Emissions of polychlorinated dibenzo-p-dioxins and dibenzofurans from catalytic and thermal oxidizers burning dilute chlorinated vapors

Emissions of polychlorinated dibenzo-p-dioxins and dibenzofurans (dioxins) have been found from 57 field tests on the oxidation of low (a few to a few hundred) parts per million levels of chlorinated and non-chlorinated volatile organic compounds (VOCs). The oxidation occurs in catalytic oxidizers with platinum, platinum/palladium or chromium(IV) oxide combustion catalysts, or in thermal oxidizers (without a catalyst). The catalyst inlet temperatures ranged from 293 to 573 degrees C. The thermal oxidizer operating temperatures (post-flame) were from 773 to 927 degrees C. Data of the toxic dioxin and furan isomers are reported and also weighted and expressed as international toxic equivalents (TEQ) of 2,3,7,8-tetrachlorodibenzo-p-dioxin. The maximum stack emissions, 1.07 ng/m3 TEQ, occurred at 293 degrees C. Salient results of this field study are: (1) TEQ levels in the stack exponentially increase with a decrease in operating temperature, an empirical equation is TEQ (ng/dscm)=8.4 exp(-0.0084T degrees C); (2) dioxin/furan production occurs at the combustion catalyst; (3) small variations in temperature cause large changes in the congener distribution of the dioxin and furan isomers; (4) molar TEQ yields from the parent compounds fed to the oxidizers are very small (10(-9)-10(-13)); (5) catalytic and thermal oxidizers may destroy dioxins fed from the ambient air; and (6) the oxidation of chlorinated VOCs with non-chlorinated VOCs reduces emissions of dioxins, likely due to the consumption of Cl in producing HCl. Laboratory investigations are needed to understand how dioxins are formed (and emitted) under conditions of this study.     

Mechanistic and kinetic study on the ozonolysis of n-butyl vinyl ether, i-butyl vinyl ether and t-butyl vinyl ether

Density functional theory (DFT) and ab initio method are employed to elucidate the mechanisms for O(3)-initiated oxidation of n-butyl vinyl ether (n-BVE) and its isomers (i-BVE and t-BVE). For each BVE, the reactions proceed via O(3) cycloaddition resulting in the formation of primary ozonides (POZs) and then two self-decomposition pathways of POZs are followed. Major products are identified to be formaldehyde and butyl formates (CH(3)CH(2)CH(2)CH(2)OCHO for n-BVE, (CH(3))(2)CHCH(2)OCHO for i-BVE and (CH(3))(3)COCHO for t-BVE). The total and individual rate constants for main product channels have been calculated using the modified multichannel Rice-Ramsperger-Kassel-Marcus (RRKM) approach. At 298 K and 101 kPa, the calculated total rate constants are 2.50×10(-16), 3.41×10(-16) and 4.17×10(-16) cm(3) molecule(-1) s(-1) for n-BVE+O(3), i-BVE+O(3) and t-BVE+O(3), respectively, which are in perfect agreement with experimental results. The total rate coefficients are almost pressure independent in the range of 0.001-101 kPa but obviously positive temperature dependent over the whole study temperature range (200-400 K). Also, the favorable reaction pathways have been determined through the estimation of branching ratios. Moreover, the influence of alkoxy group structure on the reactivity of vinyl ethers was examined.     

Contents and sources of polycyclic aromatic hydrocarbons and organochlorine pesticides in vegetable soils of Guangzhou, China

We investigated contents, distribution and possible sources of PAHs and organochlorine pesticides (Ops) in 43 surface and subsurface soils around the urban Guangzhou where variable kinds of vegetables are grown. The results indicate that the contents of PAHs (16 US EPA priority PAHs) range from 42 to 3077 microg/kg and the pollution extent is classified as a moderate level in comparison with other investigations and soil quality standards. The ratios of methylphenanthrenes to phenanthrene(MP/P), anthracene to anthracene plus phenanthrene (An/178), benz[a]anthracene to benz[a]anthracene plus chrysene (BaA/228), indeno[1,2,3-cd]pyrene to indeno[1,2,3-cd]pyrene plus benzo[ghi]perylene (In/In+BP) suggest that the sources of PAHs in the soil samples are mixed with a dominant contribution from petroleum and combustion of fossil fuel. The correlation analysis shows that the PAHs contents are significantly related to total organic carbon contents (TOC) (R2=0.75) and black carbon contents (BC) (R2=0.62) in the soil samples. Dichlorodiphenyltrichloroethane and metabolites (DDTs) and hexachlorocyclohexanes and metabolites (HCHs) account largely for the contaminants of OPs. The concentrations of DDTs range from 3.58 to 831 microg/kg and the ratios for DDT/(DDD+DDE) are higher than 2 in some soil samples, suggesting that DDT contamination still exists and may be caused by its persistence in soils and/or impurity in the pesticide dicofol. The concentrations of HCHs are 0.19-42.3 microg/kg.     

Gain and loss rates and biological half-life of PCBs and DDE in the bodies of adelie penguins

The gain and loss rates and the biological half-life of polychlorinated biphenyls (PCBs) and p,p'-DDE in wild birds were calculated using the values on burdens of these compounds in the bodies of adelie penguins in a previous report (Subramanian et al., 1986). The daily loss rate of PCBs (0.26%) was found to be higher than DDT compounds (0.12%) resulting in the longer biological half-life of the latter compounds (580 days) than PCBs (270 days). Hence, once DDT compounds are absorbed they are more persistent in the organisms' bodies due to their high lipophilicity and comparatively less metabolisable nature than PCBs.     

Advances in integrated and continuous measurements for particle mass and chemical composition

Recent improvements in integrated and continuous PM2.5 mass and chemical measurements from the Supersite program and related studies in the past decade are summarized. Analytical capabilities of the measurement methods, including accuracy, precision, interferences, minimum detectable levels, comparability, and data completeness are documented. Upstream denuders followed by filter packs in integrated samplers allow an estimation of sampling artifacts. Efforts are needed to: (1) address positive and negative artifacts for organic carbon (OC), and (2) develop carbon standards to better separate organic versus elemental carbon (EC) under different temperature settings and analysis atmospheres. Advances in thermal desorption followed by gas chromatography/ mass spectrometry (GC/MS) provide organic speciation of approximately 130 nonpolar compounds (e.g., n-alkanes, alkenes, hopanes, steranes, and polycyclic aromatic hydrocarbons [PAHs]) using small portions of filters from existing integrated samples. Speciation of water-soluble OC (WSOC) using ion chromatography (IC)-based instruments can replace labor-intensive solvent extraction for many compounds used as source markers. Thermal gas-based continuous nitrate and sulfate measurements underestimate filter ions by 10-50% and require calibration against on-site filter-based measurements. IC-based instruments provide multiple ions and report comparable (+/-10%) results to filter-based measurements. Maintaining a greater than 80% data capture rate in continuous instruments is labor intensive and requires experienced operators. Several instruments quantify black carbon (BC) by optical or photoacoustic methods, or EC by thermal methods. A few instruments provide real-time OC, EC, and organic speciation. BC and EC concentrations from continuous instruments are highly correlated but the concentrations differ by a factor of two or more. Site- and season-specific mass absorption efficiencies are needed to convert light absorption to BC. Particle mass spectrometers, although semiquantitative, provide much information on particle size and composition related to formation, growth, and characteristics over short averaging times. Efforts are made to quantify mass by collocating with other particle sizing instruments. Common parameters should be identified and consistent approaches are needed to establish comparability among measurements.     

Hydroxylated and methoxylated polybrominated diphenyl ethers and polybrominated dibenzo-p-dioxins in red alga and cyanobacteria living in the Baltic Sea

Hydroxylated polybrominated diphenyl ethers (OH-PBDEs) and methoxylated polybrominated diphenyl ethers (MeO-PBDEs) are present in the ecosystem of the Baltic Sea. OH-PBDEs are known to be both natural products from marine environments and metabolites of the anthropogenic polybrominated diphenyl ethers (PBDEs), whereas, MeO-PBDEs appear to be solely natural in origin. Polybrominated dibenzo-p-dioxins (PBDDs) are by-products formed in connection with the combustion of brominated flame retardants (BFRs), but are also indicated as natural products in a red alga (Ceramium tenuicorne) and blue mussels living in the Baltic Sea. The aims of the present investigation were to quantify the OH-PBDEs and MeO-PBDEs present in C. tenuicorne; to verify the identities of PBDDs detected previously in this species of red alga and to investigate whether cyanobacteria living in this same region of the Baltic Sea contain OH-PBDEs, MeO-PBDEs and/or PBDDs. The red alga was confirmed to contain tribromodibenzo-p-dioxins (triBDDs), by accurate mass determination and additional PBDD congeners were also detected in this sample. This is the first time that PBDDs have been identified in a red alga. The SigmaOH-PBDEs and SigmaMeO-PBDEs concentrations, present in C. tenuicorne were 150 and 4.6 ng g(-1) dry weight, respectively. In the cyanobacteria 6 OH-PBDEs, 6 MeO-PBDEs and 4 PBDDs were detected by mass spectrometry (electron capture negative ionization (ECNI)). The PBDDs and OH-PBDEs and MeO-PBDEs detected in the red alga and cyanobacteria are most likely of natural origin.     

HPLC-MSn and GC-MS methods to study sunlight and UV-lamp degradations of 1-amino-5-naphthalene sulfonate

HPLC-DAD, HPLC-MS/MS, GC-MS and spectrophotometric methods are employed to investigate the degradation process of sodium 1-amino-5-naphthalene sulfonate (1A5NS) aqueous solutions, when exposed to sunlight and UV-lamp (254 nm) irradiations. Experimental results show that both sunlight and 254 nm UV-lamp irradiations destroy the chemical and give rise to major degradation products, characterised by the same m/z ratios. Degradation times are lower for sunlight irradiation, for which a t(1/2) value of 137.4 min has been evaluated, in comparison with the value of t(1/2) of 26.8 min, observed for UV-lamp irradiation. The degradation pathway and the structures of the degradation products are proposed.     

The exchange of ozone between vegetation and atmosphere: micrometeorological measurement techniques and models

The European critical levels (CLs) to protect vegetation are expressed as an accumulative exposure over a threshold of 40 ppb (nl l(-1)). In view of the fact that these chamber-derived CLs are based on ozone (O(3)) concentrations at the top of the canopy the correct application to ambient conditions presupposes the application of Soil-Vegetation-Atmosphere-Transfer (SVAT) models for quantifying trace gas exchange between phytosphere and atmosphere. Especially in the context of establishing control strategies based on flux-oriented dose-response relationships, O(3) flux measurements and O(3) exchange simulations are needed for representative ecosystems. During the last decades several micrometeorological methods for quantifying energy and trace gas exchange were developed, as well as models for the simulation of the exchange of trace gases between phytosphere and atmosphere near the ground. This paper is a synthesis of observational and modeling techniques which discusses measurement methods, assumptions, and limitations and current modeling approaches. Because stomatal resistance for trace gas exchange is parameterized as a function of water vapor or carbon dioxide (CO(2)) exchange, the most important micrometeorological techniques especially for quantifying O(3), water vapor and CO(2) flux densities are discussed. A comparison of simulated and measured O(3) flux densities shows good agreement in the mean.     

Particle fluxes above forests: observations, methodological considerations and method comparisons

This paper reports a study designed to test, evaluate and compare micro-meteorological methods for determining the particle number flux above forest canopies. Half-hour average particle number fluxes above a representative broad-leaved forest in Denmark derived using eddy covariance range from -7x10(7) m(-2) s(-1) (1st percentile) to 5x10(7) m(-2) s(-1) (99th percentile), and have a median value of -1.6x10(6) m(-2) s(-1). The statistical uncertainties associated with the particle number flux estimates are larger than those for momentum fluxes and imply that in this data set approximately half of the particle number fluxes are not statistically different to zero. Particle number fluxes from relaxed eddy accumulation (REA) and eddy covariance are highly correlated and of almost identical magnitude. Flux estimates from the co-spectral and dissipation methods are also correlated with those from eddy covariance but exhibit higher absolute magnitude of fluxes.     

Lidar Applications in Air Pollution Research and Control

The fundamental capabilities and limitations of the lidar (laser radar) in observing particulate concentrations in the atmosphere are discussed. The advantages of the lidar technique stem from its ability to obtain measurements remotely and at a high density in space and time. The quantitative application of the technique is limited by the accuracies with which: (1) the separate effects upon the return signal of back-scatter and attenuation may be identified; and (2) the optical parameters may be related to the characteristics of the aerosol. The main areas of utility for lidar in air pollution research and control are: (1) to observe the structure and height of mixing layers; (2) to measure the transport and diffusion of plumes or clouds of particulates; and (3) to remotely determine smoke-plume opacity. These applications are briefly reviewed and exemplified.     

Biodegradability assessment of several priority hazardous substances: choice, application and relevance regarding toxicity and bacterial activity

Nineteen compounds listed in the category of priority substances (PS) were selected for a biodegradation study using standardized tests. The compounds consist of pesticides, chlorinated solvents and volatile organic compounds (VOCs). In this paper, the choice of the most suitable method is discussed in relation to the physico-chemical properties of each substance. Zahn-Wellens, manometric respirometry and closed-bottle tests are alternatively used. Experimental results are presented and interpreted. Toxicity (Microtox) and bacterial viability (Bac-light) are also used as tools to investigate the influence of each substance on the microbial population (activated sludge). In addition, experimental values are compared with predictive data calculated according to quantitative structure activity relationships (QSARs) models. Biodeg Models were permitted to correctly estimate 17 substances; Survey Models and screening tests also revealed the same behavior for 16 target compounds.     

Determination of spatially-resolved porosity, tracer distributions and diffusion coefficients in porous media using MRI measurements and numerical simulations

This work is focused on measuring the concentration distribution of a conservative tracer in a homogeneous synthetic porous material and in heterogeneous natural sandstone using MRI techniques, and on the use of spatially resolved porosity data to define spatially variable diffusion coefficients in heterogeneous media. The measurements are made by employing SPRITE, a fast MRI method that yields quantitative, spatially-resolved tracer concentrations in porous media. Diffusion experiments involving the migration of H(2)O into D(2)O-saturated porous media are conducted. One-dimensional spatial distributions of H(2)O-tracer concentrations acquired from experiments with the homogeneous synthetic calcium silicate are fitted with the one-dimensional analytical solution of Fick's second law to confirm that the experimental method provides results that are consistent with expectations for Fickian diffusion in porous media. The MRI-measured concentration profiles match well with the solution for Fick's second law and provide a pore-water diffusion coefficient of 1.75×10(-9)m(2)s(-1). The experimental approach was then extended to evaluate diffusion in a heterogeneous natural sandstone in three dimensions. The relatively high hydraulic conductivity of the sandstone, and the contrast in fluid density between the H(2)O tracer and the D(2)O pore fluid, lead to solute transport by a combination of diffusion and density-driven advection. The MRI measurements of spatially distributed tracer concentration, combined with numerical simulations allow for the identification of the respective influences of advection and diffusion. The experimental data are interpreted with the aid of MIN3P-D - a multicomponent reactive transport code that includes the coupled processes of diffusion and density-driven advection. The model defines local diffusion coefficients as a function of spatially resolved porosity measurements. The D(e) values calculated for the heterogeneous sandstone and used to simulate diffusive and advective transport range from 5.4×10(-12) to 1.0×10(-10)m(2)s(-1). These methods have broad applicability to studies of contaminant migration in geological materials.     

Sublethal and environmentally relevant concentrations of triclosan and triclocarban induce histological,genotoxic, and embryotoxic effects in Clarias gariepinus (Burchell, 1822)

Environmental Science and Pollution Research - Antimicrobial additives in personal care products (PCPs) such as triclosan (TCS) and triclocarban (TCC) are of environmental concern due to their...     

Stabilization and solidification of elemental mercury for safe disposal and/or long-term storage

A simple and highly effective stabilization/solidification (S/S) technology of elemental mercury using only sulfur with paraffin is introduced. First, elemental mercury is mixed with an excess of sulfur powder and heated to 60 degrees C for 30 min until elemental mercury is converted into mercuric sulfide (HgS black, metacinnabar) (Step 1). Then, metacinnabar with additional sulfur is poured into liquid paraffin (Step 2). Finally, the mixture is melted at 140 degrees C and settles to the bottom of the vessel where it cools and solidifies under the layer of liquid paraffin (Step 3). The proposed S/S method with sodium sulfide nonahydrate (Na2S x 9H2O) as an additive is also tested for comparison. The average toxicity characteristic leaching procedure test values are 6.72 microg/L (no additive) and 3.18 microg/L (with additive). Theses concentrations are well below the Universal Treatment Standard (25 microg/L). Effective diffusion coefficient evaluated from accelerated leach test and average headspace concentration of Hg vapor after 18 hr are 3.62 x 10(-15) cm2/sec, 0.55 mg/m3 (no additive) and 5.86 x 10(-13) cm2/sec, 0.25 mg/m3 (with additive).     

New York State urban and rural measurements of continuous PM2.5 mass by FDMS, TEOM, and BAM

Field evaluations and comparisons of continuous fine particulate matter (PM2,5) mass measurement technologies at an urban and a rural site in New York state are performed. The continuous measurement technologies include the filter dynamics measurement system (FDMS) tapered element oscillating microbalance (TEOM) monitor, the stand-alone TEOM monitor (without the FDMS), and the beta attenuation monitor (BAM). These continuous measurement methods are also compared with 24-hr integrated filters collected and analyzed under the Federal Reference Method (FRM) protocol. The measurement sites are New York City (the borough of Queens) and Addison, a rural area of southwestern New York state. New York City data comparisons between the FDMS TEOM, BAM, and FRM are examined for bias and seasonality during a 2-yr period. Data comparisons for the FDMS TEOM and FRM from the Addison location are examined for the same 2-yr period. The BAM and FDMS measurements at Queens are highly correlated with each other and the FRM. The BAM and FDMS are very similar to each other in magnitude, and both are approximately 25% higher than the FRM filter measurements at this site. The FDMS at Addison measures approximately 9% more mass than the FRM. Mass reconstructions using the speciation trends network filter data are examined to provide insight as to the contribution of volatile species of PM2.5 in the FDMS mass measurement and the fraction that is likely lost in the FRM mass measurement. The reconstructed mass at Queens is systematically lower than the FDMS by approximately 10%.     

Levels and trends of brominated flame retardants in the Arctic

Polybrominated diphenyl ethers (PBDEs) containing two to seven bromines are ubiquitous in Arctic biotic and abiotic samples (from zooplankton to polar bears (Ursus maritimus) and humans; air, soil, sediments). The fully brominated decabromodiphenyl ether (BDE-209), hexabromocyclododecane (HBCD), tetrabromobisphenol A (TBBPA) and polybrominated biphenyls (PBBs) are also present in biotic and abiotic samples. Spatial trends of PBDEs and HBCD in top predators are similar to those seen for polychlorinated biphenyls (PCBs) and indicate western Europe and eastern North America as source regions. Concentrations of tetra- to heptaBDEs have increased significantly in North American and Greenlandic Arctic biota and in Greenland freshwater sediments paralleling trends seen further south. For BDE-209, increasing concentrations in Greenlandic peregrine falcons (Falco peregrinus) and in dated lake sediment cores in the Canadian Arctic have been seen during the 1990s. BDE-47, -99, -100 and -153 are observed to biomagnify in Arctic food webs. summation operatorPBDE concentrations in Arctic samples are lower than in similar sample types from more southerly regions and are one or more orders of magnitude lower than summation operatorPCB concentrations except for some levels for air. Air and harbor sediment results for PBDEs indicate that there are local sources near highly populated areas within the Arctic. Findings of PBBs on moss and TBBPA on an air filter, and that both are found in biota at high trophic levels indicates that these compounds may also reach the Arctic by long-range atmospheric transport. Based on the evidence of their presence in the Arctic and indications that most if not all are undergoing long-range transport, these brominated flame retardants (BFRs) have characteristics that qualify them as POPs according to the Stockholm Convention.     

The Southeastern Aerosol Research and Characterization Study, part 3: continuous measurements of fine particulate matter mass and composition

Deployment of continuous analyzers in the Southeastern Aerosol Research and Characterization Study (SEARCH) network began in 1998 and continues today as new technologies are developed. Measurement of fine particulate matter (PM2.5) mass is performed using a dried, 30 degrees C tapered element oscillating microbalance (TEOM). TEOM measurements are complemented by observations of light scattering by nephelometry. Measurements of major constituents include: (1) SO4(2-) via reduction to SO2; (2) NH4+ and NO3- via respective catalytic oxidation and reduction to NO, (3) black carbon (BC) by optical absorption, (4) total carbon by combustion to CO2, and (5) organic carbon by difference between the latter two measurements. Several illustrative examples of continuous data from the SEARCH network are presented. A distinctive composite annual average diurnal pattern is observed for PM2.5 mass, nitrate, and BC, likely indicating the influence of traffic-related emissions, growth, and break up of the boundary layer and formation of ammonium nitrate. Examination of PM2.5 components indicates the need to better understand the continuous composition of the unmeasured "other" category, because it contributes a significant fraction to total mass during periods of high PM2.5 loading. Selected episodes are presented to illustrate applications of SEARCH data. An SO2 conversion rate of 0.2%/hr is derived from an observation of a plume from a coal-fired power plant during early spring, and the importance of local, rural sources of NH3 to the formation of ammonium nitrate in particulate matter (PM) is demonstrated.     

Characterization of HCHs and DDTs in urban dustfall and prediction of soil burden in a metropolis-Beijing, China

The concentrations, spatial distribution and compositional patterns of extensively used hexachlorocyclohexanes (HCHs) and dichlorodiphenyltrichloroethanes (DDTs) in urban dustfall in a metropolis-Beijing are presented in this paper. The potential sources are discussed and soil burdens are predicted based on the fluxes. The hotspots in commercial areas are identified by spatial distribution maps and the fractional value isomers indicates that dustfall in urban Beijing are affected by both current and historical usage of DDTs. It is worth noticing that there is possible application "dicofol-type of DDTs" in Beijing. The measured atmospheric deposition flux is 1.14×10(5) ng h(-1) m(-2) for HCHs and 1.47×10(5) ng h(-1) m(-2) for DDTs, respectively. However, when compared with atmospheric deposition flux, the volatilization flux estimated from concentrations in soils by fugacity model is significantly lower for HCHs (2.41 ng h(-1) m(-2)) and DDTs (0.07 ng h(-1) m(-2)). The net atmospheric flux to the soil suggests that the levels of HCHs and DDTs in soil are dominated by atmospheric deposition and the urban soil in Beijing would be a sink for HCHs and DDTs in the long term.     

Atmospheric ozone: formation and effects on vegetation

Ozone (O(3)) is present both in the troposphere and the stratosphere. Troposphere O(3) is predominantly produced by photochemical reactions involving precursors generated by natural processes and to a much larger extent by man's activities. There is evidence for a trend towards increasing tropospheric O(3) concentrations. However, tropospheric O(3) is known to account for only 10% of the vertical O(3) column above the earth's surface. The stratosphere accounts for an additional 90% of the O(3) column. There is evidence to suggest that there are losses in the stratospheric O(3) due to the updraft of O(3) destroying pollutants generated by both natural processes and by human activity. Such a loss in stratospheric O(3) can result in alterations of incidence in the ultraviolet (UV) radiation to the earth's surface. Tropospheric O(3) is known to be highly phytotoxic. Appropriate exposures to O(3) can result in both acute (symptomatic) and chronic (changes in growth, yield or productivity and quality) effects. Chronic effects are of great concern in terms of both crops and forests. A number of experimental techniques are available to evaluate the chronic effects of O(3) on plants. There are limitations attached to the use of these techniques. However, results obtained, with such techniques are valuable if interpreted in the appropriate context. Among all field evaluation techniques, open-top chambers are the most frequently used method for evaluating the chronic effects of O(3) on crops. The National Crop Loss Assessment Program (NCLAN) of the United States is the largest such effort. However, given the limitations of the open-top chambers and the experimental aspects of NCLAN, its results must be interpreted with caution. On the other hand, acute effects can be evaluated with less complexity through the use of biological indicator plants. The numerical modelling of such effects are also far less complicated than establishing numerical cause and effects relationships for chronic effects. Confounding the acute or chronic responses of plants to O(3), is the presence of other kinds and forms of pollutants in the ambient atmosphere and the incidence of pathogens and pests. The resulting complex interactions and joint effects on plants are poorly understood. Future research must address these issues. In the final analysis we have re-emphasized the fact that plant health is the product of its interaction with the physical and chemical climatology and pathogens and pests. What we have described in this context is the importance of tropospheric O(3) within the chemical climatology of our environment and its effects on vegetation.     

Fingerprinting of High Boiling Hydrocarbon Fuels,Asphalts and Lubricants

Fingerprinting of hydrocarbon products requires high resolution differentiation of individual hydrocarbon compounds in any mixture. This requires the applications of various measuring techniques. In this paper, we have chosen the heavy hydrocarbons in fuels, lubricants and paving material as examples to discuss the methods for chemical characterization and differentiation. In the category most frequently termed "semi-volatile hydrocarbons" with boiling points from about 500°F to 1200°F or higher, there are several families of hydrocarbons, both natural and refined that are not easily distinguished by conventional EPA tests. Among the groups which we will use as examples are asphalts, hydraulic fluid, transmission oil, motor lubricating oils, heating oils, crude oil and coal. These hydrocarbon families are best studied using combined gas chromatography-mass spectrometry in full scan mode and characterizing various homologous series of hydrocarbons at known fragment ions. The hydrocarbon series providing the best information are: (1) N -alkanes; (2) iso-alkanes; (3) steranes; (4) terpanes; (5) polynuclear aromatic hydrocarbons; (6) aromatic steranes; and (7) specific polycyclic compounds.