基于非分散红外技术的煤矿井下有害气体定量探测方法研究

煤矿井下有害气体的浓度监测对煤矿生产安全预警至关重要。介绍了一种基于非分散红外光谱技术能够同时定量探测煤矿井下一氧化碳、甲烷等有害气体的方法。入射红外光经过高速旋转的滤光轮,得到各种待测气体相应滤波通道的调制光信号,经怀特池中待测气体吸收后得到各种气体的吸光度。通过非线性最小二乘拟合吸收光与被测气体浓度,得到测量系统的浓度定标曲线,一氧化碳、甲烷和二氧化碳三者定标拟合相关系数分别为0.9992、0.9996和0.9998。分析了系统的测量精度,通过比较样气标准浓度与实测浓度大小,发现所有被测气体的这两组数据的相关性均大于0.998,测量误差均小于5%。实验结果表明,采用非分散红外光谱技术可以实现煤矿井下多组分有害气体的同步精确探测,为扩展煤矿安全预警技术手段提供了参考。     

溶解无机碳的拉曼光谱定量分析可行性研究

海水溶解无机碳(DIC)的平均浓度约为2.05mmol/L,其中HCO3-占93%, CO32-为6%,CO2和H2CO3共1%.HCO3-的拉曼散射活性太弱,而其他成分的浓度又过低,使得海水中DIC组分不能产生明显的拉曼散射强度,目前还未见有关溶解无机碳拉曼光谱定量分析的报道.为突破这一局限,本研究探索了一种碱化辅助的拉曼定量分析方法,以海水DIC中拉曼活性最低、占比例最大的HCO3-为研究对象进行了可行性实验研究.通过碱化处理(100mL样品中添加NaOH试剂15mg)将HCO3-转化为拉曼活性更强的CO32-,有效提高了拉曼光谱系统对HCO3-的检出限(<3mmol/L).定量分析使用内标定法,选取水在~1635cm-1附近的O—H弯曲振动谱带作为标定物.实验结果显示,该方法对与海水中浓度相当的低浓度HCO3-溶液的定量分析具有良好的精度(相对误差<6.5%).     

牛粪堆肥过程中水溶性有机物演化的光谱学研究

采用紫外-可见吸收光谱、1H-核磁共振(NMR)和同步荧光光谱,研究了牛粪堆肥水溶性有机物(DOM)的结构特征及其演化规律.紫外-可见吸收光谱分析显示,SUVA254由堆肥起始的1.161上升至堆肥结束的2.543;E465/E665在整个堆肥过程中呈现上升趋势,变化范围在2.333~3.500;260~280,460~480,600~700nm范围内的面积积分A1、A2和A3均呈现出先增大后减小的趋势,峰值分别出现在26,14, 14d.1H-NMR分析显示,堆肥0d到堆肥41d,0.5~3.1δ面积积分所占比例从43.06%下降至8.63%,3.1~5.5δ从56.07%上升至89.68%,5.5~10δ不足总体的6%且变化趋势不明显.同步荧光光谱结果显示,经过41d 的堆肥,蛋白质类物质区积分面积比例(APLR)由0.331下降到0.252,而富里酸类物质区积分面积比例(AFLR)由0.325增加到0.336,同时胡敏酸类物质区积分面积比例(AHLR)由0.344增加到0.412;AFLR/APLR比与同步荧光光谱3个荧光峰峰高存在显著相关性,AHLR/AFLR与两个荧光峰光强的比值I351/I284和I382/I351存在显著相关性.上述结果表明,随着堆肥进行, DOM中的非腐殖质物质转化为类腐殖质,同时其芳香性结构增多,碳链结构发生氧化反应,分子量从小变大,堆肥腐殖化程度加大,稳定度增加.     

武汉城市污水中微塑料的分离、鉴定及其微观特征分析

为研究武汉城市污水中微塑料的分布特点及其表面形貌特征,采用以连续浮选分离装置为基础进行改进设计的微塑料提取装置对污水中微塑料进行分离,通过用65%硝酸和30%过氧化氢混合液（体积比为1:3）对污水样品进行消解,并采用筛网（300、600、1 000目）（100目=0.147 mm）和滤膜（1 μm玻璃纤维滤膜和20 nm氧化铝滤膜）分离技术建立起对水体微塑料和纳米塑料的分离富集方法.通过傅里叶变换红外光谱（FTIR）、扫描电镜-X射能谱分析联用（SEM-EDS）等方法对所提取微塑料颗粒的组成成分、赋存特征、表面形貌特征进行分析.结果表明:①提取装置的平均回收率在92%以上.②污水中微塑料类型主要为碎片类、泡沫类、薄膜类和纤维类.③FTIR结果证实,该方法所提取的微塑料颗粒中有聚乙烯、聚丙烯等成分,且发现了羰基、聚酯类物质存在,说明提取到的微塑料中可能有可降解塑料颗粒.④SEM-EDS结果显示,各类微塑料表面粗糙、撕裂程度不同,存在不同程度的风化痕迹,并在其表面发现Si、Cu、O、Al、Na、Ca、Ba等元素的富集.研究显示:改进的微塑料分离方法能够实现对污水中微塑料的高效提取;同时,明确了武汉城市污水微塑料的表面形貌特征及赋存特征,为未来武汉城市污水中微塑料污染的针对性治理提供理论依据.      

Photoacoustic infrared spectroscopy for conducting gas tracer tests and measuring water saturations in landfills

Gas tracer tests can be used to determine gas flow patterns within landfills, quantify volatile contaminant residence time, and measure water within refuse. While gas chromatography (GC) has been traditionally used to analyze gas tracers in refuse, photoacoustic spectroscopy (PAS) might allow real-time measurements with reduced personnel costs and greater mobility and ease of use. Laboratory and field experiments were conducted to evaluate the efficacy of PAS for conducting gas tracer tests in landfills. Two tracer gases, difluoromethane (DFM) and sulfur hexafluoride (SF₆), were measured with a commercial PAS instrument. Relative measurement errors were invariant with tracer concentration but influenced by background gas: errors were 1-3% in landfill gas but 4-5% in air. Two partitioning gas tracer tests were conducted in an aerobic landfill, and limits of detection (LODs) were 3-4 times larger for DFM with PAS versus GC due to temporal changes in background signals. While higher LODs can be compensated by injecting larger tracer mass, changes in background signals increased the uncertainty in measured water saturations by up to 25% over comparable GC methods. PAS has distinct advantages over GC with respect to personnel costs and ease of use, although for field applications GC analyses of select samples are recommended to quantify instrument interferences.     

温室气体光声光谱检测系统的建立及效果分析

“双碳”目标下,温室气体在线长期稳定监测技术是全面掌握温室气体排放及其环境、气候效应,并预测未来变化趋势的重要保障。为了实时在线监测工业生产现场等环境温室气体浓度及其变化趋势,及时采取相应措施,在分析光声光谱信号产生机理及多组分气体混合监测原理的基础上,根据温室气体的主要成分,分析其吸收光谱特性,基于光声光谱的多组分温室气体的定性和定量监测技术,搭建温室气体光声光谱在线监测实验平台,分析监测器内部噪声和环境温度、湿度等外部影响因素,并通过现场测试,分析试验数据,应用吸附法降低内外部因素的影响。结果表明,对称安装传声器和非共振式光声腔能有效削弱外部噪声对测试结果的影响;空气净化器能降低空气中水蒸气和其他气体对测试结果的影响;低、高浓度混合气体监测结果偏差均小于0.5,与GC测试结果偏差小于10%。应用光声光谱技术的环境温室气体监测技术监测范围宽,选择性好,且监测精度达10^-6,适用于环境温室气体浓度在线监测。     

固体进样-电热蒸发-原子吸收法测定土壤中的镉

采用固体进样原子吸收法直接测定土壤中的镉,可以避免传统酸消解预处理过程耗时长、试剂消耗大、操作步骤繁琐等缺点,提升镉的检测效率。通过优化测镉仪的仪器参数,确定了固体进样-电热蒸发-原子吸收法的优化仪器条件。采用优化条件测定了不同浓度的土壤样品,研究了该方法的检出限、正确度、精密度。研究结果表明:镉质量范围为0~200 ng时与峰面积的线性相关系数优于0.999 5,空气流下优化的灰化温度和热解温度均为800 ℃,优化的热解气体氢气流量为300 mL/min,当样品进样量为0.1 g时,检出限为0.009 mg/kg,7次连续测定相对标准偏差为1.4%~5.0%,加标回收率为96.2%~102.1%,分析时间小于4 min。该方法操作简便,用时短,无需高压气源,可以用于土壤中镉的高效检测。     

大气二氧化硫浓度的光学测定方法

介绍了测定二氧化硫浓度的几种光学方法 ,指出了目前一些化学方法的局限性 ,特别对紫外荧光法的原理、二氧化硫的吸收光谱以及荧光光谱进行分析探讨 ,设计了实验分析系统 ,得出该方法具有操作简单、灵敏度高、可实时在线的智能化优点 ,将会成为今后研究的主导方向。     

Sorption mechanisms of cephapirin, a veterinary antibiotic, onto quartz and feldspar minerals as detected by Raman spectroscopy

Raman spectroscopy was used to investigate sorption mechanisms of cephapirin (CHP), a veterinary antibiotic, onto quartz (SiO₂) and feldspar (KAlSi₃O₈) at different pH. Sorption occurs by electrostatic attraction, monodentate and bidentate complexation. The zwitterion (CHP^o) adsorbs to a quartz⁽⁺⁾ surface by electrostatic attraction of the carboxylate anion group (-COO⁻) at low pH, but adsorbs to a quartz⁽⁻⁾ surface through electrostatic attraction of the pyridinium cation, and possibly COO⁻ bridge complexes, at higher pH. CHP⁻ bonds to quartz⁽⁻⁾ surfaces by bidentate complexation between one oxygen of -COO⁻ and oxygen from carbonyl of an acetoxymethyl group. On a feldspar^(+/−) surface, CHP^o forms monodentate complexes between CO, and possible -COO⁻ bridges and/or electrostatic attachments to localized edge (hydr)oxy-Al surfaces. CHP⁻ adsorbs to feldspar⁽⁻⁾ through monodentate CO complexation. Similar mechanisms may operate for other cephalosporins. Results demonstrate, for the first time, that Raman techniques can be effective for evaluating sorption mechanisms of antibiotics.     

Sedimentology models from activity concentration measurements: application to the “Bay of Cadiz” Natural Park (SW Spain)

A previous study on seabed sediments of the Bay of Cadiz (SW of Spain) enabled us to identify several relations between sedimentological variables and activity concentrations of environmental radionuclides such as ¹³⁷Cs, ²²⁶Ra, ²³²Th and ⁴⁰K. In this paper the study has been extended to a large neighbouring inter-tidal area in order to establish if the above mentioned models can be generalized. As a result we have determined that the measured activity concentrations are closely to the values predicted by the theoretical models (correlation coefficient range = 0.85–0.93).