Distribution of atmospheric SF6 near a large urban area as recorded in the vadose zone

Local emissions of SF6 are of interest for studying their impact on the use of SF6 as a groundwater-dating tool near source regions as well as for investigating the spatial distributions of (inert) gaseous compounds spreading from urban or industrial centers. A precondition for the use of SF6 in such studies is the capability to document the temporal and spatial evolution of SF6 in and around source regions with sufficient resolution. Here we present a time series of SF6 measurements in soil air at a site (Sparkill, NY) about 25 km north of New York City carried out between May 2000 and January 2002. The data show that, below about 2 m depth, the vadose zone integrates atmospheric SF6 mixing ratios over time scales greater than 1 month. SF6 mixing ratios in soil air at these depths match averaged high-resolution atmospheric measurements performed at Lamont-Doherty Earth Observatory in Palisades, NY, located about 3 km south of Sparkill. To a first-order approximation, a simple one-dimensional diffusion model reproduces the measured SF6 profiles in the vadose zone, suggesting that the soil indeed acts as a low-pass filter for inert atmospheric gases. These findings indicate that measurements of soil air can be used to determine the spatial pattern of SF6 excess relative to the remote atmosphere for a given region. A transect of soil profiles from Manhattan to the tip of Long Island indicates that emissions from sites close to New York City lead to significant SF6 excesses (ca. 25% or more) above the clean air mixing ratios over distances of the order of 80 km.     

Relative importance of gas-phase diffusive and advective tichloroethene (TCE) fluxes in the unsaturated zone under natural conditions

It was hypothesized that atmospheric pressure changes can induce gas flow in the unsaturated zone to such an extent that the advective flux of organic vapors in unsaturated-zone soil gas can be significant relative to the gas-phase diffusion flux of these organic vapors. To test this hypothesis, a series of field measurements and computer simulations were conducted to simulate and compare diffusion and advection fluxes at a trichloroethene-contaminated field site at Picatinny Arsenal in north-central New Jersey. Moisture content temperature, and soil-gas pressure were measured at multiple depths (including at land surface) and times for three distinct sampling events in August 1996, October 1996, and August 1998. Gas pressures in the unsaturated zone changed significantly over time and followed changes measured in the atmosphere. Gas permeability of the unsaturated zone was estimated using data from a variety of sources, including laboratory gas permeability measurements made on intact soil cores from the site, a field air pump test, and calibration of a gas-flow model to the transient, one-dimensional gas pressure data. The final gas-flow model reproduced small pressure gradients as observed in the field during the three distinct sampling events. The velocities calculated from the gas-flow model were used in transient, one-dimensional transport simulations to quantify advective and diffusive fluxes of TCE vapor from the subsurface to the atmosphere as a function of time for each sampling event. Effective diffusion coefficients used for these simulations were determined from independent laboratory measurements made on intact soil cores collected from the field site. For two of the three sampling events (August 1996 and August 1998), the TCE gas-phase diffusion flux at land surface was significantly greater than the advection flux over the entire sampling period. For the second sampling event (October 1996), the advection flux was frequently larger than the diffusion flux. When averaged over the second sampling event, the advection and diffusion fluxes were comparable in magnitude. Sensitivity analyses indicate that diffusion fluxes increase significantly with increases in air-filled porosity near land surface, whereas advection fluxes do not. For October 1996, the comparable advection and diffusion fluxes were caused by high moisture content near land surface and a subsequent reduction in the diffusion flux relative to the advection flux. These results indicate that under certain environmental conditions, the organic vapor advection flux from the unsaturated zone to the atmosphere may be equal to or greater than the diffusion flux.     

Ecohydrological factors affecting nitrate concentrations in a phreatic desert aquifer in northwestern China

Aerobic conditions in desert aquifers commonly allow high nitrate (NO3-) concentrations in recharge to persist for long periods of time, an important consideration for N-cycling and water quality. In this study, stable isotopes of NO3- (delta15N(NO3) and delta18O(NO3)) were used to trace NO3- cycling processes which affect concentrations in groundwater and unsaturated zone moisture in the arid Badain Jaran Desert in northwestern China. Most groundwater NO3- appears to be depleted relative to Cl- in rainfall concentrated by evapotranspiration, indicating net N losses. Unsaturated zone NO3- is generally higher than groundwater NO3- in terms of both concentration (up to 15 476 microM, corresponding to 3.6 mg NO3(-)-N per kg sediment) and ratios with Cl-. Isotopic data indicate that the NO3- derives primarily from nitrification, with a minor direct contribution of atmospheric NO3- inferred for some samples, particularly in the unsaturated zone. Localized denitrification in the saturated zone is suggested by isotopic and geochemical indicators in some areas. Anthropogenic inputs appear to be minimal, and variability is attributed to environmental factors. In comparison to other arid regions, the sparseness of vegetation in the study area appears to play an important role in moderating unsaturated zone NO3- accumulation by allowing solute flushing and deterring extensive N2 fixation.     

Release of CFC-11 from disposal of polyurethane foam waste

The halocarbon CFC-11 has extensively been used as a blowing agent for polyurethane (PUR) insulation foams in home appliances and for residential and industrial construction. Release of CFCs is an important factor in the depletion of the ozone layer. For CFC-11 the future atmospheric concentrations will mainly depend on the continued release from PUR foams. Little is known about rates and time frames of the CFC release from foams especially after treatment and disposal of foam containing waste products. The CFC release is mainly controlled by slow diffusion out through the PUR. From the literature and by reevaluation of an old reported experiment, diffusion coefficients in the range of 0.05-1.7 x 10(-14) m2 s-1 were found reflecting differences in foam properties and experimental designs. Laboratory experiments studying the distribution of CFC in the foam and the short-term releases after shredding showed that about 40% of the CFC is solubilized in the PUR phase, and that up to 10% of the total content will be released within a few weeks if the foam is shredded down to 2-cm sized pieces. For smaller pieces the quick release will be larger. Fifty percent of residual CFC content will be released within 9-300 years from 2-cm pieces based on the range in diffusion coefficients reported. For larger pieces the initial release is insignificant, and the release time frames are much longer than for the shredded foam.     

Pumping-induced ebullition: a unified and simplified method for measuring multiple dissolved gases

The incorporation of multiple dissolved gas measurements in biogeochemical studies remains a difficult and expensive challenge. Incompatibilities in collection, handling, and storage procedures generally force the application of multiple sampling procedures for multiple gases. This paper introduces the concept and application of pumping-induced ebullition (PIE), a unified approach for routine measurement of multiple dissolved gases in natural waters and establishes a new platform for development of in situ real-time dissolved gas monitoring tools. Ebullition (spontaneous formation of bubbles) is induced by pumping a water sample through a narrow-diametertube (a "restrictor") to decrease hydrostatic pressure (PH) below total dissolved gas pressure (PT). Buoyancy is used to trap bubbles within a collection tower where gas accumulates rapidly (1 mL/min) to support multiple chemical analyses. Providing for field collection of an essentially unlimited and unified volume of gas sample, PIE afforded accurate and precise measurements of major (N2, 02, Ar), trace (CO2, N20, CH4) and ultratrace (CFC11, CFC12, CFC113, SF6) dissolved gases in Wisconsin groundwater, revealing interrelationships between denitrification, apparent recharge age-dates, and historical land use. Compared to conventional approaches, PIE eliminates multiple gas-specific sampling methods, reduces data computations, simplifies laboratory instrumentation, and avoids aqueous production and consumption of biogenic gases during sample storage. A lake depth profile for CO2 demonstrates PIE's flexibility as an in situ real-time platform for dissolved gas measurements. The apparent departures of some gases (SF6, H2, N2O, CO2) from solubility equilibrium behavior warrant further confirmation and theoretical investigation.     

Measurement of helium isotopes in soil gas as an indicator of tritium groundwater contamination

The focus of this study was to define the shape and extent of tritium groundwater contamination emanating from a legacy burial ground and to identify vadose zone sources of tritium using helium isotopes (3He and 4He) in soil gas. Helium isotopes were measured in soil-gas samples collected from 70 sampling points around the perimeter and downgradient of a burial ground that contains buried radioactive solid waste. The soil-gas samples were analyzed for helium isotopes using rare gas mass spectrometry. 3He/4He ratios, reported as normalized to the air ratio (RA), were used to locate the tritium groundwater plume emanating from the burial ground. The 3He (excess) suggested that the general location of the tritium source is within the burial ground. This study clearly demonstrated the efficacy of the 3He method for application to similar sites elsewhere within the DOE weapons complex.     

New field method: gas push-pull test for the in-situ quantification of microbial activities in the vadose zone

Quantitative information on microbial processes in the field is important. Here we propose a new field method, the "gas push-pull test" (GPPT) for the in-situ quantification of microbial activities in the vadose zone. To evaluate the new method, we studied microbial methane oxidation above an anaerobic, petroleum-contaminated aquifer. A GPPT consists of the injection of a gas mixture of reactants (e.g., methane, oxygen) and nonreactive tracer gases (e.g., neon, argon) into the vadose zone and the subsequent extraction of the injection gas mixture together with soil air from the same location. Rate constants of gas conversion are calculated from breakthrough curves of extracted reactants and tracers. In agreement with expectations from previously measured gas profiles, we determined first-order rate constants of 0.68 h(-1) at 1.1 m below soil surface and 2.19 h(-1) at 2.7 m, close to the groundwater table. Co-injection of a specific inhibitor (acetylene) for methanotrophs showed that the observed methane consumption was microbially mediated. This was confirmed by increases of stable carbon isotope ratios in methane by up to 42.6 %. In the future, GPPTs should provide useful quantitative information on a range of microbial processes in the vadose zone.     

Capacity for biodegradation of CFCs and HCFCs in a methane oxidative counter-gradient laboratory system simulating landfill soil covers

The attenuation of methane and four chlorofluorocarbons was investigated in a dynamic methane and oxygen counter-gradient system simulating a landfill soil cover. Soil was sampled at Skellingsted Landfill, Denmark. The soil columns showed a high capacity of methane oxidation with oxidation rates of 210 g m(-2) d(-1) corresponding to a removal efficiency of 81%. CFC-11 and to a lesser extent also CFC-12 were degraded in the active soil columns. The average removal efficiency was 90% and 30% for CFC-11 and CFC-12, respectively. Soil gas concentration profiles indicated that the removal was due to anaerobic degradation, which was verified in anaerobic batch experiments where CFC-11 was rapidly degraded. HCFC-21 and HCFC-22 were also degraded in active soil columns (61% and 41%, respectively), but compared to the CFCs, the degradation was located in the upper oxic part of the column with overlapping gradients of methane and oxygen. High oxidation rates of methane and HCFCs were obtained in soil microcosms incubated with methane. When increasing the column inlet flow, the oxidation zone was moved upward in the column, and the removal efficiency of methane and HCFCs decreased. The removal of CFCs was, however, less affected since the anaerobic zone expanded with increasing inlet flow rates. This study demonstrates the complexity of landfill soil cover systems and shows that both anaerobic and aerobic bacteria may play a very important role in reducing the emission of not only methane but also trace components into the atmosphere.     

节能Y型多混聚喷燃烧器

介绍了专利产品节能Y型多混聚喷燃烧器(火口)的结构,以及燃气与空气混合、燃烧的过程和特点。混合气体经3次压缩、3次膨胀和4次混合后完全燃烧,并将有限的能量集中在狭长的火焰带中,使单位长度火焰具有较高的能量和温度;创新开发的气动无级调幅功能可根据织物幅宽调节气流压力,去除无效火焰。采用该燃烧器烧毛,工作效率高,烧毛效果可达4级以上,耗能较常规火口降低30%以上,减少了温室气体的排放。     

Impact of artificial recharge on dissolved noble gases in groundwater in California

Dissolved noble gas concentrations in groundwater can provide valuable information on recharge temperatures and enable 3H-3He age-dating with the use of physically based interpretive models. This study presents a large (905 samples) data set of dissolved noble gas concentrations from drinking water supply wells throughout California, representing a range of physiographic, climatic, and water management conditions. Three common interpretive models (unfractionated air, UA; partial re-equilibration, PR; and closed system equilibrium, CE) produce systematically different recharge temperatures or ages; however, the ability of the different models to fit measured data within measurement uncertainty indicates that goodness-of-fit is not a robust indicator for model appropriateness. Therefore caution is necessary when interpreting model results. Samples from multiple locations contained significantly higher Ne and excess air concentrations than reported in the literature, with maximum excess air tending toward 0.05 cm3 STP g(-1) (deltaNe approximately 400%). Artificial recharge is the most plausible cause of the high excess air concentrations. The ability of artificial recharge to dissolve greater amounts of atmospheric gases has important implications for oxidation-reduction dependent chemical reactions. Measured gas concentration ratios suggest that diffusive degassing may have occurred. Understanding the physical processes controlling gas dissolution during groundwater recharge is critical for optimal management of artificial recharge and for predicting changes in water quality that can occur following artificial recharge.     

Use of polymer mats in series for sequential reactive barrier remediation of ammonium-contaminated groundwater: field evaluation

A pilot-scale field trial was undertaken to evaluate the potential of in situ polymer mats (installed in series) as permeable reactive barriers within a treatment wall remediation system to induce sequential bioremediation of ammonium-contaminated groundwater. The treatment wall consisted of 10 m wide impermeable wings on either side of a 0.75 m wide permeable reactive zone flow-through box. Two polymer mats were positioned in the flow-through box. The upgradient polymer mat within the flow-through box was used to deliver oxygen to induce bacterial nitrification of the ammonium to nitrite/nitrate as the groundwater moved past. The downgradient polymer mat delivered ethanol to induce bacterial denitrification of the nitrite/nitrate to produce nitrogen gas. The field trial was carried out at a near-shore location. Initially the flow-through box was left open; however, this resulted in substantial groundwater mixing, which inhibited sequential remediation. Once the flow-through box was in-filled with gravel, groundwater mixing was reduced, achieving a greater than 90% reduction in total N. Estimated first-order half-lives for nitrification and denitrification rates were 1.2 and 0.4 d, respectively. Field nitrification half-lives were approximately an order of magnitude greater than rates determined in large-scale columns using soil and groundwater from the site, while denitrification half-lives were similar. The results of this pilot-scale field trial indicate that sequential bioremediation of ammonium-contaminated groundwater at field scale is feasible using in situ polymer mats as permeable reactive barriers, although hydraulic conditions can be complex in such barrier systems.     

Demonstrating a natural origin of chloroform in groundwater using stable carbon isotopes

Chloroform has been for a long time considered only as an anthropogenic contaminant. The presence of chloroform in forest soil and groundwater has been widely demonstrated. The frequent detection of chloroform in groundwater in absence of other contaminants suggests that chloroform is likely produced naturally. Compound-specific isotope analysis of chloroform was performed on soil-gas and groundwater samples to elucidate whether its source is natural or anthropogenic. The δ(13)C values of chloroform (-22.8 to -26.2‰) present in soil gas collected in a forested area are within the same range as the soil organic matter (-22.6 to -28.2‰) but are more enriched in (13)C compared to industrial chloroform (-43.2 to -63.6‰). The δ(13)C values of chloroform at the water table (-22.0‰) corresponded well to the δ(13)C of soil gas chloroform, demonstrating that the isotope signature of chloroform is maintained during transport through the unsaturated zone. Generally, the isotope signature of chloroform is conserved also during longer range transport in the aquifer. These δ(13)C data support the hypothesis that chloroform is naturally formed in some forest soils. These results may be particularly relevant for authorities' regulation of chloroform which in the case of Denmark was very strict for groundwater (<1 μg/L).     

Selenium dynamics in boreal streams: the role of wetlands and changing groundwater tables

The concentrations of selenium in 10 catchments of a stream network in northern Sweden were monitored over two years, yielding almost 350 observations of selenium concentrations in streamwater. The export of selenium was found to be systematically greater from forests than from mires. Accounting for atmospheric deposition, which was monitored over four years, there was a net accumulation of selenium in mires, while the export from forest soils was approximately equal to the atmospheric deposition. In forest dominated catchments the concentrations of selenium oscillated rapidly back and forth from high to low levels during spring floods. High selenium concentrations coincided with rising groundwater tables in the riparian forest soils, while low selenium concentrations were associated with receding groundwater. Thermodynamic modeling indicated that precipitation of elemental selenium would occur under reducing conditions in the riparian soils. Since changes in the redox conditions are likely to occur near the transition from the unsaturated to the saturated zone, it is hypothesized that the transport of selenium from forest soils to streams is controlled by redox reactions in riparian soils.     

Concentrations of polybrominated diphenyl ethers in air and soil on a rural-urban transect across a major UK conurbation

Polybrominated diphenyl ethers (PBDEs) were measured in air (using PUF disk passive samplers) and soil samples taken at approximately monthly intervals over 1 year at 10 locations on a transect across the West Midlands of the UK. Concentrations in air are consistent with those detected elsewhere in Europe and the Great Lakes basin. Concentrations in soil fall within the range reported for rural woodland and grassland soils in the UK and Norway. In both air and soil, concentrations clearly decrease with increasing distance from the city center, supporting the existence of an urban "pulse", indicating the West Midlands conurbation to be a source of PBDEs to the wider environment. Examination of seasonal trends revealed no evidence of a "spring pulse" in concentrations in air, with no summer peak in concentrations in air observed for 70% of sites. The PBDE congener pattern in air differs from that in soil, with ratios of congeners 47:99 higher in air than in soil. It is hypothesized that PBDEs volatilize from treated products indoors, before ventilating outdoors, where congener 99 undergoes preferential atmospheric deposition and accumulation in soil.     

Flux rates of atmospheric lead pollution within soils of a small catchment in northern Sweden and their implications for future stream water quality

It is not well-known how the accumulated pool of atmospheric lead pollution in the boreal forest soil will affect the groundwater and surface water chemistry in the future as this lead migrates through the soil profile. This study uses stable lead isotopes (206Pb/207Pb and 208Pb/ 207Pb ratios) to trace the transport of atmospheric lead pollution within the soil of a small catchment and predict future lead level changes in a stream draining the catchment. Low 206Pb/207Pb and 208Pb/207Pb ratios for the lead in the soil water (1.16 +/- 0.02; 2.43 +/- 0.03) and streamwater (1.18 +/- 0.03; 2.42 +/- 0.03) in comparison to that of the mineral soil (>1.4; >2.5) suggest that atmospheric pollution contributes by about 90% (65-100%) to the lead pool found in these matrixes. Calculated transport rates of atmospheric lead along a soil transect indicate that the mean residence time of lead in organic and mineral soil layers is at a centennial to millennial time scale. A maximum release of the present pool of lead pollution in the soil to the stream is predicted to occur within 200-800 years. Even though the uncertainty of the prediction is large, it emphasizes the magnitude of the time lag between the accumulation of atmospheric lead pollution in soils and the subsequent response in streamwater quality.     

Pesticides in western Canadian mountain air and soil

The distribution of organochlorine pesticides (OCP; in past and current use) in the mountains of western Canada was determined by sampling air, soil, and lichen along three elevational transects in 2003-2004. Two transects west of the Continental Divide were located in Mount Revelstoke and Yoho National Park, while the Observation Peak transect in Banff National Park is east of the divide. XAD-based passive air samplers, yielding annually averaged air concentrations, were deployed, and soils were collected at all 22 sampling sites, whereas lichen were only sampled in Revelstoke. Back trajectory analysis showed limited air mass transport from the Prairies to the east, but a high frequency of air arriving from the southwest, which includes agricultural regions in British Columbia and Washington State. Endosulfan, dieldrin, and a-hexachlorocyclohexane were the most prevalent OCPs in air and soil; hexachlorobenzene was only abundant in air; chlorothalonil, dacthal, and pentachloronitrobenzene were also consistently present. OCP air concentrations were similar across the three transects, suggesting efficient atmospheric mixing on a local and regional scale. Soil concentrations and soil/air concentration ratios of many OCPs were significantly higher west of the Continental Divide. The soil and lichen concentrations of most OCPs increased with altitude in Revelstoke, and displayed maxima at intermediate elevations at Yoho and Observation Peak. These distribution patterns can be understood as being determined by the balance between atmospheric deposition to, and retention within, the soils. Higher deposition, due to more precipitation falling at lower temperatures, likely occurs west of the divide and at higher elevations. Higher retention, due to higher soil organic matter content, is believed to occur in soils below the tree line. Highest pesticide concentrations are thus found intemperate mountain soils that are rich in organic matter and receive large amounts of cold precipitation.     

Ubiquitous net volatilization of polycyclic aromatic hydrocarbons from soils and parameters influencing their soil-air partitioning

Soils are a major reservoir of organic pollutants, and soil-air partitioning and exchange are key processes controlling the regional fate of pollutants. Here, we report and discuss the soil concentrations of polycyclic aromatic hydrocarbons (PAHs), their soil fugacities, the soil-air partition coefficients (K(SA)) and soil-air gradients for rural and semirural soils, in background areas of N-NE Spain and N-NW England. Different sampling campaigns were carried out to assess seasonal variability and differences between sampling sites. K(SA) values were dependent on soil temperature and soil organic quantity and type. Soil fugacities of phenanthrene and its alkyl homologues were 1-2 orders of magnitude higher than their ambient air fugacities for all sampling sites and periods. The soil to air fugacity ratio was correlated with soil temperature and soil redox potential. Similar trends for other PAHs were found but with lower fugacity ratios. The ubiquitous source of PAHs from background soils to the atmosphere found in all temperate regions in different seasons provides an indirect evidence of potential in situ generation of two to four ring PAHs and their alkyl homologues in the surface soil. We discuss this hypothetical biogenic source and other potential processes that could drive the high soil to air fugacity ratios of some PAHs.     

Use of chloroflurocarbons as internal standards for the measurement of atmospheric non-methane volatile organic compounds sampled onto solid adsorbent cartridges

Solid adsorbents have proven useful for determining the vertical profiles of volatile organic compounds (VOCs) using sampling platforms such as balloons, kites, and light aircraft, and those profiles provide valuable information about the sources, sinks, transformations, and transport of atmospheric VOCs. One of the largest contributions to error in VOC concentrations is the estimation of the volume of air sampled on the adsorbent cartridge. These errors arise from different sources, such as variations in pumping flow rates from changes in ambient temperature and pressure with altitude, and decrease in the sampling pump battery power. Another significant source for sampling rate variations are differences in the flow resistance of individual sampling cartridges. To improve the accuracy and precision of VOC measurements, the use of ambient chlorofluorocarbons (CFCs) as internal standards was investigated. A multibed solid adsorbent, AirToxic (Supelco), was chosen for its wide sampling range (C3-C12). Analysis was accomplished by thermal desorption and dual detection GC/FID/ECD, resulting in sensitive and selective detection of both VOCs and CFCs in the same sample. Long-lived chlorinated compounds (CFC-11, CFC-12, CFC-113, CCl4 and CH3CCl3) banned by the Montreal Protocol and subsequent amendments were studied for their ability to predict sample volumes using both ground-based and vertical profiling platforms through the boundary layer and free troposphere. Of these compounds, CFC-113 and CCl4 were found to yield the greatest accuracy and precision for sampling volume determination. Use of ambient CFC-113 and CCl4 as internal standards resulted in accuracy and precision of generally better than 10% for the prediction of sample volumes in ground-, balloon-, and aircraft-based measurements. Consequently, use of CFCs as reference compounds can yield a significant improvement of accuracy and precision for ambient VOC measurements in situations where accurate flow control is troublesome.     

Carbon and chlorine isotope ratios of chlorinated ethenes migrating through a thick unsaturated zone of a sandy aquifer

Compound-specific isotope analysis (CSIA) can potentially be used to relate vapor phase contamination by volatile organic compounds (VOCs) to their subsurface sources. This field and modeling study investigated how isotope ratios evolve during migration of gaseous chlorinated ethenes across a 18 m thick unsaturated zone of a sandy coastal plain aquifer. At the site, high concentrations of tetrachloroethene (PCE up to 380 μg/L), trichloroethene (TCE up to 31,600 μg/L), and cis-1,2-dichloroethene (cDCE up to 680 μg/L) were detected in groundwater. Chlorinated ethene concentrations were highest at the water table and steadily decreased upward toward the land surface and downward below the water table. Although isotopologues have different diffusion coefficients, constant carbon and chlorine isotope ratios were observed throughout the unsaturated zone, which corresponded to the isotope ratios measured at the water table. In the saturated zone, TCE became increasingly depleted along a concentration gradient, possibly due to isotope fractionation associated with aqueous phase diffusion. These results indicate that carbon and chlorine isotopes can be used to link vapor phase contamination to their source even if extensive migration of the vapors occurs. However, the numerical model revealed that constant isotope ratios are only expected for systems close to steady state.     

Atmospheric trends and radiative forcings of CF4 and C2F6 inferred from firn air

The atmospheric histories of two potent greenhouse gases, tetrafluoromethane (CF4) and hexafluoroethane (C2F6), have been reconstructed for the 20th century based on firn air measurements from both hemispheres. The reconstructed atmospheric trends show that the mixing ratios of both CF4 and C2F6 have increased during the 20th century by factors of approximately 2 and approximately 10, respectively. Initially, the increasing mixing ratios coincided with the rise in primary aluminum production. However, a slower atmospheric growth rate for CF4 appears to be evident during the 1990s, which supports recent aluminum industry reports of reduced CF4 emissions. This work illustrates the changing relationship between CF4 and C2F6 that is likely to be largely the result of both reduced emissions from the aluminum industry and faster growing emissions of C2F6 from the semiconductor industry. Measurements of C2F6 in the older firn air indicate a natural background mixing ratio of <0.3 parts per trillion (ppt), demonstrating that natural sources of this gas are negligible. However, CF4 was deduced to have a preindustrial mixing ratio of 34 -1 ppt (-50% of contemporary levels). This is in good agreement with the previous work of Harnisch et al. (18) and provides independent confirmation of their results. As a result of the large global warming potentials of CF4 and C2F6, these results have important implications for radiative forcing calculations. The radiative forcings of CF4 and C2F6 are shown to have increased over the past 50 years to values in 2001 of 4.1 x 10(-3) Wm(-2) and 7.5 x 10(-4) Wm(-2), respectively, relative to preindustrial concentrations. These forcings are small compared to present day forcings due to the major greenhouse gases but, if the current trends continue, they will continue to increase since both gases have essentially infinite lifetimes. There is, therefore, a large incentive to reduce perfluorocarbon emissions such that through the implementation of the Kyoto Protocol, the atmospheric growth rates may decline in the future.