An alternative for the nitrobenzylpyridine test for the description of the toxicity of alkylating agents

When correlating the biologic activity of alkylating agents with physicochemical parameters, the reaction rate constant of the reaction with 4-(p-nitrobenzyl) pyridine (NBP) is often used as a measure of the compounds chemical reactivity. Since the use of NBP suffers some drawbacks from an experimental point of view, it was decided to develop an alternative test method, using thiourea as a standard nucleophile.Reactivities obtained with both methods for six halogenated alkylating agents are compared, and the usefulness of the new experimental method is discussed.     

Preliminary findings on the antimony levels of Quiroga river water in the vicinity of a long-abandoned stibnite mine

A UV-Vis spectrophotometric method was developed as a preliminary approach to the determination of antimony in water samples from a river that flows very close to an abandoned mining site. The analyte is complexed with ammonium pyrrolidinedithiocarbamate and absorbance of the complex is measured at 291.06 nm. The standard additions method is mandatory in view of the matrix effect observed, and the response is linear at least up to 9.3 microg/mL of antimony. The sensitivity of the method is 2.609 x 10(-2) mL/microg, whereas the limits of detection and quantification are, respectively, 0.2 and 0.6 microg/mL. The repeatability, expressed as mean relative standard deviation of the measurements within the calibration range, is 2.0%, whereas the repeatability of the entire procedure is 0.3%. The mean analytical recovery within the calibration range was 102.6%. The method was successfully applied to river water samples.     

大气污染物等浓度曲线画法初探

介绍一种环境影响评价中大气污染物等浓度曲线的画法，可用于绘制任意接近的等浓度曲线而不会相交或相切，运算量较小且与图形大小无关。     

Alternatives to the gravimetric method for quantification of diesel particulate matter near the lower level of detection

This paper is part of the Journal of the Air & Waste Management Association's 2010 special issue on combustion aerosol measurements. The issue is a combination of papers that synthesize and evaluate ideas and perspectives that were presented by experts at a series of workshops sponsored by the Coordinating Research Council that aimed to evaluate the current and future status of diesel particulate matter (DPM) measurement. Measurement of DPM is a complex issue with many stakeholders, including air quality management and enforcement agencies, engine manufacturers, health experts, and climatologists. Adoption of the U.S. Environmental Protection Agency 2007 heavy-duty engine DPM standards posed a unique challenge to engine manufacturers. The new standards reduced DPM emissions to the point that improvements to the gravimetric method were required to increase the accuracy and the sensitivity of the measurement. Despite these improvements, the method still has shortcomings. The objectives of this paper are to review the physical and chemical properties of DPM that make gravimetric measurement difficult at very low concentrations and to review alternative metrics and methods that are potentially more accurate, sensitive, and specific. Particle volatility, size, surface area, and number metrics are considered, as well as methods to quantify them. Although the authors believe that an alternative method is required to meet the needs of engine manufacturers, the methods reviewed in the paper are applicable to other areas where the gravimetric method detection limit is approached and greater accuracy and sensitivity are required. The paper concludes by suggesting a method to measure active surface area, combined with a method to separate semi-volatile and solid fractions to further increase the specificity of the measurement, has potential for reducing the lower detection limit of DPM and enabling engine manufacturers to reduce DPM emissions in the future.     

The Application of the Karl Fischer Oven for the Determination of Water in Consumer Products

Abstract

The direct Karl Fischer (KF) titration method has known interferences for measuring water content. In addition, in analyzing some paints, KF can fail to produce an accurate analysis. The California Air Resources Board (GARB) staff has developed a KF procedure that can be used to determine the water content of consumer products. The procedure uses an oven accessory to the titration system, and is based on a distillation method developed by the California Polytechnical University at San Luis Obispo (Cal Poly). Samples are diluted in l-methoxy-2-propanol (MPA), and an aliquot is injected into an enclosed oven system, where the MPA/water azeotrope is swept directly into the KF titration vessel. The technique is accurate and precise and, thus far, proves to be a fast and reliable method for analysis.     

Minimization of the environmental impact in the unhairing of bovine hides

This study tests an alternative method to the traditional unhairing method used during the process of tanning the hides. The new method is based on the substitution of sodium sulfide by hydrogen peroxide as an unhairing agent in both hair recovery and recirculation of the floats employed in the process. The properties of the hides obtained using the two methods have been compared and the results indicate that those hides have similar physical, chemical, and organoleptic properties. However, the differences existing from an environmental point of view are significant. These include reductions of water consumption (approx 70%), chemical oxygen demand (approx 35%), toxicity (98%) and total kjendhal nitrogen (50%). Also, the risk associated with the production of hydrogen sulfide is eliminated, which implies a great improvement in terms of safety for the workers. Given the large amounts of water and chemical pollution discharged in the process, the reductions in absolute values represent a significant improvement. A financial assessment was carried out to demonstrate that the proposed new system is 16% more economic than the traditional one.     

A mass transfer based method for measuring the reaction coefficients of a photocatalyst

We have developed a new method, the mass transfer based (MTB) method, for measuring the Langmuir–Hinshelwood (L–H) rate form reaction coefficients of photocatalysts. The conventional method for determining the reaction coefficients disregards the effect of mass transfer on the reaction surface by designing and controlling a reaction process to be reaction-limited. In contrast, the new MTB method takes the mass transfer effect into account by using a computational fluid dynamics (CFD) method. The reaction coefficients can be regressed by the measured reaction rates and the calculated VOC concentrations in the air adjacent to the reaction surface. Thus, by using the new method, the reaction coefficient of a reaction process can be accurately determined even if it is not reaction-limited. This is very important in cases where it is difficult to realize reaction-limited processes, such as photocatalytic oxidation of VOCs with strong UV radiation intensity. The relative error of the regressed reaction coefficients obtained by the new method is analyzed. To illustrate, we apply this method to measuring the reaction coefficients of TiO₂ photocatalytic decomposing formaldehyde. This method is very useful in determining the reaction coefficients of the photocatalytic oxidation of various VOCs simultaneously.     

对挥发酚测定时预蒸馏前处理方法的改进

在实验的基础上,对测定挥发酚前处理方法进行简化,提出了采用水样与蒸馏水同时加入一次性蒸馏进行预处理。经过统计检验,该法与原法相比,不仅具有省时、省电等优点,而且有较高的精密度和准确度,与原法无显著性差异。     

Quantitative Determination of Formaldehyde in the Parts Per Hundred Million Concentration Level

A new method has been developed for the determination of trace quantities of formaldehyde and appears to be superior to existing methods. The procedure is based on a modification of Schiff’s test for aldehydes. A mixture of dichlorosulfitomercurate II complex and acid bleached pararosaniline hydrochloride is used as the reagent. In the presence of formaldehyde, a purple color is produced. The method is highly sensitive to formaldehyde and acetaldehyde, simple and does not require concentrated acids. When applied to air pollution studies, the method is virtually free of interferences from higher aldehydes. The paper describes the application of this method to spot sampling of the atmosphere and to continuous atmospheric analysis.     

The Hygienic Aspects of the Production and Use of Lead Antiknock Compounds

Hydrogen sulfide and other sulfides can be determined in the part per billion range in air if the air is bubbled through an absorption mixture of an alkaline suspension of cadmium hydroxide contained in a macro impinger. Rates as high as 1 cubic foot per minute can be used, or 0.1 cubic foot per minute with a midget impinger. The concentration of the trapped sulfides is then estimated by the methylene blue method. A colorimetric method and a spectrophotometric method are described.     

Alternatives to the Gravimetric Method for Quantification of Diesel Particulate Matter near the Lower Level of Detection

Abstract

This paper is part of the Journal of the Air & Waste Management Association’s 2010 special issue on combustion aerosol measurements. The issue is a combination of papers that synthesize and evaluate ideas and perspectives that were presented by experts at a series of workshops sponsored by the Coordinating Research Council that aimed to evaluate the current and future status of diesel particulate matter (DPM) measurement. Measurement of DPM is a complex issue with many stakeholders, including air quality management and enforcement agencies, engine manufacturers, health experts, and climatologists. Adoption of the U.S. Environmental Protection Agency 2007 heavy-duty engine DPM standards posed a unique challenge to engine manufacturers. The new standards reduced DPM emissions to the point that improvements to the gravimetric method were required to increase the accuracy and the sensitivity of the measurement. Despite these improvements, the method still has shortcomings. The objectives of this paper are to review the physical and chemical properties of DPM that make gravimetric measurement difficult at very low concentrations and to review alternative metrics and methods that are potentially more accurate, sensitive, and specific. Particle volatility, size, surface area, and number metrics are considered, as well as methods to quantify them. Although the authors believe that an alternative method is required to meet the needs of engine manufacturers, the methods reviewed in the paper are applicable to other areas where the gravi-metric method detection limit is approached and greater accuracy and sensitivity are required. The paper concludes by suggesting a method to measure active surface area, combined with a method to separate semi-volatile and solid fractions to further increase the specificity of the measurement, has potential for reducing the lower detection limit of DPM and enabling engine manufacturers to reduce DPM emissions in the future.     

Determination of the aerobic biodegradability of polymeric material in a laboratory controlled composting test

A laboratory method is presented for investigating the biodegradation of an organic test material in an aerobic composting system based on the evolution of carbon dioxide. In addition to carbon conversion, biodegradation can also be monitored through weight loss and physical disintegration. The test method is different from other biodegradation tests, especially aquatic tests, because of the elevated temperature representative for real composting conditions and also because of enhanced fungal degradation activities. A ring test was run using paper and poly-β-hydroxybutyrate/valerate as test materials and cellulose powder as a reference material. The test results and the experience gained by the participants showed that the method is suitable and practicable. Experience with real technical-scale composting facilities confirms that the method provides test results of high predictive value. The test is designed to become a European Standard in connection with determining the compostability of packagings and packaging materials.     

Analysis of the number of flux chamber samples and study area size on the accuracy of emission rate measurements

Monte Carlo simulations were conducted on a set of flux chamber measurements at a landfill to estimate the relationship between the number of flux chamber samples and study area size on the emission rate measurement accuracy. The spatial variability of flux was addressed in the study by utilizing an existing flux chamber measurement data set that is one of the most dense flux chamber sampling arrays published to date for a landfill. At a probability of 95%, the Monte Carlo simulations indicated that achieving an accuracy within 10% with the flux chamber method is highly unlikely. An accuracy within 20% was achieved for small areas of less than about 0.2 hectares using 220 flux chamber measurements, but achieving this level of accuracy for area emission sources, of similar or greater variability, that are larger than this is highly unlikely. An accuracy within 30% was achieved up to the Full Area of about 0.4 hectares if more than approximately 120 samples were obtained. Even for an accuracy within 50%, at least 40 flux chamber measurements were needed for the Full Area of about 0.4 hectares. Available methods of estimating the number of samples required were compared to the Monte Carlo simulation results. The Monte Carlo simulations indicate that, in general, more samples are required than determined from an existing statistical method, which is a function of the mean and standard deviation of the population. Specifying the number of samples based on a regulatory method results in very poor accuracy. A modification to the statistical method for estimating the number of samples, or for estimating an accuracy for a given probability and number of samples, is proposed.

Implications: The flux chamber method is the most widely used method of measuring fugitive emission rates from area sources. However, extrapolation of a set of individual flux chamber samples to a larger area results in area flux measurement values of unknown accuracy. Quantification of the accuracy of the extrapolation of a set of flux chamber measurements would be beneficial for understanding the confidence that can be placed on the measurement results. Guidance as to the appropriate number of flux chamber measurements to achieve a desired level of accuracy would benefit flux chamber method practitioners.     

Spectrophotometric determination of the fungicide captan

A spectrophotometric method for the determination of the fungicide captan has been developed based on its reaction with thiosemicarbazide. The absorbance was measured at 315 nm. The effects of the proportion of water, thiosemicarbazide concentration, pH and temperature on this reaction was studied to select the best chemical conditions. The calibration graph was obtained between 1.2 and 30 ppm and the detection limit is 0.5 ppm. The RSD (n = 10) was 1.34%. Possible interference of various pesticides was examined. The method was applied to the determination of captan in agrochemical formulations. Results agree well with the labelled values and also with results that were obtained by a polarographic method.     

Determination of chlorine in air with the pyridine-pyrazolone reagent

An improved method for the determination of chlorine in air is described. The principle of this method is based on the absorption of chlorine in p-toluenesulfonamide aqueous solution, followed by color development with a pyridine-pyrazolone reagent. Both the chlorine absorbed in the solution and the color developed with the reagent were stable. Positive interference by nitrogen dioxide was not observed.     

An improved extraction method to determine the initial emittable concentration and the partition coefficient of VOCs in dry building materials

Based on the extraction method presented by Smith et al. (2008), this paper proposes an improved method, the multi-emission/flush regression method, to simultaneously determine the initial emittable concentration and the partition coefficient. Compared to the extraction method, the proposed method has the following advantages: (1) it is unnecessary for the target volatile organic compounds (VOCs) to emit completely from the material, thus greatly reducing experimental time; (2) it provides a simpler way to obtain the partition coefficients of VOCs for tested materials and can avoid the measurement uncertainties at low VOC concentrations which often occur during the last few cycles of the extraction method; (3) it does not require grinding the building material into powders thus making this method more convenient to use. Comparisons were made between the initial emittable VOC concentrations determined by the original extraction method and the proposed method. Results show good agreements between these two methods. To further validate the proposed method, the type of static chamber developed by Wang et al. (2006) was used to conduct the experiment for a type of medium density board, and formaldehyde was selected as the target compound. Based on the initial emittable concentration and partition coefficient obtained using the proposed method, and the diffusion coefficient obtained by the mercury intruding porosimetry, the chamber formaldehyde concentration was predicted and compared with the experimental measurements. Results show that the predicted chamber VOC concentration using the measured parameters agree well with the experimental data.     

呼吸速率测定研究进展

本文简述了三类测定呼吸速率的方法,并就最常用的仪器法介绍了呼吸速率测定仪的分类。总结了近四十年来国内外呼吸速率测定方法与装置的研究进展状况,并对该技术的未来发展作出预测。     

Comparison of two methods for the determination of total organic halogen (TOX) in receiving waters

Two methods for the determination of total organic halogen (TOX), orginating from bleaching of pulp, in receiving waters have been compared. One of the methods (AC/MC) is based on adsorption of the halogenated matter onto an activated carbon sorbent. The halogen is determined by a microcoulometric technique after combustion of the carbon. The other method (XAD/PT) uses an XAD resin as sorbent and the determination of the halogen is carried out by potentiometric titration after a schöniger combustion of the resin eluate.Both methods showed good performance for samples consisting of spent bleach liquors diluted with distilled, fresh and brackish water. The repeatability was very good with a relative standard deviation less than a few per cent. The detection limit of the AC/MC method is about 0.1 μmol/1 and for the XAD/PT method about ten times higher. The AC/MC method gave in most cases 10–20% higher TOX concentrations compared to the XAD/PT method.     

Determination of Sulfur Oxides in the Flue Gases of the Pulping Processes

The body of information presented in this paper is directed to the operating personnel and process engineers employed in the power and recovery departments of a chemical pulping operation. The proper evaluation of the total analytical and sampling system (TASS), to be used in the determination of sulfur oxides is as important as a proper analytical and recording system (ARS). The presence of other sulfur gaseous compounds and particulates could greatly influence the results of the determination.

The analytical method employed determines sulfur dioxide and trioxide from an aliquot of the trapping solution, 3% hydrogen peroxide and 8 0% isopropyl alcohol respectively. The aliquot is titrated with barium perchlorate in the presence of Thorin indicator. The results of evaluating the method indicated negligible interference from the presence of hydrogen sulfide, mercaptans and nitrogen oxides. A blank correction of 15 parts per million (ppm) is recommended whenever 100 ppm of hydrogen sulfide or more are simultaneously present in the gas stream. Particulaies are shown to interfere either by addition or subtraction. Sulfate particulates that will add to the determination must be removed, but in doing so, care must be exerted to avoid surface-contacting conditions that promote reaction between carbonates and the sulfur oxides. The integrated method of sampling and analysis will permit determinations from a flue gas with sulfur oxides concentrations of 30 ppm and above. The relative standard deviation improves from 10% at 100 ppm SO₂ to 2.6% at 1000 ppm SO₂. In both cases, sulfides were present.     

Evaluation of the Sodium Arsenite Method for Measurement of NO2 in Ambient Air

The sodium arsenite method for measurement of nitrogen dioxide in ambient air was evaluated. The method has a constant-high collection efficiency (82%) for nitrogen dioxide, and is insensitive to normal variations in operating parameters. Nitric oxide and carbon dioxide are positive and negative interferents, respectively. The combined average effect of these interferents, over ambient levels, is a positive bias of 9.9 µg/m³. This bias, although statistically significant, is minor ( 10 % ) in relation to the ambient air standard of 100 µg NO₂/m³ and does not warrant modification of the method to remove the interference.