Adsorption characteristics of a phenoxy acetic acid herbicide on activated carbon

The adsorption of 2,4-dichlorophenoxyacetic acid (2,4-D) by two powdered coal activated carbons was studied in aqueous solution. The modelling of the adsorption equilibrium showed that the adsorption of 2,4-D fitted a Langmuir isotherm. Adsorption was influenced by the activated carbon type, adsorbent concentration and solution characteristics. The adsorption was found to decrease with an increase in pH over the range 1.5-9. Maximum adsorption occurred at pH approximately 2.5, which corresponds to the 2,4-D pKa value. The amount of 2,4-D adsorbed was also found to depend on the NaCl concentration.     

Determination of n-alkanes and polycyclic aromatic hydrocarbons in atmospheric particulate and vapour phases in Oviedo, Spain, by GC-MS

A GC-MS procedure for the determination of hydrocarbons in air samples from Oviedo, Spain, was developed. Air hydrocarbons were sampled with a high volume sampler equipped with a holder containing a glass fiber filter, to trap the particulate phase, and two polyurethane foams to capture hydrocarbons of the vapour phase. Compounds were extracted with CH2Cl2 by Soxhlet extraction and then fractionated using column chromatography with alumina silica. Analyses of the fractions were performed by GC-MS in the electron ionization mode. PAHs and n-alkanes were the compounds examined in this work. Samples collected in the vicinity of the Faculty of Chemistry (a semi-urban area) were analysed. The total concentration of PAHs in the air samples analysed ranged from 28 to 76 ng m(-3). The total concentration of n-alkanes and PAHs in the vapour phase exceeded the concentration in the particulate phase in the samples analysed.     

Transportation and fate of cationic surfactant in river water

The degradation, sorption, transportation and material balance of cationic surfactants discharged from domestic waste into river water was studied. Ion-pair solid-phase extraction behavior showed that the sorption of cationic surfactants as an ion-pair with anionic surfactant onto river sediment was so strong that little cationic surfactant was found in the bulk water. Cationic surfactant was found in river sediment at more than 500 times higher concentration than that in the bulk water. The degradation of the cationic surfactant was very slow in river water and much slower in the sediment. A material balance of cationic surfactant was estimated for a river running through Toyama City by measuring the flow rate and the concentration of cationic surfactant in the water at several points. It was found that more than 30% of cationic surfactant introduced to the river was lost during the river running through ca. 3 km in 3 h. This reduction probably comes from a quick transfer of the cationic surfactant from river water to sediment and water weed by means of adsorption or precipitation with suspending solids.     

Survey of the occurrence of residues of methyl tertiary butyl ether (MTBE) in Dutch drinking water sources and drinking water

An indicative survey has been carried out in The Netherlands investigating the presence of methyl tertiary butyl ether (MTBE) in drinking water and the corresponding sources. In total, 71 different sites used for the preparation of drinking water in The Netherlands were sampled in two successive seasons in 2001 involving the analysis of 156 samples. (ground water (n = 88), surface water (n = 17), bank filtrate water (n = 6) and drinking water (n = 45)). To combine high sample throughput with high selectivity and sensitivity, off-line purge and trap for sampling and gas chromatography mass spectrometry equipped with an automated thermal desorption sampler (TDS-GC-MS) was selected as the preferred analytical methodology. The developed procedure enabled the analysis of at least 40 samples per day and provided a limit of quantification of 2 ng l(-1). In the first period 63 samples of raw water were analyzed. Concentrations ranged between < 10 ng l(-1) and 420 ng l(-1) with a median concentration below 10 ng l(-1). The second period was focused at the re-sampling of positive locations (MTBE > 10 ng l(-1)) and a few additional drinking water utilities of which both the raw and drinking water of the utilities were analyzed. The median concentration of MTBE in the selected set of drinking water samples was 20 ng l(-1) (n = 45). At one location MTBE was found at a level of 2900 ng l(-1) caused by point source contamination of the ground water (11 900 ng l(-1)). Special attention has been paid to the quality of the results by analyzing all samples in duplicate and the analysis of control samples during each series of analyses.     

The application of HPLC-F and GC-MS to the analysis of selected hydroxy polycyclic hydrocarbons in two certified fish bile reference materials

Four selected hydroxy polycyclic aromatic hydrocarbons (OH-PAHs), 2-hydroxy-naphthalene (2-OH-NPH), 1-hydroxy-phenanthrene (1-OH-PHE), 1-hydroxy-pyrene (1-OH-PYR) and 3-hydroxy-benzo[a]pyrene (3-OH-BaP) have been analysed in two certified fish bile reference materials (CRMs) for exposure monitoring of PAHs in the aquatic environment. The two materials, BCR 720 and BCR 721, consist of bile from fish exposed to contaminated sediment and dispersed crude oil, respectively. Both bile samples have been analysed by two different analytical techniques, gas chromatography-mass spectrometry (GC-MS) and high performance liquid chromatography-fluorescence detection (HPLC-F), and the separation performance, detection limits, recoveries and reproducibility for the four target compounds were evaluated. HPLC-F requires a simple sample preparation and the separation capacity is adequate for quantification of 1-OH-PYR and 3-OH-BaP. Detection limits are excellent for 1-OH-PYR (6 pg injected) and 3-OH-BaP (3 pg injected) and generally improved with increasing molecular size. Recoveries ranged from 48 to 99% for the four selected compounds, depending on compound and concentration. Sample preparation prior to GC-MS analysis was more demanding, as reflected by the obtained recoveries for 2-OH-NPH, 1-OH-PHE and 1-OH-PYR (35 to 61%). The sensitivity improved with decreasing molecular size, 2-OH-NPH (1.2 pg injected), 1-OH-PHE (2.4 pg injected) and 1-OH-PYR (6 pg injected). Because of the superior separation power of GC and the extra selectivity of MS detection, GC-MS was the method of choice for the determination of 2-OH-NPH and 1-OH-PHE in both CRMs. In fish bile samples these two compounds are more likely to suffer from chromatographic overlap, and HPLC-F was not sufficiently selective. Determination of 1-OH-PYR was performed with success by both methods, but HPLC-F would be preferred because of the simpler and less time-consuming sample preparation. Detectable concentrations of 3-OH-BaP were present in BCR 720 and could only be determined by HPLC-F. The present work aims to present HPLC-F and GC-MS as complementary methods for the quantitative analysis of OH-PAHs in fish bile.     

Aerosol chemical characteristics of an island site in the Bay of Bengal (Bhola-Bangladesh)

Aerosol constituents (elemental carbon, organic carbon, soluble ions including organic acids, and selected trace metals) were investigated from samples of a field campaign taking place at Bhola Island in the Bay of Bengal (Bangladesh). The campaign took place in the pre-monsoon season (May 2001) using low volume samplers. Carbonaceous material comprised the majority of the analysed components. The average concentrations of EC and OC were 2.8 and 4.6 microg m(-3), respectively. Oxalic acid was the most abundant dicarboxylic acid (average 268 ng m(-3)) followed by malonic and malic acid. The contribution of carboxylic acids-carbon to organic carbon was 2.0%. Average concentrations observed for sulfate and nitrate were 3.7 microg m(-3) and 1.5 microg m(-3). Two different types of aerosol were identified at the rural background site on Bhola Island during southerly synoptic flow by means of trajectory analysis: air masses were transported from the Bay of Bengal to the sampling site in all cases. However, during "Period 1" they experienced longer residence times over the Indian Ocean, while the "Period 2" trajectories came along the Indian coast or passed over the Indian continent. During Period 1 the concentration levels of soluble ions were a factor of 4-6 lower than during Period 2. The concentrations of EC, OC and K differed less than a factor of 1.5 between the two periods. The Period 1 aerosol showed similarities to the haze layers observed during winter-monsoon conditions south of India during the INDOEX experiment. Based on EC/TC and K/EC ratios we find that around 80% of the carbonaceous aerosol from Period 1 in Bhola is from fossil fuel and only around 50% from Period 2. Absolute concentrations of carbonaceous species, soluble ions and trace metals indicate that the background site on Bhola Island is affected by emissions from urbanized regions of Southeast Asia.     

Occurrence of dissolved PAHs in the Jinsha River (Panzhihua)--upper reaches of the Yangtze River,Southwest China

16 priority polycyclic aromatic hydrocarbons (PAHs) were determined in water samples from the Jinsha River (Panzhihua part), Southwest China. Total dissolved PAH concentrations varied from 21.89 microg l(-1) to 382.8 microg l(-1). It was found that the concentration of PAHs decreased along the flow direction due to the higher density distribution of coal chemical industry in the upstream of our study rivers. The pollution levels in our study area are significantly higher than previously reported values in other waters both in China and other countries. The predominance of benzo[k]fluoranthene and indeno[1,2,3-cd]pyrene was clearly observed in all water samples. On average these two compounds accounted for 98.3% of the total dissolved PAH concentration in water. The results showed the positive correlations among total dissolved PAHs, benzo[k]fluoranthene and indeno[1,2,3-cd]pyrene, which suggested that these two predominant PAHs have similar source and environmental behaviors in our study area. When compared with the survey results of organic micropollutants two decades ago, it was found that hydrocarbon pollution both predominated and even increased with the development of coal chemical industry in this area during the past 20 years. The results therefore provide important information on the current contamination status of a key industrial city in China, and points to the need for urgent action to investigate the relationship between the PAH composition and concentration in water from the Jinsha River and the wastewater discharge from coal chemical industry, and to identify the source, transport pathway and fate of PAHs in the area. It should then be necessary to adopt appropriate and instant measures to control the pollution around this area.     

Distribution of polychlorinated biphenyls (PCBs) and organochlorine pesticides in soils from the East Antarctic coast

Concentrations of hexachlorobenzene (HCB), alpha-, beta- and gamma-hexachlorocyclohexane (HCH) isomers, 6 o,p'-and p,p'-isomers of DDT and 28 PCB congeners have been measured in eleven soil samples and one lichen collected on the Eastern coast of Antarctica from 5 Russian stations. For samples with low concentrations of PCBs (range 0.20-0.41 ng g(-1) dry weight) and pesticides (0.86-4.69 ng g(-1) and 0.11-1.22 ng g(-1) dry weight for HCHs and DDTs, respectively), atmospheric long-range transport from Africa, South America or Australia was suggested as the sole source of contamination. The profile of PCB congeners was dominated by the more volatile tri-, tetra- and penta-PCBs congeners, thus supporting long-range transport hypothesis. Four samples contained moderate levels of PCBs (range 1.98-6.94 ng g(-1) dry weight) and variable concentrations of pesticides (gamma-HCH, p,p'-DDT and o,p'-DDT being the main contaminants). For samples with high concentrations of PCBs (range 90.26-157.45 ng g(-1)) and high concentrations of pesticides, the presence of high molecular weight PCB congeners such as: 153, 180, 187, 170 etc, strongly suggest a local source (biotic) of PCBs rather than atmospheric transport. It is likely that on a local scale, biotic focussing of pollutants, due to bird activities (nesting and excrement) can cause high contamination levels and become more significant than contaminant input via abiotic pathways.     

Time dependent influx and efflux of phenol by immobilized microbial consortium

Phenol, like many other organic solvents, is toxic to micro-organisms even at low concentrations. However, some micro-organisms can withstand this toxicity to a certain concentration. To observe the uptake mechanism of phenol, bacteria were isolatedfrom a petroleum refinery effluent and identified. Study was carried out to understand the effect of varying sub-lethal concentrations of phenol, on all the isolated individual bacterial cultures. Out of the bacteria isolated, Serratia liquefaciens was found to tolerate phenol concentration up to 1500 mg l^-1. A microbial consortium of the isolated bacteriawas formulated and immobilized. Individual cultures were also immobilized and uptake of phenol by the immobilized micro-organisms was observed in a nutrient-rich and nutrient-stressed medium containing phenol as a sole source of carbon. A time-dependent uptake of phenol was exhibited by the micro-organismsin nutrient-stressed medium, after which a sudden increase in phenol concentration occurred in the extracellular medium, till it reached back to the initial concentration. This was attributedto an active efflux mechanism adopted by the micro-organisms to withstand the toxic shock.