Effects of pollution on humic substances

Abstract

To assess effects of industrial and environmental pollution on analytical characteristics of humic substances, we isolated humic acids (HA's) and fulvic acids (FA's) from unpolluted and polluted soils and sediments. Following purification, the HA's and FA's were characterized by elemental (C, H, O, N, S) and functional group (CO₂H, phenolic OH, total acidity) analyses, infrared (IR) spectrophotometry, differential thermal analysis (DTA) and by metal (Fe, Al, Cu, Mn, Pb, Ni, Co, Zn, Cr, Cd, Hg, Ca and Mg) analyses. Si was also determined in all samples.

Polluted HA's and FA's contained more N and S but less 0 and were richer in all metals and Si than were unpolluted ones. IR spectra showed that polluted humic materials were enriched in COO^‐ groups, secondary non‐cyclic amides and possible also in SO₃H groups. DTA curves indicated that polluted HA's and FA's were more thermostable than unpolluted HA's and FA's. Unusually high N, S, Cu, Cr, Zn and Hg contents of humic materials appear to be useful indicators of soil and sediment pollution.     

The conversion of chicken manure to biooil by fast pyrolysis I. Analyses of chicken manure, biooils and char by 13C and 1H NMR and FTIR spectrophotometry

Fast pyrolysis of chicken manure produced two biooils (Fractions I and II) and a residual char. All four materials were analyzed by chemical methods, 13C and 1H Nuclear Magnetic Resonance Spectrometry (13C and 1H NMR), and Fourier Transform Infrared Spectrosphotometry (FTIR). The char showed the highest C content and the highest aromaticity. Of the two biooils Fraction II was higher in C, yield and calorific value but lower in N than Fraction I. The S and ash content of the two biooil fractions were low. The Cross Polarization Magic Angle Spinning (CP-MAS) 13C NMR spectrum of the initial chicken manure showed it to be rich in cellulose, which was a major component of sawdust used as bedding material. Nuclear Magnetic Resonance (NMR) spectra of the two biooils indicated that Fraction I was less aromatic than Fraction II. Among the aromatics in the two biooils, we were able to tentatively identify N-heterocyclics like indoles, pyridines, and pyrazines. FTIR spectra were generally in agreement with the NMR data. FTIR spectra of both biooils showed the presence of both primary and secondary amides and primary amines as well as N-heterocyclics such as pyridines, quinolines, and pyrimidines. The FTIR spectrum of the char resembled that of the initial chicken manure except that the concentration of carbohydrates was lower.     

The conversion of chicken manure to bio-oil by fast pyrolysis. III. Analyses of chicken manure, bio-oils and char by Py-FIMS and Py-FDMS

Fast pyrolysis of chicken manure produced the following three fractions: bio-oil Fraction I, bio-oil Fraction II, and a char. In a previous investigation we analyzed each of the four materials by curie-point pyrolysis-gas chromatography/mass spectrometry (CpPy-FDMS). The objective of this article is to report on the analyses of the same chicken manure and the three fractions derived from it by fast pyrolysis. We now used pyrolysis-field ionization mass spectrometry (Py-FIMS) to characterize the three fractions. In addition, the two bio-oil materials were analyzed by pyrolysis-field desorption mass spectrometry (Py-FDMS). The use of both Py-FIMS and Py-FDMS produced signals over significantly wider mass ranges than did CpPy-GC/MS, and so allowed us to identify considerably larger numbers of constituents in each material. Individual compounds identified in the mass spectra were classified into the following twelve compound classes: (a) low molecular weight compounds (< m/z 62); (b) carbohydrates; (c) phenols + lignin monomers; (d) lignin dimers; (e) n-alkylbenzenes; (f) N-heterocyclics; (g) n-fatty acids; (h) n-alkanes; (i) alkenes; (j) sterols; (k) n-diols and (l) high molecular weight compounds (> m/z 562). Of special interest were the high abundances of low-molecular weight compounds in the two bio-oils which constituted close to one half of the two bio-oils. Prominent among these compounds were water, ammonia, acetic acid, acetamide, propyl radical, formamide and hydrogen cyanide. The main quantitative differences between the two bio-oils was that bio-oil Fraction I, as analyzed by the two mass spectrometric methods, contained lower concentrations of low-molecular weight compounds, carbohydrates, and N-heterocyclics than bio-oil Fraction II but was richer in lignin dimers, n-alkylbenzenes and aliphatics (n-fatty acids, n-alkanes, alkenes, and n-diols). Of special interest were the N-heterocyclics in the two bio-oils such as pyrazole, pyrazoline, substituted pyrroles, pyridine and substituted pyridines, substituted methoxazole, substituted pyrazines, indole and substituted indoles. Fatty acids in all four materials ranged from n-C(9) to n-C(33), alkanes from n-C(9) to n-C(40), alkenes from C(10:1) to C(40:1) and diols from n-C(7) to n-C(29). The chicken manure, bio-oil Fraction I, and char each contained about 4% sterols with cholesterol, ethylcholestriene, ergosterol, ethylcholestene, ethylcholesterol and beta -sitosterol as major components. Semi-quantitative estimates of the total materials identified by Py-FIMS were: chicken manure: 61.1%; bio-oil Fraction I: 81.3%; bio-oil Fraction II: 78.6%; char: 61.3%; and by Py-FDMS were: bio-oil Fraction I: 65.4%; bio-oil Fraction II: 70.0%.     

分光光度法测定地表水中总氮的监测质量控制指标研究

运用碱性过硫酸钾-紫外分光光度法对总氮的标准样品及实际样品进行研究分析,通过全国多家实验室的大量监测数据,得出了当前常用的精密度及准确度方面质量控制指标的建议值。研究表明：标准样品在0.5~3.5mg/L浓度范围内,相对标准偏差RSD≤5.0%;室间相对标准偏差RSD′≤10%;相对误差RE≤±10%;实际样品在0.07~10mg/L浓度范围内时,相对偏差RD≤10.0%;加标回收率范围为90%~110%。     

菌株 Arthrobacter sp. CN2降解对硝基苯酚的特性与动力学

为研究对硝基苯酚降解菌Arthrobacter sp.CN2在实际生产中的应用潜力,本文分别分析了p H、盐浓度和额外添加碳源对降解效率的影响,同时对降解的动力学方程进行拟合分析.菌株CN2在p H 7.0~8.0,Na Cl浓度60 g·L-1之间能够高效降解对硝基苯酚,72 h内对50 mg·L-1对硝基苯酚的降解率均大于90%.同时发现适量添加葡萄糖(0.5%)可显著促进CN2降解对硝基苯酚,与不添加葡萄糖条件下相比,达到90%降解率所需时间缩短了16 h.当对硝基苯酚浓度低于300 mg·L-1时,菌株CN2对对硝基苯酚的降解符合一级动力学方程,降解速率常数在0.021 7~0.025 0之间.在生物反应器中应用菌株CN2模拟处理工业废水,3 L含对硝基苯酚废水(100 mg·L-1)在72h的降解率大于90%.研究表明,菌株Arthrobacter sp.CN2能够高效地降解对硝基苯酚,对于环境有良好适应能力,具有良好的应用前景.     

大气细颗粒物的污染特征及对人体健康的影响

采集兰州市2005年1月1日至2007年12月31日的大气颗粒物(TSP、PM10、PM2.5、PM1.0),分析不同粒径颗粒物的污染特征及其与气象因素的相关关系,并采用时间序列半参数广义相加模型(GAM)分析了可吸入颗粒物与呼吸系统疾病和心脑血管疾病日入院人次的暴露-反应关系.结果显示,TSP和PM10的质量浓度在春季较高,PM2.5和PM1.0在冬季较高;气象因子与大气颗粒物有显著的相关关系;对于呼吸系统疾病来说,PM10、PM2.5和PM1.0每升高10μg·m-3或10粒子数·m-3,入院危险分别增加0.052%、0.604%和0.652%;对于心脑血管疾病来说,PM10、PM2.5和PM1.0每升高10μg·m-3或10粒子数·m-3入院危险分别增加0.046%、0.697%和0.935%.由此可见,兰州市不同粒径大气颗粒物均有不同程度的污染,PM10、PM2.5和PM1.0对呼吸系统疾病和心脑血管疾病入院人次均有一定影响,且PM10对呼吸系统疾病的影响较心脑血管疾病明显,而PM2.5和PM1.0则正好相反.     

SCR脱硝技术在沧东电厂4号机组中的应用

以沧东电厂4号机组进行的脱硝改造工程为例,阐述了选择性催化还原(SCR)烟气脱硝系统的工作原理,并对SCR反应器、催化剂等脱硝设备的特点进行了详细地介绍,同时对4号机组加装脱硝装置后对空预器、引风机的影响进行了详细地分析,并针对其影响提出了具体的改造措施。     

宁夏石嘴山河滨工业园区表层土壤重金属污染的时空特征

为研究西北地区工业区土壤重金属空间分布及时间变化的区域特征,以宁夏石嘴山河滨工业园区西北端面积为1.74hm2的区域为研究区,采集表层土壤样品96个,利用原子吸收分光光度计测定Cu、Zn、Pb、Cr、Cd含量,SPSS 16.0软件做描述性统计和相关分析,资料对比法结合Google earth卫星地图分析含量的时空格局变化对应性.在GS+3.0软件理论拟合基础上,利用ArcGIS 9.0软件进行克里格插值,分析空间分布特征及可能的污染源.结果表明,Zn、Cu、Cr、Pb、Cd的平均含量分别为100.29、352.86、77.56、50.52、4.06 mg.kg-1,均高于宁夏土壤背景值.Zn、Cr、Pb为非污染,Cu、Cd属轻度污染和重度污染.Zn、Cu、Cr、Pb、Cd含量较1985年该地区水平增加明显,均从西北向东南增加并局部呈岛状空间分布.土壤中Cu、Cr、Zn、Pb、Cd的含量变化与2009年后该园区企业数量迅速增加及周边另一内蒙古高耗能工业园区的工业燃煤烟尘排放密切相关,空间格局主要由主导的西北强风控制、影响范围大,局地地形和企业分布格局是岛状分布的主要因素.     

广东英德宝晶宫洞穴滴水元素季节变化与影响因素

为揭示洞穴滴水元素的季节变化特征及其影响因素,从2011年12月至2013年5月对广东英德宝晶宫洞穴内的3个滴水点滴水中的Ba、Sr、Ca、Mg元素进行为期一年半的监测,结果发现:13个滴水点滴水中的元素浓度基本上都表现出明显的季节变化特征,但不同的元素之间和不同的滴水点之间的季节变化趋势存在差异,表明不同的滴水点其不同的元素浓度变化的影响机制各有不同.2强降水对洞穴滴水的元素浓度具有稀释作用,Drip1和Drip2各元素浓度在有强降雨的5、6月都呈现低值.33个滴水点的Mg/Ca和Sr/Ca比值都具有较强的正相关关系,且都表现出旱季高,雨季低的特点.表明宝晶宫3个滴水点的Mg/Ca、Sr/Ca很可能受到降水量、岩溶水来源、上覆土壤的淋滤作用以及碳酸盐先期沉积作用等因素共同影响,并能较好地反映该地区的干湿变化.     

超期服役的导弹发射装药贮存安全性试验评估

目的研究超期服役的某型导弹发射装药是否满足安全贮存使用要求,结合性能试验准确评估装药的贮存安全性。方法通过分析发射装药性能老化与失效可能引发的安全风险,构建装药贮存安全性评估参数体系。在此基础上,对贮存14 a与5 a的发射装药分别进行结构完整性、力学性能、热安定性、易损性等贮存安全性相关试验。结果通过试验结果与数据分析,获取了对应的评估参数,贮存14 a与5 a的装药性能相比,装药总体结构安全系数由3.85降至2.86。在相同试验温度下,抗拉强度、抗压强度和抗冲击强度的最大降低幅度分别为18.35%、14.05%、7.85%,装药安定剂含量由98%降至93%,摩擦感度与撞击感度分别增高33.28%、36.77%,据此综合评估了发射装药的贮存安全性。结论超期服役的某型导弹发射装药贮存安全性仍满足技术标准要求,装药经过长期贮存后,力学性能和热安定性的劣化程度较小,结构完整性与易损性对应参数变化较大,表明装药的使用安全性明显下降。