Quantification of elemental and total carbon in combustion particulate matter using thermal-oxidative analysis

The use of a two-step thermal-oxidative analysis (TOA) technique for quantification of the mass of total carbon (TC) and elemental carbon (EC) of turbine engine-borne particulate matter (PM) has been evaluated. This approach could be used in lieu of analysis methods which were developed to characterize diluted PM. This effort is of particular interest as turbine engine PM emissions typically have a higher EC content than ambient aerosols, and filter sample mass loadings can be significantly greater than recommended for existing analysis techniques. Analyses were performed under a pure oxygen environment using a two-step temperature profile; reference carbon and actual PM samples were used to identify appropriate analysis conditions. Thermal gravimetric analysis (TGA) methods were used to provide guidance on the nature of the carbon in several of the materials. This was necessary as a standard reference material does not exist for determination of the EC fraction in PM. The TGA also assisted in identifying an appropriate temperature range for the first-stage of the TOA method. Quantification of TC and EC for turbine engine PM samples using TOA was compared to results obtained using the NIOSH 5040 thermal-optical method. For first-stage TOA temperatures of 350°C and 400°C, excellent agreement between the techniques was observed in both the quantified TC and EC, supporting the viability for using TOA for analysis of turbine engine PM samples. A primary benefit of using TOA for these types of PM samples is that filters with relatively high PM mass loadings (sampled at the emission source) can be readily analyzed. In addition, an entire filter sample can be evaluated, as compared to the use of a filter punch sample for the NIOSH technique. While the feasibility of using a TOA method for engine PM samples has been demonstrated, future studies to estimate potential OC charring and oxidation of EC-type material may provide additional data to assess its impact on the OC/EC fractions for other carbon-type measurements.

Implications: This work presents results and procedures of an analytical method for the determination of total and elemental carbon, i.e., TC and EC present in combustion source particulate matter samples. In general, it is shown that the LECO TOA methodology is as reliable and comprehensive as NIOSH 5040 for determining TC and EC carbon types in particulate matter present in turbine emission sources, and should be considered as an alternative. Principles of the methodology, differences, and corresponding agreement with the standard NIOSH 5040 method and TGA analysis are discussed.     

Energy comparison in three cases of pesticide versus bio-control pest management

The deletrious effects of chemical pesticides on many plant and animal populations have been described. Rapidly increasing costs of convenient energy sources have increased cost-benefit ratios of chemical pesticides used. We compared biological control techniques versus chemical pesticides for inputs of human labor, machinery, and fuel per hectare at each pertinent step of the production procedure. Three pest-crop systems were selected and all applicable factors converted into kilocalories of energy required. These were: (1) citrus-red scale (Aonidiella aurantii), using oil as a chemical and the predator wasp, Aphytis melinus as a biological control; (2) greenhouse cucumbers-white fly (Trialeurodes vaporariorum), using Orthene or the wasp, Encarsia formosa; (3) tomato-hornworm (Manduca quinquemaculata) using Sevin or the bacterium, Bacillus thurengiensis.For citrus-red scale, the pesticide required 5 248 405 kcal, the use of A. melinus 100 793 kcal; for cucumber-white fly the pesticide required 29 300 kcal, E. formosa 154 500 kcal; for tomato-hornworm the pesticide 26 693, B. thurengiensis 207 240 kcal.     

Size regulation in larvae of the crustacean Balanus eburneus (Cirripedia: Thoracica)

We tested the hypothesis that larval size in the acorn barnacle Balanus eburneus Gould (Cirripedia Thoracica) varies in relation to food availability. In March–November 1980, and March–July 1981, larvae were obtained from adult Balanus eburneus collected in the Newport River, North Carolina, USA. Carapace length and width of larvae reared at three different food concentrations were measured. Mean naupliar instar size was independent of food concentration. Mean size of the cypris instar increased with increasing food level. Greater cypris size could be attributed to increased food reserves in the preceding naupliar stage, and was coinciden with inmarked increase in metamorphic success. Variation in instar size remained constant or declined during naupliar development, but increased sharply at the molt to the cyprid. Naupliar size regulation involved: (1) conservation of a molt increment specific for each naupliar-naupliar molt, (2) an inverse relationship between premolt size and the molt increment during the first five naupliar instars, and (3) an increase in the precision of the molt increment at the molt to the sixth naupliar instar. Experimental evidence implies that size regulation in Balanus eburneus limits variation about a fixed final naupliar size (e.g. volume). Measurement of naupliar size, accumulated energy reserves, survival and development time, and cypris metamorphic success indicated that naupliar cuticular growth is the most conservative feature of larval development. The data suggest that maximum naupliar size is limited by escalating metabolic costs during development, while minimum naupliar size is limited by size-related feeding effectiveness.     

Multiplicity-adjusted Inferences in Risk Assessment: Benchmark Analysis with Continuous Response Data

We develop and study multiplicity adjustments for low-dose inferences in environmental risk assessment. Application is intended for risk analysis studies where human, animal, or ecological data are used to set safe levels of a hazardous environmental agent. A modern method for making inferences in this setting is known as benchmark analysis, where attention centers on the dose at which a fixed benchmark level of risk is achieved. Both upper confidence limits on the risk and lower confidence limits on the “benchmark dose” are of interest. In practice, a number of possible benchmark risks may be under study; if so, corrections must be applied to adjust the limits for multiplicity. In this note, we discuss approaches for doing so with continuous, nonquantal response data.     

Aerobic biodegradation of dichloroethylenes in surface and subsurface soils

Laboratory studies were conducted to examine the aerobic biodegradation of dichloroethylenes (cis-1,2-DCE, trans-1,2-DCE and 1,1-DCE) in soil and groundwater. Authentic surface and subsurface materials with no reported DCE exposure history were used. All DCE isomers were observed to biodegrade to varying degrees in the soils examined. Use of radiolabeled [14C] test chemicals allowed correlation of DCE disappearance with mineralization to 14CO2. Study results indicate that naturally occurring microorganisms in soil and groundwater are capable of degrading cis-1,2-, trans-1,2- and 1,1-DCE without laboratory supplementation of exogenous organic nutrients, or previous exposure history. The data further suggest that degradative potential may vary with soil type, DCE isomer structure, and concentration.     

A carbon-13 method for evaluating degradation of starch-based polymers

A new method for evaluating biodegradability of starch-based and certain other polymer blends uses the pre- and postexposure stable carbon isotope composition of material coupled with weight loss data to determine which components have degraded. The naturally occurring stable isotope of carbon.¹³C, is enriched in corn starch (¹³C, approx. –11) compared to petroleum-derived synthetic polymers (¹³C, approx. –32). Results on starch-synthetic polymer blends indicate that the ¹³C signatures of these blends are near-linear mixtures of their component ¹³C. Values of a ¹³C for starch-synthetic polymer blends exposed to biologically active laboratory soil and artificial seawater conditions are depleted in¹³C compared to unexposed samples, suggesting loss of the starch component. Combined with weight loss data for the exposed samples, the ¹³C values are statistically consistent with models requiring loss of the soluble component glycerin, followed by loss of starch, then petrochemical polymer, or simultaneous loss of starch and petrochemical polymer. Replicate ¹³C analyses of starch-synthetic polymer blends increase the statistical power of this relatively inexpensive, accessible technique to discriminate between degrading components.     

Determination of Endosulfans in Soil/Sediment Samples from Point Mugu, Oxnard, California Using Capillary Gas Chromatography/Mass Selective Detection (GC/MSD)

The extent of contamination by endosulfans in soil samples collected from the Point Mugu watershed near Oxnard, California was determined using capillary gas chromatography/mass selective detection (GC/MSD). The study was designed to detect three organochlorinated pesticides: endosulfan , endosulfan and endosulfan sulfate. Thirteen sets of two soil samples each were taken from various sites in the region. Our results show that the endosulfan levels in these soils range from trace amounts to nearly 30 ppm, with endosulfan being the most abundant and endosulfan sulfate the least. Two sites of the study, Hueneme and Revolon and Farm and Revolon, showed high amounts of endosulfans and , with concentrations between 20 and 30 ppm. The majority of the other sites studied in this research produced concentrations of less than 10 ppm for each of the three endosulfans monitored. At five areas in particular, Pleasant Valley and Creek, Laguna and Creek, Etting and Creek, Road and Creek and Hueneme and Creek, less than 2 ppm or only trace amounts of endosulfans , and sulfate were detected.     

Elemental and spectroscopic characterization of fractions of an acidic extract of oil sands process water

‘Naphthenic acids’ (NAs) in petroleum produced water and oil sands process water (OSPW), have been implicated in toxicological effects. However, many are not well characterized. A method for fractionation of NAs of an OSPW was used herein and a multi-method characterization of the fractions conducted.     

Monocyclic and monoaromatic naphthenic acids: synthesis and characterisation

Characterisation of the complex mixtures of carboxylic acids (naphthenic acids) occurring in crude oils and in degraded oil sands is environmentally important. Indeed some acids in waters from oil platforms are apparently hormonally active, and the oil sands acids are said to be toxic to a wide range of biota. Previous attempts to identify monocyclic and monoaromatic naphthenic acids have been hampered by the lack of authenticated synthetic reference compounds. Some studies have indicated that acids with ethanoic acid side chains are present in the naphthenic acids mixtures, so in the present study, we synthesised and characterised by mass spectrometry, a range (C_8–14) of monoaromatic and monocyclic ethanoic acids. Using 2-D comprehensive gas chromatography–mass spectrometry, we then compared the retention times and mass spectra of the synthetic acids with those of a commercial naphthenic acids mixture. Some alicyclic and numerous aromatic acids were successfully identified.