• Title/Summary/Keyword: Chlorinated Hydrocarbons

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Thermal Degradation Characteristics of Carbon Tetrachloride in Excess Hydrogen Atmosphere (과잉수소 반응조건하에서 사염화탄소의 고온 분해반응 특성 연구)

  • Won, Yang-Soo;Jun, Kwan-Soo;Choi, Seong-Pil
    • Journal of Environmental Science International
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    • v.5 no.5
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    • pp.569-577
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    • 1996
  • pure compound chloromethanes; methyl chloride, methylene chloride, chloroform and The carbon tetrachloride were used as a model of chlorocarbon system with Cl/H ratio to investigate thermal stability and hydrodechlorination process of carbon tetrachloride under excess hydrogen atmosphere. The parent thermal stability on basis of temperature required for 99% destruction at 1 second no was evaluated as $875^{\circ}C$ for $CH_3Cl$, $780^{\circ}C$ for $CH_2Cl_2$, $675^{\circ}C$ for $CHCl_3$ and $635^{\circ}C$ for $CCl_4$. Chloroform was thermally less stable than $CCl_4$ at fairly low temperatures $(<570^{\circ}C).$ The lion of $CCl_4$ became more sensitive to increasing temperature, and $CCl_4$ was degraded CHCl3 at above $570^{\circ}C.$ The number and quantity of chlorinated products decreases with increasing temperature for the Product distribution of $CCl_4$ decomposition reaction system. Formation of non-chlorinated hydrocarbons such as $CH_4$, $C_2H_4$ and C_2H_6$ increased as the temperature rise and particularly small amount of methyl chloride was observed above $850^{\circ}C$ in $CC1_4$/$H_2$ reaction system. The less chlorinated products are more stable, with methyl chloride the most stable chlorocarbon in this reaction system.

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Development and Application of an In Situ Technology to Treat Various Soil and Groundwater Contaminants

  • Goltz, Mark N.
    • Proceedings of the Korean Society of Soil and Groundwater Environment Conference
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    • 2003.10a
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    • pp.89-110
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    • 2003
  • The limitations of conventional soil and groundwater contamination remediation technologies have motivated a search for innovative technologies; particularly in situ technologies that do not require extraction of contaminants from the subsurface. All engineered in situ remediation systems require that the contaminant be mixed with a remedial compound. Horizontal flow treatment wells (HFTWs), an innovative technology that consists of a pair of dual-screened treatment wells, were used at a trichloroethylene (TCE) contaminated site to efficiently achieve this mixing of contaminant and remedial compound in order to effect in situ bioremediation (McCarty et al., 1998). In this paper, the potential of HFTWs to treat chlorinated aliphatic hydrocarbons (CAHs) as well as other soil and groundwater contaminants of concern, such as nitroaromatic compounds (NACs), perchlorate, and methyl-tert-butyl ether (MTBE), is examined. Through a combination of laboratory studies, model analyses, and field evaluations, the effectiveness of this innovative technology to manage these contaminants is investigated.

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Insecticide Targets: Learning to Keep Up with Resistance and Changing Concepts of Safety

  • Casida, John E.;Quistad, Gary B.
    • Journal of Applied Biological Chemistry
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    • v.43 no.4
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    • pp.185-191
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    • 2000
  • Pest insect control is dependent on about 200 insecticides that work by relatively few mechanisms. The targets they disrupt are mostly involved in the nervous system, respiratory chain, growth and development, or the gut. The major nerve targets are: acetylcholinesterase for the organophosphates and methylcarbamates; the nicotinic acetylcholine receptor for the neonicotinoids; the $\gamma$-aminobutyric acid receptor for several chlorinated hydrocarbons and fipronil; the voltage-gated sodium channel for DDT and pyrethroids. Selection of resistant strains often confers cross-resistance to some or all other insecticides working at the same site. The toxicological properties of different compounds acting on the same target are increasingly considered together, summating the risk even though the compounds are of quite diverse chemical types. Continuing attention is also being given to secondary targets not involved in the primary mechanism of toxicity but instead in side effects that must be considered in the overall safety evaluation. Research on insecticide targets is important in learning to keep up with resistance and changing concepts and policies on safety. These relationships are illustrated by recent studies in the Environmental Chemistry and Toxicology Laboratory of the University of California at Berkeley.

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Field Studios of In-situ Aerobic Cometabolism of Chlorinated Aliphatic Hydrocarbons

  • Semprini, Lewts
    • Proceedings of the Korean Society of Soil and Groundwater Environment Conference
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    • 2004.04a
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    • pp.3-4
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    • 2004
  • Results will be presented from two field studies that evaluated the in-situ treatment of chlorinated aliphatic hydrocarbons (CAHs) using aerobic cometabolism. In the first study, a cometabolic air sparging (CAS) demonstration was conducted at McClellan Air Force Base (AFB), California, to treat chlorinated aliphatic hydrocarbons (CAHs) in groundwater using propane as the cometabolic substrate. A propane-biostimulated zone was sparged with a propane/air mixture and a control zone was sparged with air alone. Propane-utilizers were effectively stimulated in the saturated zone with repeated intermediate sparging of propane and air. Propane delivery, however, was not uniform, with propane mainly observed in down-gradient observation wells. Trichloroethene (TCE), cis-1, 2-dichloroethene (c-DCE), and dissolved oxygen (DO) concentration levels decreased in proportion with propane usage, with c-DCE decreasing more rapidly than TCE. The more rapid removal of c-DCE indicated biotransformation and not just physical removal by stripping. Propane utilization rates and rates of CAH removal slowed after three to four months of repeated propane additions, which coincided with tile depletion of nitrogen (as nitrate). Ammonia was then added to the propane/air mixture as a nitrogen source. After a six-month period between propane additions, rapid propane-utilization was observed. Nitrate was present due to groundwater flow into the treatment zone and/or by the oxidation of tile previously injected ammonia. In the propane-stimulated zone, c-DCE concentrations decreased below tile detection limit (1 $\mu$g/L), and TCE concentrations ranged from less than 5 $\mu$g/L to 30 $\mu$g/L, representing removals of 90 to 97%. In the air sparged control zone, TCE was removed at only two monitoring locations nearest the sparge-well, to concentrations of 15 $\mu$g/L and 60 $\mu$g/L. The responses indicate that stripping as well as biological treatment were responsible for the removal of contaminants in the biostimulated zone, with biostimulation enhancing removals to lower contaminant levels. As part of that study bacterial population shifts that occurred in the groundwater during CAS and air sparging control were evaluated by length heterogeneity polymerase chain reaction (LH-PCR) fragment analysis. The results showed that an organism(5) that had a fragment size of 385 base pairs (385 bp) was positively correlated with propane removal rates. The 385 bp fragment consisted of up to 83% of the total fragments in the analysis when propane removal rates peaked. A 16S rRNA clone library made from the bacteria sampled in propane sparged groundwater included clones of a TM7 division bacterium that had a 385bp LH-PCR fragment; no other bacterial species with this fragment size were detected. Both propane removal rates and the 385bp LH-PCR fragment decreased as nitrate levels in the groundwater decreased. In the second study the potential for bioaugmentation of a butane culture was evaluated in a series of field tests conducted at the Moffett Field Air Station in California. A butane-utilizing mixed culture that was effective in transforming 1, 1-dichloroethene (1, 1-DCE), 1, 1, 1-trichloroethane (1, 1, 1-TCA), and 1, 1-dichloroethane (1, 1-DCA) was added to the saturated zone at the test site. This mixture of contaminants was evaluated since they are often present as together as the result of 1, 1, 1-TCA contamination and the abiotic and biotic transformation of 1, 1, 1-TCA to 1, 1-DCE and 1, 1-DCA. Model simulations were performed prior to the initiation of the field study. The simulations were performed with a transport code that included processes for in-situ cometabolism, including microbial growth and decay, substrate and oxygen utilization, and the cometabolism of dual contaminants (1, 1-DCE and 1, 1, 1-TCA). Based on the results of detailed kinetic studies with the culture, cometabolic transformation kinetics were incorporated that butane mixed-inhibition on 1, 1-DCE and 1, 1, 1-TCA transformation, and competitive inhibition of 1, 1-DCE and 1, 1, 1-TCA on butane utilization. A transformation capacity term was also included in the model formation that results in cell loss due to contaminant transformation. Parameters for the model simulations were determined independently in kinetic studies with the butane-utilizing culture and through batch microcosm tests with groundwater and aquifer solids from the field test zone with the butane-utilizing culture added. In microcosm tests, the model simulated well the repetitive utilization of butane and cometabolism of 1.1, 1-TCA and 1, 1-DCE, as well as the transformation of 1, 1-DCE as it was repeatedly transformed at increased aqueous concentrations. Model simulations were then performed under the transport conditions of the field test to explore the effects of the bioaugmentation dose and the response of the system to tile biostimulation with alternating pulses of dissolved butane and oxygen in the presence of 1, 1-DCE (50 $\mu$g/L) and 1, 1, 1-TCA (250 $\mu$g/L). A uniform aquifer bioaugmentation dose of 0.5 mg/L of cells resulted in complete utilization of the butane 2-meters downgradient of the injection well within 200-hrs of bioaugmentation and butane addition. 1, 1-DCE was much more rapidly transformed than 1, 1, 1-TCA, and efficient 1, 1, 1-TCA removal occurred only after 1, 1-DCE and butane were decreased in concentration. The simulations demonstrated the strong inhibition of both 1, 1-DCE and butane on 1, 1, 1-TCA transformation, and the more rapid 1, 1-DCE transformation kinetics. Results of tile field demonstration indicated that bioaugmentation was successfully implemented; however it was difficult to maintain effective treatment for long periods of time (50 days or more). The demonstration showed that the bioaugmented experimental leg effectively transformed 1, 1-DCE and 1, 1-DCA, and was somewhat effective in transforming 1, 1, 1-TCA. The indigenous experimental leg treated in the same way as the bioaugmented leg was much less effective in treating the contaminant mixture. The best operating performance was achieved in the bioaugmented leg with about over 90%, 80%, 60 % removal for 1, 1-DCE, 1, 1-DCA, and 1, 1, 1-TCA, respectively. Molecular methods were used to track and enumerate the bioaugmented culture in the test zone. Real Time PCR analysis was used to on enumerate the bioaugmented culture. The results show higher numbers of the bioaugmented microorganisms were present in the treatment zone groundwater when the contaminants were being effective transformed. A decrease in these numbers was associated with a reduction in treatment performance. The results of the field tests indicated that although bioaugmentation can be successfully implemented, competition for the growth substrate (butane) by the indigenous microorganisms likely lead to the decrease in long-term performance.

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Distribution of Persistent Organic Pollutants (POPs) in Different Sizes of Particles in the Ambient Air of the Pyeongteak Area (평택지역 대기 중 먼지 입경별 잔류성유기오염물질 분포특성 연구)

  • Kim, Dong-Gi;Woo, Jung-Sik;Kim, Yong-Jun;Jung, Hye-Eun;Park, Ju-Eun;Cho, Duck-Hee;Moon, Hee-Chun;Oh, Jo-Gyo
    • Journal of Environmental Health Sciences
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    • v.46 no.2
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    • pp.192-203
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    • 2020
  • Objectives: The concentration distributions of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), dioxin-like polychlorinated biphenlys (dl-PCBs), and polycyclic aromatic hydrocarbons (PAHs) in fine particles were investigated to provide basic data on POP behavior and composition analysis. Methods: The concentrations of PCDD/Fs, dl-PCBs, and PAHs by particle size were evaluated for TSP, PM10, and PM2.5. Also, fine dust component analysis and factor analysis were performed to identify the source of PCDD/Fs. Results: The particle size distribution was found to account for 24.3% of >10 ㎛, 14.5% of 2.5-10 ㎛, and 61.2% of <2.5 ㎛. The average contributions of coarse particles (>2.5 ㎛) and fine particles (<2.5 ㎛) were PCDD/Fs 67%, dl-PCBs 66%, benzo (a) pyrene 83% and PAHs 84%, and the contributions of fine particles (<2.5 ㎛) were higher than coarse particles (>2.5 ㎛). However, the contributions of coarse particles increased in April to September with higher temperatures, while those of fine particles increased in February to March with lower temperatures. Conclusions: Low chlorinated (4Cl-5Cl) PCDD/Fs were more adsorbed compared to coarse particles due to the influence of pollutant migration from particulate to gas phase according to temperature rise, whereas high chlorinated (6Cl-8Cl) PCDD/Fs were more adsorbed compared to fine particles. PCDD/Fs sources were assessed to be major sources of emissions, such as incineration facilities and/or open burning.

Structure-dependent Mechanism of Action of Poly Aromatic Hydrocarbons in Cultured Primary Hepatocytes (간세포에서 PAH의 구조 의존적 작용기전)

  • Kim Sun-Young;Hong Sung-Bum;Yang Jae-Ho
    • Toxicological Research
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    • v.22 no.1
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    • pp.23-30
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    • 2006
  • Among poly aromatic hydrocarbons, dioxin and PCBs are the most controversial environmental pollutants in our modern life. These pollutants are known as human carcinogens, and liver is the most sensitive target in animal cancer models. Specific aims of the study were focused on the mechanism of carcinogenesis in hepatocytes and the structure-activity relation among these diverse environmental chemicals. Because key mechanisms of dioxin-induced carcinogenesis in human epithelial cell model are the alteration of signal transduction pathway and PKC isoforms, the alteration of the signal transduction pathways and other factors associated with carcinogenesis were studied. Rat hepatocytes cultured under the sandwich protocols were exposed with the various concentration of dioxins and PCBs, and signal transduction pathway, protein kinase C isoforms, oxidant stress, and apoptotic nuclei were evaluated. Since it is important to understand the structure-activity relation among these chemicals to properly assess the carcinogenic potentials, the study analyzed the parameters associated with carcinogenic processes, based on their structural characteristics. In addition, signal transduction pathways and PKC isoforms involved in inhibition of UV-induced apoptosis were also analyzed to elaborate the tumor promotion mechanism of these chemicals. Induction of apoptosis by UV irradiation was optimal at $60\;J/m^2$ in primary hepatocyte in culture. Compared to non coplanar PCBs such as PCB 114 and PCB 153, coplanar PCBs such as PCB 77 and PCB126 showed a stronger inhibition of apoptosis induced by UV irradiation. Production of reactive oxygen species (ROS) was more stimulated by non-coplanar PCBs than coplanar PCBs with the most potent induction of ROS by chlorinated non-coplanar PCB. As compared to the level of induction by PCB126, non-coplanar PCB153 showed a higher increase of intracellular concentrations. Besides the alteration of intracellular calcium concentration, translocation of PKC from cytosolic fraction to membrane fraction was clearly observed upon the exposure of non-coplanar PCB. Taken together, the present study demonstrated that there is a potent structure-activity relationship among PCB congeners and the mechanism of PAH-induced carcinogenesis is structure-specific. The study suggested that more diverse pathways of PAH-induced carcinogenesis should be taken into account beyond the boundary of Ah receptor dogma to assess the health impact of PAH with more accuracy.

Prediction of $EC_{50}$ of Photobacterium phosphoreum for CAHs and Chlorophenol Derivatives Using QSAR (QSAR방법을 이용한 CAHs와 Chlorophenol 유도체에 대한 $EC_{50}$값 예측)

  • Lee, Hong-Joo;Yoo, Seung-O;Lee, Jeong-Gun;Kim, Byung-Yong;Chun, Uck-Han
    • Microbiology and Biotechnology Letters
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    • v.27 no.1
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    • pp.54-61
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    • 1999
  • Measurement of inhibition of bioluminescence in Photobacterium phosphoreum has been porposed as a sensitive and rapid procedure to monitor toxic substances. However, at first, $EC_{50}$ which shows degree of toxicity to each toxic substances must be calculated. QSAR (Quantitative Structure Activity Relationship) model can be used to estimate $EC_{50}$ to save time and endeavor. Moderately high correlation coefficients ($r^2{\geq}$ 0.97) were calculated from the linear correlation between $EC_{50}$ and molecular connectivity indices of CAHs (chlorinated aliphatic hydrocarbons)such as $^0X$, $^0X^V$, $^1X$, $^2X$ and $^3X^v_c$ and quadratic correlation between $EC_{50}$ and $^0X$, $^0X^V$, $^2X^V$, $^3X_c$, $^3X^V_c$ and P. It shows that the molecular connection indices in carbon structure is contributed to biological characters with linear relation and that in the other one with quadratic relation. The $EC_{50}$ of chlorophenol derivatives had quadratic relation with the value of octanol/water prtition coefficients ($r^2$=0.99) and linear and quadratic relation with the number of chlorine compound (($r^2{\geq}$0.94). This confirms the already known trend of increasing toxicity with increasing ability of a compound to diffuse through cell membrane and number of chlorine substitution.

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Contamination of Sediments and Histological Alterations in Barfin Plaice Pleuronectes pinnifasciatus from Amursky Bay(Peter the Great Bay, East Sea/Sea of Japan)

  • Vaschenko Marina A.;Syasina Iraida G.;Durkina Valentina B.;Zhadan Petr M.
    • Ocean and Polar Research
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    • v.25 no.1
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    • pp.31-40
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    • 2003
  • In August-September 2001, 15 samples of bottom sediments were collected in the inner, middle and open parts of Amursky Bay near Vladivostok, Russia, and barfin plaice Pleuronectes pinnifasciatus was sampled from the inner and the middle locations of the bay. In the sediments from all three sites elevated concentrations of several heavy metals, i.e. Zn ($102-115{\mu}/g$ dry weight), Ni $(70-73{\mu}g/g)$ and Cu $(27-35{\mu}g/g)$ were discovered. The contents of oil hydrocarbons were very close to or slightly higher than the maximal normal environmental background level, $100{\mu}g/g$ dry weight. The sediments contained negligible amounts of hexachlorocyclohexane, while DDT concentrations were quite high (1.7-16.3ng/g dry weight). Generally, there were no substantial differences in the pollution levels of the locations studied and our results resembled those reported for Amursky Bay in the 1990s. Surprisingly, in 2001 'fiesh' DDT comprised 70-85% of the total DDT content in sediment from all the locations studied. In fish liver total DDTs concentrations were 212.8 and 122.54 ng/g wet weight for the inner and the middle locations, respectively, and 'fresh' DDT comprised 35 and 64% of DDTs, respectively. These results provide evidence of recent input of DDT from an unknown source into the ecosystem of Amursky Bay. Histopathological changes revealed in the plaice liver (vacuolization of hepatocytes, coagulative necrosis of hepatocytes, inflammatory reaction, and necrosis of epithelial cells of bile ducts) are probably connected with an intensive metabolism of DDT in the fish organism. No histological and histomorphometric differences were found in the state of the interrenal tissue. Similar condition of the liver and the interrenal tissue in barfin plaice sampled from the inner and the middle locations of Amursky Bay may be explained by the absence of great differences in the pollution levels of these sites.

Evaluation of Concentration Polarization at Feed in the Permeation of VOCs/$N_2$ mixtures through PDMS membrane (VOCs/질소 혼합물 증기투과시 공급액부 경계층에서의 농도분극 분석을 위한 모델식 확립)

  • 염충균;이상학;최정환;이정민
    • Membrane Journal
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    • v.11 no.2
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    • pp.74-82
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    • 2001
  • By using a phenomenological approach, model equations incorporating the resistance-in¬series concept were established to evaluate quantitatively concentration polarization in the boundary layer in feed adjacent to the membrane surface in the vapor permeation and separation of volatile organic compounds (VOCS)/$N_2$ mixture through po]y(dimethylsiloxane) (PDMS) membrane. The vapor permeations of various VOCS/$N_2$ mixtures through PDMS membrane were carried out at various feed flow rates. Chlorinated hydrocarbons, such as, methylene chloride, chlorofonn, 1,2-clichloroethane and 1,1,2-trichloroethane were used as organic vapor. By fitting the model equations to the experimental penneation data. the model parameters were detennined. respectively. Both the mass transfer coefficient of VOC across tbe boundary layer and concentration polarization modulus as a measure of the extent of concentration polarization were eitimated Quantitatively by the mooe1 equations with the determined model parameters. From the analysis on the detennined model parameters, the boundary layer resistance due to the concentration polarization of VOCs component was found to be more significant when the condensability of voe was greater. This study seeks to emphasize the importance of the boundary resistance on the vapor penneation of the vapor/gas mixtures with high permeability and high selectivity towards the minor component VOC.

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Characterization of Forest Fire Emissions and Their Possible Toxicological Impacts on Human Health

  • Kibet, Joshua;Bosire, Josephate;Kinyanjui, Thomas;Lang'at, Moses;Rono, Nicholas
    • Journal of Forest and Environmental Science
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    • v.33 no.2
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    • pp.113-121
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    • 2017
  • In flight particulate matter particularly emissions generated by incomplete combustion processes has become a subject of global concern due to the health problems and environmental impacts associated with them. This has compelled most countries to set standards for coarse and fine particles due to their conspicuous impacts on environment and public health. This contribution therefore explores forest fire emissions and how its particulates affects air quality, damage to vegetation, water bodies and biological functions as architects for lung diseases and other degenerative illnesses such as oxidative stress and aging. Soot was collected from simulated forest fire using a clean glass surface and carefully transferred into amber vials for analysis. Volatile components of soot were collected over 10 mL dichloromethane and analyzed using a QTOF Premier-Water Corp Liquid Chromatography hyphenated to a mass selective detector (MSD), and Gas Chromatograph coupled to a mass spectrometer (GC-MS). To characterize the size and surface morphology of soot, a scanning electron microscope (SEM) was used. The characterization of molecular volatiles from simulated forest fire emissions revealed long chain compounds including octadec-9-enoic acid, octadec-6-enoic acid, cyclotetracosane, cyclotetradecane, and a few aromatic hydrocarbons (benzene and naphthalene). Special classes of organics (dibenzo-p-dioxin and 2H-benzopyran) were also detected as minor products. Dibenzo-p-dioxin for instance in chlorinated form is one of the deadliest environmental organic toxins. The average particulate size of emissions using SEM was found to be $11.51{\pm}4.91{\mu}m$. This study has shown that most of the emissions from simulated forest fire fall within $PM_{10}$ particulate size. The molecular by-products of forest fire and particulate emissions may be toxic to both human and natural ecosystems, and are possible precursors for various respiratory ailments and cancers. The burning of a forest by natural disasters or man-made fires results in the destruction of natural habitats and serious air pollution.