Diurnal Variation of Aerosol Trace Element Concentrations In Livermore,California*

Concentrations of 15 atmospheric aerosol trace elements in Livermore, California, were measured by neutron activation analysis in 2–hour filter samples for 58 hours during 3 typical summer days. All elements showed cyclic patterns with concentration variations of factors of 3 to 10. Three basic patterns were seen: (1) Na and Cl in phase with each other and nearly perfectly out of phase with the others, with a late night maximum for both; (2) All other elements except Br, showing a midafternoon maximum; and (3) Br, which had morning and evening peaks suggestive of automotive sources. Details of the patterns suggest a diurnal circulation model for the Livermore Valley involving alternation between fresh and aged marine air. Comparison of the trace element patterns with those of CO, NO₂, and “oxidant” was not definitive.     

An Evaluation of the Tapered Element Oscillating Microbalance Method for Measuring Diesel Particulate Emissions

Abstract

We determined the usefulness of tapered element oscillating microbalances (TEOMs) for researchers and engineers involved with measuring diesel particulate mass. Two different test facilities were used for generating diesel particulates and comparing the TEOM to the commonly used U.S. Environmental Protection Agency (EPA) manual filter method. The EPA method is very labor-intensive and requires long periods of time to complete. The TEOM is an attractive approach because it has the potential to reduce the amount of time and labor required in diesel testing, as well as to provide real-time particulate-mass data that are not obtainable with the EPA method. It was found that the TEOM was a precise and easy-to-operate instrument that could measure the mass concentration (MC) of diesel particulate emissions in real time. Although the TEOM diesel particulate MC measurements were highly correlated with the manual filter measurements, the two techniques were not equivalent because the TEOM consistently reported MC results that were 20–25% lower than those obtained using the manual filter technique. In conclusion, the TEOM can be used to increase test-cell throughput and to measure transient values of diesel par-ticulate emissions at sites performing diesel-engine testing. However, unless EPA is able to certify the TEOM as an equivalent method, it cannot replace the manual filter method for diesel certification work.     

Distributions and determinants of mercury concentrations in toenails among American young adults: the CARDIA Trace Element Study

Since data on mercury (Hg) levels in Caucasians and African Americans (AAs) of both genders are lacking, this study aims to present toenail Hg distributions and explore the potential determinants using data from the Coronary Artery Risk Development in Young Adults Trace Element Study. Data from 4,344 Americans, aged 20–32 in 1987, recruited from Oakland, Chicago, Minneapolis, and Birmingham were used to measure toenail Hg levels by instrumental neutron-activation method. The Hg distribution was described with selected percentiles and geometric means. Multivariable linear regression (MLR) was used to examine potential determinants of Hg levels within ethnicity–gender subgroups. The geometric mean of toenail Hg was 0.212 (95 % CI?=?0.207–0.218)?μg/g. Hg levels varied geographically with Oakland the highest [0.381 (0.367–0.395) μg/g] and Minneapolis the lowest [0.140 (0.134–0.147) μg/g]. MLR analyses showed that male gender and AA ethnicity were negatively associated with toenail Hg levels, and that age, living in Oakland city, education level, alcohol consumption, and total fish intake were positively associated with toenail Hg concentrations within each ethnicity–gender subgroup. Current smokers were found to have higher Hg only in AA men. This study suggested age, gender, ethnicity, study center, alcohol, education level, and fish consumption consistently predict toenail Hg levels. As fish consumption was the key determinant, avoiding certain types of fish that have relatively high Hg levels may be crucial in reducing Hg intake.     

Selected Ion Chromatograms and Tandem Mass Spectrometry for Detection of Trace Polycyclic Aromatic Hydrocarbons in Diesel Exhaust

Abstract

Polycyclic aromatic hydrocarbon (PAH) measurements are essential for scientists and engineers who investigate these anthropogenic compounds. Diesel engines contribute to the problem, so analysts are measuring PAHs from these sources. However, diesel exhaust presents special problems for precise analytical measurements. The exhaust matrix is very complex; consequently, PAH detection sensitivity deteriorates, especially for trace PAHs in the exhaust. Yet, these are conditions and amounts that exist in real samples. Nonetheless, selected ion chromatogram (SIC) and tandem mass spectrometry (MS/MS) techniques improve trace PAH detection; ion trap technology makes both mass techniques possible. The purpose of this investigation was to evaluate SIC and MS/MS for applications to measure PAHs in diesel exhaust samples. The signal-to-noise ratio for accurate quantitation improves, relative to traditional mass techniques, because these techniques ignore or eliminate interfering components. On a VF-5MS chromatographic column, these techniques improve sensitivity and reproducibility. They produce a superior limit of detection in the useful range for PAH samples extracted from actual engine exhaust, 10–30 pg for the smaller PAHs and 1–6 ng for the larger PAHs. The results with SIC and MS/MS are reproducible, so analysts can report PAH amounts with defined statistical confidence intervals. SIC and MS/MS improve detection for trace PAHs in convoluted diesel exhaust samples.     

Laboratory Evaluation of an Aldehyde Scrubber System Specifically for the Detection of Acrolein

Abstract

We demonstrate the use of an aldehyde scrubber system to resolve isobaric aldehyde/alkene interferences in a proton transfer reaction mass spectrometer (PTR-MS) by selectively removing the aldehydes from the gas mixture without loss of quantitative information for the alkene components. The aldehyde scrubber system uses a bisulfite solution, which scrubs carbonyl compounds from the gas stream by forming water-soluble carbonyl bisulfite addition products, and has been evaluated using a synthetic mixture of acrolein and isoprene. Trapping efficiencies of acrolein exceeded 97%, whereas the transmission efficiency of isoprene was better than 92%. Quantification of the PTR-MS response to acrolein was validated through an intercomparison study that included two derivatization methods, dinitrophenylhydrazine (DNPH) and O-(4-cyano-2-ethoxybenzyl)hydroxylamine (CNET), and a spectroscopic method using a quantum cascade laser infrared absorption spectroscopy (QCL) instrument. Finally, using cigarette smoke as a complex matrix, the acrolein content was assessed using the scrubber and compared with direct QCL-based detection.     

Estimate of Contribution of Jet Aircraft Operations To Trace Element Concentration at or near Airports

Samples of ASTM type A jet fuel were analyzed for trace element content by instrumental neutron activation techniques. Forty-nine elements were sought. Only ten, aluminum, gold, indium, lanthanum, titanium, vanadium, barium, dysprosium, tellurium, and uranium, were observed at levels above the detection limits encountered; of these only aluminum, titanium, and barium were present at concentrations greater than 0.1 ppm. Estimates of exhaust gas. concentrations are made, and the ambient contribution at or near airports is calculated by using the Los Angeles International Airport dispersion model. It is shown that the ambient contribution is about an order of magnitude below typical urban levels for virtually all elements sought.     

南京市第二制药厂风险源潜在危险性评估

选取了危险性大、地处居民稠密区的南京市第二制药厂作为评估对象,对该厂的危险品用量、危险品储存量、厂区附近情况等逐一作了调查,对其风险源的潜在危险性进行了评估并预测了事故突发后的危害范围,为环保部门实施应急监测提供档案式信息和行动指导。     

水中阴离子表面活性剂的测量不确定度评定

简要介绍了测量不确定度的概念，运用《测量不确定度评定与表示》的技术规范，通过对阴离子表面活性剂的测定过程，分析了影响阴离子表面活性剂测量不确定度的因素，给出了相对标准不确定度分量，并具体阐明了测量不确定度的评定步骤，得出测量扩展不确定度的结果。     

Potential interferences in photolytic nitrogen dioxide converters for ambient air monitoring: Evaluation of a prototype

ABSTRACT

Mixing ratios of the criteria air contaminant nitrogen dioxide (NO₂) are commonly quantified by reduction to nitric oxide (NO) using a photolytic converter followed by NO-O₃ chemiluminescence (CL). In this work, the performance of a photolytic NO₂ converter prototype originally designed for continuous emission monitoring and emitting light at 395 nm was evaluated. Mixing ratios of NO₂ and NO_x (= NO + NO₂) entering and exiting the converter were monitored by blue diode laser cavity ring-down spectroscopy (CRDS). The NO₂ photolysis frequency was determined by measuring the rate of conversion to NO as a function of converter residence time and found to be 4.2 s^?1. A maximum 96% conversion of NO₂ to NO over a large dynamic range was achieved at a residence time of (1.5 ± 0.3) s, independent of relative humidity. Interferences from odd nitrogen (NO_y) species such as peroxyacyl nitrates (PAN; RC(O)O₂NO₂), alkyl nitrates (AN; RONO₂), nitrous acid (HONO), and nitric acid (HNO₃) were evaluated by operating the prototype converter outside its optimum operating range (i.e., at higher pressure and longer residence time) for easier quantification of interferences. Four mechanisms that generate artifacts and interferences were identified as follows: direct photolysis, foremost of HONO at a rate constant of 6% that of NO₂; thermal decomposition, primarily of PAN; surface promoted photochemistry; and secondary chemistry in the connecting tubing. These interferences are likely present to a certain degree in all photolytic converters currently in use but are rarely evaluated or reported. Recommendations for improved performance of photolytic converters include operating at lower cell pressure and higher flow rates, thermal management that ideally results in a match of photolysis cell temperature with ambient conditions, and minimization of connecting tubing length. When properly implemented, these interferences can be made negligibly small when measuring NO₂ in ambient air.

Implications: A new near-UV photolytic converter for measurement of the criteria pollutant nitrogen dioxide (NO₂) in ambient air by CL was characterized. Four mechanisms that generate interferences were identified and investigated experimentally: direct photolysis of HONO which occurred at a rate constant 6% that of NO₂, thermal decomposition of PAN and N₂O₅, surface promoted chemistry involving HNO₃, and secondary chemistry involving NO in the tubing connecting the converter and CL analyzer. These interferences are predicted to occur in all NO₂ P-CL systems but can be avoided by appropriate thermal management and operating at high flow rates.     

Trace Metal Pollution in the Environment

Trace metals introduced to the environment from fuel combustion, incineration, and industrial emission sources are causing increasing concern to air pollution researchers. Several metals in urban air, including lead and vanadium, are associated with particles in the predominantly submicrometer diameter range thereby presenting an inhalation threat. There is also growing evidence that some metals emitted from stationary sources are concentrated in submicrometer sized particles which may pass through emission control devices. This report summarizes the concentration and size of trace metals in urban air, the concentration ranges found in selected fuels and emission sources, and describes the areas where further studies are needed.     

Evaluation of a Coulometric Procedure For the Detection of Strong and Weak Acid Components in Rainwater

A rapid coulometric procedure is described for the determination of non-volatile strong and non-volatile and volatile weak acids in rain samples. A constant current with known amperage is passed into a measured volume of the sample, with and without volatiles, and the changes in the electromotive force monitored with a potentiometer. Molarities of the different acids are calculated by plotting the function of the electromotive force against time in seconds according to Gran’s theory. The method is useful at acid concentrations of 10^-6 to 10^-4 M.     

离子选择电极分析法测定标样中氟化物的不确定度评定

通过对离子选择电极法测定标样中氟化物的过程研究，分析了该方法测量不确定度的来源，给出了相对不确定度分量，得出测量扩展不确定度的结果。     

Assessment of the Commercial Potential for the High Intensity Ionizer in the Electric Utility Industry

The high intensity ionizer (HII) has reached a level of development where projections can be made of its potential for enhancing electrostatic precipitator (ESP) performance within the electric utility industry. Future ESP performance requirements are forecast based on a scenario of possible changes in regulations for mass emissions, fine particulate, and opacity. An assessment is made of the alternative means of upgrading ESP performance over the next 15 years. It is concluded that of 570 ESP estimated to require upgrading by 1995 to meet possibly more stringent regulations, approximately 20%—or 117 units—may employ HII.     

离子色谱法测定标样中硫酸根含量的测量不确定度评定

通过对离子色谱法测定标样中硫酸根含量的过程研究,分析了该方法测定结果的不确定度来源,并对各不确定度分量进行了评定.     

Trace elements in major solid-pesticides used in the Gaza Strip

This study describes the purity of pesticides used in Gaza in terms of trace elements. A semi-quantitative EMMA-XRF technique and quantitative ICP/OES was used to determine the concentrations of Al, As, Ba, Br, Ca, Cd, Co, Cr, Cu, Fe, K, Mn, Ni, Pb, Rb, Sc, Se, Sr, Ti and Zn in 50 of the most commonly used solid pesticides collected from the five central shops in the Gaza Strip. The results revealed that the pesticides contain considerable amounts of trace elements and do not comply with the expected-theoretical structure of each species. Moreover, they do not reflect the actual constituents mentioned in the trade labels. Interviews with market owners and field surveys confirmed that the pesticides were not pure. In some cases they have been mixed in local markets with minor inorganic species without a scientific basis. They may also have been smuggled into Gaza with differing impurities. The results indicate that pesticides should be considered as a source of certain trace metals (particularly Cu, Mn and Zn) and other elements (Br, Sr and Ti), which may affect their mass balances in soil and groundwater as well as their plant uptake. Different scenarios and calculation models of the transport of trace elements in soil and groundwater of the Gaza Strip should include pesticides as an additional source.     

Potential of different species for use in removal of DDT from the contaminated soils

Dichlorodiphenyltrichloroethane (DDT) and its main metabolites, p,p'-DDD and p,p'-DDE (DDTs in this study included DDT, DDD and DDE), are frequently detected in agricultural soils even though its usage in agriculture was banned in 1980s or earlier. In this study, eleven plants including eight maize (Zea mays) cultivars and three forage species (alfalfa, ryegrass and teosinte) widely cultivated in China were grown in the soils spiked with DDTs to investigate their potential for removal of DDT from the contaminated soils. The plants varied largely in their ability to accumulate and translocate DDTs, with the bioconcentration factor (BCF; DDT concentration ratio of the plant tissues to the soils) ranging from 0.014 to 0.25 and the translocation factor (TF; DDT concentration ratio of the shoots to the roots) varying from 0.35 (Zea mays cv Chaotian-23) to 0.76 (Zea mays spp. mexicana). The amount of DDT phytoextraction ranged from 3.89mug (ryegrass) to 27.0mug (teosinte) and accounted for <0.1% of the total initial DDTs spiked in the soils. After 70d, the removal rates reached 47.1-70.3% of the total initial DDTs spiked in the soils with plants while that was only 15.4% in the soils without plant. Moreover, the higher removal rates of DDTs occurred at the first 20d of experiment, and then the removal rate decreased with time. The highest amount of DDTs phytoextracted was observed in teosinte, followed by Zea mays spp. mexicana, but the highest removal rate of DDTs was found in maize (Zea mays cv Jinhai-6). Even though phytoextraction is not the main removal process for DDTs, the plant species especially Zea mays cv Jinhai-6 showed high potential for removing DDTs from the contaminated soils.     

Recent Advances in Liquid Scrubbing for Fine Particulate Collection

Lone Star Steel has developed a family of high performance, long life, low capital, and low operating cost Hydro-Sonic* cleaners. A choice of driving mediums is available; either a compressible fluid ejector or fan may be used. The ejector models have no moving parts in the gas stream. Where available, waste heat may be used to power the cleaners. Cleaning levels are adjustable by the user by the selective input of energy. The Coalescer model employs a unique pressure recovery device for separation thereby reducing energy requirements for the cleaner. The Hydro-Sonic cleaners are operational In the steel, paper, and other industries.     

Simultaneous Determination of Imidacloprid,Thiacloprid, and Thiamethoxam in Soil and Water by High-performance Liquid Chromatography with Diode-array Detection

Abstract

A high-performance liquid chromatography method with diode-array detection (HPLC-DAD) is described for the determination of three neonicotinoid insecticides imidacloprid, thiacloprid, and thiamethoxam in soil and water. The soil samples were extracted with acetonitrile, while the water samples were extracted using C₁₈ cartridges. The mean recoveries plus standard deviations for spiked soil samples were 82 ± 4.2% for thiamethoxam, 99 ± 4.2% for imidacloprid and 94 ± 1.4% for thiacloprid. The recoveries for water samples ranged from 87 ± 3.4% for thiamethoxam to 97 ± 3.9% for imidacloprid and 97 ± 2.6% for thiacloprid. The limits of quantitation (LOQ) were 0.1, 0.1, 0.01 mg/kg in soil (5 g), and 2, 2, 0.5 µg/L in water (50 mL) for thiamethoxam, imidacloprid, and thiacloprid, respectively.