Characterisation of Organic Matter and Carbon Cycling in Rehabilitated Lignite-rich Mine Soils

Open-cast lignite mining in the Lusatian mining district resulted in rehabilitated mine soils containing up to four organic matter types: (1) recent plant litter, (2) lignite deposited by mining activity, (3) carbonaceous ash particles deposited during amelioration of the lignite-containing parent substrate and (4) airborne carbonaceous particles deposited during contamination. The influence of lignite-derived carbon types on the organic matter development and their role in the soil carbon cycle was unknown. This paper presents the findings obtained during a six year project concerning the impact of lignite on soil organic matter composition and the biogeochemical functioning of the ecosystem. The organic matter development after rehabilitation was followed in a chronosequence of rehabilitated mine soils afforested in 1966, 1981 and 1987. A differentiation of the organic matter types and an evaluation of their role within the ecosystem was achieved by the use of ¹⁴C activity measurements, ¹³C CPMAS NMR spectroscopy and wet chemical analysis of plant litter compounds. The results showed that the amount and degree of decomposition of the recent organic matter derived from plant material of the 30 year old mine soil was similar to natural uncontaminated forest soil which suggests complete rehabilitation of the ecosystem. The decomposition and humification processes were not influenced by the presence of lignite. On the other hand it was shown that lignite, which was thought to be recalcitrant because of its chemical structure, was part of the carbon cycle in these soils. This demonstrates the need to elucidate further the stabilisation mechanisms of organic matter in soils.     

Effect of Cross-Linking Waste Protein with Dialdehydes on Its Biodegradation Under Anaerobic Conditions

Most native polymers used in processing and application technologies are admittedly disposable from the environment in a biologic manner, but products possess low mechanical strength. One of the paths to increasing this attribute (if feasible) is their cross-linking, which may, however, affect their readiness to biodegradation. In the presented work this condition was observed on the example of waste protein (Hykol B) cross-linking by means of glutardialdehyde and glyoxal. Degree and course of cross-linking were determined through impedance spectroscopy. The objective of this work also was to obtain data for constructing a sensor capable of following the cross-linking course in real time, for potential industrial application of Hykol in continuous production. Impedance spectroscopy proved to be applicable even to this kind of material marked by considerable water content and exhibiting relatively high electric conductivity; so far it had been used only for materials of low conductivity. An aqueous environment inoculated with digested anaerobic sludge from a municipal wastewater treatment plant was selected for modeling anaerobic conditions. The relation was studied between cross-linking degree given by content of cross-linking agent (determined by impedance spectroscopy) and biodegradation degree under anaerobic conditions. It was confirmed that network density as given by quantity of added agent not only reduced breakdown degree but also slowed the course of the process. This fact is particularly obvious with cross-linking by means of glyoxal; network density is thus dependent on type of employed substance, which affect type and structure of created network. That not merely forms an obstacle during polymer swelling and dissolution but also prevents access of bacteria to source of metabolized organic carbon.     

Using multivariate regression modeling for sampling and predicting chemical characteristics of mixed waste in old landfills

Municipal solid waste landfills pose a threat on environment and human health, especially old landfills which lack facilities for collection and treatment of landfill gas and leachate. Consequently, missing information about emission flows prevent site-specific environmental risk assessments. To overcome this gap, the combination of waste sampling and analysis with statistical modeling is one option for estimating present and future emission potentials. Optimizing the tradeoff between investigation costs and reliable results requires knowledge about both: the number of samples to be taken and variables to be analyzed.This article aims to identify the optimized number of waste samples and variables in order to predict a larger set of variables. Therefore, we introduce a multivariate linear regression model and tested the applicability by usage of two case studies. Landfill A was used to set up and calibrate the model based on 50 waste samples and twelve variables. The calibrated model was applied to Landfill B including 36 waste samples and twelve variables with four predictor variables.The case study results are twofold: first, the reliable and accurate prediction of the twelve variables can be achieved with the knowledge of four predictor variables (Loi, EC, pH and Cl). For the second Landfill B, only ten full measurements would be needed for a reliable prediction of most response variables. The four predictor variables would exhibit comparably low analytical costs in comparison to the full set of measurements. This cost reduction could be used to increase the number of samples yielding an improved understanding of the spatial waste heterogeneity in landfills.Concluding, the future application of the developed model potentially improves the reliability of predicted emission potentials. The model could become a standard screening tool for old landfills if its applicability and reliability would be tested in additional case studies.     

长期施肥下浙江稻田不同颗粒组分有机碳的稳定特征

依托浙江水网地区稻田长期定位施肥试验(1996~2013年),利用固态13C核磁共振波谱技术,研究长期不同施肥措施下土壤各颗粒组分有机碳含量及其化学结构特征.结果表明,与不施肥对照(CK)相比,秸秆与化肥配施(NPKRS)、栏肥与化肥配施(NPKOM)、单施化肥(NPK)和单施栏肥(OM)处理均显著(P0.05)增加了砂粒(2~0.02 mm)、粉粒(0.02~0.002mm)和黏粒(0.002 mm)组分中有机碳含量;而单施秸秆(RS)处理仅显著增加砂粒组分有机碳含量.此外,与单施化肥处理相比,有机肥和化肥配施促进了新增有机碳在粉粒和黏粒组分的分配,更有利于新增有机碳的稳定.应用13C-NMR波谱技术进行结构表征,结果表明粉粒和黏粒组分有机碳的化学结构存在明显差异,粉粒组分烷氧碳、芳香碳的相对含量高于黏粒,而烷基碳、羰基碳的相对含量低于黏粒.长期有机肥与化肥配施下粉粒和黏粒烷基碳相对含量较单施有机肥处理分别降低9.1%~11.9%和13.7%~19.9%,烷氧碳的相对含量则分别增加2.9%~6.3%和13.4%~22.1%,表明有机肥与化肥配施处理降低了粉粒和黏粒组分有机碳的分解程度.长期单施化肥处理下粉粒和黏粒组分有机质的芳化度和疏水性低于单施有机肥处理和不施肥处理,有机质的矿化稳定性较低.长期有机肥与化肥配施,尤其是NPKOM处理,通过增加化学抗性化合物和碳水化合物的积累,并且减缓活性组分的分解提高粉粒和黏粒组分有机碳含量,是促进稻田土壤有机碳可持续积累的有效措施.     

Effect of oxide nanoparticles on the morphology and fluidity of phospholipid membranes and the role of hydrogen bonds

Engineered oxide nanoparticles (NPs) are widely applied in insulators, catalyzers, paints, cosmetic products, textiles and semiconductors. Their attachment on cell membrane may lead to cytotoxicity. The effects of Al₂O₃, Fe₂O₃, SiO₂, TiO₂ and ZnO NPs on membrane integrity and fluidity were studied using giant or small unilamellar vesicles in this study. Al₂O₃ and SiO₂ NPs disrupted the oppositely charged membrane, indicating the important role of electrostatic attraction. However, Fe₂O₃, TiO₂ and ZnO NPs did not cause serious membrane disruption as Al₂O₃ and SiO₂ NPs. Membrane fluidity was evaluated by the generalized polarity (GP) values of Laurdan fluorescent emission. SiO₂ NPs induce the membrane gelation of both positively and negatively charged membrane. Al₂O₃ and ZnO NPs induced the gelation of the oppositely charged membrane, but did not cause obvious membrane gelation to the like charged membrane. The phospholipid molecular structural changes after NP exposure were analyzed by Fourier transform infrared (FT-IR) spectroscopy. FT-IR spectra revealed the hydrogen bond formation between NPs and the carbonyl/phosphate groups of phospholipids. Al₂O₃ and SiO₂ NPs showed strongest evidence of hydrogen bonding on their FT-IR spectra. It was consistent with the microscopic observation and fluorescent data that Al₂O₃ and SiO₂ NPs caused more serious membrane disruption and gelation. This study on membrane damage provides further knowledge on the cytotoxicity of nanomaterials and the safety of NP application.     

覆盖金属氧化物对湖泊沉积物溶解性有机质特征的影响

为揭示不同金属氧化物对湖泊沉积物DOM（溶解性有机质）影响机制,通过室内模拟试验,在沉积物表层分别覆盖Fe、Al、Mn氧化物及湖沙后培养1 a,并利用三维荧光和紫外光谱方法进行表征.结果表明:① 覆盖Al、Fe、Mn氧化物和湖沙主要降低了0~3 cm沉积物的w（DOC）,降幅分别为8.61%、6.27%、22.38%和0.44%. ② 沉积物中DOM的类络氨酸峰（peak B₁）和类色氨酸峰（peak T₂）均产生较大变化.其中三种氧化物均显著降低了上层沉积物中DOM的peak T₂,使底层DOM的peakT₂显著增加. Mn氧化物使DOM的peak B₁降低,Fe和Al氧化物使DOM的peak B₁增加,湖沙则使两类峰均降低. ③ 覆盖金属氧化物改变了沉积物DOM结构特征,其中覆盖Fe氧化物增强了其芳香性,而覆盖Mn氧化物和Al氧化却降低其芳香性,但三者均使DOM腐质化程度及官能团数量增加,并使FI（Fluorescence Index,荧光指数）增大,表明DOM向生物源转化.研究显示,沉积物表层覆盖金属氧化物影响了沉积物中DOM迁移和转化,并促进了其降解,导致其分子量和腐殖化程度增加.      

典型水库型湖泊中CDOM吸收及荧光光谱变化特征:基于沿岸生态系统分析

为进一步了解水库型湖泊溶解性有机质(DOM)的地球化学特征,本文以三峡库区典型内陆水库型湖泊——长寿湖为研究对象,利用紫外-可见和三维荧光光谱,并结合湖区周边生态系统分析,讨论了长寿湖水体中CDOM的组成、来源和空间分布特征.结果表明,长寿湖不同采样点DOM浓度(DOC和CDOM)存在一定程度的空间分布差异,但各点FDOM分布较为稳定.回水区出现DOM累积,由于受陆源输入影响有限,水体内源活动主导,具有较明显"内源控制"特征,芳香性和分子量相对较低;而周边陆地以人工林兼旅游开发为主的采样点,陆源输入在带入较多腐殖化(高芳香性)组分的同时,人为活动排放也是导致其类蛋白组分丰富的重要原因;入湖区尽管周边果林和居民生活对水体DOM有一定影响,但上游河流输入的影响也不容忽视.另外,各采样点也出现了不受周边生态系统影响的独立的相关性特征,例如芳香性特征常数(SUVA280)和光谱斜率[S(275~295)]显著负相关、CDOM和FDOM极显著正相关、CDOM和S(275~295)负相关等.同时,长寿湖水体中CDOM的生色团主要由具有芳香性结构的大分子组分构成;至少51%的CDOM波动可以通过FDOM变化来进行解释,其中回水区荧光组分对CDOM变动的影响最为明显.在采用传统FI值无法区分DOM来源差异性时,结合采样点沿岸生态系统,综合紫外-可见和荧光光谱特征,有助于对DOM组成及来源进行解析.     

X射线光电子能谱在HTPB推进剂老化机理研究中的应用

采用X射线光电子能谱（XPS）法研究了HTPB推进剂在80℃热空气烘箱内分别老化0周、13周和24周的元素组成、化学价态及含量变化。通过拟合C,O,N,Cl等元素的XPS谱图,推测该推进剂在常温（25℃）贮存老化初期应是氧化交联,后期则出现降解断链,并认为NH4ClO4缓慢分解,攻击C C不饱和双键,使得C C双键含量降低是HTPB推进剂老化失效的主要原因。Al粉被包裹在推进剂粘合剂内部,XPS法未能检出Al粉。由于Al粉比较稳定,不参与推进剂老化过程,故XPS仍可用于HTPB推进剂老化机理研究。     

水溶性有机物电子转移能力与荧光峰强度的关系研究

以不同来源的水溶性有机物（DOM）为供试材料,采用电化学方法和荧光光谱法研究了DOM电子转移能力及其与荧光峰强度的关系.采用库仑安培法测定DOM电子转移能力,其中测得的电子接受能力为635.6～1 049.3μmol.（g.C）-1,电子供给能力为27.3～42.3μmol.（g.C）-1.利用循环伏安法研究DOM电化学活性,发现其氧化还原电位在-731～-996 mV（vs.Ag/AgCl）之间.经过电位跃阶法三次氧化还原循环后电子转移能力仍可维持在232.1～897.2μmol.（g.C）-1之间,电子循环率为36.7%～78.2%,说明DOM具有重复利用、反复转移电子的特性.采用荧光激发发射光谱法（EEMS）测定DOM的类富里酸荧光峰强度并比较其与DOM电子转移能力的关系,发现DOM的类富里酸荧光峰强度与DOM的电子循环率具有显著相关（r2=0.92）.实验结果为理解DOM在元素循环、污染物降解以及生物地球化学循环中的作用提供科学依据.     

几种水合金属氧化物的磷酸根吸附性能

利用简单的碱沉淀法制备不同的水合金属氧化物,并对所得七种水合金属氧化物的磷酸根吸附等温线进行了系统的探讨比较.研究表明,25℃条件下,Al、Fe、Ni、Cu和Ce的水合金属氧化物对磷酸根的吸附最符合Langmuir线性吸附方程,而水合氧化锌和水合氧化钴吸附剂最符合线性等温线模型.所有这七种水合金属氧化物对磷酸根的吸附都...