工业废水中溶解态有机物分析方法研究

采用0．45μm玻璃纤维滤膜将工业废水分离为悬浮态和溶解态有机物质,以二氯甲烷为萃取剂,采用液液萃取一气质联用法对工业废水中溶解态有机物进行测定。优化的最佳萃取条件为：每个pH范围各萃取2次,静置时间5min,氯化钠加入量15g。方法的加标回收率为91．1％～103％,测定结果的相对标准偏差小于5％fH=6）。该法分析时间短,易于操作。     

光化学降解溶解有机物及其对生物过程的影响

溶解有机物对控制海洋和淡水水生系统的化学、生物和物理特性有重要的影响.光化学降解溶解有机物改变了生态体系的溶解有机碳、有机物的分子量及光学特性,并且产生复杂的反应性氧化合物、二氧化碳、一氧化碳、小分子量的有机酸、氨基酸、二硫化碳等,对生物过程有重要的影响.本文简要综述了光化学降解溶解有机物的过程机理及其对生物过程的影响.     

可溶性有机质对污染土壤中铊迁移行为的影响

目的 为了查明可溶性有机质（DOM）对土壤中污染元素铊赋存形态的影响,方法 采用形态分级提取方法,将土壤中的铊重金属分成酸可交换态、铁锰氧化物结合态、有机质结合态和残留态4组分,并采用Elan 6100型ICP-MS质谱仪测定各组分中铊的质量浓度.结果 DOM可降低酸可交换态的Tl,增加铁锰氧化物结合态和有机质结合态Tl的百分含量,但对残留态Tl的百分含量没有明显影响.因此,DOM可降低铊在土壤中的活动性,从而改变了铊在土壤中的迁移行为.结论 可溶性有机质（DOM）自身的络合（螯合）能力及其吸附特性是改变重金属铊形态分布的主要因素.     

天然水体中可溶性有机质的自由基光化学行为

可溶性有机质在天然水体中广泛分布,是全球碳循环的重要组成部分。大部分的可溶性有机质含有苯环、羧基、羟基和羰基等发色团,能够吸收特定波长的太阳光,产生水合电子、单线态氧、羟基自由基等活性自由基,从而影响天然水体污染物的光化学转化以及降解过程。本文综述了20世纪90年代以来可溶性有机质的自由基光化学行为以及其在水体污染物转化中的作用方面的研究进展,并探讨了今后研究中应该关注的问题。     

Sustainable Plant Growth Promotion and Chemical Composition of Pyroligneous Acid When Applied with Biochar as a Soil Amendment

The pyrolysis of biomass material results in pyroligneous acid (PA) and biochar, among other by-products. In agriculture, PA is recognized as an antimicrobial agent, bio-insecticide, and bio-herbicide due to antioxidant activity provided by a variety of constituent materials. Application of PA to crop plants and soil can result in growth promotion, improved soil health, and reduced reliance on polluting chemical crop inputs. More detailed information regarding chemical compound content within PA and identification of optimal chemical profiles for growth promotion in different crop species is essential for application to yield effective results. Additionally, biochar and PA are often applied in tandem for increased agricultural benefits, but little is known regarding the optimal proportion of each crop input. This work reports on the effect of combined applications of different proportions of PA (200- and 800-fold dilutions) and chemical fertilizer rates (100%, 75%, 50%, and 0%) in the presence or absence of biochar on Komatsuna (Brassica rapa var. perviridis, Japanese mustard spinach) plant growth. To elucidate the chemical composition of the applied PA, four different spectroscopic measurements of fluorescence excitation were utilized for analysis—excitation-emission matrix, ion chromatography, high-performance liquid chromatography, and gas chromatography-mass spectrometry. It was determined that PA originating from pyrolysis of Japanese pine wood contained different classes of biostimulants (e.g., tryptophan, humic acid, and fulvic acid), and application to Komatsuna plants resulted in increased growth when applied alone, and in different combinations with the other two inputs. Additionally, application of biochar and PA at the higher dilution rate increased leaf accumulation of nutrients, calcium, and phosphorus. These effects reveal that PA and biochar are promising materials for sustainable crop production.     

电喷雾电离源结合傅立叶变换离子回旋共振质谱分析地下水中可溶性有机质分子组成

应用电喷雾电离源结合傅立叶变换离子回旋共振质谱(ESI FT-ICR MS)对地下水进行分析,基于高精确度的分子量检测结果,鉴定出O_x,N_1O_x和N_2O_x3大类,共计27小类含杂原子的化合物。杂原子化合物中O_x类化合物占绝大多数,而含N化合物则以结合大量氧原子的形式广泛存在。结合各类杂原子化合物的等效双键数(DBE)及碳数分布,发现O_x类化合物中存在大量的羧酸结构,推测含氮化合物可能来自于O_x类化合物的衍生反应。实验结果拓宽了对地下水中可溶性有机质的认识,为进一步确定其中杂原子化合物的结构类型奠定了基础。     

Electron Transfer Capacities of Dissolved Organic Matter Derived from Swine Manure Based on Eletrochemical Method

Dissolved organic matter (DOM) is the most active fraction of compost organic matter. The presence of the redox-active functional groups in DOM allows it to act an electron shuttle to promote the electron transfer between microorganisms and terminal electron acceptors. In this study, the electron transfer capacities (ETCs) of compost DOM samples at eight different composting stages were determined by electrochemical method. 2,2’-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) and Diquat dibro-mide monohydrate (DQ) were used to measured electron donating capacity (EDC) and electron accepting capacity (EAC) at working voltage 0.61 V/–0.49 V, respectively. The evolution characteristics of the chemical structures and components were analyzed by combining the three-dimensional fluorescence spectra, Fourier transform infrared (FTIR) spectra and elemental analysis. The results showed that the EDC of DOM increased from 16.850 μmol e^? (g C)^?1 to 22.077 μmol e^? (g C)^?1, The EAC decreased from 1.866 μmol e^? (g C)^?1 to 1.779 μmol e^? (g C)^?1. The results of three-dimensional fluorescence spectroscopy showed that the relative contents of humic-like and protein-like components gradually increased and decreased, respectively, during the composting process. The humuc-like components were the main contributor for the ETC of DOM. FTIR spectra showed that there was no significant change in the hydroxyl and carboxyl group contents of DOM during composting, suggesting no contribution of these function groups to the ETC of DOM. The elemental analysis showed that the content of oxygen in the DOM increased during the composting process, while the sulfur-containing group might be dominated contributor for its ETC.     

三峡库区水体溶解有机质的荧光光谱特性

利用荧光发射和三维荧光光谱(EEM)研究了三峡库区(TGRA)长江干流及嘉陵江、乌江两支流水体溶解有机质(DOM)的荧光特性.结合采样段面溶解有机碳(DOC)、氧化还原电位(ORP)、pH等参数,考察了干流、两支流及其汇合后各水体DOM的荧光指数f450/500和类腐殖酸与类富里酸强度比值rC/D变化,分析了类腐殖酸、类富里酸及类蛋白质在库区支流与干流、上游与下游水体的来源、组成、分布及环境行为.实验表明: 干流水体中DOM以类富里酸、类蛋白质荧光有机质为主;嘉陵江水体DOM以类蛋白质为主,富里酸次之; 在朝天门与长江汇合后,类蛋白峰强减弱而类腐殖酸有一定增加;乌江以类富里酸为主,汇合干流后,富里酸和类蛋白质峰增强;库区上游水体DOM主要受嘉陵江影响;干流DOM受陆源性影响.初步揭示了水体DOM的EEM特性与库区水质参数的相关性,为水体监测与分析提供参考.     

城市污水处理过程中有机污染物三维荧光特性的变化规律

采用三维荧光光谱法研究了城市污水处理过程中溶解性有机物的三维荧光特性变化规律。研究结果表明,生活污水中荧光类溶解性有机物主要以类蛋白有机物、UV腐殖质和可见腐殖质为主;污水生物处理前后特征荧光峰中心位置和强度均发生明显的改变,表明污水中有机物的相对组成和含量随生物处理过程而变化。三维特征荧光参数可以反映污水处理过程中污染物的种类、性质和含量变化等丰富信息。其测定迅速简便、灵敏度高,可用于污水处理效果的定性分析、定量评价,易于实现污水处理过程的实时在线监测,指导污水处理工艺的设计、运行、管理和控制。     

Simple Derivatization–Gas Chromatography–Mass Spectrometry for Fatty Acids Profiling in Soil Dissolved Organic Matter

Dissolved organic matter is an important component of the global carbon cycle that allows the distribution of carbon and nutrients. Therefore, analysis of soil dissolved organic matter helps us to better understand climate change impacts as it is the most dynamic and reactive fraction in terrestrial ecosystems. Its characterization at the molecular level is still challenging due to complex mixtures of hundreds of compounds at low concentration levels in percolating water. This work presents simple methods, such as thermochemolysis– or derivatization–gas chromatography, as an alternative for the analysis of fatty acids in dissolved organic matter without any purification step. The variables of the protocols were examined to optimize the processing conditions for the C₉–C₁₈ range. As a proof of concept, fatty acid distributions of soil percolating water samples from a long-term field experiment were successfully assessed. The variability of dissolved organic acid distributions was pronounced through depth profile and soil treatment but no major change in composition was observed. However, although the optimization was done from C₉ to C₁₈, detection within the C₆-C₃₂ fatty acids range was performed for all samples.     

基于超高分辨质谱的溶解性有机质分子转化机理分析

本研究对比分析了不同处理工艺对制药废水中溶解性有机质(DOM)的降解, 通过三维荧光图谱(EEM)、总有机碳(TOC)、zeta电位以及动态光散射技术进行表征分析, 并利用超高分辨质谱进一步探究了过硫酸钾(PS), 碳纳米管(CNTs), CNTs/PS工艺诱导的DOM分子转化机制. 结果表明, PS通过静电聚合作用和氧化作用对DOM中的缩合芳香类化合物(76%)和蛋白质/多肽类(65%)去除较大, CNTs通过吸附作用对不饱和水平较低的含氧化合物(木质素类、蛋白质/多肽类和氨基糖类(90%))的去除最为显著, 而CNTs/PS则是通过吸附作用、电子转移以及单线态氧(¹O₂)的生成以实现不同组分的DOM的高效去除. 化学参数定量分布以及线性拟合分析表明, PS和CNTs/PS体系对于DOM分子的化学参数分布影响较小, 而CNTs的吸附作用会导致残留分子的平均氧碳比(O/C)、芳香指数(AI_mod)、等价双键(DBE)和碳的名义氧化态(NOSC)数值增加, 且氧原子对DBE的贡献作用增大. 本研究结果为进一步理解DOM在水环境中的去除和分子转化提供了理论依据.     

溶解有机质对光照自然水体生物膜体系中H2O2生成的影响

通过模拟实验研究了生物膜胞外聚合物(EPS)和乙二胺四乙酸(EDTA) 2种典型溶解有机质(DOM)成分对自然水体生物膜体系中过氧化氢(H₂O₂)生成特征的影响, 并研究了体系初始pH值、 DOM浓度、 溶解氧(DO)等因素的影响. 结果表明, DOM的存在对自然水体生物膜体系中H₂O₂的生成有明显影响. 光照能促使EPS产生H₂O₂, 而EPS的存在对生物膜产生H₂O₂的直接影响不显著, EPS与生物膜共存体系中的H₂O₂由二者共同产生; EDTA本身不产生H₂O₂, 且对H₂O₂分解影响很小, 但会显著抑制生物膜产生H₂O₂, 且浓度越高抑制作用越明显. 体系pH值、 DOM浓度和DO均能不同程度影响EPS产生H₂O₂及EDTA抑制生物膜产生H₂O₂的作用.     

Characterization of Functional Groups in Estuarine Dissolved Organic Matter by DNP-enhanced 15N and 13C Solid-State NMR

Estuaries are key ecosystems with unique biodiversity and are of high economic importance. Along the estuaries, variations in environmental parameters, such as salinity and light penetration, can modify the characteristics of dissolved organic matter (DOM). Nevertheless, there is still limited information about the atomic-level transformations of DOM in this ecosystem. Solid-state NMR spectroscopy provides unique insights into the nature of functional groups in DOM. A major limitation of this technique is its lack of sensivity, which results in experimental time of tens of hours for the acquisition of ¹³C NMR spectra and generally precludes the observation of ¹⁵N nuclei for DOM. We show here how the sensitivity of solid-state NMR experiments on DOM of Seine estuary can be enhanced using dynamic nuclear polarization (DNP) under magic-angle spinning. This technique allows the acquisition of ¹³C NMR spectra of these samples in few minutes, instead of hours for conventional solid-state NMR. Both conventional and DNP-enhanced ¹³C NMR spectra indicate that the ¹³C local environments in DOM are not strongly modified along the Seine estuary. Furthermore, the sensitivity gain provided by the DNP allows the detection of ¹⁵N NMR signal of DOM, in spite of the low nitrogen content. These spectra reveal that the majority of nitrogen is in the amide form in these DOM samples and show an increased disorder around these amide groups near the mouth of the Seine.     

三峡水库溶解有机质的三维荧光光谱研究

在三峡水库首次蓄水175 m最高水位及其消落至145 m最低水位期间, 分别采集三峡水库 8个段面的水样, 应用三维荧光光谱(EEM)研究了三峡水库中溶解有机质(DOM), 考察了DOM在整个三峡水库的组成、分布及其来源, 着重探讨了30 m水位消落对DOM的影响, 并拟合了DOM中各荧光峰强的比值变化及其与pH、溶解氧(DO)、溶解有机碳(DOC)、氧化还原电位(ORP)等环境因子的线性关系. 结果显示, 水库干流DOM的EEM均表现出4个荧光峰, 归属为类蛋白质、类腐殖酸、类富里酸. 最高水位时, 从三峡水库上游至下游, 荧光峰强逐渐增强, 在大坝前最强|最低水位时, 荧光峰强较其高水位均显著提高, 受丰水期沿岸不同的陆源汇流影响, 最强荧光峰出现在三峡水库中、上游. 各荧光峰强与环境因子的线性关系在枯水期高水位时较好, 在丰水期低水位时仅有DO与类蛋白有正相关性. 揭示了三峡水库水质主要受丰水期的陆源汇流影响, 而大坝运行模式的影响不显著.     

堆肥过程不同分子量水溶性有机物电子转移能力的演变及影响因素

利用超滤技术、电化学方法和光谱技术, 以堆肥水溶性有机物的不同分子量(MW)组分为研究对象, 分析在堆肥过程中不同分子量水溶性有机物(DOM)的组成特征、结构演变和电子转移能力变化的影响因素.结果表明, 类蛋白物质主要存在于堆肥前期的DOM(MW<1 kDa)中, 随着堆肥的进行, 类蛋白物质不断降解, 类富里酸物质持续合成, 堆肥后期类蛋白物质被完全降解, 类富里酸物质成为DOM(MW<1 kDa)主要的荧光组分.类腐殖物质是DOM(MW=1～3 kDa)、DOM(MW=3～5 kDa)和DOM(MW>5 kDa)的主要荧光组分, 堆肥过程中类腐殖质物质在3种不同分子量组分的变化各不相同, 但是堆肥后期类腐殖质物质在3个不同分子量组分的含量均高于堆肥初期. 堆肥过程中DOM(MW<1 kDa)的电子供给能力(EDC)呈降低趋势, 而电子接受能力(EAC)呈升高趋势; DOM(MW>5 kDa)的EDC在堆肥过程中呈上升趋势, 而EAC则无明显的变化规律.DOM(MW=1～3 kDa)和DOM(MW=3～5 kDa)的EDC和EAC在整个堆肥过程无明显变化规律.不同分子量组分堆肥DOM 的EAC受控于堆肥过程木质素降解产物的含量, 而其EDC变化与荧光参数和紫外参数无明显关系.     

Sustainable Diesel from Pyrolysis of Unsaturated Fatty Acid Basic Soaps: The Effect of Temperature on Yield and Product Composition

The production of sustainable diesel without hydrogen addition remains a challenge for low-cost fuel production. In this work, the pyrolysis of unsaturated fatty acid (UFA) basic soaps was studied for the production sustainable diesel (bio-hydrocarbons). UFAs were obtained from palm fatty acids distillate (PFAD), which was purified by the fractional crystallization method. Metal hydroxides were used to make basic soap composed of a Ca, Mg, and Zn mixture with particular composition. The pyrolysis reactions were carried out in a batch reactor at atmospheric pressure and various temperatures from 375 to 475 °C. The liquid products were obtained with the best yield (58.35%) at 425 °C and yield of diesel fraction 53.4%. The fatty acids were not detected in the pyrolysis liquid product. The gas product consisted of carbon dioxide and methane. The liquid products were a mixture of hydrocarbon with carbon chains in the range of C₇ and C₂₀ containing n-alkane, alkene, and iso-alkane.     

Correlation Analysis of the Carboxyl and Carbonyl Groups of Natural Organic Matter and the Formation Potential of Trihalomethanes and Chloral Hydrate

Natural organic matter (NOM) has always been considered the main precursor of disinfection by-products (DBPs) during the chlorine disinfection of drinking water. This research focuses on investigating the correlation between the functional group (carboxyl and carbonyl groups) content of NOM and the formation of trichloromethane (TCM) and chloral hydrate (CH). The quantitative determination of carboxyl groups, carbonyl groups, TCM, and CH were conducted during the drinking water treatment processes with different coagulant dosages and with/without pre-oxidation by KMnO₄ or NaClO. The most appropriate coagulant for the removal of conventional components was polyaluminum chloride (PAC), and the dosage was 110 mg/L. Up to 43.7% and 14.5% of the carboxyl and carbonyl groups, respectively, were removed through the coagulation and sedimentation processes, which can be enhanced by increasing PAC dosage. The filtration process further increased the removal rates of these two functional groups to 59.8% and 33.5%, respectively. The formation potential of the TCM and CH decreased as the PAC dosage increased. Pre-oxidation by KMnO₄ (0.8–1.0 mg/L) effectively controlled the formation of DBPs while increasing the carboxyl and carbonyl group content. Pre-oxidation by NaClO decreased the formation of TCM rather than CH, and a suitable amount (0.5–1.0 mg/L) decreased the carboxyl and carbonyl groups. It was found that there was a good linear correlation between carboxyl groups and TCM and CH. The linear fit R² values of the carboxyl groups to TCM and CH were 0.6644 and 0.7957, respectively. The linear fit R² values of the carbonyl groups to TCM and CH were 0.5373 and 0.7595, respectively.     

HYPY/SE提取固体有机质中生物标志化合物的研究

采用催化加氢热解技术提取了高演化沉积有机质中共价键结合生物标志物分子。催化加氢热解是在高氢压(>10MPa)、较慢的升温速率(5℃min)和高分散型催化剂作用下的还原反应,是一种对提取高收率、少结构重排的干酪根和沥青质分子骨架中共价键结合的生物标志化合物有独特作用的分析性手段。实验结果表明,通过催化加氢热解处理可以合理释放出高演化沉积有机质分子骨架中的具有原生性的组分,在油油对比、油源对比、油藏有机质沉积环境以及油藏的次生改造等研究方面可获得较好的应用。特别是针对高演化沉积物和一些后期严重降解的油藏而言,在恢复原始有机地球化学信息研究方面更具有重要意义。     

高温高压水中干酪根热解的拉曼光谱原位研究

利用对顶砧压腔装置,以金刚石作为顶砧,通过观测和采用拉曼光谱对干酪根在高温高压水中热解的具体过程进行了原位研究.由于金刚石顶砧只在约1 332 cm-1波数出现一个很强很尖锐的峰,因此用于压 标的石英、介质水以及样品干酪根的拉曼峰都未受影响.测试了在450℃和850 MPa条件下干酪根变化的拉 曼峰.随着温度和压力的增加,干酪根在1 600 cm-1波数附近由于芳香环振动引起拉曼峰的最大峰位置 (vmax)和半高宽(FWHM)存在转折变化.在干酪根热解之前,其芳香环结构和无序结构之间的缺陷向有序化变化.而对于干酪根的热解过程,先是热解为液相碳氢化合物,随后进一步热解为更小分子的成分,如 CH4.干酪根的热解过程与压力密切相关,增加压力对热解存在抑制作用.     

基于有机硼酸的共价键有机框架研究进展

共价键有机框架(Covalent Organic Frameworks,COFs)是具有明确孔径分布的多孔晶体材料,在气体贮藏、催化、分离、光学器件和化学传感等方面均有应用前景。有机硼酸中硼原子最外层空的p轨道能与π键产生特殊的轨道作用,也可与路易斯碱发生配位作用。上述特点使其能够作为结构和功能导向的基元而用于构筑共价键有机框架。本文从合成、结构以及性质等方面对有机硼酸构筑的共价键有机框架进行了介绍。