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.     

Determination of the working level of radon/thoron mixtures by personal α-dosimeters and environmental α-monitors using gross α-counting

Analytical procedures are presented which permit the determination of the Working Levels of the radon and thoron progenies with personal α-dosimeters and α-particle environmental monitors, operating on time integrating principles, from gross α-counts. Experiments have been carried out in an underground uranium mine and in a radon/thoron environmental chamber, specially designed for calibration purposes, to verify theoretical data. In general, and notwithstanding a number of complicating factors, fair to good agreement has been found between theoretical and experimental data. Experimental values have been found to be lower than theoretical values, an observation which is partly ascribed to plate-out of decay products in the instrument's sampling heads.     

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.     

Dose-time-response functions for toxic chemicals

In many situations, the effect of a toxic chemical on a biological system depends on both the intensity and the duration of exposure. The dependence on the time dimension can be the expression of a range of processes including the physical accumulation of toxic chemicals or their metabolites and the functional accumulation of damage. Measures and functions that have been used to describe this dependence are reviewed.Some of these functions are compared through a case study of the neurotoxicity of methylmercury. Use is made of data that indicates a dependency between the blood concentration at which monkeys were exposed and the length of time before damage was detected. Several exposure functions are fitted to these data and their appropriateness is compared. Using the most appropriate function, an exposure-response relationship is developed using probit analysis. An alternative data analysis procedure is also investigated. The apparent threshold after a 100 day exposure is estimated to be greater by a factor of 3–5 compared to the threshold for chronic exposure. Applying this factor to man, the blood concentration threshold for chronic exposure is estimated to be 40–170 ppb, a finding consistent with recent reports of neurological damage in humans exposed below the generally accepted threshold.     

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.     

Integration of modeling,monitoring and laboratory observation to determine reasons for air quality violations

An attempt was made to explain ambient air quality violations in the vicinity of industrial plants. Micrometeorology, diffusion calculaations, ambient readings, and plant engineering data are all taken into consideration to ascertain whether the plant is or is not the principal offender.Scrutiny of hi-vol filters using scanning electron microscopy for particle size analysis and particle chemical make-up as an assessment technique is also described.Case histories using the above analytical techniques are discussed.Presented at the 16th National Conference on Energy and the Environment, May 23, 1979     

Determination of biomass burning emission factors: Methods and results

Biomass burning, in a broad sense, encompasses different burning practices, including open and confined burnings, and different types of vegetation. Emission factors of gaseous or particulate trace compounds are directly dependent both on the fuel type and the combustion process. Emission factors are generally calculated by stoichiometric considerations using the carbon mass balance method, applied either to combustion chamber experiments or to field experiments based on ground-level measurements or aircraft sampling in smoke plumes. There have been a number of experimental studies in the last 10 years to investigate wildfires in tropical, temperate, or boreal regions. This article presents an overview of measurement methods and experimental data on emission factors of reactive or radiatively active trace compounds, including trace gases and particles. It focuses on fires in tropical regions, that is, forest and savanna fires, agricultural burns, charcoal production, use of fuelwood, and charcoal combustion.