Mechanism of oxidation and catalysis of organic matter abiotic humification in the presence of MnO2

Humification plays a critical role in the environmental fate of organic wastes, and MnO_2 holds great promise for enhancing this reaction. However, the effects of MnO_2 on the enhancement of the humification reaction remain ambiguous. To better reveal the mechanism by which MnO_2 enhances the reaction and investigate the fate of the humification products, abiotic humification experiments were performed using increasing concentrations of dissolved organic matter(DOM) to a fixed amount of MnO_2. DOM was represented by model humic precursors consisting of catechol, glucose and glycine. The results indicate that the reduction of MnO_2 played a dominant role in the formation of fulvic-like acids(FLAs), and the subsequent reduction products, MnOOH and Mn(II), acted as catalysts in the formation of humic-like acids(HLAs). Moreover, CO_2 release occurred during the formation of FLAs, and a strong linear correlation between CO_2 release and the formation of FLAs was observed(p 0.01), where 0.73–1.87 mg of CO_2 was released per mg dissolved organic carbon(DOC)FLAs. Furthermore, the concentration of MnO_2 had a pronounced influence on the product behavior, where a lower MnO_2 concentration decreased the quantity of FLAs produced.     

Transformations in carbon and nitrogen-forms in peat subjected to progressive thermal stress as revealed by analytical pyrolysis

To study the characteristic N-forms of humic-type materials, samples of sapric peat from Galicia (northern Spain) were heated at 350 °C for 60, 90, 120, 150 and 180 s, and studied by Curie-point Py-GC/MS, solid-state CPMAS ¹³C-NMR and ¹⁵N-NMR spectroscopies. NMR analysis of the peat samples in the progressive heating stages showed the concentration of heterocyclic N-forms, the maximum structural transition amide-to-heterocyclic forms being observed in samples heated for 120 s (56% heterocyclic N and 34% aromatic C). Under more drastic conditions all N-forms were depleted. Correlation between spectroscopic and pyrolytic data betrayed specific pyrolytic markers for the different N-forms. The intensity of the ¹⁵N-NMR amide peak tended to be positively correlated to the yield of indoles, imidazoles and pyrazoles, and negatively correlated to those of benzonitriles and pyrazines. Analytical pyrolysis also showed a progressive enrichment in lipids and alkyl macromolecules with increasing heating intensity, and a decrease in lignin-derived, polysaccharide-derived and N-containing compounds. The relative abundance of non-methoxyphenolic aromatic compounds did not change. The N-compounds in peat samples unheated or heated for 60–90 s released methylpyrazole, dimethylpyrroline, methyldiphenylindole and pyrazole, whereas peat samples heated for 120 s mainly yielded methylpyrazine and methyldiphenylindole. Dimethylpyrroline and pyrazine prevailed in samples heated for 150 s, whereas samples heated for 180 s yielded mainly pyrrole. Pyrolysis data presented low possibilities for forecasting the extent of the O-alkyl domain, but reflected quantitatively the transformations in the lignin-like moiety. Both techniques coincide in pointing out the accumulation of a recalcitrant alkyl domain possibly derived from abiotic condensations or inherited lipid biomacromolecules.     

Products of laccase catalyzed reaction of 1-hydroxypyrene

The formation of residues in soils and sediments which are not readily extractable is an important fate for hydrophobic organic contaminants. Reaction of 1-hydroxypyrene, a known fungal and terrestrial invertebrate metabolite and photo-oxidation product of pyrene, with a commercially prepared laccase (an oxidoreductive enzyme) in solution provides a test system to study the fate of residues in nature. The reaction of dissolved 1-hydroxypyrene with laccase produced a distinct color change and caused a precipitate to form. At least six products were shown by HPLC analysis with photodiode array detection. The most prominent peak was composed of 1,6- and 1,8-pyrene-dione as confirmed by proton NMR analysis. LC/MS data on remaining peaks indicate that radical coupling produces acetonitrile soluble dimers and at least one trimer. Proposed structures consistent with MS and photodiode array data indicate that pyrene subunits are linked predominantly by ether bonds. Additional products, insoluble in acetonitrile, were also formed. The formation of complex products in vitro, indicates that the same mechanisms could produce bound residues in soil.     

不同结构水钠锰矿催化氧化对苯二酚腐殖化程度的差异及其原因分析

本文合成了一系列不同氧化度的酸性和碱性水钠锰矿,以对苯二酚作为腐殖质形成的前驱物,分析水钠锰矿矿物类型和亚结构变化对对苯二酚腐殖化程度的影响。取得的主要结果有:水钠锰矿的矿物类型和亚结构(锰氧化度、八面体空位、H+、Mn4+和Mn3+含量)对对苯二酚的腐殖化程度具有重要的影响,且矿物类型的影响大于同种矿物不同亚结构产生的影响。酸性水钠锰矿比碱性水钠锰矿含有更多的H+,导致酸性水钠锰矿比碱性水钠锰矿具有更高的氧化容量,反应达到平衡后,对苯二酚腐殖化程度更高。因此,水钠锰矿物中H+含量对对苯二酚腐殖化程度的影响要大于矿物中Mn4+和Mn3+含量的影响。同种类型水钠锰矿氧化度越高,得电子量将越多,氧化容量越大,反应达到平衡后,对苯二酚腐殖化程度越高。     

水溶液中4-氯酚在光照下的矿化和聚合化

在光照条件下,４－氯酚溶液浓度随着光照时间的延长而降低,ＣＯ２的释放表明在４－氯酚光化学反应过程中存在矿化作用,通过光子相关光谱表征,确定反应体系存在聚合作用,聚合物具有荧光性。对反应体系进行ＵＶ、ＩＲ光谱表征,表明这一过程中存在腐殖化作用,有类腐殖质生成,聚合化与矿化相比较,前者是主要过程。     

黄浦江溶解有机质光学特性与消毒副产物NDMA生成潜能的关系

对黄浦江表层水样的过滤液进行紫外吸收光谱和荧光光谱扫描,并测定了溶解有机碳(DOC)、N-亚硝基二甲胺(NDMA)及其生成潜能(NDMA-FP),探讨了黄浦江溶解有机质(DOM)的光学特性与消毒副产物NDMA生成潜能的关系.结果表明,黄浦江水中NDMA-FP随DOC浓度增加而增加(r=0.487,P<0.01),但与DOM的比吸收系数(SUVA254)和腐殖化指数(HIX)均呈负相关(r=-0.605,P<0.01;r=-0.396,P<0.01);NDMA-FP还与相对较低分子量的类酪氨酸、类色氨酸等类蛋白物质的荧光强度呈显著正相关(r=0.421,P<0.01;r=0.426,P<0.01),而与类腐殖质的荧光强度则呈显著负相关(r=-0.422,P<0.01).因此,黄浦江水中消毒副产物NDMA的生成潜能随着溶解有机质含量的增加而增加,特别是与DOM中的类蛋白组分含量密切相关,但随着DOM的芳香性和腐殖化程度的增强而减少.     

乌梁素海沉积物孔隙水中溶解有机质的荧光及紫外光谱研究

运用紫外可见光吸收光谱与荧光光谱研究乌梁素海沉积物孔隙水中溶解有机质的来源、结构及腐殖化程度。r_(A,C)、HIX、SUVA₂₈₀和SUVA₂₅₄等被用于表征DOM的腐殖化程度和芳香构化程度及结构,f_450/500用于指示DOM的来源。研究结果表明：腐殖化程度最高的点为湖泊东部的W4样点,腐殖化程度最低的为总排干影响区域的W1样点。E_253/203表明湖泊入口处沉积物孔隙水中有机质主要为不可取代的芳香环结构。荧光指数f_450/500为1.57～1.82之间。总体而言,f_450/500的值更接近于1.6,处于2个端源中间,说明乌梁素海DOM中的腐殖质主要来源于陆源输入。相关分析的结果表明, DOM的不同来源对其腐殖化程度产生影响。随着腐殖化值的增大,DOM的来源由生物源向陆源过渡。     

多方法研究呼伦湖表层沉积物有机质的赋存特征及来源

湖泊沉积物有机质是全球碳循环的重要组成部分之一.寒旱区湖泊由于地理位置和气候条件的特殊性,其沉积物有机质的赋存和迁移转化特征更容易受到气候变化的影响.以我国寒旱区典型代表湖泊——呼伦湖为例,采用连续提取法、C/N（碳氮比值）、δ13C（碳稳定同位素）、三维荧光光谱技术对呼伦湖表层沉积物有机质的含量和组分的时空分布特征、污染来源及稳定性进行了研究.结果表明:①2018年10月（秋季）、2019年3月（冬季）、2019年5月（春季）、2019年7月（夏季）,呼伦湖表层沉积物中w（TOC）的平均值分别为（25.05±9.73）（26.92±11.60）（24.68±10.19）（24.36±10.01）g/kg,呈冬季高、夏季低,由西北部向东南部递减的时空分布趋势.②w（WEOM）（WEOM为水提态有机质）、w（FA）（FA为富里酸）、w（HA）（HA为胡敏酸）和w（HM）（HM为胡敏素）的年均值分别为（0.63±0.33）（2.31±1.26）（3.42±1.49）（19.21±7.83）g/kg,w（WEOM）:w（FA）:w（HA）:w（HM）为1.0:3.7:5.5:30.7,其中HM为有机质的优势组分.③WEOM包括类富里酸组分C1,类腐殖酸组分C2和C3,以及类色氨酸组分C4共4个荧光组分,其中,类腐殖质组分（C1+C2+C3）贡献了总荧光强度的79.2%,为优势荧光组分.④沉积物有机质主要来自于陆源,陆源有机质的平均贡献率在80%左右.⑤沉积物PQ值（胡敏酸占腐殖酸的比例）和WEOM的HIX（腐殖化指数）年均值分别为0.55和6.39,表明现阶段呼伦湖表层沉积物有机质腐殖化程度较高且相对稳定.研究显示:呼伦湖表层沉积物有机质含量较高,表现出季节和空间分布差异性;有机质主要来自陆源,以类腐殖质为主,具有腐殖化程度高和相对稳定的特点.      

头孢菌素发酵菌渣电子束辐照-好氧堆肥无害资源化处理技术研究

采用电子束辐照联合好氧堆肥工艺对头孢菌素发酵菌渣进行无害化处理和资源化利用.堆肥原料为头孢菌素菌渣、鸡粪和秸秆,菌渣未辐照直接进行堆肥的反应器（1号）与菌渣辐照50 kGy后再进行堆肥的反应器（2号）平行运行进行对比.结果表明：2号反应器的堆体温度、温度上升速率以及高于55 ℃天数均大于1号反应器.在30 d堆肥周期中,2号堆体的平均温度比1号堆体高3.3 ℃;1号和2号堆体温度高于55 ℃的天数分别为5 d和7 d.2号堆体的有机质含量和溶解性TOC浓度下降均较快,表明其有机物的利用效率较高.辐照预处理可促进菌渣好氧堆肥腐殖化进程,2号堆体的腐殖化指数比1号堆体高15%~51%.2号堆体中抗生素头孢菌素C的浓度到第10 d即可降至液相色谱无法检出.此外,两个反应器堆肥过程中抗性基因ermB丰度有所减小,sul2丰度升高.堆肥产品中无抗生素残留,有机质指标远高于有机肥料国家标准,其作为优质肥料进行安全再利用需重点关注抗性基因的影响.