The electron density distribution in pyridinium and bipyridylium compounds and its relevance to their adsorption by expanding lattice clays

Abstract

Charge distributions in 1, 1'‐ethylene‐2, 2'‐bipyridylium (diquat), 1,1'‐dimethyl‐4,4'‐bipyridylium (paraquat) and 1‐methylpyridinium organocations were calculated by a Complete Neglect of Differential Overlap semi‐empirical quantum mechanical procedure. The data show that the positive charges in the organocations are distributed around the molecules and are greatest in the positions ortho and para to the heterocyclic nitrogen atoms. Earlier interpretations of the mechanisms of adsorption of paraquat and diquat by soils and clays assumed that the charges were located in the heterocyclic nitrogen atoms. Here some consideration is given to the influence of the charge delocalizations on the processes of adsorption by montmorillonite and vermiculite clay preparations.     

Environmental and Biological Assessment of Exposure to Benzene in Petroleum Workers

Occupational exposure to benzene was measured in two gasoline marketing terminals and five major refineries in Singapore. A total of 280 workers were monitored over two years. This assessment was carried out with two primary objectives: (1) To find out the extent of occupational exposure to benzene in the petroleum industry in Singapore, (2) To identify suitable biomarkers for monitoring of low levels of benzene exposure. The exposure was measured in five different categories of petroleum and petrochemical workers, i.e., truck drivers, despatch assistant, process operators, oil movements operators and laboratory technicians. The results revealed wide variations in exposure, from 0.01 to 13.6 ppm for personal time weighted average (TWA) exposure over the whole workshift. The exposure of truck drivers appeared to be the highest, with geometric mean (GM) of 1.98 ppm (ranged from 0.25 to 13.6 ppm). The average benzene exposure for process operators was relative low with a GM of 0.04 ppm. Lowest benzene exposure was found in the laboratory technicians, with a GM of 0.02 ppm. As cigarette smoking is known to affect metabolism of benzene, data analyses on the relationships with environmental exposure were conducted only on the 190 nonsmokers. The results showed that urinary trans, trans-muconic acid (ttMA), unmetabolized benzene in urine (UBZ) and benzene in blood (BBZ) were better biomarkers for low level benzene exposure as compared to urinary phenolic metabolites in urine, such as hydroquinone, phenol and catechol.     

Assessment of pumped mercury vapour adsorption tubes as passive samplers using a micro-exposure chamber

Mercury vapour adsorption tubes manufactured for pumped sampling and analysis have been evaluated for their performance as passive samplers. This has been done by exposing these tubes in a novel micro-exposure chamber. The uptake rates of these tubes have been found to be low (approximately 0.215 ml min(-1)) as compared to bespoke passive samplers for mercury vapour (typically in excess of 50 ml min(-1)). The measured uptake rates were shown to vary significantly between tubes and this was attributed to the variability in the air-sorbent interface and the proportion of the cross sectional area removed by the crimp in the quartz tubes used to secure the sorbent material. As a result of this variability the uptake rate of each tube must be determined using the micro-exposure chamber prior to deployment. Results have shown that the uptake rate determined in the micro-exposure chamber is invariant of concentration, and therefore these uptakes rates may be determined at a high mercury vapour concentration for many tubes at once in less than one hour. The uptake rate of the adsorption tubes under these conditions may be determined with a precision of 5%. Measurements made on a limited field trial in indoor and outdoor ambient air have shown that these tubes give results in acceptable agreement with more traditional pumped sampling methods, although longer sampling periods are required in order to reduce the uncertainty of the measurement, which is currently approximately 30%.