Performance evaluation of a sorbent tube sampling method using short path thermal desorption for volatile organic compounds

Air sampling, using sorbents, thermal desorption and gas chromatography, is a versatile method for identifying and quantifying trace levels of volatile organic compounds (VOCs). Thermal desorption can provide high sensitivity, appropropriate choices of sorbents and method parameters can accommodate a wide range of compounds and high humidity, and automated short-path systems can minimize artifacts, losses and carry-over effects. This study evaluates the performance of a short-path thermal desorption method for 77 VOCs using laboratory and field tests and a dual sorbent system (Tenax GR, Carbosieve SIII). Laboratory tests showed that the method requirements for ambient air sampling were easily achieved for most compounds, e.g., using the average and standard deviation across target compounds, blank emissions were < or = 0.3 ng per sorbent tube for all target compounds except benzene, toluene and phenol; the method detection limit was 0.05 +/- 0.08 ppb, reproducibility was 12 +/- 6%, linearity, as the relative standard deviation of relative response factors, was 16 +/- 9%, desorption efficiency was 99 +/- 28%, samples stored for 1-6 weeks had recoveries of 87 +/- 9%, and high humidity samples had recoveries of 102 +/- 12%. Due to sorbent, column and detector characteristics, performance was somewhat poorer for phenol groups, ketones, and nitrogen containing compounds. The laboratory results were confirmed in an analysis of replicate samples collected in two field studies that sampled ambient air along roadways and indoor air in a large office building. Replicates collected under field conditions demonstrated good agreement except for very low concentrations or large (> 41 volume) samples of high humidity air. Overall, the method provides excellent performance and satisfactory throughput for many applications.     

Temporal variation in a coral reef community at Pattaya Bay,Gulf of Thailand

Changes in the fringing coral reef community of a small island (Ko Nok) at Pattaya Bay, Gulf of Thailand, were examined at the beginning and at the end of a 3-year period using 7m×7m permanent quadrats for benthic organisms, and visual census along 100m transects for fish. The coral community was dominated by Porites lutea in terms of colony number and areal cover throughout the period. Variations in the community structure parameters on opposite sides of the island indicated increasing dissimilarity with time. Little variation in live coral cover was noted, but colony number and species diversity declined on both sides. The abundance of edible fish species dropped while that of non-edible species increased over the 3-year period, indicating selective removal of the former category through fishing. Impacts from both human and natural influences are implicated in these changes.     

Organochlorine and mercury residues in Swainson's and ferruginous hawk eggs collected in North and South Dakota, 1974–79

Residues of organochlorine pesticides, polychlorinated biphenyls (PCBs), and mercury were measured in eggs of Swainson's hawks (Buteo swainsoni) and ferruginous hawks (B. regalis) collected in North and South Dakota during 1974–79. DDE was the most common compound detected in the eggs, but residues were below levels known to have adverse effects on reproduction. Other organochlorine compounds and mercury were found at low levels. Eggs of ferruginous hawks tended to contain more compounds with higher residues than eggs of Swainson's hawks.     

An evaluation of in situ microcosms for validating aquatic fate and transport models

The fates of two compounds, 2,4 Dichlorophenoxy Acetic Acid Butoxyethyl Ester (2,4-DBEE) and 1,4 Dichlorobenzene (1,4-DCB), were examined in in situ microcosms placed in a pond and compared with the fates in the pond itself. Results also were compared with predictions of an aquatic fate and transport model (EXAMS). Decay rates of 2,4-DBEE were not significantly different among the microcosms, pond and model predictions. The decay rate of 1,4-DCB in the microcosms was significantly lower than the rate for the pond, and lower than the rate predicted by the model. The low volatility of 1,4-DCB in the microcosms is attributed primarily to lack of water surface turbulence in the microcosms.     

Second derivative spectroscopy for the determination of volatilized ammonia from urea-amended soil

A second derivative spectrometer custom fitted with a 1 m stainless steel White cell and maintained at 105°C is used to make real-time measurements of volatilized NH₃ from urea-amended soil. Comparison of the technique to impinger data shows a 5–16% discrepancy between the two techniques; however, other experiments presented suggests that this is not real. Sulfur dioxide and nitrous oxide interferences are discussed, though they were not found to be present in this study. Instrument response time is shown to be fast if 67% of the total response is achieved in less than 5 min. Fast response is achieved for ammonia if wall-adsorption effects are minimal and if ammonia mass flow is maintained at 0.2 μg min^-1.     

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.     

Environmental monitoring of historical change in arsenic deposition with tree bark pockets

ICP-MS analysis recorded historical change (c. 1846 to 2002) in the arsenic concentration of bark included within the trunks (tree bark pockets) of two Japanese oak trees (Quercus crispula), collected at an elevated location approximately 10 km from the Ashio copper mine and smelter, Japan. The arsenic concentration of the bark pockets was 0.016 +/- 0.003 microg cm(-2) c. 1846 (n = 5) and rose 50-fold from c. 1875 to c. 1925, from approximately 0.01 to 0.5 microg cm(-2). The rise coincided with increased copper production in Ashio from local sulfide ores, from 46 tons per year in 1877 to 16,500 tons per year in 1929. Following a decline in arsenic concentration and copper production, in particular during the Second World War, a second peak was observed c. 1970, corresponding to high levels of production from both local (6,000 tons per year) and imported (30,000 tons per year) ores, smelted from 1954. Compared to the local ores, the contribution of arsenic from imported ores appeared relatively low. Arsenic concentrations declined from c. 1970 to the present following the closure of the mine in 1974 and smelter in 1989, recording 0.058 +/- 0.040 microg cm(-2) arsenic (n = 5) in surface bark collected in 2002. The coincident trends in arsenic concentration and copper production indicated that the bark pockets provided an effective record of historical change in atmospheric arsenic deposition.     

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.