Identification of sources,characteristics and photochemical transformations of dissolved organic matter with EEM-PARAFAC in the Wei River of China

• The source of DOM in surface water and sediment is inconsistent. • The DOC content changes differently in surface water and sediment. • The content of DOC in the surface water is lower than that in the sediment. • The DOM in the surface water had higher photodegradation potentials than sediment. Dissolved organic matter (DOM) in rivers is a critical regulator of the cycling and toxicity of pollutants and the behavior of DOM is a key indicator for the health of the environment. We investigated the sources and characteristics of DOM in surface water and sediment samples of the Wei River, China. Dissolved organic carbon (DOC) concentration and ultraviolet absorbance at 254 nm (UV₂₅₄) increased in the surface water and were decreased in the sediment downstream, indicating that the source of DOM in the water differed from the sediment. Parallel factor (PARAFAC) analysis of the excitation-emission matrices (EEM) revealed the presence of terrestrial humus-like, microbial humus-like and tryptophan-like proteins in the surface water, whereas the sediment contained UVA humic-like, UVC humic-like and fulvic-like in the sediment. The DOM in the surface water and sediment were mainly derived from microbial metabolic activity and the surrounding soil. Surface water DOM displayed greater photodegradation potential than sediment DOM. PARAFAC analysis indicated that the terrestrial humic-like substance in the water and the fulvic-like component in the sediment decomposed more rapidly. These data describe the characteristics of DOM in the Wei River and are crucial to understanding the fluctuations in environmental patterns.     

Fluorescence spectroscopic studies of the effect of granular activated carbon adsorption on structural properties of dissolved organic matter fractions

This work investigated the effect of granular activated carbon adsorption (GACA) on fluorescence characteristics of dissolved organic matter (DOM) in secondary effluent, by means of excitation–emission matrix (EEM) spectra, the fluorescence regional integration (FRI) method, synchronous spectra, the fluorescence index defined as the ratio of fluorescence emission intensity at wavelength 450 nm to that at 500 nm at excitation (λ_ex)=370 nm, and the wavelength that corresponds to the position of the normalized emission band at its half intensity (λ_0.5). DOM in the secondary effluent from the North Wastewater Treatment Plant (Shenyang, China) was fractionated using XAD resins into 5 fractions: hydrophobic acid (HPO–A), hydrophobic neutral (HPO–N), transphilic acid (TPI–A), transphilic neutral (TPI–N) and hydrophilic fraction (HPI). Results showed that fluorescent materials in HPO–N and TPI–N were less readily removed than those in the other fractions by GACA. The relative content of fluorescent materials in HPO–A, TPI–A and HPI decreased whereas that in HPO–N and TPI–N increased as a consequence of GACA. Polycyclic aromatics in all DOM fractions were preferentially absorbed by GACA, in comparison with bulk DOM expressed as DOC. On the other hand, the adsorption of aromatic amino acids and humic acid-like fluorophores exhibiting fluorescence peaks in synchronous spectra by GACA seemed to be dependent on the acid/neutral properties of DOM fractions. All five fractions had decreased fluorescence indices as a result of GACA. GACA led to a decreased λ_0.5 value for HPO–A, increased λ_0.5 values for HPO–N, TPI–A and HPI, and a consistent λ_0.5 value for TPI–N.     

长江重庆段溶解性有机物的荧光特性分析

利用三维荧光光谱(EEMs),并结合平行因子分析(PARAFAC)及主成分分析(PCA),研究了长江重庆段溶解有机物(DOM)的荧光组分特征及其污染来源,并探讨了荧光强度同溶解性有机碳(DOC)及溶解氧(DO)的相关性.结果表明,PARAFAC模型识别出长江重庆段DOM由2类6个荧光组分组成,即类腐殖质荧光组分C1(350/422 nm)、C4(245,305/395 nm)、C5(260,340/420 nm)、C6(260/480 nm)及类蛋白荧光组分C2(275/300 nm)、C3(227,278/329 nm).在DOM来源组成中,陆源的类腐殖质含量占62.56%,类蛋白物质含量占31.31%.类腐殖质组分的荧光强度同DOC的含量存在明显的线性正相关(r=0.73),类蛋白组分的荧光强度同DO的含量呈明显的线性负相关(r=0.80).EEMs-PARAFAC不仅可以表征长江重庆段DOM的光谱特征,示踪长江重庆段的有机污染程度,还可以为三峡库区水体保护提供依据.     

Excitation-emission matrix (EEM) fluorescence spectroscopy for characterization of organic matter in membrane bioreactors: Principles,methods and applications

• Principles and methods for fluorescence EEM are systematically outlined. • Fluorophore peak/region/component and energy information can be extracted from EEM. • EEM can fingerprint the physical/chemical/biological properties of DOM in MBRs. • EEM is useful for tracking pollutant transformation and membrane retention/fouling. • Improvements are still needed to overcome limitations for further studies. The membrane bioreactor (MBR) technology is a rising star for wastewater treatment. The pollutant elimination and membrane fouling performances of MBRs are essentially related to the dissolved organic matter (DOM) in the system. Three-dimensional excitation-emission matrix (3D-EEM) fluorescence spectroscopy, a powerful tool for the rapid and sensitive characterization of DOM, has been extensively applied in MBR studies; however, only a limited portion of the EEM fingerprinting information was utilized. This paper revisits the principles and methods of fluorescence EEM, and reviews the recent progress in applying EEM to characterize DOM in MBR studies. We systematically introduced the information extracted from EEM by considering the fluorescence peak location/intensity, wavelength regional distribution, and spectral deconvolution (giving fluorescent component loadings/scores), and discussed how to use the information to interpret the chemical compositions, physiochemical properties, biological activities, membrane retention/fouling behaviors, and migration/transformation fates of DOM in MBR systems. In addition to conventional EEM indicators, novel fluorescent parameters are summarized for potential use, including quantum yield, Stokes shift, excited energy state, and fluorescence lifetime. The current limitations of EEM-based DOM characterization are also discussed, with possible measures proposed to improve applications in MBR monitoring.     

Modeling the seasonal autochthonous sources of dissolved organic carbon and nitrogen in the upper Chesapeake Bay

In this paper we investigate the seasonal autochthonous sources of dissolved organic carbon (DOC) and nitrogen (DON) in the euphotic zone at a station in the upper Chesapeake Bay using a new mass-based ecosystem model. Important features of the model are: (1) carbon and nitrogen are incorporated by means of a set of fixed and varying C:N ratios; (2) dissolved organic matter (DOM) is separated into labile, semi-labile, and refractory pools for both C and N; (3) the production and consumption of DOM is treated in detail; and (4) seasonal observations of light, temperature, nutrients, and surface layer circulation are used to physically force the model. The model reasonably reproduces the mean observed seasonal concentrations of nutrients, DOM, plankton biomass, and chlorophyll a. The results suggest that estuarine DOM production is intricately tied to the biomass concentration, ratio, and productivity of phytoplankton, zooplankton, viruses, and bacteria. During peak spring productivity phytoplankton exudation and zooplankton sloppy feeding are the most important autochthonous sources of DOM. In the summer when productivity peaks again, autochthonous sources of DOM are more diverse and, in addition to phytoplankton exudation, important ones include viral lysis and the decay of detritus. The potential importance of viral decay as a source of bioavailable DOM from within the bulk DOM pool is also discussed. The results also highlight the importance of some poorly constrained processes and parameters. Some potential improvements and remedies are suggested. Sensitivity studies on selected parameters are also reported and discussed.     

Effect of acetate and propionate on the production and characterization of soluble microbial products (SMP) in aerobic granular sludge system

It is well known that soluble microbial products (SMP) derived from biological systems found in wastewater treatment plant effluent are responsible for chemical oxygen demand (COD). Aerobic granular sludge (AGS) is recognized as an efficient and innovative approach for wastewater treatment. Acetate and propionate as two dominant organic substances in wastewater need to be effectively removed before discharge. The aim of this study was to investigate the effectiveness of acetate and propionate to interfere with the accumulation, molecular weight (MW) distribution and composition of SMP in aerobic granular sludge (AGS) system using two identical sequencing batch reactors (SBR) named R1 and R2, respectively, thus reducing the COD. The results demonstrated that more SMP accumulated in R1 in presence of acetate compared to R2 treated with propionate. A positive correlation for SMP formation was detected as evidenced by aeration rates, but a negative correlation with hydraulic retention time (HRT). The MW distribution analysis suggested that small molecules (MW <3?kDa) were the dominant fraction of SMP in R1 and R2, accounting for 57–79% and 39–61%, respectively. In addition, gas chromatography-mass spectrometry (GC-MS) demonstrated that esters, alkanes, alkenes and alcohols were the predominant low-MW SMP in R1 and R2. More peaks were present in R2 (61) than R1 (46). Esters were the predominant SMP (39%) in R1, while alkanes were the predominant SMP (31%) in R2. Further, microbial community analysis indicated that more α- and γ-Proteobacteria groups which readily utilize low-MW SMP were found in R2 compared to R1-granules which may have contributed to less SMP accumulated in R2. The abundant genera in the granules were Zoogloea and Azoarcus, in particular, a greater quantity of Azoarcus was detected in R2 than R1-granules, which may be associated with higher degradation of aromatics in SMP.     

Spatial connectivity in a large river system: resolving the sources and fate of dissolved organic matter

Large rivers are generally heterogeneous and productive systems that receive important inputs of dissolved organic matter (DOM) from terrestrial and in situ sources. Thus, they are likely to play a significant role in the biogeochemical cycling of the DOM flowing to the oceans. The asymmetric spatial gradient driven by directional flow and environmental heterogeneity contributes to the fate of DOM flowing downstream. Yet, the relative effects of spatial connectivity and environmental heterogeneity on DOM dynamics are poorly understood. For example, since environmental variables show spatial heterogeneity, the variation explained by environmental and spatial variables may be redundant. We used the St. Lawrence River (SLR) as a representative large river to resolve the unique influences of environmental heterogeneity and spatial connectivity on DOM dynamics. We used three-dimensional fluorescence matrices combined with parallel factor analysis (PARAFAC) to characterize the DOM pool in the SLR. Seven fluorophores were modeled, of which two were identified to be of terrestrial origin and three from algal exudates. We measured a set of environmental variables that are known to drive the fate of DOM in aquatic systems. Additionally, we used asymmetric eigenvector map (AEM) modeling to take spatial connectivity into account. The combination of spatial and environmental models explained 85% of the DOM variation. We show that spatial connectivity is an important driver of DOM dynamics, as a large fraction of environmental heterogeneity was attributable to the asymmetric spatial gradient. Along the longitudinal axis, we noted a rapid increase in dissolved organic carbon (DOC), mostly controlled by terrestrial input of DOM originating from the tributaries. Variance partitioning demonstrated that freshly produced protein-like DOM was found to be the preferential substrate for heterotrophic bacteria undergoing rapid proliferation, while humic-like DOM was more correlated to the diffuse attenuation coefficient of UVA radiation.     

管网生物膜菌株胞外聚合物的提取方法比较

以饮用水管网生物膜样品中一株强成膜能力的菌株Pleomorphomonas oryzae作为研究对象,考察了8种方法(高速离心法、超声法、加热法、EDTA法、H2SO4法、NaOH法、SDS法、甲醛法)对菌株胞外聚合物(EPS)的提取效果,并结合三维荧光光谱(EEM)和傅立叶红外光谱(FTIR)对提取的EPS进行成分分析.结果表明,EDTA法和H2SO4法既能提高EPS的提取效率,提取量分别为64.77 mg.g-1SS和74.43 mg.g-1SS,是离心方法提取量的1.62倍和1.86倍,又不会在提取过程中对菌株细胞造成破坏,是较为理想的EPS提取方法.EEM分析进一步证实,NaOH法对菌株细胞破坏严重,造成EPS成分变化较大.FTIR分析则说明,化学提取方法相较于物理提取方法会引入杂质对组分测定造成干扰.     

Molecular weight fractionation of dissolved organic matter in coastal seawater by ultrafiltration

Fractionation of molecular weight of dissolved organic matter (DOM) in coastal seawater of Tokyo Bay (Japan) was performed by ultrafiltration. Ultrafiltration membranes Diaflo UM-05, UM-10 and XM-100 were used for DOM fractionation, and dissolved organic carbon (DOC) was determined for ultrafiltrates of each membrane. In surface water of Station 1, near the center of Tokyo Bay, low-molecular weight DOM (molecular weight less than 500) which passed through a Diaflo UM-05 membrane was 0.3 to 2.6 mgC/l (24 to 42% of the total DOC) during August, 1971 to September, 1972. The macromolecular DOM (molecular weight greater than 100,000) retained on an XM-100 membrane, ranged from 0.1 to 1.0 mgC/l. These fractions accounted for 8 to 23% of the total DOC. The precision of the method was within ± 0.1 mgC/l, and therefore may be employed for coastal seawater of high DOC content.     

花生壳活性炭对反渗透(RO)浓水的吸附特性

以花生壳活性炭对RO浓水进行吸附处理,利用傅立叶红外光谱(FTIR)和荧光光谱(EEM)研究花生壳活性炭对不同pH的RO浓水的吸附特性.结果表明,花生壳活性炭对溶解性有机碳(DOC)的吸附遵循准二级吸附动力学方程,特别是碱性条件下,DOC的吸附量随着pH的升高而降低.而且pH越高,达到吸附平衡的时间越长.通过FTIR光谱分析发现,活性炭的芳香结构吸收峰在吸附后红移至1630 cm-1,表明被吸附的有机物在该处有明显的特征吸收峰,而C—O和O—H官能团的吸收峰则因为钙离子等物质的吸附而显著降低.由EEM光谱分析可知,RO浓水的荧光物质主要由腐殖酸类腐殖质和富里酸类腐殖质组成,其荧光强度与DOC之间具有较好的线性相关性.     

Photosensitivity sources of dissolved organic matter from wastewater treatment plants and their mediation effect on 17α-ethinylestradiol photodegradation

● EE2 photodegradation behavior in the presence of four WWTPs’ DOM was explored. ● The ³DOM* played a major role in the EE2 photodegradation mediated by WWTPs’ DOM. ● The A²/O process DOM contained more aromatic and oxygen-containing substances. ● Possible photosensitivity sources of DOM in the A²/O process were proposed. Dissolved organic matter (DOM) from each treatment process of wastewater treatment plants (WWTPs) contains abundant photosensitive substances, which could significantly affect the photodegradation of 17α-ethinylestradiol (EE2). Nevertheless, information about EE2 photodegradation behavior mediated by DOM from diverse WWTPs and the photosensitivity sources of such DOM are inadequate. This study explored the photodegradation behavior of EE2 mediated by four typical WWTPs’ DOM solutions and investigated the photosensitivity sources of DOM in the anaerobic-anoxic-oxic (A²/O) process. The parallel factor analysis identified three varying fluorescing components of these DOM, tryptophan-like substances or protein-like substances, microbial humus-like substances, and humic-like components. The photodegradation rate constants of EE2 were positively associated with the humification degree of DOM (P < 0.05). The triplet state substances were responsible for the degradation of EE2. DOM extracted from the A²/O process, especially in the secondary treatment process had the fastest EE2 photodegradation rate compared to that of the other three processes. Four types of components (water-soluble organic matter (WSOM), extracellular polymeric substance, humic acid, and fulvic acid) were separated from the A²/O process DOM. WSOM had the highest promotion effect on EE2 photodegradation. Fulvic acid-like components and humic acid-like organic compounds in WSOM were speculated to be important photosensitivity substances that can generate triplet state substances. This research explored the physicochemical properties and photosensitive sources of DOM in WWTPs, and explained the fate of estrogens photodegradation in natural waters.     

不同有机碳源对小球藻的生长与产油量的影响

该研究探讨了葡萄糖和乙酸钠两种碳源对小球藻（Chlorella protothecoides）的生长与产油量的影响,并对小球藻在两种碳源混合培养下的生长与产油情况进行了分析.研究结果表明,葡萄糖和乙酸钠的浓度对小球藻的生物量和产油量都有较大的影响,最优的浓度分别为15 g/L和20.5 g/L.相对于以葡萄糖为碳源的小球藻,以乙酸钠为碳源的小球藻的生物量与含油量均较低.在混合培养条件下,葡萄糖最先被小球藻吸收利用.图5,表1,参8.     

黄浦江原水中各类有机物在铝盐混凝过程中的去除效果

通过XAD-8/XAD-4吸附树脂联用技术将黄浦江微污染原水中溶解性有机物分为疏水酸、非酸疏水物质、弱疏水物质及亲水物质4类有机物,研究了铝盐混凝工艺对黄浦江水中4类有机物的去除效果.硫酸铝在最佳混凝条件下,即投加量为8 mg·l~(-1)(以Al计),pH=5.5时,水中的DOC和UV_(254)的去除率分别达到23%和32%.有机物的亲疏水性对混凝工艺有较大影响,混凝法倾向于优先去除水中疏水性有机物,而疏水性有机物的酸碱性对混凝工艺没有明显影响,酸性和非酸类疏水物质均能破混凝工艺所去除.疏水酸是水中最主要的三氯甲烷类消毒副产物的前体物质,混凝工艺对于三氯甲烷类消毒副产物有良好的控制作用,总体减少了 39%的生成量.而不同类的有机物之间,混凝工艺对消毒副产物控制效果不同,其中对疏水酸的控制三氯甲烷消毒副产物的效果最好,减少了63%的生成量,亲水物质的控制效果最差,三氯甲烷生成量仪减少了3%.疏水酸表现出比亲水物质更强的生物毒性,混凝工艺能明显降低原水的毒性.     

印染废水生化出水中有机污染物特性及在硫酸镁混凝过程中的去除行为

以某印染废水二级生化出水为研究对象,考察了生化出水中有机污染物中各组分含量、分子量分布特点等特性,以及各类有机物在硫酸镁混凝处理过程中的去除行为.实验结果表明,该印染废水的生化出水溶解性有机物的主要成分是疏水性物质,以溶解性有机碳（DOC）表征时占总DOC的78%,其中非酸疏水物质约占46%,而以UV254表征时约占总55%,以美国染料生产协会色度值（ADMI7.6）表征时为97%,其中以非酸疏水物质的贡献最大,达到66%,并且非酸疏水物质中不饱和双键或芳香环有机物的含量较高.生化出水中的DOC主要集中在小于1000 D的有机物上,占37%.在硫酸镁的最佳混凝条件下,可以有效地去除由大分子量的非酸疏水物质引起的色度,而对小分子量的有机物也有一定的去除效果.     

焦化废水中溶解性有机物组分的特征分析

焦化废水是典型的具有复杂有机质的工业废水,其复杂的有机构成制约了水处理的水质达标,且可能对排入水体构成危害.为了探明其溶解性有机物的组成,采用XAD-8大孔树脂将焦化废水中的溶解性有机物分为亲水性组分(HIS)、疏水酸性组分(HOA)、疏水碱性组分(HOB)和疏水中性组分(HON),分析了各组分的溶解性有机物(DOC)、紫外-可见光谱、色度,并采用GC/MS对各组分中有机物进行定性分析.结果表明,焦化废水中的有机物主要为HIS和HOA组分,其DOC含量分别占总DOC的44.3%和32.4%;焦化废水在200—250 nm和300—400 nm范围内有特征吸收峰,且吸收光强度顺序为HIS>HOA>HON>HOB;焦化废水的色度主要由HOA和HON构成,其在525 nm和436 nm处的吸光度分别占焦化废水吸光度的42.9%(HON)、42.1%(HON)和21.4%(HOA)、15.8%(HOA);焦化废水中亲水性物质主要是苯胺、苯酚、喹啉、异喹啉,疏水酸性物质中主要是各种甲基取代的酚类物质,疏水碱性物质主要是各种胺类和含氮杂环化合物,疏水中性物质主要是吲哚及其衍生物.     

Effect of the addition of organic carbon sources on nitrous oxide emission in anaerobic-aerobic (low dissolved oxygen) sequencing batch reactors

The effect of additional organic carbon sources on the production of nitrous oxide (N₂O) in anaerobic-aerobic (low dissolved oxygen) real wastewater treatment system was investigated. In this paper, three laboratory-scale sequencing batch reactors (SBRs) (SBR-1, SBR-2 and SBR-3) were operating under an anaerobic-aerobic (low dissolved oxygen, 0.15–0.45 mg·L^-1) configuration. The SBRs were ‘long-term cultured’ respectively with a single municipal wastewater sample, sodium acetate, and a waste-activated sludge alkaline fermentation liquid as the additional carbon sources of real wastewater. Off-gas analysis showed that N₂O was emitted into the atmosphere during the aerobic (low dissolved oxygen) period in the three SBRs, and the order of N₂O emission rate was SBR-2>SBR-1>SBR-3. It was observed that the higher poly-β-hydroxyvalerate fraction of polyhydroxyalkanoates, the lower glycogen transformation and less nitrite accumulation was in SBR-3, while the opposite behavior was observed in SBR-2. Further research indicated that the interaction of the factors above potentially affected the N₂O emission in the anaerobic-aerobic (low dissolved oxygen) system.     

Examining the coupling of carbon and nitrogen cycles in Appalachian streams: the role of dissolved organic nitrogen

Although regional and global models of nitrogen (N) cycling typically focus on nitrate, dissolved organic nitrogen (DON) is the dominant form of nitrogen export from many watersheds and thus the dominant form of dissolved N in many streams. Our understanding of the processes controlling DON export from temperate forests is poor. In pristine systems, where biological N limitation is common, N contained in recalcitrant organic matter (OM) can dominate watershed N losses. This recalcitrant OM often has moderately constrained carbon:nitrogen (C:N) molar ratios (approximately 25-55) and therefore, greater DON losses should be observed in sites where there is greater total dissolved organic carbon (DOC) loss. In regions where anthropogenic N pollution is high, it has been suggested that increased inorganic N availability can reduce biological demand for organic N and therefore increase watershed DON losses. This would result in a positive correlation between inorganic and organic N concentrations across sites with varying N availability. In four repeated synoptic surveys of stream water chemistry from forested watersheds along an N loading gradient in the southern Appalachians, we found surprisingly little correlation between DON and DOC concentrations. Further, we found that DON concentrations were always significantly correlated with watershed N loading and stream water [NO3-] but that the direction of this relationship was negative in three of the four surveys. The C:N molar ratio of dissolved organic matter (DOM) in streams draining watersheds with high N deposition was very high relative to other freshwaters. This finding, together with results from bioavailability assays in which we directly manipulated C and N availabilities, suggests that heterotrophic demand for labile C can increase as a result of dissolved inorganic N (DIN) loading, and that heterotrophs can preferentially remove N-rich molecules from DOM. These results are inconsistent with the two prevailing hypotheses that dominate interpretations of watershed DON loss. Therefore, we propose a new hypothesis, the indirect carbon control hypothesis, which recognizes that heterotrophic demand for N-rich DOM can keep stream water DON concentrations low when N is not limiting and heterotrophic demand for labile C is high.     

Controlling various contaminants in wastewater effluent through membranes and engineered wetland

For effective wastewater reclamation and water recovery, the treatment of natural and effluent organic matters (NOM and EfOM), toxic anions, and micropollutants was considered in this work. Two different NOM (humic acid of the Suwannee River, and NOM of US and Youngsan River, Korea), and one EfOM from the Damyang wastewater treatment plant, Korea, were selected for investigating the removal efficiencies of tight nanofiltration (NF) and ultrafiltration (UF) membranes with different properties. Nitrate, bromate, and perchlorate were selected as target toxic anions due to their well known high toxicities. Tri-(2-chloroethyl)-phosphate (TCEP), oxybenzone, and caffeine, due to their different K _ow and pK _a values, were selected as target micropollutants. As expected, the NF membranes provided high removal efficiencies in terms of all the tested contaminants, and the UF membrane provided fairly high removal efficiencies for anions (except for nitrate) and the relatively hydrophobic micropollutant, oxybenzon. Through the wetlands, nitrate was successfully removed. Therefore, a fair process of combining membranes with an engineered wetland could be proposed for sustainable wastewater reclamation and optimum control of contaminats.     

热带滨海区不同土地利用背景下土壤溶解性有机氮的组成与粒径分布特征

溶解态有机氮(DON)是土壤中活跃的氮库,其生态环境行为与它的化学组成和粒径分布密切相关。为评估热带滨海区不同土地利用方式对不同粒径中土壤溶解性有机氮组成特征的影响,从水稻田、橡胶园、菜园和果园采集土壤样品,通过一系列微滤和超滤(0.7,0.45,0.2,0.1μm,100,10,1 kDa)对土壤溶解性有机氮分级,并使用连续流动分析仪、三维荧光光谱和红外光谱研究了滤液中溶解态有机氮、无机氮的含量及荧光组分和有机官能团特征。结果表明,4种土地利用背景下土壤DON值的范围为5.25-10.88 mg·kg^-1,其大小顺序为水稻>菜园>果树>橡胶,且DON与溶解性总氮(DTN)的比值范围为26.08%-67.11%,其中橡胶土最高,水稻土最低;不同粒径下4种土地利用类型土壤DON主要集中在<100 kDa的粒径中,其值范围为4.85-9.48 mg·kg^-1,占全量的85.89%-92.41%。三维荧光光谱(3D-EEMs)及平行因子分析表明,4种土地利用背景下土壤DON含有两种类腐殖质组分及一种类蛋白质组分,且以类腐殖质组分为主,占比54.00%-77.67%;类蛋白组分对土地利用变化敏感,且随着粒径的减小,类蛋白组分占比增加,在<1 kDa组分中比例最高。红外光谱结果表明,4种土地利用背景下土壤DON主要在6个位置有相似的吸收峰,包含3410 cm^-1、1636 cm^-1、1402 cm^-1、1138-1035 cm^-1、673 cm^-1、602 cm^-1,不同土地利用背景下各吸收峰的透光度不同,强度最大的吸收来自游离的胺类N-H伸缩振动;水稻、菜园土壤DON芳香物质含量较高,结构较复杂。了解DON的组成与粒径分布对土地利用的响应,对进一步研究其生态环境行为具有重要意义。     

Effects of a diesel oxidation catalyst on gaseous pollutants and fine particles from an engine operating on diesel and biodiesel

The effects of a diesel oxidation catalytic (DOC) converter on diesel engine emissions were investigated on a diesel bench at various loads for two steady-state speeds using diesel fuel and B20. The DOC was very effective in hydrocarbon (HC) and CO oxidation. Approximately 90%–95% reduction in CO and 36%–70% reduction in HC were realized using the DOC. Special attention was focused on the effects of the DOC on elemental carbon (EC) and organic carbon (OC) fractions in fine particles (PM_2.5) emitted from the diesel engine. The carbonaceous compositions of PM_2.5 were analyzed by the method of thermal/optical reflectance (TOR). The results showed that total carbon (TC), OC and EC emissions for PM_2.5 from diesel fuel were generally reduced by the DOC. For diesel fuel, TC emissions decreased 22%–32% after the DOC depending on operating modes. The decrease in TC was attributed to 35%–97% decrease in OC and 3%–65% decrease in EC emissions. At low load, a significant increase in the OC/EC ratio of PM_2.5 was observed after the DOC. The effect of the DOC on the carbonaceous compositions in PM_2.5 from B20 showed different trends compared to diesel fuel. At low load, a slight increase in EC emissions and a significant decrease in OC/EC ratio of PM_2.5 after DOC were observed for B20.