Collection and Identification of Trace Organic Compounds in Atmospheric Deposition from a Semi-Rural Site in the U.K.

Abstract

The collection of rainwater, aerosol and vapour samples at a semi-rural site in the UK was achieved using a PTFE-lined wet-only rainfall collector and a high-volume filter/adsorption trap air sampler, respectively. Analysis of atmospheric deposition revealed the presence of several hundred compounds, many of which were of anthropogenic origin, e.g.: PAH, phenols and alkylbenzenes. Amounts of compounds varied from low nanograms to tens of micrograms per litre in rainwater samples and from low picograms to high nanograms per cubic metre in aerosols. Phenolic compounds were the most abundant group of organics identified in rainwater and were present at total concentrations of >20μg1^?1 in some of the samples analysed. In the high-volume air samples most anthropogenic compounds were detected in the adsorbent rather than the filter extract. Seasonal variations in the PAH content of the adsorbent extracts were observed. The presence of siloxanes in the air samples was thought to be the result of contamination.     

Assessment of recent trends in concentrations of alkyl-lead compounds in rainwater

Concentrations of tetra-, tri and di-alkyl-lead compounds in rain have been measured at rural and urban sites in England. The measurements are compared with similar data collected in the early 1980s, prior to a 72% reduction in the emission of lead from combustion of leaded petrol. Whilst concentrations of inorganic lead have fallen broadly in line with emissions of automotive lead, alkyl-lead concentrations in rain have fallen by only 50% or less, and thus the ratio of alkyl-lead to inorganic lead in rain has increased appreciably. The reason for this phenomenon is unclear. The data suggest that lead in rainwater would fall to approximately 2 μg dm^?3 if automotive lead emissions fell to zero.     

Interlaboratory programme for the quality control of trimethyllead determination in the environment

Determinations of the trimethyllead moiety in environmental samples are carried out by a number of laboratories in Europe. To verify the quality of such determinations, the Measurements and Testing Programme (formerly BCR) of the European Commission organised an interlaboratory exercise which allowed discussion and comparison of the different techniques used so far in lead speciation analyses. In addition, this first step enabled a study of the feasibility of the preparation of candidate reference materials (CRMs) for the determination of the trimethyllead moiety in simulated rainwater to be carried out. The solutions used in this study were carefully prepared and their homogeneity and stability verified. This paper describes the organisation and the results of the intercomparison and discusses the further development of the project.     

Trace analysis of acids and bases by conductometric titration with multiparametric non-linear regression

A chemometric method for analysis of conductometric titration data was introduced to extend its applicability to lower concentrations and more complex acid-base systems. Auxiliary pH measurements were made during the titration to assist the calculation of the distribution of protonable species on base of known or guessed equilibrium constants. Conductivity values of each ionized or ionizable species possibly present in the sample were introduced in a general equation where the only unknown parameters were the total concentrations of (conjugated) bases and of strong electrolytes not involved in acid-base equilibria. All these concentrations were adjusted by a multiparametric nonlinear regression (NLR) method, based on the Levenberg-Marquardt algorithm. This first conductometric titration method with NLR analysis (CT-NLR) was successfully applied to simulated conductometric titration data and to synthetic samples with multiple components at concentrations as low as those found in rainwater (∼10 μmol L⁻¹). It was possible to resolve and quantify mixtures containing a strong acid, formic acid, acetic acid, ammonium ion, bicarbonate and inert electrolyte with accuracy of 5% or better.     

Isotopic Characterization of Lead in the Scottish Upland Environment

Abstract

Experimental plots have been set up at two Research Stations in upland areas of Scotland with the intention of characterising environmental samples using lead isotopic composition which varies according to the original source of the lead. Thermal ionisation mass spectrometry (TIMS) was used to measure lead isotope ratios with high precision. The ²⁰⁶Pb/²⁰⁷Pb ratios in rainwater were in the range from 1.101 to 1.153 over a period of two years at the two sites. Low ratios were associated with the very low ratios found in Britain in petrol additives during that period whereas higher ratios indicated a larger component derived from industrial sources at the Hartwood site. The ²⁰⁶Pb/²⁰⁷Pb ratios in the surface (0–2.5 cm) soil from a roadside plot were low (1.1126 and 1.1159 in 1989 and 1990, respectively) but the ratios in surface soils in plots distant from the road were considerably higher. Whereas the lead in roadside soil had a ²⁰⁶Pb/²⁰⁷Pb ratio indicating its source to be predominantly in recent petrol lead, there were significant components from other sources in the soils away from the road. The washing of grass samples resulted in no significant change in the lead isotope ratios. The lead isotope ratios measured in grass samples reflect the isotopic character of current atmospheric inputs but those in surface soil samples are an integrated record of atmospheric deposition over a long period of time. An undisturbed plot under a tree canopy had high concentrations of lead in the surface soil and low ²⁰⁶Pb/²⁰⁷Pb ratios. The ratios in fallen leaves on this plot were slightly but significantly lower than those in the grass grown on the plot. It would appear that the tree canopy is effective at scavenging lead carried in the atmosphere.     

离子色谱法同时测定大气降水中7种阴离子

建立离子色谱法同时测定大气降水中F^-,Cl^-,NO2^-,Br-,NO3^-,SO4^2-和PO43^-7种阴离子的分析方法。选用IonPac■AS19型色谱柱(4 mm×250 mm),以KOH梯度淋洗,用抑制电导检测器进行测定。7种阴离子在各自的质量浓度范围内与色谱峰面积成良好的线性关系,相关系数均不小于0.997,方法检出限为0.002~0.004 mg/L。测定结果的相对标准偏差为0.80%~3.38%(n=6),样品加标回收率为75.0%~98.7%。该方法简便、快速,灵敏度高,适用于大气降水中F^-,Cl^-,NO2^-,Br^-,NO3^-,SO4^2-和PO43^-7种阴离子的同时测定。     

离子色谱法同时测定大气降水中的5种阴离子

以保留时间定性、峰面积外标法定量,建立了离子色谱同时测定大气降水中F–,Cl–,NO2–,NO3–,SO42–5种阴离子的分析方法。结果表明,5种阴离子标准曲线线性相关系数均大于0.999 8,检出限(3s/k)在0.000 3~0.006 6 mg/L之间。F–,Cl–,NO2–,NO3–,SO42–测定结果的相对标准偏差(n=10)分别为1.70%,2.46%,9.30%,0.73%,0.67%。用该方法对水样进行测定并进行加标回收试验,5种阴离子加标回收率在91.2%~102.7%之间。该方法灵敏度高,简便、快速,能满足大气降水中阴离子分析的要求。     

雨载作用下浮顶结构有限元分析的载荷修正法

浮顶结构的受力与变形之间存在着非线性的耦合关系,这给计算分析带来了很大的麻烦。为了解决这一问题,本文提出了单盘式浮顶结构在雨水载荷作用下有限元分析的载荷修正计算方法。通过对浮顶结构力学模型的分析,建立了浮顶结构载荷与单盘挠度之间的关系式,并基于这一关系式给出了浮顶结构有限元分析的载荷修正法和相应计算方案。载荷修正法的基本思想是,首先利用有限元方法对浮顶结构进行几何大变形非线性分析,然后通过迭代修正来调整载荷大小,使得计算得到的载荷与挠度满足给定关系式,最终获得浮顶结构的变形与受力情况。最后,将计算结果与试验结果进行了比较,验证了本文提出的计算方法的有效性和可靠性,为浮顶结构的进一步有限元分析打下基础。     

Dynamically adaptive tree grid modeling for simulation and visualization of rainwater overland flow

Modeling and visualization of a rainwater overland flow is an important tool for a risk assessment, preparation, evacuation planning, and real‐time forecasting of flood warning. The objective of this research is to develop a numerical software to visualize the rainwater overland flow based on a finite volume method for shallow water equations and in combination with the dynamically adaptive tree grid technique and the dynamic domain‐defining method. The obtained simulations for several experiments were tested and compared with results in literature, both theoretical and experimental results. The comparisons with non‐adaptive grids show that the developed algorithm for simulation is very efficient and has a potential for practical usages, in terms of computational times and accuracy. Copyright © 2015 John Wiley & Sons, Ltd.     

Interlaboratory exercises to compare analytical method performances

Three intercomparison exercises on simulated rainwater were held in the period 1991–93 involving 72 to 99 laboratories in Europe and South America. The exercises required the analysis of pH, conductivity, main anions (Cl^–, NO ₃ ^– and SO ₄ ^2– ) and main cations (Ca²⁺, K⁺, Mg²⁺, Na⁺ and NH ₄ ⁺ ). The concentrations of the single ions ranged between 5 and 150 moll^–1. Results were used to evaluate and compare the precision of the analytical methods. A general improvement in precision was observed in the course of the exercises.