A review of environmental characteristics and effects of low-molecular weight organic acids in the surface ecosystem

Low molecular weight organic acids （LMWOAs） are prevalent on the earth＇s surface. They are vital intermediate products during metabolic pathways of organic matter and participate in the tricarboxylic acid cycle during life activities. Photochemical reactions are pivotal for LMWOAs＇ origination and play a large role in determining their diversity and their ultimate fate. Within the long time that organic matter is preserved in sediments, it can be decomposed and converted to release organic and inorganic pollutants as well as C, N, and P nutrients, which are of potential ecological risk in causing secondary pollution to lake water. The sediment pool is a comprehensive and complex compartment closely associated with overlying water by various biochemical processes, during which LMWOAs play critical roles to transport and transform elements. This article elucidates geochemical behaviors of LMWOAs in the surface environment in details, taking natural water, soil, and aerosol as examples, focusing on reviewing research developments on sources and characteristics, migration and mineralization of LMWOAs and relevant environmental effects. Simultaneously, this review article depicts the categories and contents of LMWOAs or their contribution to DOC in environmental media, and evaluates their importance during organic matter early diagenesis. Through concluding and discussing the conversion mechanisms and influencing factors, the next research orientations on LMWOAs in lake ecosystems are determined, mainly concerning relationships with hydrochemical parameters and microorganisms, and interactions with pollutants. This will enrich the knowledge on organic matter degradation and related environmental effects, and help reconstruct a theoretical framework for organic compound succession and influencing factors, providing basic data for lake eutrophication and ecological risk assessment, conducive to better control over water pollution and proper management of water quality.     

Effects of ozonation and coagulation on effluent organic matter characteristics and ultrafiltration membrane fouling

Effluent organic matter （EfOM） is the major cause of fouling in the low pressure membranes process for wastewater reuse. Coagulation and oxidation of biological wastewater treatment effluent have been applied for the fouling control of microfiltration membranes. However, the change in EfOM structure by pre-treatments has not been clearly identified. The changes of EfOM characteristics induced by coagulation and ozonation were investigated through size exclusion chromatography, UV/Vis spectrophotometry, fluorescence spectrophotometry and titrimetric analysis to identify the mechanisms in the reduction of ultrafiltration （UF） membrane fouling. The results indicated that reduction of flux decline by coagulation was due to modified characteristics of dissolved organic carbon （DOC） content. Total concentration of DOC was not reduced by ozonation. However, the mass fraction of the molecules with molecular weight larger than 5 kDa, fluorescence intensity, aromaticity, highly condensed chromophores, average molecular weight and soluble microbial byproducts decreased greatly after ozonation. These results indicated that EfOM was partially oxidized by ozonation to low molecular weight, highly charged compounds with abundant electron- withdrawing functional groups, which are favourable for alleviating UF membrane flux decline.     

水位变化对消落带氨氧化微生物丰度和多样性的影响

南水北调来水进入密云水库将直接引起水库水位上涨,这必将影响消落带土壤中氨氧化微生物的丰度和多样性,从而影响消落带中氮循环过程.采用分子生物学方法,探讨了水位变化对消落带氨氧化细菌(AOB)和古菌(AOA)的生物多样性和丰度的影响.Real-time PCR结果显示,2015年9月消落带岸上/水陆界面土壤和沉积物中AOA和AOB的丰度范围分别为1.00×10~7~3.91×10~7copies·g~(-1)和5.49×10~6~9.77×10~6copies·g~(-1).2015年11月水位比9月上升3 m,淹没区土壤/沉积物中AOA和AOB的丰度范围分别为5.80×106~1.56×10~7copies·g~(-1)和2.14×10~6~4.40×106copies·g~(-1),比被淹没前有所下降,但AOA的丰度始终高于AOB,说明AOA比AOB更适合在低氨氮的消落带环境中生长,并且更能适应低氧环境.水位上升3 m后,水陆交界面土壤中AOA和AOB的多样性均有所增加,而在沉积物中多样性减少.水位上涨之前,AOA大多数OTU属于Nitrososphaera、Nitrosopumilus,而水位上涨之后,大多数OTU归属于土壤簇Nitrososphaera,即在低氧消落带环境中土壤簇Nitrososphaera为优势AOA菌.对于AOB,水陆交界面土壤和沉积物中Nitrosopira和Nitrosomonas分别在氨氧化过程中发挥作用.     

低分子有机酸对三峡库区沉积物吸附Pb2+影响研究

以长江三峡库区万州段消落带区的沉积物为研究对象,通过等温吸附平衡实验研究不同浓度的柠檬酸、草酸对沉积物吸附Pb2+的影响.实验结果表明:消落带沉积物对Pb2+的吸附量随着Pb2+离子平衡浓度的增加而增大,Pb2+平衡浓度在0.08～80 mg/L时,其最大吸附量为8 762.00 mg/Kg.不同浓度的柠檬酸、草酸会在不同程度上抑制沉积物对Pb2+吸附,2 mmol/L柠檬酸对沉积物吸附Pb2+的能力是浓度为4 mmol/L时的1.12倍,草酸条件下为1.02倍.即高浓度的低分子有机酸抑制消落带沉积物对Pb2+的吸附.     

玉米秸秆烟尘中正构脂肪酸的分子与碳同位素组成

在模拟的明火燃烧和闷烧条件下对4种玉米秸秆进行了焚烧试验,用GC/MS和GC/C/IRMS分别测定烟尘中正构脂肪酸的分子与碳同位素组成.结果表明,在明火烟尘中正构脂肪酸由C7~C_(34)组成,其平均总含量为13 895.0 mg·kg-1.其低碳数(≤C_(16))与高碳数(C_(16))正构脂肪酸的含量比(L/H)平均值为1.1.C_(18)/C_(16)、C_(24)/C_(16)、C_(24)/C_(18)、C_(24)/(C_(22)+C_(26))(CAR)的平均值分别为0.33、0.17、0.50、1.2.正构脂肪酸单体表现出以C_(16)、C_(24)为主、次峰碳数的双峰式分布模式.其碳优势指数(CPI)的平均值为4.5.在闷烧烟尘中正构脂肪酸由C_6~C_(34)组成,其平均总含量为50 183.7 mg·kg-1.L/H、C_(18)/C_(16)、C_(24)/C_(16)、C_(24)/C_(18)、CAR的平均值分别为1.3、0.33、0.20、0.60、1.6.也具有与明火烟尘相同的分布模式.其CPI的平均值为6.1.明火烟尘中C_(14)~C_(26)单体的δ~(13)C平均值在-21.0‰~-24.8‰之间变化,总平均值为-23.5‰.该值与玉米秸秆中对应值之差(Δ~(13)C)达-0.7‰.闷烧烟尘中C_(14)~C_(26)单体δ~(13)C平均值的变化范围为-21.8‰~-25.4‰,总平均值为-23.3‰.其Δ~(13)C值达-0.5‰.与玉米秸秆相比,两种烟尘中正构脂肪酸的分子组成和碳同位素组成均发生了明显的改变.L/H、C_(24)/C_(16)、C_(24)/C_(18)、CAR、δ~(13)C等指标可用于识别大气气溶胶中玉米秸秆燃烧来源的正构脂肪酸.     

低分子有机酸对硫杆菌活性的抑制作用及对土壤重金属脱除的影响

施用有机肥能够降低污染土壤重金属溶解性和生物可利用性,但在淹水厌氧等环境中,有机肥会分解产生大量低分子有机酸,会抑制嗜酸性硫杆菌的生物活性.通过摇瓶实验研究了低分子有机酸对硫杆菌的毒害抑制效果和不同硫杆菌对各类有机酸的耐受水平.结果表明,纯体系培养下,A.ferrooxidans和A.thiooxidans活性抑制率在72 h内达到90%以上,所需甲、乙、丙、丁酸最低浓度分别为41.2、78.3、43.2、123.4 mg·L~(-1)和81.9、230.4、170.1、123.4 mg·L~(-1).其中,甲酸对A.ferrooxidans和A.thiooxidans的抑制作用最显著,A.thiooxidans相比A.ferrooxidans对4种有机酸具有更高的耐受性.新鲜重金属污染土壤在生物酸化初期(0 h)加入4种有机酸对后续土壤酸化过程影响较小,但12 h后加入有机酸却能使土壤生物酸化基本停止,导致土壤重金属脱除率大幅度下降.这为有机肥改良重金属污染土壤的生物修复可行性提供一定理论依据.     

O3/UV降解含氮杂环化合物喹啉

本研究采用O3/UV工艺降解喹啉溶液,系统地探讨了喹啉初始浓度、反应后置时间、初始p H、HCO-3浓度等因素对降解过程的影响.通过测定降解过程中的中间产物,分析了喹啉的降解机制及途径.结果表明随着喹啉初始浓度增加,反应表观速率常数和去除率都降低;p H(7~9)碱性条件时降解效果最好;HCO-3的存在明显降低了喹啉的去除率,加入100 mg·L-1HCO-3喹啉去除率降低了42.01%;反应后置时间对喹啉的去除率及矿化率基本没有影响.喹啉的降解中间产物主要为8-羟基喹啉、5-羟基喹啉、2(1H)-喹啉酮、2-吡啶甲醛等,喹啉在O3/UV体系中的降解途径主要由羟基自由基(·OH)、O3氧化剂发生的加成反应、取代反应、亲电反应等.     

Characterization of dissolved organic matter fractions from Lake Hongfeng, Southwestern China Plateau

With XAD-series and ion exchange resins, dissolved organic matter (DOM) from Lake Hongfeng in Southwestern China Plateau was isolated into 6 fractions, i.e., humic acid (HA), fulvic acid (FA), hydrophobic neutrals (HON), hydrophilic acids (HIA), hydrophilic bases (HIB) and hydrophilic neutrals (HIN). Those fractions were characterized by high performance size exclusion chromatography, fluorescence spectroscopy and UV absorbance. Among the 6 fractions, FA was predominant and accounted for 51% of the total DOM. The weight-average (M_w) and number-averaged (M_n) molecular weight of these fractions ranged from 1688 to 2355 Da and from 1338 to 1928 Da, respectively. A strong correlation was observed between specific UV absorbance at 280 nm, E₂/E₃ (absorbance at 250 nm to 365 nm), and the molecular weight for DOM fractions. UV-Vis fulvic-like fluorescence peaks were found in all fractions. Protein-like fluorescence peaks existed in HON may indicate that microbial activity was severely in Lake Hongfeng. There was a significant relationship between fluorescence intensities and specific UV absorbance at 254 nm for those DOM fractions, suggesting their similar luminescence characteristics. The values of fluorescence index (f_450/500) indicated that hydrophobic fractions may derive from terrestrial sources, and the hydrophilic fractions from microbial and terrestrial origins. Those results suggest that there were inter-relationships between molecular weight, fluorescence and absorbance characteristics, and also subtle consistencies between the hydrophilic and hydrophobic properties and the sources for these 6 fractions from Lake Hongfeng.     

沸石床多级生物膜焦化废水处理系统的NH+4-N去除稳定性研究

焦化废水处理中预处理蒸氨工艺不稳定容易引起生物处理出水NH⁺₄-N的波动,为了在有机物去除的同时提高生物系统对NH⁺₄-N的去除效果和稳定性,采用对NH⁺₄-N有良好吸附性能的天然斜发沸石为生物填料构建沸石床多级生物膜系统,考察了进水负荷对系统运行稳定性的影响、抗冲击负荷能力以及系统的功能分区和污染物迁移转化规律.结果表明,当系统进水NH⁺₄-N负荷≤0.21 kg/(m³·d)、COD负荷≤1.35　kg/(m³·d)时,出水NH⁺₄-N和COD的平均浓度分别为(2.2±1.2)mg/L和(228±60)mg/L,平均去除率分别达(99.1±0.5)%和(86.0±2.6)%.在低、高两次NH⁺₄-N冲击负荷［0.03　kg/(m³·d)和0.06　kg/(m³·d)］条件下,系统对NH⁺₄-N的平均去除率仍然分别高达99.0%和92.9%,高于对比系统的96.8%和89.3%,表现出良好的抗NH⁺₄-N冲击负荷性能与处理稳定性.系统好氧单元反应器沿程出现脱碳/硝化功能区(C/N区)和硝化功能区(N区),其中N区的NH⁺₄-N 降解速率为C/N区的2～8倍.系统进水中相对分子质量＜1×10³、 1×10³～1×10⁴、 ＞1×10⁴的TOC浓度分别为227.6、104.8和35.0 mg/L,处理出水中的TOC浓度分别为31.2、 22.9和31.5 mg/L,其中相对分子质量＜1×10³和1×10³～1×10⁴这2个范围的有机物降解良好,出水残余物质主要为相对分子质量＞1×10³的有机物.