Uncertainties in charring correction in the analysis of elemental and organic carbon in atmospheric particles by thermal/optical methods

Thermal/optical methods are widely used in the determination of aerosol organic carbon (OC) and elemental carbon (EC) collected on quartz filters. A fraction of OC undergoes charring to form pyrolytically generated EC (PEC) during thermal analysis. The correct speciation of OC and EC in thermaVoptical methods depends on one of the following two assumptions: (1) PEC evolves before native EC evolves in the analysis or (2) PEC and native EC have the same apparent light absorption coefficient (sigma) at the monitoring light wavelength. Neither of these assumptions has actually ever been checked or tested. The first assumption is invalidated by the observation that the combustion of PEC overlaps that of native EC despite multiple stepwise combustion at temperatures ranging from 575 to 910 degrees C. An examination of sigma versus EC evolution indicates that the sigma values of PEC and EC are not the same in most cases and the a value of PEC is not constant during a single thermal analysis. The second assumption is thus invalid as well. The measured EC concentrations can either overestimate or underestimate the true native EC concentrations depending on the relative magnitude of the a values of the PEC and native EC at the point where the instrument sets the EC/OC split line. Both over- and underestimation have been observed in real aerosol samples. The unequal a values of PEC and EC also explain that different temperature programs, when employed to analyze the same filter samples, systematically yield different EC and OC concentrations. Our findings imply that minimizing charring improves the accuracy of the EC/OC split in thermal/optical methods.     

Intercomparison of thermal and optical measurement methods for elemental carbon and black carbon at an urban location

Despite intensive efforts during the past 20 years, no generally accepted standard method exists to measure black carbon (BC) or elemental carbon (EC). Data on BC and EC concentrations are method specific and can differ widely (e.g. Schmid et al., 2001, ten Brink et al., 2004). In this study, a comprehensive set of methods (both optical and thermal) is compared. Measurements were performed under urban background conditions in Vienna, Austria, a city heavily impacted by diesel emissions. Filter and impactor samples were taken during 3 weeks in summer 2002 and analyzed for EC with thermal methods: a modified Cachier method (Cachier et al., 1989), a thermal-optical method (Schmid et al., 2001), and the VDI method (VDI, 1996); for BC with optical methods: a filter transmission method and the integrating sphere method (Hitzenberger et al., 1996); and for total carbon (TC) with a combustion method (Puxbaum and Rendl, 1983). The online methods aethalometer (Hansen et al., 1984) and the multiangle absorption photometer MAAP (Petzold et al., 2002) to measure BC were also used. The average values of BC and EC obtained with the methods agreed within their standard deviations. A conversion table was set up to allow comparisons between data measured elsewhere under urban background conditions (with similar source characteristics) with different instruments. An approach to estimate the absorption coefficient from attenuation data is derived so that existing records of aethalometer data in urban environments may be used to obtain also the absorption coefficients.     

Colorimetric study of the interactions between different families of red wine pigments using transmittance and reflectance measurements

The aim of this work was to conduct a detailed colorimetric study, using transmittance and reflectance measurements, to evaluate the possible interactions occurring among the different families of pigments comprising to colour matter of red wines and their contribution to the colour in aged red wines.To accomplish this, the phenolic material of monovarietal red wines obtained from Tempranillo and Graciano varieties, and their blends, were fractionated by gel permeation chromatography in order to separate the coloured fractions with different chemical compositions. The binary blends at different concentrations of the fractions having higher anthocyanin monoglucoside proportions with fractions having higher pyranoanthocyanin derivative contents and direct flavanol-anthocyanin condensation products were carried out in order to determine the effect of adding these derivatives on the colour of the anthocyanin monoglucosides, the major wine pigments. It was observed that the addition of derived pigments to the anthocyanin monoglucosides fraction resulted in colour differences perceptible by the human eye. These variations were mainly quantitative (changes in chroma and lightness), and were also qualitative (changes in hue) in monovarietal wines.Studying the phenolic fractions of wines implies an approach to the chemical reality of the wines, more than the studies on model solutions, since they can lead to the knowledge of those components having more influence on the final colour of the wine. With these results the wineries could conduct the vinifications towards a higher extraction of the components or families of components more important for the intensity and stability of colour.     

Possibilities of using near infrared reflectance/transmittance spectroscopy for determination of polymeric protein in wheat

Possibilities of using near‐infrared reflectance and near‐infrared transmittance (NIR/NIT) spectroscopic techniques for detecting differences in amount and size distribution of polymeric proteins in wheat were investigated. To evaluate whether differences in polymeric protein due to genetic or environmental variations were detectable by NIR/NIT techniques, wheat materials of different background were used. Size‐exclusion high‐performance liquid chromatography was applied to detect variation in polymeric protein. Partial least squares regression gave high R² values between many protein parameters and NIR/NIT spectra (particularly second‐derivative spectra of NIR 1100–2500 nm region) of flours, while no such relationship was found for whole wheat grains. Most and highest correlations were found for total amount of extractable and unextractable proteins and monomer/polymer protein ratio. Some positive relationships were found between percentage of total unextractable polymeric protein in the total polymeric protein and percentage of large unextractable polymeric protein in the total large polymeric protein and NIR/NIT spectra. Thus, it was possible to detect differences in polymeric proteins with NIR/NIT techniques. The highest amount of positive correlations between NIR/NIT spectra and protein parameters was found to be due to environmental influences. Some correlations were found for breeding lines with a broad variation in gluten strength and polymeric protein composition, while a more homogeneous sample showed less correlation. Thereby, detection of variation in amount and size distribution of polymeric protein due to cultivar differences with NIR/NIT methods might be difficult. Copyright © 2007 Society of Chemical Industry     

Roles of sulfuric acid in elemental mercury removal by activated carbon and sulfur-impregnated activated carbon

This work addresses the discrepancy in the literature regarding the effects of sulfuric acid (H(2)SO(4)) on elemental Hg uptake by activated carbon (AC). H(2)SO(4) in AC substantially increased Hg uptake by absorption particularly in the presence of oxygen. Hg uptake increased with acid amount and temperature exceeding 500 mg-Hg/g-AC after 3 days at 200 °C with AC treated with 20% H(2)SO(4). In the absence of other strong oxidizers, oxygen was able to oxidize Hg. Upon oxidation, Hg was more readily soluble in the acid, greatly enhancing its uptake by acid-treated AC. Without O(2), S(VI) in H(2)SO(4) was able to oxidize Hg, thus making it soluble in H(2)SO(4). Consequently, the presence of a bulk H(2)SO(4) phase within AC pores resulted in an orders of magnitude increase in Hg uptake capacity. However, the bulk H(2)SO(4) phase lowered the AC pore volume and could block the access to the active surface sites and potentially hinder Hg uptake kinetics. AC treated with SO(2) at 700 °C exhibited a much faster rate of Hg uptake attributed to sulfur functional groups enhancing adsorption kinetics. SO(2)-treated carbon maintained its fast uptake kinetics even after impregnation by 20% H(2)SO(4).     

Effect of protein and temperature on cutting time prediction in goats' milk using an optical reflectance sensor

An objective method for determining the coagulum cutting time is needed to improve consistency and processing efficiency of goats' cheese. A fibre optic sensor was used to measure the backscatter of near-infrared radiation at 880 nm during the coagulation of skimmed goats' milk for the purpose of predicting coagulum cutting time. A randomised block design, replicated three times, was used to test the effect of three protein concentrations (3, 5 and 7% (w/w)) on diffuse reflectance parameters for cutting time prediction of milk coagulated at five different temperatures (20, 25, 30, 35 and 40 degrees C) to assure a wide range of coagulation rates. The inclusion of a protein term in the existing algorithms was essential to reduce the standard error of prediction to under 6.2 min. An algorithm including a time-based parameter and a protein term, Tcut=beta0 T2min (1 + gamma% Protein) was found to predict cutting time with a SEP of 2.42 min and an R2 of 0.98. Gamma was considered constant (gamma=-0.0674, goats' milk) representing the protein effect on beta0. Algorithms using response-based parameters (such as change in reflectance ratio) and the composition parameter protein required additional regression parameters such as temperature and an intercept term to predict the cutting time with the same precision as algorithms using only time-based parameters. Time-based parameters were found to decrease proportionally with increasing temperature and decreasing protein concentration. Response-based and mixed-based parameters were found to decrease with decreasing temperature. Reflectance ratio at cutting time did not significantly change with protein concentration for skimmed goats' milk. The activation energy of kappa-casein hydrolysis was calculated based on changes in reflectance profile parameters and was found to be in the range 63-72 kJ mol(-1).     

Comparison of elemental carbon in lake sediments measured by three different methods and 150-year pollution history in Eastern China

Concentrations of elemental carbon (EC) were measured in a 150 yr sediment record collected from Lake Chaohu in Anhui Province, eastern China, using three different thermal analytical methods: IMPROVE_A thermal optical reflectance (TOR), STN_thermal optical transmittance (TOT), and chemothermal oxidation (CTO). Distribution patterns for EC concentrations are different among the three methods, most likely due to the operational definition of EC and different temperature treatments prescribed for each method. However, similar profiles were found for high-temperature EC fractions among different methods. Historical soot(TOR) (high-temperature EC fractions measured by the IMPROVE_A TOR method) from Lake Chaohu exhibited stable low concentrations prior to the late 1970s and a sharp increase thereafter, corresponding well with the rapid industrialization of China in the last three decades. This may suggest that high-temperature thermal protocols are suitable for differentiating between soot and other carbon fractions. A similar soot(TOR) record was also obtained from Lake Taihu (~200 km away), suggesting a regional source of soot. The ratio of char(TOR) (low-temperature EC fraction measured by the IMPROVE_A TOR method, after correction for pyrolysis) to soot(TOR) in Lake Chaohu shows an overall decreasing trend, consistent with gradual changes in fuel use from wood burning to increasing fossil fuel combustions. Average higher char(TOR)/soot(TOR) was observed in Lake Taihu than in Lake Chaohu in the past 150 years, consistent with the longer and more extensive industrialization around the Taihu region.     

Effect of starch on the thermal kinetics and transmittance properties of lysozyme

Lysozyme is being tested for use as a preservative in the food industry. The interaction between starch and lysozyme will help in recommending starch or starch fractions as carriers for lysozyme. The effect of starch fractions on the folding and unfolding of lysozyme was estimated by differential scanning calorimetry (DSC), kinetics and transmittance turbidometry. Lysozyme was unfolded (heated to 90 °C) and folded (cooled to 20 °C) five times in the presence of starch fractions. Starch was added at 1 and 2%. Overall, a trend of higher onset temperature (T_o) values occurred at 2% addition of all starch fractions except amylose. The increase in the number of cycles influenced the effect of starch on lysozyme denaturation. The percentage of lysozyme's ΔH values decreased as a new heating and cooling cycle was performed (ie 74.4% of the ΔH remained from the first cycle). The effect of amylose (AM) and amylopectin (AP) on the kinetics of lysozyme unfolding and folding was found to be different based on the assumption that the peak DSC temperature is the fastest step of the reaction. The unfolding showed higher activation energy (E_a) in the presence of both AM and AP, while the folding was not significantly changed. The turbidity of the solution containing lysozyme and potato starch showed transmittance in between that of lysozyme and starch. Stirring of the blend kept the transmittance unchanged while an increase in the transmittance was noticed when stirring ceased. Copyright © 2004 Society of Chemical Industry     

Effects of sampling artifacts and operating parameters on the performance of a semicontinuous particulate elemental carbon/organic carbon monitor

The carbonaceous component of atmospheric particulate matter (PM) is considered very important with respect to the observed adverse health effects of PM. Particulate organic and elemental carbon have traditionally been measured off-line after daily, time-integrated particle collection on filters. However, the subdaily or hourly variability of elemental carbon (EC) and organic carbon (OC) can help to assess the variability of sources, ambient levels, and human exposure. In this study, the performance of the Sunset Laboratory Inc. semicontinuous EC/OC monitorwas assessed in a Los Angeles location representing typical urban pollution. An intermonitor comparison showed high precision (R2 of 0.98 and 0.97 for thermal OC and EC, respectively). By changing the inlet configurations of one of the monitors (adding a denuder, a Teflon filter, or both), the influences of positive and negative sampling artifacts were investigated. The positive artifact was found to be relatively large (7.59 microg/m3 on average), more than 50% of measured OC, but it was practically eliminated with a denuder. The negative artifact was much smaller (less than 20% of the positive artifact) and may be neglected in most cases. A comparison of different temperature profiles, including a fast 4-min analysis using optical EC correction, showed good agreement among methods. Finally, a novel configuration using a size selective inlet impactor removing particles greater than 250 nm in diameter allowed for semicontinuous size-fractionated EC/OC measurements. Evolution of OC at different temperatures of the thermal analysis showed higher volatility OC in larger particles.     

Relationship between elemental carbon, total carbon, and diesel particulate matter in several underground metal/non-metal mines

Elemental carbon (EC) is currently used as a surrogate for diesel particulate matter (DPM) in underground mines since it can be accurately measured at low concentrations and diesels are the only source of submicrometer EC in underground mines. A disadvantage of using EC as a surrogate for DPM is that the fraction of EC in DPM is a function of various engine parameters and fuel formulations, etc. In order to evaluate how EC predicts DPM in the underground mining atmosphere, measurements of total carbon (TC; representing over 80% of the DPM) and EC were taken away from potential interferences in four underground metal/non-metal mines during actual production. In a controlled atmosphere, DPM mass, TC, and EC measurements were also collected while several different types of vehicles simulated production with and without different types of control technologies. When diesel particulate filters (DPFs) were not used, both studies showed that EC could be used to predict DPM mass or TC. The variability of the data started to increase at TC concentrations below 230 microg/m3 and was high (> +/- 20%) at TC concentrations below 160 microg/m3, probably due to the problem with sampling organic carbon (OC) at these concentrations. It was also discovered that when certain DPFs were used, the relationship between DPM and EC changed at lower DPM concentrations.     

Quality evaluation of pickling cucumbers using hyperspectral reflectance and transmittance imaging: Part I. Development of a prototype

This article reports on the development of a hyperspectral imaging prototype for online evaluation of external and internal quality of pickling cucumbers. The prototype consisted of a two-lane round belt conveyor, two illumination sources (one for reflectance and one for transmittance), and a hyperspectral imaging unit. It had a novel feature of simultaneous imaging under reflectance mode in the visible region (400–675 nm) and transmittance mode for the red and near-infrared region (Red-NIR) (675–1000 nm). Reflectance information from the visible region was intended for evaluating the external characteristics of cucumbers such as skin color, whereas transmittance information from Red-NIR was used for internal defect detection (i.e., hollow center). Additional features of the prototype included simultaneous acquisition of reflectance and transmittance from calibration references that were installed in the system, to provide real-time, continuous corrections of individual hyperspectral images from each sample. Methods and algorithms were developed of estimating cucumber fruit size and correcting the effect of fruit size on transmittance measurements. The system was calibrated and evaluated for detecting the color, size, and internal defect of pickling cucumbers.     

Trace elemental composition of curry by inductively coupled plasma optical emission spectrometry (ICP-OES)

A methodology based on inductively coupled plasma optical emission spectrometry (ICP-OES) after microwave-assisted acid digestion was developed to determine the content of traces elements in curry samples from the Spanish market. The methodology was validated in terms of accuracy by the analysis of citrus and tomato leaf reference materials achieving comparable results with the certified values. The trace metal content of curry samples was compared with data available from previously published reports concerning Indian samples, especially in terms of heavy metal composition, in order to guarantee the quality of the commercially available spices in the European countries. Values found for the analysis of arsenic, lead and cadmium were significantly lower than the maximum limit allowed by European Union statutory limits for heavy metals and lower than those obtained for Indian curry leaves reported by Indian research teams by using neutron activation and γ-ray analysis.     

Discrimination the geographical origin of Yanchi Tan Lamb with different muscle sections by stable isotopic ratios and elemental profiles

In the study, lamb, feed and soil samples were collected from three regions of China in the year 2017 and 2018. The δ¹³C and δ¹⁵N values in lamb (defatted dry mass and lipids) and grass and the contents of nine elements in lamb, grass and soil were determined. The results indicated that except for Fe, Zn and Rb, most variables of lamb showed significant differences among two or three regions, and the contents of Fe, Sr and Cs showed significant differences between two years, and the contents of Cu and Zn showed significant differences among different muscle sections. Besides, significant correlations were found for δ¹³C between defatted lamb and lipid (r² = 0.973, P < 0.05) and for the element contents between lamb and soil. Finally, four key variables δ¹³C, δ¹⁵N, Sr and Mo were selected through stepwise canonical discriminant analysis with the cross-validation correct classification rate of 99.1%.     

基于近红外漫反射光谱技术判别柿子品种和 贮藏期的研究

目的 通过近红外漫反射光谱技术建立了柿子不同品种和贮藏期的快速判别方法。方法 实验对置于冷库(0±0.5℃)贮藏20d、40d、60d的磨盘柿和阳丰甜柿的近红外光谱(400～2500nm)进行平滑处理、一阶倒数和标准正常化处理(SNV)处理,采用主成分分析法(PCA)建立判别模型。结果 在全波长范围内,不同品种定标模型的正确分类率达到100%;阳丰甜柿不同贮藏期的正确分类率达到97.78%;磨盘柿不同贮藏期的正确分类率达到98.89%。3个预测模型的累积准确率达到96.67%。结论 通过近红外漫反射光谱技术,判别不同品种的柿子并预测其贮藏期具有应用价值。     

Feasibility of conventional and Roundup Ready® soybeans discrimination by different near infrared reflectance technologies

Identification and proper labelling of genetically modified organisms is required and increasingly demanded by legislation and consumers worldwide. In this study, the feasibility of three near infrared reflectance technologies (a chemical imaging unit, a commercial diode array instrument, and a light tube non-commercial instrument) were compared for discriminating Roundup Ready® and not genetically modified soybean seeds. Over 200 seeds of each class (Roundup Ready® and conventional) were used. Principal Component Analysis with Artificial Neural Networks (PCA–ANN) and Locally Weighted Principal Component Regression (LW-PCR) were used for creating the discrimination models. Discrimination accuracies when new tested seeds belonged to samples included in the training sets achieved accuracies over 90% of correctly classified seeds for LW-PCR models. The light tube performed the best, while the imaging unit showed the worse accuracies overall. Models validated with new seeds from samples not included in the training set had accuracies of 72–79%.     

Determination of the previous maximum temperature of heat-treated minced meat by near infrared reflectance spectroscopy

Determination of the heat treatment given to minced meat has been explored on a preliminary basis by near infrared reflectance (NIR) analysis. Minced meat samples from beef were heated at five different temperatures from 50 to 95°C. Correlating NIR-determined temperatures ranging against actual laboratory treatment temperatures gave correlation coefficients of 0.987 for ‘wet’ meat and 0.992 for freeze dried meat samples. The minimum root mean square of determination errors obtained were 3.9°C for ‘wet’ meat and 2.5°C for freeze dried meat samples.     

碳纳米管改性相变微胶囊的力学与热学性能

为改善相变微胶囊制备蓄热调温纺织品时存在易破损、传热效率低的问题,通过原位聚合法以三聚氰胺、尿素、甲醛为壁材并掺杂等离子体处理的碳纳米管(CNTs)包覆正十八烷制备相变微胶囊,探讨CNTs对微胶囊力学、热学性能的影响。采用扫描电子显微镜、傅里叶红外光谱分析仪、原子力显微镜、差式扫描量热仪和热常数分析仪对所制备的相变微胶囊的表面形貌、力学性能、热学性能进行表征与分析。结果表明：掺杂CNTs的微胶囊近似圆球形,表面较为光滑,力学性能、热传导性能均有提高;当CNTs添加量为2%时,其弹性模量提高了约190%、导热系数提高了近187%;平均相变焓可达到224.4 J/g、包覆率为74.07%。掺杂CNTs对微胶囊的力学、热学性能的改善有利于提高蓄热调温纺织品调温性能。     

Estimating deoxynivalenol contents of wheat samples containing different levels of Fusarium-damaged kernels by diffuse reflectance spectrometry and partial least square regression

Fusarium head blight is a fungal disease causing yield losses and mycotoxin contamination in wheat and other cereals. Wheat kernels (cultivar Ritmo) were sampled in 2001, 2002, 2003, and 2006 and Fusarium-damaged kernels were separated from sound grain based on visual assessment. Subsequently, grain lots containing 0, 20, 40, 60, 80, and 100% of damaged kernels were compiled. Each lot was split and the spectrometric reflectance (wavelengths 350-2500 nm) was measured using subgroup one, while the concentration of the mycotoxin deoxynivalenol (DON) was determined by high-performance liquid chromatography in subgroup two. DON concentrations in batches classified as sound were not significantly different from 0. Estimating DON contents from the percentage of Fusarium-damaged kernels was impeded by vast variability, resulting in a coefficient of determination of 0.49. Using spectrometric data subjected to partial least square regression allowed estimating DON contents with higher accuracy, in particular at elevated percentages of damaged kernels. The coefficient of determination was 0.84 for the relationship between DON contents estimated based on spectrometric data and the DON contents measured. The intercept of a regression line fitted through a plot of estimated versus measured DON contents was 0.89 ± 3.61 mg/kg. Since intercept + standard error was larger than the actual legal limit (1.25 mg DON per kg dry grain in the European Union), the spectrometric procedure was still not precise enough to allow a reliable separation of grain samples with DON contents below 1.25 mg/kg from samples with DON contents above the limit. However, spectrometric data also allowed estimating the DON content of the average damaged kernel within a given lot composed of sound and damaged kernels, which is probably the reason for the reduction of the fraction of unexplained variance by 35% compared to the visual approach and illustrates that spectrometric approaches can make a contribution to reducing DON contents of wheat grain.     

不同菌种比例和温度对发酵酸奶的影响

通过不同配比的混合菌种和不同温度对发酵酸奶影响的研究,获得了发酵酸奶的最佳菌种比例（嗜热链球菌：保加利亚乳酸杆菌＝４：１）和最佳发酵温度（４０℃～４５℃）,为指导酸奶生产提供了依据。