Effect of photo-biodegradation and biodegradation on the biogeochemical cycling of dissolved organic matter across diverse surface water bodies

The objective of this research was to quantify the temporal variation of dissolved organic matter(DOM) in five distinct waterbodies in watersheds with diverse types of land use and land cover in the presence and absence of sunlight. The water bodies were an agricultural pond, a lake in a forested watershed, a man-made reservoir, an estuary, and a bay. Two sets of samples were prepared by dispensing unfiltered samples into filtered samples in 1:10 ratio(V/V). The first set was exposed to sunlight(10 hr per day for 30 days) for examining the combined effect of photo-biodegradation, while the second set was stored in dark for examining biodegradation alone. Spectroscopic measurements in tandem with multivariate statistics were used to interpret DOM lability and composition. The results suggest that the agricultural pond behaved differently compared to other study locations during degradation experiments due to the presence of higher amount of microbial humic-like and protein-like components derived from microbial/anthropogenic sources. For all samples, a larger decrease in dissolved organic carbon(DOC) concentration(10.12% ±9.81% for photo-biodegradation and 6.65% ± 2.83% for biodegradation) and rapid transformation of DOM components(i.e., terrestrial humic-like components into microbial humic and protein-like components) were observed during photo-biodegradation experiments.Results suggest that sunlight facilitated DOM biodegradation, resulting in simpler recalcitrant molecules regardless of original composition. Overall, it was found that combined effects of light and bacteria are more efficient than bacterial effects alone in remineralizing and altering DOM, which highlights the crucial importance of sunlight in transforming aquatic DOM.     

Efficient purification of Al30 by organic complexation method

A method was developed for preparing high purity Al₃₀O₈(OH)₅₆(H₂O)₂₄^18 + (Al₃₀) through elimination of impurities by complexation. Polyaluminum chloride II (PAC₃₀) with Al_c content of 75% was adopted as the source of Al₃₀. The PAC₃₀ was prepared under conditions of total aluminum concentration 0.1?mol/L and OH^?/Al ratio 2.2 to obtain the highest content of Al₃₀. A precipitation/metathesis method, organic solvent precipitation method and organic complexation method were examined to separate and purify Al₃₀. It was found that only by the organic complexation method could high purity Al₃₀ products be obtained in large yield economically. In the experiments, benzoic acid was used as the coordinating reagent to decompose the main impurity AlO₄Al₁₂(OH)₂₄(H₂O)₁₂^7 + (Al₁₃), and the Al₃₀ product could be obtained by precipitation and metathesis operations. It was noteworthy that the decomposition of impurities by benzoic acid could be completed in 2?hr. The Al₃₀ product was characterized by Ferron assay, ²⁷Al-NMR, SEM, XRD and TGA. The results showed that the purity of the Al₃₀ product could exceed 92%.     

廊坊市开发区冬季颗粒物碳组分污染特征及来源分析

廊坊市是北京市及周边传输通道“2+26”城市之一.为研究廊坊市开发区冬季颗粒物中碳组分污染特征,于2018年1月5日—2月5日在廊坊市开发区国控点位同步开展PM_2.5及PM₁₀样品采集,使用DRI分析OC（有机碳）与EC（元素碳）的质量浓度.结果表明:廊坊开发区冬季ρ（PM_2.5）、ρ（PM₁₀）分别为（54.5±46.0）（91.0±58.2）μg/m3.PM_2.5中ρ（OC）、ρ（EC）分别为14.64、3.54 μg/m3,PM₁₀中分别为17.07、4.58 μg/m3;PM_2.5、PM₁₀中ρ（OC）与ρ（EC）相关性均较好,R2均为0.91（P < 0.01）,表明二者具有相似的来源;在PM_2.5和PM₁₀中OC/EC〔ρ（OC）/ρ（EC）,下同〕分别为4.46和4.16,ρ（SOC）（SOC为二次有机碳）分别为6.15和5.88 μg/m3,分别占ρ（OC）的42.1%和37.7%,表明二次污染较严重.碳组分丰度及主成分分析结果表明,PM_2.5与PM₁₀中碳组分来源基本一致,主要来源于汽车尾气、水溶性极性化合物、生物质燃烧及燃煤的混合源,柴油车排放,以及道路扬尘.后向气流轨迹聚类结果表明,颗粒物及碳组分质量浓度受途径内蒙古自治区及河北省中部、北京市南部气团的影响较大;对于碳组分来源,道路扬尘及汽车尾气受气团传输的影响较大,而生物质燃烧、燃煤等受气团传输的影响较小.研究显示,汽车尾气、燃烧源及道路扬尘为廊坊市开发区冬季碳组分的主要来源.      

Enhanced removal of organic matter and typical disinfection byproduct precursors in combined iron–carbon micro electrolysis-UBAF process for drinking water pre-treatment

The organic matter and two types of disinfection byproduct(DBP) precursors in micropolluted source water were removed using an iron–carbon micro-electrolysis(ICME)combined with up-flow biological aerated filter(UBAF) process. Two pilot-scale experiments(ICME-UBAF and UBAF alone) were used to investigate the effect of the ICME system on the removal of organic matter and DBP precursors. The results showed that ICME pretreatment removed 15.6% of dissolved organic matter(DOM)and significantly improved the removal rate in the subsequent UBAF process. The ICME system removed 31% of trichloromethane(TCM) precursors and 20% of dichloroacetonitrile(DCAN) precursors. The results of measurements of the molecular weight distribution and hydrophilic fractions of DOM and DBP precursors showed that ICME pretreatment played a key role in breaking large-molecular-weight organic matter into low-molecular-weight components, and the hydrophobic fraction into hydrophilic compounds, which was favorable for subsequent biodegradation by UBAF.Three-dimensional fluorescence spectroscopy(3D-EEM) further indicated that the ICME system improved the removal of TCM and DCAN precursors. The biomass analysis indicated the presence of a larger and more diverse microbial community in the ICME-UBAF system than for the UBAF alone. The high-throughput sequencing results revealed that domination of the genera Sphingomonas, Brevundimonas and Sphingorhabdus contributed to the better removal of organic matter and two types of DBP precursors. Also, Nitrosomonas and Pseudomonas were beneficial for ammonia removal.     

Investigating the coagulation of non-proteinaceous algal organic matter: Optimizing coagulation performance and identification of removal mechanisms

The removal of algal organic matter(AOM) is a growing concern for the water treatment industry worldwide. The current study investigates coagulation of non-proteinaceous AOM(AOM after protein separation), which has been minimally explored compared with proteinaceous fractions. Jar tests with either aluminum sulphate(alum) or polyaluminium chloride(PACl) were performed at doses of 0.2–3.0 mg Al per 1 mg of dissolved organic carbon in the p H range 3.0–10.5. Additionally, non-proteinaceous matter was characterized in terms of charge, molecular weight and carbohydrate content to assess the treatability of its different fractions. Results showed that only up to 25% of non-proteinaceous AOM can be removed by coagulation under optimized conditions. The optimal coagulation p H(6.6–8.0 for alum and 7.5–9.0 for PACl) and low surface charge of the removed fraction indicated that the prevailing coagulation mechanism was adsorption of non-proteinaceous matter onto aluminum hydroxide precipitates. The lowest residual Al concentrations were achieved in very narrow p H ranges, especially in the case of PACl. High-molecular weight saccharidelike organics were amenable to coagulation compared to low-molecular weight( 3 k Da)substances. Their high content in non-proteinaceous matter(about 67%) was the reason for its low removal. Comparison with our previous studies implies that proteinaceous and nonproteinaceous matter is coagulated under different conditions due to the employment of diverse coagulation mechanisms. The study suggests that further research should focus on the removal of low-molecular weight AOM, reluctant to coagulate, with other treatment processes to minimize its detrimental effect on water safety.     

Raman spectroscopy of diesel and gasoline engine-out soot using different laser power

We studied engine-out soot samples collected from a heavy-duty direct-injection diesel engine and port-fuel injection gasoline spark-ignition engine. The two types of soot samples were characterized using Raman spectroscopy with different laser powers. A Matlab program using least-square-method with trust-region-reflective algorithm was developed for curve fitting. A DOE (design of experiments) method was used to avoid local convergence. The method was used for two-band fitting and three-band fitting. The fitting results were used to determine the intensity ratio of D (for “Defect” or “Disorder”) and G (for “Graphite”) Raman bands. It is found that high laser power may cause oxidation of soot sample, which gives higher D/G intensity ratio. Diesel soot has consistently higher amorphous/graphitic carbon ratio, and thus higher oxidation reactivity, compared to gasoline soot, which is reflected by the higher D/G intensity ratio in Raman spectra measured under the same laser power.     

混凝沉淀-UF工艺去除二级出水中ARGs效能研究

为了研究混凝沉淀-UF工艺对城市污水处理厂二级出水中ARGs（抗生素抗性基因）去除的影响,以PACl（聚合氯化铝）和PFS（聚合硫酸铁）作为混凝剂,采用qPCR（实时荧光定量聚合酶链式反应）和EEM（三维荧光光谱）等分析混凝沉淀-UF工艺对ARGs的削减及其影响因素.结果表明:① PACl、PFS投加量（分别以Al、Fe计,下同）分别为0.85、0.50 mmol/L时,与直接UF工艺相比,混凝沉淀-UF工艺对水中各类ARGs的去除量高2~3个数量级,其中PACl-UF工艺的效果更好,去除量为2.51~3.52个数量级;对水中DOC（溶解性有机碳）、富里酸类及溶解性微生物代谢产物的去除效果更好,DOC去除率由18%升至36%.②直接UF、PACl-UF、PFS-UF 3种工艺膜进、出水的线性拟合结果显示,ARGs浓度与ρ（DOC）、16S rDNA浓度均呈显著正相关.研究显示,混凝沉淀-UF工艺可以有效去除二级出水中的ARGs,且有机物、16S rDNA的去除有助于ARGs的削减.      

秋冬交替季节白洋淀沉积物有机质特性研究

为了研究白洋淀沉积物中有机质释放对秋冬交替季节淀区水环境的影响.将白洋淀分为自然保护区、旅游区、村落密集区、淀中村区和出淀口区五部分,在20个代表性采样点采集沉积物样品,采用光谱学方法表征样品中有机质特性,并研究氮、磷的溶解释放特征.结果表明:①在自然保护区、淀中村区和出淀口区,沉积物中有机质的腐殖化和芳香化程度较高,主要为陆源可见光类腐殖酸组分（C1）、海源可见光类腐殖酸组分（C3）和紫外光类腐殖酸组分（C4）;而在旅游区和村落密集区,有机质的腐殖化和芳香化程度较低,主要为类色氨酸组分（C2）,表明这些区域受人为活动影响大.②紫外吸收光谱和荧光光谱参数具有很好的相关性,可用于表征沉积物中有机质特征;类色氨酸组分的荧光强度与沉积物中w（TN）和w（TP）具有良好的正相关关系,显示出同源性特征.③与以类腐殖酸为主要成分的沉积物样品相比,氮、磷更易从以类蛋白为主要成分的沉积物中释放.研究显示,秋冬交替季节白洋淀沉积物中有机质以类蛋白和类腐殖酸为主,且类蛋白具有促进共存氮、磷溶解释放的作用.      

垃圾填埋有色溶解性有机质与铜络合机制

为了阐明填埋场中重金属的形态演变机制,采用三维荧光光谱、荧光猝灭滴定技术及平行因子分析,研究了不同填埋年限垃圾中有色溶解性有机物(colored dissolved organic matter,CDOM)与Cu(Ⅱ)的络合过程.结果表明,填埋垃圾CDOM中含有类蛋白、类富里酸及类胡敏酸物质,随着填埋时间的延伸,类蛋白物质含量呈下降趋势,而类富里酸和类胡敏酸含量呈上升趋势.填埋垃圾CDOM中类蛋白物质对Cu(Ⅱ)络合能力和参与络合的荧光基团比例存在差异,络合的条件稳定常数在4.00~5.75之间,参与络合的荧光基团比例在22.78%~95.30%之间;而类腐殖质与Cu(Ⅱ)作用的条件稳定常数和参与络合的荧光基团比例变化较小,类胡敏酸物质与Cu(Ⅱ)络合的条件稳定常数在4.71~5.54之间,参与络合的荧光基团比例在42.35%~61.46%之间,类富里酸物质与Cu(Ⅱ)络合的条件稳定常数在4.44~5.25之间,参与络合的荧光基团比例在46.14%~57.22%之间.类富里酸和类胡敏酸与Cu(Ⅱ)的结合能力都随着填埋年限的增加而降低,但参与络合的荧光基团比例增加,并且类胡敏酸物质与重金属的结合能力强于类富里酸,但参与配位的官能团较类富里酸少.     

荧光溶解性有机质EEMs的新旧自组织映射图解析方法比较研究

目前,对地表水体荧光溶解性有机质(Fluorescent Dissolved Organic Matter,FDOM)三维激发发射矩阵(Excitation-Emission Matrices,EEMs)数据的解析仍旧存在挑战.本文结合原始EEMs和从中分离的荧光平行因子分析(Parallel Factor Analysis,PARAFAC)组分,利用自组织映射图(Self-Organizing Maps,SOM),开展了基于传统EEMs-SOM和新型PARAFAC-SOM神经网络模型的复杂荧光数据解析能力对比研究,以此探索和改进EEMs多元解析方法技术体系.模型以已发表论文原始数据为基础构建,研究对象为南太湖重要入湖河流东苕溪水系.结果显示:EEMsSOM模型需依赖常规"摘峰法"对各荧光峰做出主观判断,不能有效识别重叠荧光峰,且人为割裂多激发共发射荧光物质峰之间的联系,从而弱化分析结果的实际环境意义,但神经元的模式荧光光谱可视化效果较佳,且操作简便,耗时较少;PARAFAC-SOM模型克服了上述缺陷,可清除EEMs中的噪声或无用信息,大幅降低输入变量数(从1742个降至4个),缩减运算时间,较大地改善了输出结果的准确性,获得无损可靠且实际环境意义较强的结果,但该法的PARAFAC预处理要求较高,工作量较大;两类模型解析结论大体一致,对前期研究进行了全新的阐述和补充,且生动揭示了FDOM在多级河流水体中的空间赋存变化规律及河流的动态污染过程.综上,推荐在今后研究中综合使用两类优势互补的模型以实现对EEMs的深度解析.