Kinetics of simazine advanced oxidation in water

Comparison of the effects and kinetics of UV photolysis and four advanced oxidation systems (ozone, ozone/hydrogen peroxide, ozone/UV radiation and UV radiation/hydrogen peroxide) for the removal of simazine from water has been investigated. At the conditions applied, the order of reactivity was ozone < ozone/hydrogen peroxide < UV radiation < ozone/UV radiation and UV radiation/hydrogen peroxide. Rate constants of the reactions between ozone and simazine and hydroxyl radical and simazine were found to be 8.7 M-1s-1 and 2.1 x 10(9) M-1s-1, respectively. Also, a quantum yield of 0.06 mol.photon-1 was found for simazine at 254 nm UV radiation. The high value of the quantum yield corroborated the importance of the direct photolysis process. Percentage contributions of direct reaction with ozone, reaction with hydroxyl radicals and direct photolysis were also quantified.     

Potential antitermite compounds from Juniperus procera extracts

Thin layer chromatography (TLC) analysis revealed that destructive distillation of Juniperus procera tree gave ten major components, whereas Croton megalocarpus tree yielded five components. This was confirmed by gas chromatography (GC). The components were isolated by column chromatography and analysed using infrared, ultra-violet, visible and mass spectroscopy (MS) techniques. The whole extract was about 30.3% of the starting material (sawdust) and consisted of 77.5% water and 22.5% oily reddish-brown layer. The extracts had alcoholic and phenolic compounds together with acids. Cedrol, a tertiary tricyclic alcohol, was found to be in the greatest proportion in the oily layer. IR spectra with a peak beyond 3000 cm(-1), UV-VIS absorption maxima at 230 nm and mass spectra with m/e 204 suggested the presence of cedrene in the extract.     

Degradation of ethinyl estradiol by nitrifying activated sludge

Degradation of ethinyl estradiol (EE2) by nitrifying activated sludge was studied with micro-organisms grown in a reactor with feedback of sludge fed with only a mineral salts medium containing ammonium as the sole energy source. Ammonium was oxidised by this sludge at a rate of 50 mg NH4+ g(-1) DW h(-1). This activated sludge was also capable of degrading EE2 at a maximum rate of 1 microg g(-1) DW h(-1). Using sludge with an insignificant nitrifying capacity of 1 mg NH4+ g(-1) DW h(-1), no degradation of EE2 was detected. Oxidation of EE2 by nitrifying sludge resulted in the formation of hydrophilic compounds, which were not further identified. Most probably degradation by nitrifying sludge results in a loss of estrogenic activity, as hydroxylated derivatives of EE2 are known to have a substantially lower pharmacological activity than EE2.     

What is the potential measurement error in occupational exposure studies?

This paper demonstrates statistical methods that estimate measurement error from available industrial hygiene data. Errors in measuring a continuous exposure variable may arise when all individuals in a work area are assigned the same exposure. An example is when the mean of exposure measurements obtained on a sample of individuals is assigned to all workers with similar jobs. This may lead to inaccurate point and interval estimates in exposure-response modeling. A method of simulating the distribution of true (i.e., unobserved) individual exposures is described in order to estimate the mean and variance of measurement error. The minimum variance unbiased estimator approximates the mean of lognormally distributed exposure measurements. The distribution of true individual exposures is approximated by the distribution of simulated estimates of mean exposure. The methodology is illustrated by exposure data from work areas manufacturing refractory ceramic fiber (RCF) and RCF products. Results show that exposure is slightly underestimated in work areas with between 25 and 113 exposure measurements; measurement error variance averages about 1.3% of the total variance.     

Systematic biases in measured PM10 values with U.S. Environmental Protection Agency-approved samplers at Owens Lake, California

From 1993 through 1998, Wedding or Graseby high-volume PM10 samplers were collocated with tapered element oscillating microbalance (TEOM) samplers at three sites at Owens Lake, CA. The study area is heavily impacted by windblown dust from the dry Owens Lake bed, which was exposed as a result of water diversions to the city of Los Angeles. A dichotomous (dichot) sampler and three collocated Partisol samplers were added in 1995 and 1999, respectively. U.S. Environmental Protection Agency (EPA) operating procedures were followed for all samplers, except for a Wedding sampler that was not cleaned for the purpose of this study. On average, the TEOM and Partisol samplers agreed to within 6%, and the dichot, Graseby, and Wedding samplers measured lower PM10 concentrations by about 10, 25, and 35%, respectively. Surprisingly, the "clean" Wedding sampler consistently measured the same concentration as the "dirty" Wedding sampler through 85 runs without cleaning. The finding that the Graseby and Wedding high-volume PM10 samplers read consistently lower than the TEOM, Partisol, and dichot samplers at Owens Lake is consistent with PM10 sampler comparisons done in other fugitive dust areas, and with wind tunnel tests showing that sampler cut points can be significantly lower than 10 microns under certain conditions. However, these results are opposite of the bias found for TEOM samplers in areas that have significant amounts of volatile particles, where the TEOM reads low due to the vaporization of particles on the TEOM's heated filter. Coarse particles like fugitive dust are relatively unaffected by the filter temperature. This study shows that in the absence of volatile particles and in the presence of fugitive dust, a different systematic bias of up to 35% exists between samplers using dichot inlets and high-volume samplers, which may cause the Graseby and Wedding PM10 samplers to undermeasure PM10 by up to 35% when the PM10 is predominantly from coarse particulate sources.     

An alternative supercritical fluid extraction system for aqueous matrices and its application in pesticides residue analysis

Supercritical fluid extraction (SFE) is a rapid and convenient method for the isolation of organic compounds from environmental samples. This paper describes a supercritical carbon dioxide (CO2) extraction system that uses a newly designed extraction cell to recover organic compounds from an aqueous matrix. Analysis of the extracts by gas chromatography-electron capture detector (GC-ECD) indicated that the herbicide trifluralin (2,6-dinitro-N,N-dipropyl-4-trifluoromethylaniline) could be quantitatively extracted by using the SFE system proposed with small amounts of sample. The percentage of recovery obtained with the SFE system described was twice as high as the result obtained using a conventional solid-phase extraction technique. Extraction by SFE was completed in a short period of time using a simple and low-cost home-made system that did not require the use of organic solvents.     

Development of a sample equilibration system for the TEOM continuous PM monitor

In recent years, scientific discussion has included the influence of thermodynamic conditions (e.g., temperature, relative humidity, and filter face velocity) on PM retention efficiency of filter-based samplers and monitors. Method-associated thermodynamic conditions can, in some instances, dramatically influence the presence of particle-bound water and other light-molecular-weight chemical components such as particulate nitrates and certain organic compounds. The measurement of fine particle mass presents a new challenge for all PM measurement methods, since a relatively greater fraction of the mass is semi-volatile. The tapered element oscillating microbalance (TEOM) continuous PM monitor is a U.S. Environmental Protection Agency (EPA) PM10 equivalent method (EQPM-1090079). Several hundred of these monitors are deployed throughout the United States. The TEOM monitor has the unique characteristic of providing direct PM mass measurement without the calibration uncertainty inherent in mass surrogate methods. In addition, it provides high-precision, near-real-time continuous data automatically. Much attention has been given to semi-volatile species retention of the TEOM method.     

The Aerosol Research and Inhalation Epidemiology Study (ARIES): PM2.5 mass and aerosol component concentrations and sampler intercomparisons

The Aerosol Research and Inhalation Epidemiology Study (ARIES) was designed to provide high-quality measurements of PM2.5, its components, and co-varying pollutants for an air pollution epidemiology study in Atlanta, GA. Air pollution epidemiology studies have typically relied on available data on particle mass often collected using filter-based methods. Filter-based PM2.5 sampling is susceptible to both positive and negative errors in the measurement of aerosol mass and particle-phase component concentrations in the undisturbed atmosphere. These biases are introduced by collection of gas-phase aerosol components on the filter media or by volatilization of particle phase components from collected particles. As part of the ARIES, we collected daily 24-hr PM2.5 mass and speciation samples and continuous PM2.5 data at a mixed residential-light industrial site in Atlanta. These data facilitate analysis of the effects of a wide variety of factors on sampler performance. We assess the relative importance of PM2.5 components and consider associations and potential mechanistic linkages of PM2.5 mass concentrations with several PM2.5 components. For the 12 months of validated data collected to date (August 1, 1998-July 31, 1999), the monthly average Federal Reference Method (FRM) PM2.5 mass always exceeded the proposed annual average standard (12-month average = 20.3 +/- 9.5 micrograms/m3). The particulate SO4(2-) fraction (as (NH4)2SO4) was largest in the summer and exceeded 50% of the FRM mass. The contribution of (NH4)2SO4 to FRM PM2.5 mass dropped to less than 30% in winter. Particulate NO3- collected on a denuded nylon filter averaged 1.1 +/- 0.9 micrograms/m3. Particle-phase organic compounds (as organic carbon x 1.4) measured on a denuded quartz filter sampler averaged 6.4 +/- 3.1 micrograms/m3 (32% of FRM PM2.5 mass) with less seasonal variability than SO4(2-).     

Combustion aerosols: factors governing their size and composition and implications to human health

Particulate matter (PM) emissions from stationary combustion sources burning coal, fuel oil, biomass, and waste, and PM from internal combustion (IC) engines burning gasoline and diesel, are a significant source of primary particles smaller than 2.5 microns (PM2.5) in urban areas. Combustion-generated particles are generally smaller than geologically produced dust and have unique chemical composition and morphology. The fundamental processes affecting formation of combustion PM and the emission characteristics of important applications are reviewed. Particles containing transition metals, ultrafine particles, and soot are emphasized because these types of particles have been studied extensively, and their emissions are controlled by the fuel composition and the oxidant-temperature-mixing history from the flame to the stack. There is a need for better integration of the combustion, air pollution control, atmospheric chemistry, and inhalation health research communities. Epidemiology has demonstrated that susceptible individuals are being harmed by ambient PM. Particle surface area, number of ultrafine particles, bioavailable transition metals, polycyclic aromatic hydrocarbons (PAH), and other particle-bound organic compounds are suspected to be more important than particle mass in determining the effects of air pollution. Time- and size-resolved PM measurements are needed for testing mechanistic toxicological hypotheses, for characterizing the relationship between combustion operating conditions and transient emissions, and for source apportionment studies to develop air quality plans. Citations are provided to more specialized reviews, and the concluding comments make suggestions for further research.     

Heavy metals in urban soils of East St. Louis, IL. Part II: Leaching characteristics and modeling

The city of East St. Louis, IL, has a history of abundant industrial activities including smelters of ferrous and non-ferrous metals, a coal-fired power plant, companies that produced organic and inorganic chemicals, and petroleum refineries. Following a gross assessment of heavy metals in the community soils (see Part I of this two-part series), leaching tests were performed on specific soils to elucidate heavy metal-associated mineral fractions and general leachability. Leaching experiments, including the Toxicity Characteristic Leaching Procedure (TLCP) and column tests, and sequential extractions, illustrated the low leachability of metals in East St. Louis soils. The column leachate results were modeled using a formulation developed for fly ash leaching. The importance of instantaneous dissolution was evident from the model. By incorporating desorption/adsorption terms into the source term, the model was adapted very well to the time-dependent heavy metal leachate concentrations. The results demonstrate the utility of a simple model to describe heavy metal leaching from contaminated soils.