Atmospheric chemistry of alkanes

The reactions of the alkanes under atmospheric conditions and in the presence of oxides of nitrogen are reviewed and evaluated. Particular emphasis is placed upon their subsequent reactions after the initial OH radical reaction under conditions where the alkyl peroxy radicals produced react predominantly with NO, rather than with HO₂ and/or RO₂ radicals. Methods are discussed for estimating the overall OH radical rate constants, the number of molecules of NO consumed per alkane molecule reacted, and the products formed and their yields.     

Estimating product yields of carbon-containing products from the atmospheric photooxidation of ambient air alkenes

The yields of products have been calculated for the reactions of hydroxyl radicals and ozone with 19 of the two-through-six carbon anthropogenic alkenes. Based on their rate of reaction, mechanisms of reactions and the ambient air distribution for these alkenes their seasonal ambient air yields have been estimated.Aldehydes predominate as products irrespective of season, with smaller yields of several ketones. Other minor products include carboxylic acids, carbon monoxide, carbon dioxide, and alkenes. About a two-fold increase is estimated in the yields of hot biradicals and their products from summer to winter.One sensitivity analysis was made by recomputing yields at a different OH radical to O₃ concentration than assumed most likely in the calculations discussed above. In addition, the sensitivity of product yields to an estimated range of seasonally averaged sunset-to-sunrise NO₃ radical concentrations was calculated. The effects of free radical reactions are discussed, but these are believed to make a relatively minor contribution within the NO _x -rich atmospheres that contain anthropogenic alkenes.The uncertainties in product yields associated with the range of NO₃ radical concentrations assumed present is relatively small for aldehydes, as is the decrease in yield of the one carbon hot biradical. Larger uncertainties occur for ketones. Significant decreases in yields occur for larger hot biradicals, especially the branched-chain hot radicals in the presence of NO₃ radicals.     

Laboratory measurements of the <Superscript>12</Superscript>C/<Superscript>13</Superscript>C kinetic isotope effects in the gas-phase reactions of unsaturated hydrocarbons with Cl atoms at 298 ± 3 K

The carbon kinetic isotope effects (KIEs) in the reactions of several unsaturated hydrocarbons with chlorine atoms were measured at room temperature and ambient pressure using gas chromatography combustion isotope ratio mass spectrometry (GCC-IRMS). All measured KIEs, defined as the ratio of the rate constants for the unlabeled and labeled hydrocarbon reaction k ₁₂/k ₁₃, are greater than unity or normal KIEs. The KIEs, reported in per mil according to ^Cl ɛ = (k ₁₂/k ₁₃−1) × 1000‰ with the number of experimental determinations in parenthesis, are as follows: ethene, 5.65 ± 0.34 (1); propene, 5.56 ± 0.18 (2); 1-butene, 5.93 ± 1.16 (1); 1-pentene, 4.86 ± 0.63 (1); cyclopentene, 3.75 ± 0.14 (1); toluene, 2.89 ± 0.31 (2); ethylbenzene, 2.17 ± 0.17 (2); o-xylene, 1.85 ± 0.54 (2). To our knowledge, these are the first reported KIE measurements for reactions of unsaturated NMHC with Cl atoms. Relative rate constants were determined concurrently to the KIE measurements. For the reactions of cyclopentene and ethylbenzene with Cl atoms, no rate constant has been reported in refereed literature. Our measured rate constants are: cyclopentene (7.32 ± 0.88) relative to propene (2.68 ± 0.32); ethylbenzene (1.15 ± 0.04) relative to o-xylene (1.35 ± 0.21), all × 10⁻¹⁰ cm³ molecule⁻¹ s⁻¹. The KIEs in reactions of aromatic hydrocarbons with Cl atoms are similar to previously reported KIEs in Cl-reactions of alkanes with the same numbers of carbon atoms. Unlike the KIEs for previously studied gas-phase hydrocarbon reactions, the KIEs for alkene–Cl reactions do not exhibit a simple inverse dependence on carbon number. This can be explained by competing contributions of normal and inverse isotope effects of individual steps in the reaction mechanism. Implications for the symmetries of the transition state structures in these reactions and the potential relevance of Cl-atom reactions on stable carbon isotope ratios of atmospheric NMHC are discussed.     

Natural and anthropogenic C2 to C6 hydrocarbons in the central-eastern Venezuelan atmosphere during the rainy season

The levels of low molecular weight hydrocarbons were measured at pristine sites and rural locations affected by hydrocarbon emissions from oil and gas producing fields in Venezuela. At the clean sites, lower concentrations of C₂ to C₆ alkanes were observed, whereas, in comparison with remotes sites, very much higher levels were measured at the polluted sites. Alkenes present relatively high concentrations, with isoprene being the most abundant, all over the study region. The main sources of alkenes are likely to be natural, mainly from vegetation. The levels of alkanes recorded at the clean sites and the alkene levels found everywhere in the region are in agreement with the values reported for other clean sites in the tropics. The increase of ozone production capacity due to the anthropogenic emissions of alkanes from oil and gas fields was estimated. Due to the presence in the atmosphere of important amounts of naturally emitted isoprene, ethene and propene, which makes a substantial contribution to the reactivity of the hydrocarbon mixture, a small increase (<5%) was estimated to occur in the capacity of the ozone production at a regional scale during the rainy season.     

Kinetics of the Gas-Phase Reactions of OH and NO3 Radicals and O3 with the Monoterpene Reaction Products Pinonaldehyde, Caronaldehyde, and Sabinaketone

Using a relative rate method, rate constants have been measured for the gas-phase reactions of OH and NO3 radicals with pinonaldehyde, caronaldehyde and sabinaketone at 296 ± 2 K. The OH radical reaction rate constants obtained are (in units of 10–12 cm3 molecule–1 s–1): pinonaldehyde, 48 ± 8; caronaldehyde, 48 ± 8; and sabinaketone, 5.1 ± 1.4, and the NO3 radical reaction rate constants are (in units of 10–14 cm3 molecule–1 s–1): pinonaldehyde, 2.0 ± 0.9; caronaldehyde, 2.5 ± 1.1; and sabinaketone, 0.036 ± 0.023, where the error limits include the estimated overall uncertainties in the rate constants for the reference compounds. Upper limits to the O3 reaction rate constants were also obtained, of <2 × 10–20 cm3 molecule–1 s–1 for pinonaldehyde and caronaldehyde, and <5 × 10–20 cm3 molecule–1 s–1 for sabinaketone. These reaction rate constants are combined with estimated ambient tropospheric concentrations of OH radicals, NO3 radicals and O3 to calculate tropospheric lifetimes and dominant transformation process(es) of these and other monoterpene reaction products.     

Primary Product Distribution from the Reaction of Hydroxyl Radicals with Toluene at ppb NOX Mixing Ratios

A study has been conducted to examine the OH-initiated degradation products of toluene in the presence of sub part-per-million levels of NO_X. The experiments were conducted in a dynamic reactor to minimize the conversion of the aromatic compounds while allowing a sufficient mass of products to be collected for analysis. The major primary products detected in the toluene system (with molar yields) include glyoxal (0.238), methylglyoxal (0.167), o-cresol (0.120), benzaldehyde (0.06), 4-oxo-2-pentenal (0.03), and p-cresol (0.03). Six other reaction products, most being ring cleavage products, were measured at yields below 3%. Corrections for secondary OH reactions with the products were made where necessary. The formation of the cresol isomers was found to be invariant to the NO₂ concentrations which indicates that under atmospheric conditions the initial hydroxycyclohexadienyl radical reaction with NO₂ is a minor process and that most of the reaction occurs with O₂. The product yields found in this study are expected to be representative of those that occur in the urban atmosphere at ambient NO₂ concentrations.     

Chlorine initiated oxidation studies of hydrochlorofluorocarbons: Results for HCFC-123 (CF3CHCl2) and HCFC-141b (CFCl2CH3)

Oxidation reactions of the proposed CFC substitutes HCFC-123 (CF₃CHCl₂) and HCFC-141b (CFCl₂CH₃) have been studied in the laboratory using long-path Fourier transform infrared spectroscopy. The air oxidation of the HCFCs was initiated by the photolysis of Cl₂ forming Cl atoms that abstract H atoms from the HCFC. CF₃C(O)Cl was the only carbon containing compound observed in the infrared spectrum of the products of the HCFC-123/Cl₂ irradiations and its yield was approximately one. The product data are consistent with formation of CF₃C(O)Cl by Cl elimination of the intermediate halogenated alkoxy radical CF₃CCl₂O. The Cl-initiated oxidation of HCFC-141b led to the formation of CO and C(O)FCl. The product data are consistent with a 1 : 1 relationship between C(O)FCl formed and HCFC-141b reacted. Product data were compatible with both decomposition by cleavage of the C–C bond of the radical CFCl₂CH₂O leading to the prompt generation of C(O)FCl and reaction of the radical with O₂ forming the two carbon halogenated aldehyde CFCl₂CH(O), which in the presence of Cl was likely oxidized to C(O)FCl. An approximate method was developed in which the ratio was extracted from analysis of the time evolution of HCFC-141b, C(O)FCl, and CO. The data suggest that the contributions are comparable.     

泰州市大气挥发性有机物化学组分特征、活性及来源解析

挥发性有机物（VOCs）是臭氧和大气颗粒物的重要前体物,本研究利用在线气相色谱-质谱仪（Online-GC-MS）于2018年5—6月对江苏省泰州市大气中98种VOCs进行监测,依据监测结果对泰州市大气VOCs的组成特征、日变化趋势进行分析,对醛酮类VOCs数据进行参数化拟合探究其一次二次贡献,并采用正矩阵因子分解模型（PMF）对VOCs数据进行来源分析,用最大增量反应活性（MIR）计算臭氧生成潜势（OFP）.研究结果表明：泰州市大气VOCs中烷烃占比最高,其次为醛酮;烷烃、烯烃、卤代烃和芳香烃浓度日变化趋势明显,特征相近;参数化方法表明醛类物质主要来自于二次生成,而酮类物质主要来自一次排放;PMF模型结果表明泰州市VOCs的主要贡献源分别为机动车排放、油气溶剂挥发、生物质燃烧、其他工业和天然源;OFP的主要贡献物种为烯烃类,占比34.18%.研究结果表明,控制工业排放和溶剂使用是泰州市大气污染物控制的重点.     

Product study of the reaction of OH radicals with isoprene in the atmosphere simulation chamber SAPHIR

Atmospheric oxidation of isoprene and its oxidation products methacrolein (MACR) and methyl vinyl ketone (MVK) have an important impact on the photochemical activity in the boundary layer, in particular in forested areas. The oxidation of isoprene by OH radicals was investigated in chamber experiments conducted under tropospheric conditions in the atmosphere simulation chamber SAPHIR at the Research Center Jülich. The aim was to determine the product yield of MVK and MACR in the OH-induced isoprene oxidation and the rate constant of their reaction with OH under real atmospheric conditions. The recently published updated degradation scheme for isoprene from Geiger et al. (2003) was used to determine rate constants and product yields. The fractional yields in the isoprene peroxy radical reaction with NO were found to be 0.41±0.03 for MVK and 0.27±0.03 for MACR. The rate coefficient for MACR with OH was found to be in very good agreement with the recommended value of IUPAC Atkinson (Atkinson et al., 2005). while the rate coefficient for MVK with OH was 27% lower.     

Biogenic Volatile Organic Compounds (VOC): An Overview on Emission, Physiology and Ecology

This overview compiles the actual knowledge of the biogenic emissions of some volatile organic compounds (VOCs), i.e., isoprene, terpenes, alkanes, alkenes, alcohols, esters, carbonyls, and acids. We discuss VOC biosynthesis, emission inventories, relations between emission and plant physiology as well as temperature and radiation, and ecophysiological functions. For isoprene and monoterpenes, an extended summary of standard emission factors, with data related to the plant genus and species, is included. The data compilation shows that we have quite a substantial knowledge of the emission of isoprene and monoterpenes, including emission rates, emission regulation, and biosynthesis. The situation is worse in the case of numerous other compounds (other VOCs or OVOCs) being emitted by the biosphere. This is reflected in the insufficient knowledge of emission rates and biological functions. Except for the terpenoids, only a limited number of studies of OVOCs are available; data are summarized for alkanes, alkenes, carbonyls, alcohols, acids, and esters. In addition to closing these gaps of knowledge, one of the major objectives for future VOC research is improving our knowledge of the fate of organic carbon in the atmosphere, ending up in oxidation products and/or as aerosol particles.     

Products and mechanism of the reaction of NO3 with selected acyclic monoalkenes

The gas-phase reactions of NO₃ with 2-methyl-2-butene, isobutene,trans-butene, 1-butene and propene, were investigated in a flow-tube at room temperature. Experiments were performed in the pressure range 1–1000 mbar in synthetic air as well as at a total pressure of 800 mbar with varying concentrations of oxygen in nitrogen.The main products found were oxiranes, nitroxy-carbonyl compounds (ketonitrates) and ketones or aldehydes. The product distribution was a function of pressure. In each case, in synthetic air, the oxirane yield increased with decreasing total pressure up to a value of about 100% at pressures less than 1 mbar.It was concluded that oxirane is a product of the excited adduct radical formed in the electrophilic addition of NO₃ to the double bond. Experiments with very low partial pressures of oxygen showed that the quenched adduct radicals also produce the corresponding oxirane.Under tropospheric conditions (1000 mbar synthetic air) the following yields of the corresponding oxiranes were found: 2-methyl-2-butene 9%, isobutene 7%,trans-butene 12%, 1-butene 18%, propene 28%. In the case oftrans-butene the total oxirane yield consists of 72%trans- and 28%cis-isomer.Dedicated to Professor Wolfgang Rolle on the occasion of his 60th birthday.     

Ambient biogenic hydrocarbons and isoprene emissions from a mixed deciduous forest

Experiments were conducted during the growing season of 1993 at a mixed deciduous forest in southern Ontario, Canada to investigate the atmospheric abundance of hydrocarbons from phytogenic origins, and to measure emission rates from foliage of deciduous trees. The most abundant phytogenic chemical species found in the ambient air were isoprene and the monoterpenes -pinene and -pinene. Prior to leaf-bud break during spring, ambient hydrocarbon mixing ratios above the forest remained barely above instrument detection limit (20 parts per trillion), but they became abundant during the latter part of the growing season. Peak isoprene mixing ratios reached nearly 10 parts per billion (ppbv) during mid-growing season while maximum monoterpene mixing ratios were close to 2 ppbv. Both isoprene and monoterpene mixing ratios exhibited marked diurnal variations. Typical isoprene mixing ratios were highest during mid-afternoon and were lowest during nighttime. Peak isoprene mixing ratios coincided with maximum canopy temperature. The diurnal pattern of ambient isoprene mixing ratio was closely linked to the local emissions from foliage. Isoprene emission rates from foliage were measured by enclosing branches of trees inside environment-controlled cuvette systems and measuring the gas mixing ratio difference between cuvette inlet and outlet airstream. Isoprene emissions depended on tree species, foliage ontogeny, and environmental factors such as foliage temperature and intercepted photosynthetically active radiation (PAR). For instance, young (<1 month old) aspen leaves released approximately 80 times less isoprene than mature (>3 months old) leaves. During the latter part of the growing season the amount of carbon released back to the atmosphere as isoprene by big-tooth and trembling aspen leaves accounted for approximately 2% of the photosynthetically fixed carbon. Significant isoprene mixing ratio gradients existed between the forest crown and at twice canopy height above the ground. The gradient diffusion approach coupled with similarity theory was used to estimate canopy isoprene flux densities. These canopy fluxes compared favorably with values obtained from a multilayered canopy model that utilized locally measured plant microclimate, biomass distribution and leaf isoprene emission rate data. Modeled isoprene fluxes were approximately 30% higher compared to measured fluxes. Further comparisons between measured and modeled canopy biogenic hydrocarbon flux densities are required to assess uncertainties in modeling systems that provide inventories of biogenic hydrocarbons.     

Sensitivity of an ecosystem model to hydrology and temperature

We tested the sensitivity of a dynamic ecosystem model (LPJ-GUESS) to the representation of soil moisture and soil temperature and to uncertainties in the prediction of precipitation and air temperature. We linked the ecosystem model with an advanced hydrological model (JULES) and used its soil moisture and soil temperature as input into the ecosystem model. We analysed these sensitivities along a latitudinal gradient in northern Russia. Differences in soil temperature and soil moisture had only little influence on the vegetation carbon fluxes, whereas the soil carbon fluxes were very sensitive to the JULES soil estimations. The sensitivity changed with latitude, showing stronger influence in the more northern grid cell. The sensitivity of modelled responses of both soil carbon fluxes and vegetation carbon fluxes to uncertainties in soil temperature were high, as both soil and vegetation carbon fluxes were strongly impacted. In contrast, uncertainties in the estimation of the amount of precipitation had little influence on the soil or vegetation carbon fluxes. The high sensitivity of soil respiration to soil temperature and moisture suggests that we should strive for a better understanding and representation of soil processes in ecosystem models to improve the reliability of predictions of future ecosystem changes.     

Tropospheric degradation products of CH2FCF3 (HFC-134a)

Chlorine atom-initiated photooxidations of CH₂FCF₃ (HFC-134a) in O₂-N₂ diluent were carried out to identify the products formed from the \(CF_3 CHF\dot O\) radical reactions and to determine the product yields as a function of temperature, pressure and O₂ concentration. CF₃C(O)F and HC(O)F were the major ‘first-generation’ products observed, along with smaller yields of C(O)F₂ and, as yet, undetermined yields of CF₃OOOCF₃ and CF₃OOC(O)F. The relative importance of the two major \(CF_3 CHF\dot O\) reaction pathways, is expressed by the rate constant ratio $$k_{O_2 } /k_d = 3.2 \times 10^{ - 25} e^{(3510 \pm 470)/T} cm^3 molecule^{ - 1}$$ The decomposition reaction leading to HC(O)F and ?F₃ radical products is predicted to be the dominant pathway at the Earth's surface while mainly CF₃C(O)F formation will occur at the tropopause.     

The Gas Phase Reaction of Unsaturated Oxygenates with Ozone: Carbonyl Products and Comparison with the Alkene-Ozone Reaction

Carbonyl products have been identified and their formation yields measured in the gas phase reaction of ozone with unsaturated oxygenates in experiments carried out at ambient T, p = 1 atm. of purified humid air (RH = 50%) and with sufficient cyclohexane added to scavenge the hydroxyl radical. The compounds studied are the esters methyl acrylate, vinyl acetate and cis-3-hexenyl acetate, the carbonyl crotonaldehyde, the hydroxy-substituted diene linalool, the ether ethylvinyl ether and the keto-ether trans-4-methoxy-3-buten-2-one. The alkene 1-pentene was included for comparison. The nature and formation yields of the carbonyl products from this study and those measured in earlier work under the same conditions are compared to those of alkenes and are supportive of a reaction mechanism that is similar to that for the reaction of ozone with alkenes, i.e. O₃ + R₁R₂C=CR₃X (R₁COR₂ + R₃XCOO) + (1 – )(R₃COX + R₁R₂COO), where R_i are the alkyl substituents, X is the oxygen-containing substituent (–CHO for aldehydes; –C(O)R for ketones; –C(O)OR and –OC(O)R for esters; –OH and hydroxyalkyl for alcohols; and –OR for ethers), R₁COR₂ is the primary carbonyl, R₃COX is the other primary product and R₁R₂COO and R₃XCOO are the carbonyl oxide biradicals. The biradicals lead to carbonyls in reactions that are also analogous to those involved in carbonyl formation from biradicals in the ozone-alkene reaction. These features make it possible to predict the nature and formation yields of the major carbonyl products of the reaction of ozone with unsaturated oxygenates that may be components of biogenic emissions.     

Alkyl nitrate formation from the atmospheric photoxidation of alkanes; a revised estimation method

The available experimental data concerning the yields of alkyl nitrates in the reactions of alkyl peroxy radicals with NO have been used to derive a revised expression for the estimation of alkyl nitrate yields in the atmospheric photooxidation of alkanes as a function of temperature and pressure. This revised expression gives more reasonable predictions of alkyl nitrate yields under high altitude tropospheric conditions than that which has been previously published.     

Measurements of Volatile Organic Compounds (VOC) During POPCORN 1994: Applying a New On-Line GC–MS-Technique

Atmospheric concentrations of ca. 250 C6–C15 hydrocarb on and C4–C12 oxygenated volatile organic compounds (VOC) including alkanes, benzene and alkyl benzenes, monoterpenes and aldehydes were measured in August 1994 during the POPCORN campaign (POPCORN = Photo-Oxidant formation by Plant emitted Compounds and OH Radicals in North-Eastern Germany). About 80 substances together contributed 90% of the atmospheric carbon in this range of molecular weight. During this field campaign VOC-emissions from several crop and tree species and the ambient concentrations of CO, C2–C7 non-methane hydrocarbons (NMHC), C1 and C2 aldehydes, nitrogen oxides, ozone and hydroxyl-radicals (OH) were also measured. These data were used to interpret the VOC measurements presented here. The on-line GC–MS used for the VOC measurements combines adsorptive sampling with thermal desorption and GC–MS analysis in an automated system. Internal standards were used to quantify the measurements. Ozone was destroyed prior to the sample preconcentration through the gas phase reaction with NO. Aromatic compounds like benzene, toluene and xylenes were the most abundant compound class among the measured substances, -pinene and 3-carene, most probably originating from pineforests ca. 1 km away from the measuring site, were the most abundant monoterpenes. The highest mixing ratios of most compounds were measured in nights with strong inversion situations. The toluene mixing ratios then reached 630 pptv; -pinene mixing ratios went up to 430 pptv. The median of all toluene and -pinene measurements during the campaign was 125 pptv or 22 pptv, respectively. These values are on the lower end of ambient measurements reported for continental sites. In most samples also n-pentanal, n-hexananl, n-nonanal and n-undecanal were present. Median mixing ratios were 9, 16, 14 and 8 pptv, respectively. Emission studies indicate that these highly reactive compounds are most probably emitted from maize. It is shown by a simple first order approach that the potential for ozone formation during the POPCORN campaign was roughly equal for anthropogenic and biogenic VOC. From measured concentrations of ozone, OH-radicals, methane, CO, C2–C15 nonmethane hydrocarbons (NMHC) and C5–C11 aldehydes a photochemical production of ozone in the order of 3.5 ppb/h can be estimated. Apart from formaldehyde and acetaldehyde, which are at least partly products of VOC oxidation, the substance group with the largest contribution to the VOC turnover are the monoterpenes. They contribute ca. 30%. However, the mechanism of terpene oxidation is very complex and presently only partly understood. Thus the actual contribution of monoterpenes to ozone formation is very uncertain. Other measured compound classes such as light alkenes, alkanes, aromatics, and C5–C11 aldehydes contribute each between 10% and 15% to ozone formation. The measuring site was not influenced directly from strong biogenic or anthropogenic sources, and the results obtained during the POPCORN campaign can be regarded as a typical picture of a remote rural central European environment.     

Reactions of Cl Atoms with Selected VOCs: Kinetics, Products and Mechanisms

The reactions of isoprene, MBO (2-methyl-3-buten-2-ol) and toluene with chlorine atoms have been studied at 298 ± 5 K and 740 ± 5 Torr with the use of FTIR spectroscopy. Major products of the isoprene-Cl reaction and of the MBO-Cl reaction have been identified and quantified, and reaction mechanisms have been tentatively proposed in order to explain the products formed. The reaction between isoprene and Cl atoms yields mainly HCl, formyl chloride, formic acid, methylglyoxal (pyruvic aldehyde), CO and CO2, while the MBO-Cl reaction forms acetone, HCl, formyl chloride, formic acid, CO, CO2. As products from the reaction between toluene and Cl we identified and quantified HCl and benzaldehyde. The rate constants for the reactions of isoprene and toluene with Cl atoms have also been determined using a relative rate method. The measured values are: kisoprene = (5.5 ± 1.0) × 10–10 cm3 molecule–1 s–1 and ktoluene = (5.6 ± 1.3) × 10–11 cm3 molecule–1 s–1. Atmospheric lifetimes have been estimated from these values.     

Modeling carbon stores in Oregon and Washington forest products: 1900–1992

A new model, FORPROD, for estimating the carbon stored in forest products, considers both the manufacture of the raw logs into products and the fate of the products during use and disposal. Data for historical patterns of harvest, manufacturing efficiencies, and product use and disposal were used for estimating the accumulation of carbon in Oregon and Washington forest products from 1900 to 1992. Pools examined were long- and short-term structures, paper supplies, mulch, open dumps, and landfills. The analysis indicated that of the 1,692 Tg of carbon harvested during the selected period, only 396 Tg, or 23%, is currently stored. Long-term structures and landfills contain the largest fraction of that store, holding 74% and 20%, respectively. Landfills currently have the highest rates of accumulation, but total landfill stores are relatively low because they have been used only in the last 40 years. Most carbon release has occurred during manufacturing, 45% to 60% lost to the atmosphere, depending upon the year. Sensitivity analyses of the effects of recycling, landfill decomposition, and replacement rates of long-term structures indicate that changing these parameters by a factor of two changes the estimated fraction of total carbon stored less than 2%.