、SO42-）含量升高REE吸附率降低，其中SO42-对REE吸附的影响最大，说明Na＋质量效应和阴离子配合的影响；同时由于不同阴离子与轻重R陇的络合差异所致，阴离子含量越高，轻重稀土的分馏越明显（La／Yb＝0.14-0.96），一般为阴离子含量的增加使得重稀土更多的被吸附，其中C1-和SO42+的影响最为明显。HCO3-虽然与REE有较强配合，但可能由于我们的HCO3-实验浓度低（＜0.0O25mol／L），在我们的实验结果中其对REE吸附和分馏的影响较小。5、由于不同pH和介质条件下，REE的络合形态分布不同，它们可以影响其在水／粒界面的分配。应用MINEQL＋模型，考虑REE的氢氧化物、碳酸盐和腐殖酸的影响，研究了REE的形态分布，结果表明fIA的存在对REE形态有很大影响：在HA不存在时，pH7-8间REECO3＋为主要的REEs形态，在更低和更高pH值，REE主要存在形式分别为REE加和REE（CO3）2-；而当HA存在时，在1）H值3-9，REEHA成为主要形态，在低pH（＜3）和高pH（＞9）时REE3+和REE（CO3）2-分别为主要形态。6、在较宽的pH范围HA能吸附在粘土上意味着在大多数含HA的天然水体中，粘土表面被HA覆盖。随H增加粘土对HA的吸附降低，反应了配位体交换或表面络合反应引起的专属吸附，其他如疏水性、、腐殖物质的溶解和HA的结构变化可能也影响了吸附。HA含量、矿物表面积和离子强度等理化条件对HA吸附会产生影响，从而影响HA对粘土表面的覆盖和接下来的粘土对REE的吸附。7、溶液介质条件对REE在粘土（Kga-1b和SWy-2）／水界面分配和分馏的影响表明：主要与静电相互作用、离子交换反应相对应，除低PH外，REE在高岭土上的吸附表现出弱的pH依赖性；而随pH增加REE在蒙脱土上的吸附呈下降趋势，显示交换反应为吸附过程的主要因素。在两种粘土中REE吸附均为随离子强度增加而降低，反应了Na质量效应。8、腐殖物质在粘土表面的吸附改变了吸附剂的属性。HA存在时REE在固液界面的分配反应了REEHA在固液界面的分配和HA在高岭土或蒙脱土／水界面上的分配，其他如静电吸附等机制也影响了吸附：在高岭土中，HA会增加低pH（＜4）吸附，随pH增加（＞5）HA会降低吸附。与此不同，在整个PH范围（3-10），HA的存在明显降低了REE在蒙脱土上的吸附。REE吸附在高岭土上随队含量增加是先增加后降低。而蒙脱土实验中，在低HA含量（＜5mg／L）处，RE阮吸附率与HA含量增加呈线性降低至几个百分比，而在高队含量处，REEs吸，附率无明显变化。这些清楚地说明水体环境中有机物的存在通常降低微量金属吸，附在微粒上，增加微量金属在水体中的溶解量，从而促进微量金属在水体环境中的长距离迁移。9、HA存在和不存在时，吸附／解吸过程中的REE分馏随pH或离子强度的变化都不明显，但由于REE系列与腐殖物质和矿物络合的差异，会随队含量的变化发生明显变化。通常溶液中高队含量增加了LREE在高岭土／蒙脱土上的吸附。这些结果是在HA存在时，微粒相上产生LREE富集的一个实验证实，也和大多数天然水体中的REEs分馏相一致。

Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry with a matrix of carbon nanotubes for the analysis of low-mass compounds in environmental samples

The use of matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) for environmental analysis has been mainly focused on qualitative analysis of high-mass molecules, such as toxins, humic acid, and microorganisms. Herein,we describe a novel MALDI-TOF-MS method with a matrix of oxidized carbon nanotubes for analysis of low-mass compounds in environmental samples. A number of chemicals in the environment were qualitatively analyzed by the present method, and it was found that most of them, especially the highly polar chemicals, were measurable with high sensitivity. With the intrinsic ability to measure high-mass chemicals, this method can compensate for the current shortage of methods for environmental analysis for the measurement of highly polar or high-mass chemicals. For sample analysis, arsenic speciation in Chinese traditional medicines was qualified and diphenylolpropane in water samples was quantified. With the relatively high tolerance of the method to interfering molecules, a simple pretreatment or even no pretreatment could be employed before MS detection. Furthermore, this method can be employed in a high-throughput format.

Direct and Indirect Effects of Dissolved Organic Matter Source and Concentration on Denitrification in Northern Florida Rivers

Using a natural gradient of dissolved organic carbon (DOC) source and concentration in rivers of northern Florida, we investigated how terrestrially-derived DOC affects denitrification rates in river sediments. Specifically, we examined if the higher concentrations of DOC in blackwater rivers stimulate denitrification, or whether such terrestrially-derived DOC supports lower denitrification rates because (1) it is less labile than DOC from aquatic primary production; whether (2) terrestrial DOC directly inhibits denitrification via biochemical mechanisms; and/or whether (3) terrestrial DOC indirectly inhibits denitrification via reduced light availability to-and thus DOC exudation by-aquatic primary producers. We differentiated among these mechanisms using laboratory denitrification assays that subjected river sediments to factorial amendments of NO3- and dextrose, humic acid dosing, and cross-incubations of sediments and water from different river sources. DOC from terrestrial sources neither depressed nor stimulated denitrification rates, indicating low lability of this DOC but no direct inhibition; humic acid additions similarly did not affect denitrification rates. However, responses to addition of labile C increased with long-term average DOC concentration, which supports the hypothesis that terrestrial DOC indirectly inhibits denitrification via decreased autochthonous production. Observed and future changes in DOC concentration may therefore reduce the ability of inland waterways to remove reactive nitrogen. © 2013 Springer Science+Business Media New York.

Quantifying mircoorganism/organic matter interactions in saturated porous media.

Proteins and humic acids are common constituents of waste water. Latex colloids (colloids) acted as surrogates for microorganisms in multiple pulse dynamic column experiments (MPEs) that permitted colloid mobility to be quantified before and after the injection of either BSA (a protein), or Suwannee River humic acid (SRHA).
At low OM coverage colloid breakthrough curves demonstrated both BSA and SRHA reduced colloid deposition rates, but did not affect colloid irreversible deposition mechanisms. By contrast, high levels of SRHA surface coverage not only further reduced the matrix’s ability to attenuate colloids, but also resulted in reversible adsorption of a significant fraction of colloids deposited. Modelling of colloid responses using random sequential adsorption modelling suggested that 1 microgram of SRHA had the same effect as the deposition of 5.90±0.14 x109 colloids; the model suggested that adsorption of the same mass of BSA was equivalent to the deposition of between 7.1x108 and 2.3x109 colloids.
Colloid responses in MPEs where BSA coverage of colloid deposition sites approached saturation demonstrated the sand matrix remained capable of adsorbing colloids. However, in contrast to responses observed in MPEs at low surface coverage, continued colloid injection showed that the sand’s attenuation capacity increased with time, i.e. colloid concentrations declined as more were deposited (filter ripening).
Importance: Study results highlight the contrasting responses that may arise due to the interactions between colloids and OM in porous media. Results not only underscore that colloids can interact differently with various forms of deposited OM, but also that a single type of OM may generate dramatically different responses depending on the degree of surface coverage. The MPE method provides a means of quantifying the influence of OM on microorganism mobility in porous media such as filter beds, which may be used for either drinking water treatment or waste water treatment. In the wider environment study findings have potential to allow more confident predictions of the mobility of sewage derived pathogens discharging to groundwater.

Phenol degradation by powdered metal ion modified titanium dioxide photocatalysts

Conventional water purification and disinfection generally involve potentially hazardous substances, some of which known to be carcinogenic in nature. Titanium dioxide photocatalytic processes provide an effective route to destroy hazardous organic contaminants. This present work explores the possibility of the removal of organic pollutants (phenol) by the application of TiO2 based photocatalysts. The production of series of metal ions doped or undoped TiO2 were carried out via a sol–gel method and a wet impregnation method. Undoped TiO2 and Cu doped TiO2 showed considerable phenol degradation. The efficiency of photocatalytic reaction largely depends on the photocatalysts and the methods of preparation the photocatalysts. The doping of Fe, Mn, and humic acid at 1.0 M% via sol–gel methods were detrimental for phenol degradation. The inhibitory effect of initial phenol concentration on initial phenol degradation rate reveals that photocatalytic decomposition of phenol follows pseudo zero order reaction kinetics. A concentration of > 1 g/L TiO2 and Cu doped TiO2 is required for the effective degradation of 50 mg/L of phenol at neutral pH. The rise in OH- at a higher pH values provides more hydroxyl radicals which are beneficial of phenol degradation. However, the competition among phenoxide ion, Cl- and OH- for the limited number of reactive sites on TiO2 will be a negative influence in the generation of hydroxyl radical. The dependence of phenol degradation rate on the light intensity was observed, which also implies that direct sunlight can be a substitute for the UV lamps and that photocatalytic treatment of organic pollutants using this technique shows some promise.

Comparing the influence of two different natural organic matter types on colloid deposition in saturated porous medium

Humic acid and protein are two major organic matter types encountered in natural and polluted environment, respectively. This study employed Triple Pulse Experiments (TPEs) to investigate and compare the influence of Suwannee River Humic Acid (SRHA) (model humic acid) and Bovine Serum Albumin (BSA) (model protein) on colloid deposition in a column packed with saturated iron oxide-coated quartz sand. Study results suggest that adsorbed SRHA may inhibit colloid deposition by occupying colloid sites on the porous medium. Conversely, BSA may promote colloid deposition by a 'filter ripening' mechanism. This study provides insight to understand the complex behavior of colloids in organic matter-presented aquifers and sand filters. © (2012) Trans Tech Publications, Switzerland.

Comparison of AGNES (absence of gradients and Nernstian equilibrium stripping) and SSCP (scanned stripping chronopotentiometry) for trace metal speciation analysis

The free metal ion concentrations obtained by SSCP (stripping chronopotentiometry at scanned deposition potential) and by AGNES (absence of gradients and Nernstian equilibrium stripping) techniques have been compared and the usefulness of the combination of both techniques in the same electrochemical cell for trace metal speciation analysis is assessed. The free metal ion concentrations and the stability constants obtained for lead(II) and cadmium(II) complexation by pyridinedicarboxylic acid, by 40 nm radius carboxylated latex nanospheres and by a humic acid extracted from an ombrotrophic peat bog were determined. Whenever possible, the free metal ion concentrations were compared with the theoretical predictions of the code MEDUSA and with the free metal ion concentrations estimated from ion selective electrodes (ISE). SSCP values were in agreement with the ones obtained by AGNES, and both of them agreed reasonably with the ISE values and the theoretical predictions. For the lead(II)-humic acid, it was not possible to obtain the stability constants by SSCP due to the heterogeneity effect. However, using AGNES it is possible to obtain, for these heterogeneous systems, the free bulk metal concentration, which allows us to retrieve the stability constant at bulk conditions.

The mechanism of bacterial indigo reduction

The reduction of water-insoluble indigo by the recently isolated moderate thermophile, Clostridium isatidis, has been studied with the aim of developing a sustainable technology for industrial indigo reduction. The ability to reduce indigo was not shared with C. aurantibutyricum, C. celatum and C. papyrosolvens, but C. papyrosolvens could reduce indigo carmine (5,5-indigosulfonic acid), a soluble indigo derivative. The supernatant from cultures of C. isatidis, but not from cultures of the other bacteria tested, decreased indigo particle size to one-tenth diameter. Addition of madder powder, anthraquinone-2,6-disulfonic acid, and humic acid all stimulated indigo reduction by C. isatidis. Redox potentials of cultures of C. isatidis were about 100 mV more negative than those of C. aurantibutyricum, C. celatum and C. papyrosolvens, and reached –600 mV versus the SCE in the presence of indigo, but potentials were not consistently affected by the addition of the quinone compounds, which probably act by modifying the surface of the bacteria or indigo particles. It is concluded that C. isatidis can reduce indigo because (1) it produces an extracellular factor that decreases indigo particle size, and (2) it generates a sufficiently reducing potential.

Immobilization of glucose oxidase enzyme (GOD) in large pore ordered mesoporous cage-like FDU-1 silica

Large pore ordered mesoporous silica FDU-1 with three-dimensional (3D) face-centered cubic, Fm3m arrangement of rnesopores, was synthesized under strong acid media using B-50-6600 poly(ethylene oxide)-poly(butylene oxide)-poly(ethylene oxide) triblock copolymer (EO(39)BO(47)EO(39)), tetraethyl orthosilicate (TEOS) and trimethyl-benzene (TMB). Large pore FDU-1 silica was obtained by using the following gel composition 1TEOS:0.00735B50-6600:0.00735TMB:6HCl:155H(2)O. The pristine material exhibited a BET specific surface area of 684 m(2) g(-1), total pore volume of 0.89 cm(3) g(-1), external surface area of 49 m(2) g(-1) and microporous volume of 0.09 cm(3) g(-1). The enzyme activity was determined by the Flow Injection Analysis-Chemiluminescence (FIA-CL) method. For GOD immobilized on the FDU-1 silica, GOD supernatant and GOD solution, the FIA-CL results were 9.0, 18.6 and 34.0 U, respectively. The value obtained for the activity of the GOD solution with FIA-CL method is in agreement with the 35 U, obtained by spectrophotometry. (C) 2011 Elsevier B.V. All rights reserved.

Physical, chemical and biological characterization of membrane fouling

In this chapter, advanced characterization of membrane fouling as a diagnostic tool has been summarized to prevent membrane fouling. Physical, chemical and biological analyses as membrane autopsies are mainly utilized to better understand membrane foulant. The physical characterization gives structure, roughness, charge effect, strength and hydrophobicity of membrane fouling. The chemical methods provide qualitative and quantitative measurements of different inorganic and organic matter. The biological properties present the spatial biofilm distribution, structure of dominant microorganisms and isolation and identification of microorganisms. In addition, detailed membrane foulant types are reviewed in terms of structure, roughness, hydrophobicity, charge effect, strength, calcium, magnesium, aluminum, iron, silicate, particle, functional group, biopolymer, humic acid, polysaccharide, structural composition, biofilm structure, microorganism and foulant interaction.

Effect of coagulants on the fouling and performance of ultrafiltration (UF) membranes

The combined coagulation and ultrafiltration (UF) system (C-UF system) is an advanced technology to treat natural organic matter (NOM) present in water. Traditional coagulants — prehydrolyzed inorganic coagulants, organic coagulants and composite coagulants were chosen to treat synthetic water containing humic acid (HA) in order to find an efficient coagulant that could remove NOM from the water effectively. The fouling, removal efficiency of UF and the chlorine decay in the permeate were used to evaluate the effectiveness of the coagulants. The initial UV254 absorption of the tested water samples were from 0.208 to 0.234, and the UV254 after coagulation was from 0.05 to 0.184. The UV254 did not increase after coagulation. Since the humic acid used was soluble, the initial turbidity of the tested water samples were very close to zero. The turbidity increased after coagulation, as the coagulants react with humic acid to form micro-flocs, which cannot be removed fully by sedimentation. The results showed that polyferric chloride could not remove humic acid efficiently during coagulation process, but removed the humic acid well when used in the C-UF system. Moreover, for polyferric chloride and UF system, the concentration of organic compounds in permeates were minimal indicating very low levels of disinfection by-product formation, if chlorinated.

Effect of natural organic compounds on the removal of organic carbon in coagulation and flocculation processes

Natural organic matter (NOM) in water contains organic compounds that are both hydrophobic and hydrophilic with a wide range of molecular weights. It is composed of non-homogeneous organic compounds such as humic substances, amino acids, sugars, aliphatic and aromatic acids, and other chemical synthetic organic matters. NOM in water is a major concern not only because of its contribution to the formation of disinfection by-products (DBPs) and taste and odor, but also its influence on the demand for coagulants and disinfectants, the removal efficiency of water treatment processes, etc. This research aims at identifying the influence of NOM in coagulation and flocculation processes in order to optimize the coagulation and flocculation conditions. In this study, pretreated pond water was used as the source water. It was observed from the experimental results that: (1) The optimum pH for coagulation to remove NOM is around 7. (2) The optimum alum dose at this pH can vary from 125-1,225 mgl-1 when the TOC is increased from 4 to 25 mgl-1. (3) The presence of secondary compounds such as Ca2+, Mg2+ divalent cations had no significant effect on the removal of organic matter. (4) The presence of clay increased the organic removal by 15%. (5) The organic compound with higher molecular weight has higher removal affinity in coagulation process. (6) Floc size and settling velocity of floc and sludge production all increased with the increase in NOM concentration. From the results of Capillary Suction Time (CST) tests, the floc formed with lower TOC readily released the water to make the dewatering process easier. (7) The organic removal efficiency was significantly different for natural water containing non-homogeneous organic compounds compared to the synthetic water containing humic acid only (homogeneous organic matter). For example, the NOM removal efficiency was 80% for the synthetic water containing humic acid with TOC of 7 mgl-1 at pH 7; but the NOM removal for the pretreated pond water was 60%.

Photocatalytic degradation of phenanthrene on soil surfaces in the presence of nanometer anatase TiO2 under UV-light

The effect of nanometer anatase TiO2 was investigated on the photocatalytic degradation of phenanthrene on soil surfaces under a variety of conditions. After being spiked with phenanthrene, soil samples loaded with different amounts of TiO2 (0 wt.%, 1 wt.%, 2 wt.%, 3 wt.%, and 4 wt.%) were exposed to UV-light irradiation for 25 hr. The results indicated that the photocatalytic degradation of phenanthrene followed the pseudo first-order kinetics. TiO2 significantly accelerated the degradation of phenanthrene with the half-life reduced from 45.90 to 31.36 hr for TiO2 loading of 0 wt.% and 4 wt.%, respectively. In addition, the effects of H2O2, light intensity and humic acid on the degradation of phenanthrene were investigated. The degradation of phenanthrene increased with the concentration of H2O2, light intensity and the concentration of humic acids. It has been demonstrated that the photocatalytic method in the presence of nanometer anatase TiO2 was a very promising technology for the treatments of soil polluted with organic substances in the future.

Effects of mucor mucedo on corncob decomposition in pyr-contaminated soil remediation

The effect of polycyclic aromatic hydrocarbon and highly effective degradation fungi Mucor mucedo (MU) was studied on corncob decomposition in Pyr-contaminated soil for 120 days to identify the impact of a degradable immobilized carrier on the remediation of soil contaminated by persistent organic pollutants. Results showed that the corncob was mainly composed of hemicelluloses, cellulose, and water dissolved (WD) material, which accounted for 85 percent of its total weight. MU addition significantly affected corncob decomposition. Thus, humic acid production and WD and benzene-ethanol dissolved material degradation increased. The peaking of the WD content was delayed for 30 days or more. The extractable pyrene content positively correlated with the WD content in the corncob during the decomposition. These results theoretically support a refined remediation principle of immobilized microorganisms.