Improved Titrilog Sensitivity

ABSTRACT

A method was developed to reproducibly measure environmental tobacco smoke (ETS) components generated by different cigarettes. Measurements were carried out in an unventilated, controlled environment chamber. True ETS (the aged and diluted combination of exhaled mainstream plus sidestream smoke) was generated by human smokers. To reliably quantitate components normally present at trace levels, the comparisons were carried out at elevated ETS concentrations—greater than 40 times those typically encountered in “real-world” settings.

The method was applied to four commercially available cigarettes and a cigarette prototype that primarily heats tobacco. Forty-three properties and components of the gas and particulate phases of ETS generated by the different cigarettes were measured. Good precision of measurement was obtained both within and between tests. Statistically significant differences in the concentration of ETS components were observed among the different commercial cigarettes and between the commercial and prototype cigarettes. Most ETS components from the prototype cigarette were reduced by >90% when compared to the commercial cigarettes. The method was used to determine the effect of cigarette design changes on the generation of ETS.     

土壤及其主要化学组分对五氯酚吸附特征研究

研究了土壤原样及其去锰氧化物、去铁氧化物、去有机质和去水溶性有机质(DOM)土壤样品对五氯酚(PCP)的吸附规律,分析了土壤及其主要化学组分对PCP的吸附机制.实验结果表明,Langmuir方程可较好地描述PCP在各土壤样品上的热力学吸附过程.PCP在土壤上的吸附行为与自身性质和土壤理化性质密切相关,有机质和铁氧化物对PCP的吸附起到促进作用,而锰氧化物和DOM则能在一定程度上抑制PCP的吸附.通过Langmuir方程得到的拟合结果,可判断PCP在各土壤样品上的最大吸附量为去锰氧化物土壤样品＞去铁氧化物土壤样品＞去DOM土壤样品＞土壤原样＞去有机质土壤样品.     

Environmental screening by capillary gas chromatography combined with mass spectrometry and atomic emission spectroscopy

Capillary gas chromatography (GC) combined with mass spectrometry (MS) and atomic emission spectroscopy (AED) was utilized for a comprehensive investigation of organic micropollutants in a marine sediment. Most compounds were found and identified by GC-MS library search. The elemental information from GC-AED was utilized for confirmation purposes, for analyte characterization in cases where identification by GC-MS was impossible, and for screening on heteroatomic components. In addition, GC-AED was effectively used for the quantitative part, where the total amount of GC amenable material, classes of compounds, and individual components were determined.     

Use of pattern recognition in the evaluation of PCDD and PCDF residue data from GC/MS analyses

We used the chemometric approach with SIMCA (soft independent modeling by class analogy) multivariate statistical programs, based on principal components modeling to examine complex PCDD and PCDF residues in environmental samples. This approach was employed to determine the acceptability of measured tetrachloro isotope ratios when three ion intensities, m^+., (m+2)^+., and (m+4)^+., were measured by monitoring multiple ions. Isotope labeled internal standards and native compounds were examined. Principal components contain information about similarity of samples and variability in measurement. The data for the observed ion ratios were merged with the theoretical ion ratios and a calculated set of data that deviated from the theoretical values over a range of +/− 10 % for each ion pair. Thus the plot of principal components sample scores contains the error boundaries for accepting data that meet this quality assurance criterion and identifies the samples and calibration data that are within the acceptable range. In addition, GC/MS peaks having more than one constituent with different degrees of chlorination were readily detected. Residues of PCDDs in eggs of herring gulls ( ) collected from colonies in the Great Lakes region in 1981 – 1984 were measured by GC/MS. Principal components modeling of the normalized residue data demonstrated that the sample residue profiles differed according to the sample's origin and that sample profiles remained remarkably similar over the 4-year period in which the samples were collected.     

Effect of nitrogenous air pollutants on changes in protein spectra with the onset of winter in the leaves and shoots of the bilberry (Vaccinium myrtillus L.)

Electrophoretic profiles of 0.1 m Tris-HCl (pH 9.0)-soluble proteins in the leaves and stems of the bilberry (Vaccinium myrtillus L.) were investigated in the latter part of the growing season (July-October), in a highly-polluted industrial area with serious forest damage (main emissions NO(2), SO(2), NH(3), urea and fertilizer dust) in Oulu, northern Finland, and in an unpolluted control forest with the same climatic and edaphic conditions. About ten protein components in the leaves and seven in the stems increased in concentration in SDS-PAGE towards the autumn, while one to four other components decreased in concentration. The pollutants in the industrial area caused a considerable decrease in the concentrations of soluble proteins, particularly in the leaves in August and September. A decrease was obtained in six components in the leaves and three components in the stems, while increases were observed in one component in the leaves (10 kDa) and four components in the stems (10, 43, 50 and 65 kDa). One reason for the lowered cold-resistance in the bilberry caused by air pollutants could thus be the lowered concentrations of certain soluble cytoplasmic proteins that protect the plant against winter conditions.     

GC-profiles of chlorinated terpenes (Toxaphenes) in some Finnish environmental samples

The profiles of chlorinated terpenes in Finnish environmental samples were compared by GLC-SIM technique with those of toxaphene and Eastern European “dark”. The profiles in the seal blubber in the Northern and in the Eastern Baltic Sea proved to be similar. Chlorinated terpenes were found to be present in Finnish human milk.The spent bleach liquor of pine kraft pulp mill contained components having similar retention times and responses to those from toxaphene components.     

Lead adsorption to metal oxides and organic material of freshwater surface coatings determined using a novel selective extraction method

Surface coatings were collected in three lakes and a river in China to study the role of the components of natural surface coatings in controlling Pb adsorption. Chemical reagents, 0.02 mol/l NH2OH HCl+0.01 mol/l HNO3, 0.4 mol/l Na2S2O4 and 10% oxalic acid, were employed to extract one or more components from surface coatings, and then Pb adsorption to extracted and unextracted surface coatings was carried out. The observed Pb adsorption to extracted and Unextracted surface coatings were analyzed using the nonlinear least squares fitting (NLSF) to estimate the relative contribution of components to the total Pb adsorption. The amounts of Pb absorption to components described by estimated gamma(max) ranged from 0.1126 to 0.7291 (mol Pb/mol Mn) for Mn, 0.0528 to 0.1927 (mol Pb/mol Fe) for Fe and 0.0196 to 0.1020 (mol Pb/kg COD) for organic material, respectively. In all waters studied, metal oxides contributed most to Pb adsorption with a lesser role indicated for organic material.     

负载型Mn-Ce／TiO2催化剂的制备及其低温脱硝活性

以成型TiO2作为载体，通过浸渍法制备了Mn-Ce／TiO2低温SCR催化剂，并系统研究了制备方法、煅烧条件、活性组分担载量、Mn含量等参数对催化剂催化还原NO性能的影响。结果表明，煅烧温度的升高会促使活性组分结晶度的提高，从而引起催化活性的降低，在500℃和600℃下所得Mn-Ce／TiO2催化剂活性组分为无定型态，表现出较高的脱硝活性。活性组分担载量的增加有利于催化活性的提高。Mn含量对Mn-Ce／TiO2催化剂的活性有较大影响，当Mn／（Mn＋Ce）摩尔比为40％和85％时，催化剂活性最高。     

糖蜜酒精蒸馏废液色素研究

采用凝胶渗透色谱方法测定从甘蔗糖蜜酒精废液中提纯的色素的分子量。通过吸收光谱、原子吸收光谱、氨基酸分析、溶剂析出等方法，确定色素的成分。结果表明，该色素具有三个不同分子量的组分，重均分子量分别为21889、987和439Da。主要有酚类色素、焦糖色素和美拉德色素等3种色素，其质量分数分别为20%、67.7%和12.3%。色素中铁质量分数为0.12%，水解氨基酸质量分数为5.23%。     

Refinery evaluation of optical imaging to locate fugitive emissions

Fugitive emissions account for approximately 50% of total hydrocarbon emissions from process plants. Federal and state regulations aiming at controlling these emissions require refineries and petrochemical plants in the United States to implement a Leak Detection and Repair Program (LDAR). The current regulatory work practice, U.S. Environment Protection Agency Method 21, requires designated components to be monitored individually at regular intervals. The annual costs of these LDAR programs in a typical refinery can exceed US$1,000,000. Previous studies have shown that a majority of controllable fugitive emissions come from a very small fraction of components. The Smart LDAR program aims to find cost-effective methods to monitor and reduce emissions from these large leakers. Optical gas imaging has been identified as one such technology that can help achieve this objective. This paper discusses a refinery evaluation of an instrument based on backscatter absorption gas imaging technology. This portable camera allows an operator to scan components more quickly and image gas leaks in real time. During the evaluation, the instrument was able to identify leaking components that were the source of 97% of the total mass emissions from leaks detected. More than 27,000 components were monitored. This was achieved in far less time than it would have taken using Method 21. In addition, the instrument was able to find leaks from components that are not required to be monitored by the current LDAR regulations. The technology principles and the parameters that affect instrument performance are also discussed in the paper.     

Neural networks and periodic components used in air quality forecasting

Forecasting of air quality parameters is one topic of air quality research today due to the health effects caused by airborne pollutants in urban areas. The work presented here aims at comparing two principally different neural network methods that have been considered as potential tools in that area and assessing them in relation to regression with periodic components. Self-organizing maps (SOM) represent a form of competitive learning in which a neural network learns the structure of the data. Multi-layer perceptrons (MLPs) have been shown to be able to learn complex relationships between input and output variables. In addition, the effect of removing periodic components is evaluated with respect to neural networks. The methods were evaluated using hourly time series of NO₂ and basic meteorological variables collected in the city of Stockholm in 1994–1998. The estimated values for forecasting were calculated in three ways: using the periodic components alone, applying neural network methods to the residual values after removing the periodic components, and applying only neural networks to the original data. The results showed that the best forecast estimates can be achieved by directly applying a MLP network to the original data, and thus, that a combination of the periodic regression method and neural algorithms does not give any advantage over a direct application of neural algorithms.     

城市生活垃圾典型组分的热解动力学分析

利用热分析仪对城市生活垃圾中典型组分的热解过程进行了热重分析实验，采用不同形式的反应机理函数对实验结果进行了线性拟合计算，得到了针对不同组分的最合理的反应机理函数形式，并求出了相应的反应活化能E及频率因子A，由此构建了能更准确地反映垃圾各组分的热解反应过程的动力学模型。计算结果表明，垃圾中多数组分的热解过程用扩散模型来表示最为合理。     

Potential antitermite compounds from Juniperus procera extracts

Thin layer chromatography (TLC) analysis revealed that destructive distillation of Juniperus procera tree gave ten major components, whereas Croton megalocarpus tree yielded five components. This was confirmed by gas chromatography (GC). The components were isolated by column chromatography and analysed using infrared, ultra-violet, visible and mass spectroscopy (MS) techniques. The whole extract was about 30.3% of the starting material (sawdust) and consisted of 77.5% water and 22.5% oily reddish-brown layer. The extracts had alcoholic and phenolic compounds together with acids. Cedrol, a tertiary tricyclic alcohol, was found to be in the greatest proportion in the oily layer. IR spectra with a peak beyond 3000 cm(-1), UV-VIS absorption maxima at 230 nm and mass spectra with m/e 204 suggested the presence of cedrene in the extract.     

Comparison between urban Toronto PM and selected materials: aerosol characterization using laser ablation/ionization mass spectrometry (LAMS)

Laser ablation/ionization mass spectrometry (LAMS) of particulate matter (PM) was undertaken on-line in order to extend and contrast PM characterization. Qualitative on-line LAMS results for certified materials and Toronto source materials demonstrated the versatility and limitations of the technique. The observation of organic and inorganic components of certified materials verified the proper working condition of the in-house on-line LAMS. Organic and inorganic components of Toronto source materials were also observed with the on-line LAMS. Common components identified from both types of materials were Na, Al, Ca, Fe, and K. Other recognized components were compared with marker elements reported for some common PM emission sources. An in-house off-line LAMS was used to analyze urban Toronto PM deposited on glass substrates, while the on-line LAMS analyzed individual urban Toronto PM particles that were introduced directly into the instrument. Scanning electron microscopy (SEM), X-ray spectrometry and inductively coupled plasma atomic emission spectrometry (ICP-AES) were used for confirmatory purposes. Organic and inorganic components of urban Toronto PM at their typical ng/m3 concentrations were successfully observed in mass spectra using both off-line LAMS and on-line LAMS. Identified ions unique to each analyzed material were compared to identified ions of urban Toronto PM. The ability of LAMS to analyze individual respirable PM particles (viz. < 2 microns), both for inorganic trace elements and for organic components, greatly extended our capability to characterize PM and also to achieve estimates of concentration contributions of each material.     

The persistence of insecticidal chemicals in soils treated with granular formulations of disulfoton and their uptake by potato plants

Abstract

Potatoes were grown from cut seed in Plainfield sand treated in‐furrow with disulfoton (Di‐Syston 15G, 3.36 kg Al/ha) in 1983 and from whole seed in similarly treated loam in 1991. Soils were contained in 2 m² field plots. Soil, seed potato and foliage were analyzed for the insecticide and its sulfoxide and sulfone metabolites during the 8–12 wk following planting. Disulfoton disappeared at different rates from the two soils (k_sand=0.024 day^‐1, k_loam=0.056 day^‐1) with partial conversion to the sulfoxide and sulfone in both. Larger quantities of the three insecticidal components were absorbed by the seed potato in the cut‐seed/sand combination. The relative amounts of these components in the seed potato also differed between treatments with disulfoton being the largest component of the cut‐seed/sand and smallest in the whole‐seed/loam. Disulfoton sulfoxide and sulfone were the major insecticidal components of the foliage and concentrations in the initial foliage (each ca. 10 ppm) were similar for both treatments. Sulfoxide concentrations in the foliage decreased more rapidly than the sulfone and the decrease in concentration of each of the components was similar for the two treatments.     

GC/MS在监测甲胺磷工业废水中的应用

就甲胺磷工业废水监测中甲胺磷及其干扰组分进行了色谱分离及质谱定性分析,并以火焰光度检定量,用甲胺磷工业原油作为标准,圆满完成了甲胺磷工业废水的监测任务。     

Relations between PM10 composition and cell toxicity: a multivariate and graphical approach

Previous studies have used particle mass and size as metrics to link airborne particles with deleterious health effects. Recent evidence suggests that particle composition can play an important role in PM-toxicity; however, little is known about the specific participation of components (individually or acting in groups) present in such a complex mixture that accounts for toxicity. This work explores relationships among PM(10) components in order to identify their covariant structure and how they vary in three sites in Mexico City. Relationships between PM(10) with cell toxicity and geographical location were also explored. PM(10) was analyzed for elemental composition, organic and elemental carbon, endotoxins and the induction of inhibition of cell proliferation, IL-6, TNFalpha and p53. PM(10) variables were evaluated with principal component analysis and one-way ANOVA. The inhibition of cell proliferation, IL-6 and TNFalpha were evaluated with factorial ANOVA and p53 with the Welch test. The results indicate that there is heterogeneity in particle mass, composition and toxicity in samples collected at different sites. Multivariate analysis identified three major groups: (1) S/K/Ca/Ti/Mn/Fe/Zn/Pb; (2) Cl/Cr/Ni/Cu; and (3) endotoxins, organic and elemental carbon. Groups 1 and 3 showed significant differences among sites. Factorial ANOVA modeling indicated that cell proliferation was affected by PM concentration; TNFalpha and IL-6 by the interaction of concentration and site, and p53 was different by site. Radial plots suggest the existence of complex interactions between components, resulting in characteristic patterns of toxicity by site. We conclude that interactions of PM(10) components determine specific cellular outcomes.     

Fixation of metals in soil constituents and potential remobilization by hyperaccumulating and non-hyperaccumulating plants: results from an isotopic dilution study

In this study isotopic dilution methods were used to investigate the hypothesis that access to metals associated with specific chemical components in the soil that are not available to non-accumulator species could be involved in hyperaccumulation. The hyperaccumulator Thlaspi caerulescens and a non-accumulator species, Brassica napus, were grown in Cd and Zn enriched soil components calcite, goethite, charcoal and cryptomelane. The metal enriched components were aged to allow transformation of a proportion of added metals to non-labile forms. Results from the isotopic dilution L value method showed that despite taking up more metals, T. caerulescens accessed the same pool of metals as B. napus. Hence differential access to different solid-phase pools of metals appears to be an unlikely mechanism underlying metal hyperaccumulation. For all components except charcoal, L values for Cd and Zn were greater than the corresponding E values suggesting that E values may tend to underestimate the bioavailable fraction of metals in soils.     

Analysis of chemical compositions contributable to chemical oxygen demand (COD) of oilfield produced water

This work was to give a comprehensive estimation for the chemical compositions contributable to COD of the produced water treatment system. For this purpose, the wastewater samples were collected from an onshore wastewater treatment plant. The chemical compositions of the wastewater were investigated, and the COD contributed by each component was estimated. The results showed that the COD levels of O&G and SS presented decreasing trends during the whole process and achieved total removal percentages of 95.1% and 62.3%, respectively. The final COD of organic acids and low-molecular-weight carbonyl compounds were respectively lowered to nearly 64% and 35% of their initial levels, and no regular trends were found for the COD of these chemicals during the whole treatment process. The COD of inorganic components presented minor variations at all sampling spots. The majority of COD was originated from O&G in raw wastewater. The COD contributed by O&G decreased greatly with continuous treatment and finally was lower than 17% of measured COD. At each sampling spot, the ratios of COD contributed by SS did not exceed 7.6% of measured COD. Other measured chemicals, including organic acids, carbonyl compounds, volatile phenols, reductive anions, metals and TDP were not the main sources of COD during the whole treatment process, and the ratio of COD was below 9% at each sampling spot. Most of the soluble components contributable to residual COD were still unknown after biological treatment, and the COD contributed by these components was greater than 57% of measured COD.     

Molecular properties of a fermented manure preparation used as field spray in biodynamic agriculture

Manure products fermented underground in cow horns and commonly used as field spray (preparation 500) in the biodynamic farming system, were characterized for molecular composition by solid-state nuclear magnetic resonance [¹³?C cross-polarization magic-angle-spinning NMR (¹³?C-CPMAS-NMR)] spectroscopy and offline tetramethylammonium hydroxide thermochemolysis gas chromatography-mass spectrometry. Both thermochemolysis and NMR spectroscopy revealed a complex molecular structure, with lignin aromatic derivatives, polysaccharides, and alkyl compounds as the predominant components. CPMAS-NMR spectra of biodynamic preparations showed a carbon distribution with an overall low hydrophobic character and significant contribution of lignocellulosic derivatives. The results of thermochemolysis confirmed the characteristic highlighted by NMR spectroscopy, revealing a molecular composition based on alkyl components of plant and microbial origin and the stable incorporation of lignin derivatives. The presence of biolabile components and of undecomposed lignin compounds in the preparation 500 should be accounted to its particularly slow maturation process, as compared to common composting procedures. Our results provide, for the first time, a scientific characterization of an essential product in biodynamic agriculture, and show that biodynamic products appear to be enriched of biolabile components and, therefore, potentially conducive to plant growth stimulation.