三维荧光光谱结合荧光区域指数分析方法评估堆肥腐熟度

评估堆肥腐熟度是确保堆肥产品质量的重要保证. 采用三维荧光光谱结合荧光区域指数分析方法快速评估菜粕和稻糠堆肥过程中的腐熟度. 结果表明:菜粕和稻糠堆肥可在16 d内完成一次发酵,其中第7～14天为高温期(>50 ℃,共8 d);随后,堆体进入降温期,第16天降至32 ℃. 堆肥初期(第0～6天)DOC(溶解性有机碳)、DON(溶解性有机氮)质量浓度和EC(电导率)先稳定在一个较低的水平;在堆肥高温期(第7～14天),ρ(DOC)、 ρ(DON)和EC则分别迅速升至10.47 mg/L、7.52 mg/L和5.76 mS/cm. 堆肥腐熟度相关指标〔即ρ(DOC)、 ρ(DON)和EC〕与FRI(荧光区域指数)方法中P_Ⅲ,n、P_Ⅴ,n、P_Ⅴ,n/P_Ⅲ,n指标的变化趋势一致,并且具有极显著相关性(R>0.942,P<0.01);而与P_Ⅰ,n变化趋势相反,也具有显著的相关性(R<-0.871,P<0.05). 因此,P_Ⅲ,n、P_Ⅴ,n、P_Ⅴ,n/P_Ⅲ,n与P_Ⅰ,n可以用于表征堆肥腐熟度.      

Insights on the solubilization products after combined alkaline and ultrasonic pre-treatment of sewage sludge

This work provides insights on the solubilization products after a simultaneous combination of alkaline and ultrasonic (ALK + ULS) pre-treatment of sewage sludge. Soluble chemical oxygen demand (SCOD) increased from 1200 to 11,000 mg/L after such treatment. Organics with molecular weight around 5.6 kDa were solubilized because of the synergistic effect of ultrasound and alkali. Organics with molecular weight larger than 300 kDa increased from 7.8% to 60%, 16% and 42.3% after ULS, ALK and ALK + ULS treatment, respectively. Excitation emission matrix fluorescence spectroscopy analysis identified soluble microbial product-like and humic acid-like matters as the main solubilization products. Sludge anaerobic biodegradability was significantly enhanced with the simultaneous application of ALK + ULS pre-treatment. ALK + ULS pre-treatment resulted in 37.8% biodegradability increase compared to the untreated sludge. This value was higher compared to the biodegradability increase induced by individual ALK pre-treatment (5.7%) or individual ULS pre-treatment (20.7%) under the same conditions applied.     

城市雨水管网沉积物不同分子量溶解性有机质空间分布及光谱特征

采用超滤法、紫外-可见吸收光谱和三维荧光光谱分析法研究了北京市西城区4个典型功能区(居民区、文教区、交通区、商业区)雨水管网表层沉积物中不同分子量溶解性有机质(DOM)的分布特征和光谱特性。结果表明:雨水管网沉积物DOM以小分子量组分为主,约占整体水平的60%~70%。通过分析还发现,沉积物中小分子量(小于3k Da)DOM主要是类蛋白物质,而腐殖类物质主要集中在DOM的大分子量(大于10k Da)区域,微生物活动对小分子量DOM贡献作用显著,由此可见,DOM的分子组成和结构特性在一定程度上可以作为雨水管网沉积物DOM主成分和来源的衡量指标。4个功能区DOM腐殖化水平较低,表现出随分子量增大DOM腐殖化程度升高的规律。     

Fluorescence excitation-emission spectroscopy with regional integration analysis for assessment of compost maturity

Composting of animal manures is believed as an alternative way for directly recycling them in farms, and therefore assessment of compost maturity is crucial for achieving high quality compost. Fluorescence excitation-emission matrices (EEMs) combined with regional integration analysis is presented to assess compost maturity. The results showed that the EEM contours of water-extract organic matter (WEOM) from immature composts exhibited four peaks at excitation/emission (Ex/Em) of 220/340 nm, 280/340 nm, 220/410 nm, and 330/410 nm, whereas EEM contour of WEOM from mature composts had only two peaks at Ex/Em of 230/420 nm and 330/420 nm. Pearson correlation demonstrated that peaks intensity rather than their ratios had a significantly correlation with the common indices assessing compost maturity, whereas the normalized excitation-emission area volumes (Φ_i,ns) from regional integration analysis had a stronger correlation with the common indices assessing compost maturity than peaks intensity. It is concluded that the Φ_i,ns from regional integration analysis are more suitable to assess the maturity of compost than the intensities of peaks. Therefore, the fluorescence spectroscopy combined with regional integration analysis can be used as a valuable industrial and research tool for assessing compost maturity, given its high sensitivity and selectivity.     

Fluorescence excitation–emission matrix spectra coupled with parallel factor and regional integration analysis to characterize organic matter humification

The present several humification indexes cannot provide the whole fluorescence information on organic matter composition and the evaluation results from them are inconsistent sometimes. In this study, fluorescence excitation–emission matrix spectra coupled with parallel factor analysis and fluorescence regional integration analysis were utilized to investigate organic matter humification, and the projection pursuit cluster (PPC) model was applied to form a suitable index for overcoming the difficulties in multi-index evaluation. The result showed that the ratio between the volume of humic- and fulvic-like fluorescence region and the volume of protein-like fluorescence region not only revealed the heterogeneity of organic matter, but also provided more accurate information on organic matter humification. In addition, the results showed that the PPC model could be used to characterize integrally the humification, and the projected characteristic value calculated from the PPC model could be used as the integrated humification evaluation index.     

浑太水系水体中不同粒径有机胶体荧光光谱特性

将超滤系统与孔径(相对分子质量)为100×103和1×103超滤膜结合,对浑太水体中总溶解有机质(DOM)进行分级,并运用三维荧光光谱技术对不同级有机质的荧光光谱特性进行了对比分析.结果表明,浑太水系水体的荧光图谱表现为紫外光区类腐殖质、可见光区类腐殖质、类色氨酸(短波和长波激发峰)4个荧光峰,其中,类腐殖质荧光物质主要赋存于胶体形态(相对分子质量<100×103)和真溶解态(相对分子质量<1×103)中,由于类蛋白物质与水体中胶体的相互作用,使得胶态类蛋白荧光物质也占有相当大的比例.峰、枯两水期相比,丰水期由于陆源汇流的冲击作用,阻止了胶体颗粒的凝聚,使DOM中小胶态和真溶解态有机质所占的质量分数较高.通过比较不同粒径有机质的荧光指数、生物源指数、腐殖化指数以及DOM与荧光强度的相关性分析可以得出,真溶解态中腐殖质主要源自于内源作用,而胶态腐殖质具有陆源特征,新产生的有机质在真溶解态中占有更大的比例,水体中类腐殖质是溶解有机碳(DOC)的主要来源,但由于浑太水系各采样断面存在不同程度的污染,类蛋白物质对DOC的贡献也不能忽略.     

Insights on the solubilization products after combined alkaline and ultrasonic pre-treatment of sewage sludge

This work provides insights on the solubilization products after a simultaneous combination of alkaline and ultrasonic (ALK + ULS) pre-treatment of sewage sludge. Soluble chemical oxygen demand (SCOD) increased from 1200 to 11,000 mg/L after such treatment. Organics with molecular weight around 5.6 kDa were solubilized because of the synergistic effect of ultrasound and alkali. Organics with molecular weight larger than 300 kDa increased from 7.8% to 60%, 16% and 42.3% after ULS, ALK and ALK + ULS treatment, respectively. Excitation emission matrix fluorescence spectroscopy analysis identified soluble microbial product-like and humic acid-like matters as the main solubilization products. Sludge anaerobic biodegradability was significantly enhanced with the simultaneous application of ALK + ULS pre-treatment. ALK + ULS pre-treatment resulted in 37.8% biodegradability increase compared to the untreated sludge. This value was higher compared to the biodegradability increase induced by individual ALK pre-treatment (5.7%) or individual ULS pre-treatment (20.7%) under the same conditions applied.     

交替冻融对东北典型土壤腐殖质的影响

以受季节性冻融过程影响显著的东北地区的黑土、暗棕壤和水稻土为例,采用实验室模拟的方法,研究交替冻融循环过程（分别在-20℃和20℃下处理）对土壤腐殖质的影响。研究表明：交替冻融后,黑土和暗棕壤松结态腐殖质质量分数分别增加了39%和28%,HA/FA分别上升了45%和35%;水稻土松结态腐殖质质量分数和HA/FA分别下降了18%和31%。三维荧光结果进一步验证,黑土、暗棕壤在交替冻融中土壤芳香化程度增高,HA/FA上升,而水稻土则相反。黑土和暗棕壤松结态腐殖质和HA/FA升高,主要是微生物分解作用和土壤大团聚体破坏等原因造成,水稻土松结态腐殖质和HA/FA降低,主要是水稻土的缺氧环境造成。     

Different analysis techniques for fluorescence excitation-emission matrix spectroscopy to assess compost maturity

Assessment of compost maturity is essential for achieving high quality compost. In this study, fluorescence excitation-emission matrix spectroscopy combined with different analysis techniques was applied to improve the sensitivity of compost maturity assessment. Results showed that composts in two parallel piles could be believed mature after 37 d when combined with the evolution of temperature, chemical and biological indices in the two piles. Pearson correlation between the common maturity indices and fluorescence analysis parameters demonstrated that fluorescence regional integration (FRI) had a higher correlation coefficient than that of fluorescence intensities and the ratios of peaks, suggesting that FRI technique is more suitable to characterize the maturity of compost than the other two analysis techniques, i.e., peak intensity and peak ratio. Furthermore, the fluorescence spectroscopy combined with FRI analysis could be used as a valuable industrial and research tool for assessing compost maturity.     

神农架大九湖泥炭地孔隙水溶解有机碳特征及其影响因素

溶解性有机碳（Dissolved Organic Carbon, DOC）是泥炭地碳循环的重要组成部分。以往的研究大多集中在北方泥炭地,而对亚热带季风区泥炭地DOC动力学的认识十分有限。利用紫外可见光光谱（UV-Vis）和三维荧光光谱结合平行因子分析法（EEM-PARAFAC）研究了神农架大九湖泥炭地孔隙水的DOC浓度与化学组成及其影响因素。EEM-PARAFAC的结果表明：大九湖泥炭地孔隙水DOC主要包含3种类腐殖质组分。紫外可见光和荧光指标表明,泥炭孔隙水DOC表观分子较小,而芳香度较高。深度剖面数据表明,泥炭孔隙水DOC浓度随深度降低,0~10 cm深度浓度最高为24.16 mg/L,150~160 cm深度浓度最低为9.72 mg/L,并且深层DOC以微生物代谢产生的新鲜有机物为主,具有较低的腐殖化度。此外,氧化还原电位（ORP）与DOC浓度及化学性质关系密切。以上结果表明,在亚热带泥炭地中,微生物来源或受微生物改造的有机物是泥炭孔隙水DOC的重要组成部分;垂向输送或选择性保存是影响该亚热带亚高山泥炭地DOC动力学的重要因素。