The flux of chloroform and tetrachloromethane along an elevational gradient of a coastal salt marsh, East China

The fluxes of trichloromethane (CHCl(3), CM) and tetrachloromethane (CCl(4), TCM) were seasonally measured using static flux chambers over an annual cycle in a coastal salt marsh, East China. The salt marsh presented as a large sink for both the compounds in the growing season (from April to October), but it was a minor source for the gas species in the non-growing season. Generally, the cordgrass marsh acted as a sink of CM and TCM. The net consumption of CM and TCM observed in the study marsh may result from the high ambient atmospheric concentrations and enriched soil organic matter that result in anoxic sediments. Higher plants were suggested to be an important sink for CM and TCM in the growing season, but a net source in the non-growing season. However, the mechanism responsible for the plant removal process is not clear.     

Effects of environmental factors on N2O emission from and CH4 uptake by the typical grasslands in the Inner Mongolia

The fluxes of N2O emission from and CH4 uptake by the typical semi-arid grasslands in the Inner Mongolia, China were measured in 1998-1999. Three steppes, i.e. the ungrazed Leymus chinensis (LC), the moderately grazed Leymus chinensis (LC) and the ungrazed Stipa grandis (SG), were investigated, at a measurement frequency of once per week in the growing seasons and once per month in the non-growing seasons of the LC steppes. In addition, four diurnal-cycles of the growing seasons of the LC steppes, each in an individual stage of grass growth, were measured. The investigated steppes play a role of source for the atmospheric N2O and sink for the atmospheric CH4, with a N2O emission flux of 0.06-0.21 kg N ha(-1) yr(-1) and a CH4 uptake flux of 1.8-2.3 kg C ha(-1) yr(-1). Soil moisture primarily and positively regulates the spatial and seasonal variability of N2O emission. The usual difference in soil moisture among various semi-arid steppes does not lead to significantly different CH4 uptake intensities. Soil moisture, however, negatively regulates the seasonal variability in CH4 uptake. Soil temperature of the most top layer might be the primary driving factor for CH4 uptake when soil moisture is relatively low. The annual net emission of N2O and CH4 from the ungrazed LC steppe, the moderately grazed LC steppe and the ungrazed SG steppe is at a CO2 equivalent rate of 7.7, 0.8 and -7.5 kg CO2-C ha(-1) yr(-1), respectively, which is at an ignorable level. This implies that the role of the semi-arid grasslands in the atmospheric greenhouse effect in terms of net emission of greenhouse gases (CO2, CH4 and N2O) may exclusively depend upon the net exchange of net ecosystem CO2 exchange.     

Fluxes of carbon dioxide, methane and nitrous oxide in two contrastive fringing zones of coastal lagoon, Lake Nakaumi, Japan

We measured fluxes of carbon dioxide (CO(2)), methane (CH(4)), and nitrous oxide (N(2)O) simultaneously in two typical fringing zones, sandy shore and salt marsh, of coastal lagoon, Lake Nakaumi, Japan, in mid-summer 2003. Our aim was to quantify net the greenhouse gases (GHGs) fluxes and examine key factors, which control variation of the GHGs fluxes in the two sites. Net CO(2) and CH(4) fluxes were markedly different between the two sites; magnitudes and variations of the both fluxes in sandy shore were lower than those of salt marsh. Meanwhile, magnitude and variation of net N(2)O flux in the two sites were similar. In sandy shore, temporal and spatial variation of the three GHGs fluxes were highly controlled by water level fluctuation derived from astronomic tide. In salt marsh, spatial variation of the three GHGs fluxes were correlated with aboveground biomass, and temporal variation of CO(2) and CH(4) fluxes were correlated with soil temperature. The sum of global warming potential, which was roughly estimated using the observed GHGs fluxes, was ca. 174-fold higher in salt marsh than in sandy shore.     

Total mercury and methylmercury in freshwater and salt marsh soils of the Mississippi river deltaic plain

Mercury entering wetland environments can be microbially methylated to methylmercury. The purpose of this study was to investigate the historical rate of mercury accumulation and distribution of total and methylmercury in soil profile of Louisiana coastal marshes. Two sediment cores each were taken from Louisiana freshwater marsh and salt marsh. Vertical accretion was determined using the 137Cs dating technique. Total and methylmercury were determined with depth in the soil profiles. The fresh marsh soil on a dry weight basis contained more total and methylmercury than the salt marsh. Average vertical accretion rates in freshwater marsh and salt marsh were 0.90 and 0.75 cm year(-1), respectively. Average total and methylmercury content (to a depth of 30 cm) was 140 and 4.19 microg kg(-1) and 80 and 1.34 microg kg(-1) for the fresh and salt marsh, respectively. Due to greater sediment input resulting in a higher bulk density the salt marsh contained more total mercury per m2 (to 30 cm depth) than the fresh water marsh (5340 microg m(-2) as compared to 2929 microg m(-2)). The amount of methylmercury per m2 to depth of 30 cm was approximately the same for each marsh.     

The methane sink associated to soils of natural and agricultural ecosystems in Italy

In the present work, the CH4 sink associated to Italian soils was calculated by using a process-based model controlled by gas diffusivity and microbial activity, which was run by using a raster-based geographical information system. Georeferenced data included land cover CLC2000, soil properties from the European Soil Database, climatic data from the MARS-STAT database, plus several derived soils properties based on published algorithms applied to the above mentioned databases. Overall CH4 consumption from natural and agricultural sources accounted for a total of 43.3 Gg CH4 yr(-1), with 28.1 Gg CH4 yr(-1) removed in natural ecosystems and 15.1 Gg CH4 yr(-1) in agricultural ecosystems. The highest CH4 uptake rates were obtained for natural areas of Southern Apennines and islands of Sardinia and Sicily, and were mainly associated to areas covered by sclerophyllous vegetation (259.7+/-30.2 mg CH4 m(-2) yr(-1)) and broad-leaved forest (237.5 mg CH4 m(-2) yr(-1)). In terms of total sink strength broad-leaved forests were the dominant ecosystem. The overall contribution of each ecosystem type to the whole CH4 sink depended on the total area covered by the specific ecosystem and on its exact geographic distribution. The latter determines the type of climate present in the area and the dominant soil type, both factors which showed to have a strong influence on CH4 uptake rates. The aggregated CH4 sink, calculated for natural ecosystems present in the Italian region, is significantly higher than previously reported estimates, which were extrapolated from fluxes measured in other temperate ecosystems.     

Degradation rates of CFC-11, CFC-12 and CFC-113 in anoxic shallow aquifers of Araihazar, Bangladesh

Chlorofluorocarbons CFC-11 (CCl(3)F), CFC-12 (CCl(2)F(2)), and CFC-113 (CCl(2)F-CClF(2)) are used in hydrology as transient tracers under the assumption of conservative behavior in the unsaturated and saturated soil zones. However, laboratory and field studies have shown that these compounds are not stable under anaerobic conditions. To determine the degradation rates of CFCs in a tropical environment, atmospheric air, unsaturated zone soil gas, and anoxic groundwater samples were collected in Araihazar upazila, Bangladesh. Observed CFC concentrations in both soil gas and groundwater were significantly below those expected from atmospheric levels. The CFC deficits in the unsaturated zone can be explained by gas exchange with groundwater undersaturated in CFCs. The CFC deficits observed in (3)H/(3)He dated groundwater were used to estimate degradation rates in the saturated zone. The results show that CFCs are degraded to the point where practically no (<5%) CFC-11, CFC-12, or CFC-113 remains in groundwater with (3)H/(3)He ages above 10 yr. In groundwater sampled at our site CFC-11 and CFC-12 appear to degrade at similar rates with estimated degradation rates ranging from approximately 0.25 yr(-1) to approximately 6 yr(-1). Degradation rates increased as a function of reducing conditions. This indicates that CFC dating of groundwater in regions of humid tropical climate has to be carried out with great caution.     

Carbon dioxide fluxes over a grazed prairie and seeded pasture in the Northern Great Plains

Temperate grasslands are vast terrestrial ecosystems that may be an important component of the global carbon (C) cycle; however, annual C flux data for these grasslands are limited. The Bowen ratio/energy balance (BREB) technique was used to measure CO2 fluxes over a grazed mixed-grass prairie and a seeded western wheatgrass [Pascopyrum smithii (Rybd) L?ve] site at Mandan, ND from 24 April to 26 October in 1996, 1997, and 1998. Above-ground biomass and leaf area index (LAI) were measured about every 21 days throughout the season. Root biomass and soil organic C and N content were determined to 110 cm depth in selected increments about mid-July each year. Peak above-ground biomass and LAI coincided with peak fluxes and occurred between mid-July to early August. Biomass averaged 1227 and 1726 kg ha(-1) and LAI 0.44 and 0.59, for prairie and western wheatgrass, respectively. Average CO2 flux for the growing season was 279 g CO2 m(-2) for prairie and 218 g CO2 m(-2) for western wheatgrass (positive flux is CO2 uptake and negative flux is CO2 loss to the atmosphere). Using prior measured dormant season CO2 fluxes from the prairie sites gave annual flux estimates that ranged from -131 to 128 g CO2 m(-2) for western wheatgrass and from -70 to 189 g CO2 m(-2) for the prairie. This wide range in calculated annual fluxes suggests that additional research is required concerning dormant season flux measurements to obtain accurate estimates of annual CO2 fluxes. These results suggest Northern Great Plains mixed-grass prairie grasslands can either be a sink or a source for atmospheric CO2 or near equilibrium, depending on the magnitude of the dormant season flux.     

Key factors affecting spatial variation of methane emissions from freshwater marshes

To understand the mechanism for spatial variation of CH(4) emissions from marshes grown with different type of plants in a region and plots within a certain marsh grown with one type of plants, we measured CH(4) emissions from a region in which eutrophic freshwater marshes were divided into three types: Carex lasiocarpa, Carex meyeruana and Deyeuxia angustifolia according to plant type as well as CH(4) concentration in porewater, aboveground plant biomass and stem density in situ in Sanjiang Plain of Northeast China in August 2001. Spatial variation of CH(4) emissions from both different marshes in a region and different plots within a certain marsh was high. The flux rates of CH(4) emissions from three marshes ranged from 17.2 to 66.5 mg CH(4) m(-2)h(-1) with 34.76% of variation coefficient, whereas the values in Carex lasiocarpa, Carex meyeriana and Deyeuxia angustifolia marshes varied from 21.6 to 66.5 (39.61%), from 17.2 to 45.0 (29.26%) and from 19.1 to 33.0 mg CH(4) m(-2)h(-1) (17.51%), respectively. Both the flux rates and spatial variation of CH(4) emissions strongly increased as standing water depth increased significantly. Standing water depth greatly governed the spatial variation of CH(4) emissions from different marshes in a region by changing the amount of plant litters inundated in standing water, which provided labile organic C for methanogens and controlled CH(4) concentrations in porewater. Moreover, the aboveground plant biomass determined spatial variation of CH(4) emissions from plots within a certain marsh by controlling the pathways (stem density) of CH(4) emissions from the marsh into the atmosphere.     

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.     

Elevational patterns of sulfur deposition at a site in the Catskill Mountains,New York

In this paper we report measurements of SO^2-₄ fluxes in throughfall and bulk deposition across an elevational transect from 800 to 1275 m on Slide Mountain in the Catskill Mountains of southeastern New York State. The net throughfall flux of SO^2-₄ (throughfall-bulk deposition), which we attribute to cloud and dry deposition, increased by roughly a factor of 13 across this elevational range. Part of the observed increase results from the year-round exposure of evergreen foliage at the high-elevation sites, compared to the lack of foliage in the dormant season in the deciduous canopies at low elevations. Comparison of the net throughfall flux with estimates of cloud deposition suggests that both cloud deposition and dry deposition increased with elevation. Dry deposition estimates from a nearby monitoring site fall within the measured range of net throughfall flux for SO^2-₄. The between-site variation in net throughfall flux was very high at the high-elevation sites, and less so at the lower sites, suggesting that studies of atmospheric deposition at high-elevations will be complicated by extreme spatial variability in deposition rates. Studies of atmospheric deposition in mountainous areas of the eastern U.S. have often emphasized cloud water deposition, but these results suggest that elevational increases in dry deposition may also be important.     

Theory and laboratory study of a tall passive chamber for measuring gas fluxes at soil surface

A tall passive flux chamber with a height significantly greater than its horizontal dimensions is proposed for measuring fluxes of volatile organic compounds (VOCs) at the soil surface. The main feature of this tall chamber is the presence of a vertical concentration gradient of the target gas in the chamber. The emission and transport behavior of the target gas in the soil-chamber system are analyzed using the diffusion theory. A mathematical model is developed to estimate the flux from the soil into the tall chamber, providing the target gas establishes a detectable vertical concentration gradient in the chamber. To obtain the data required for calculating flux, only two gas concentrations (C1 and C2) at two heights (h1 and h2) within the chamber need to be measured at the end of a short chamber placement time (tp). To evaluate the applicability of the tall chamber for measuring flux, several laboratory tests have been conducted, using CH2Cl2 and CH3Br as the target gases. The results indicate that the proposed tall chamber has promising potential as a method for measuring fluxes of VOCs at the soil surface.     

Mineralization of CCl4 by the UVC-photolysis of hydrogen peroxide in the presence of methanol

A method for a photochemically induced mineralization of CCl4 is described in which use is made of reductive radicals. The UVC-photolysis (254 nm) of H2O2 added to aqueous solutions of CCl4 is leading to the homolysis of the oxidant yielding hydroxyl radicals (HO) that subsequently react with added methanol to generate hydroxymethyl radicals (CH2OH). The latter radicals initiate mineralization of CCl4 by reductive C-Cl bond splitting. CHCl3, C2Cl4 and C2Cl6 were found as reaction intermediates, but are quantitatively depleted in a parallel oxidative reaction manifold leading to mineralization. Carbon dioxide radical anion, CO2(-), an intermediate in the mineralization pathway of methanol, is also shown to initiate the mineralization of CCl4 by reductive dechlorination. A reaction mechanism is proposed and validated with computer simulations of all the experimental results.     

Direct VUV photolysis of chlorinated methanes and their mixtures in an oxygen stream using an ozone producing low-pressure mercury vapour lamp

The gas-phase photooxidations of CCl(4), CHCl(3), CH(2)Cl(2) and their binary mixtures in an O(2) stream were studied in a flow reactor under various experimental conditions using a low-pressure mercury lamp as light source covered with a high-purity silica sleeve being used. The 184.9 nm VUV irradiation emitted is responsible for the Cl-C bond rupture in the chlorinated methanes and for the formation of O(3) from O(2). The rate of degradation of H-containing chlorinated methanes increased sharply on increase of their initial concentrations, most probably of a (*)Cl chain reaction, as indicated by the increase in the molar ratio of the amount of HCl formed to the amount of H-containing target substance decomposed. The experimental results suggested that the further transformations of the radicals and products formed play an important role as (*)Cl sources, causing a considerably higher rate of decomposition of the H-containing target substances. In a humidified O(2) stream, the (*)OH formed opens up another route for oxidation of the target substances. Thus, the rates of degradation of CH(2)Cl(2) and CHCl(3) increased on increase of the relative humidity, whereas the water vapour had no effect at all on the decomposition of CCl(4). At the same time, competition occurs between (*)Cl or (*)OH for reactions with the target substance. The photooxidation of binary mixtures was investigated too. The addition of CCl(4) or CHCl(3) to CH(2)Cl(2) strongly increased its degradation rate. The addition of CH(2)Cl(2) did not have a considerable effect on the rate of degradation of CHCl(3).     

Trichloroacetic acid cycling in Sitka spruce saplings and effects on sapling health following long term exposure

Trichloroacetic acid (TCA, CCl(3)COOH) has been associated with forest damage but the source of TCA to trees is poorly characterised. To investigate the routes and effects of TCA uptake in conifers, 120 Sitka spruce (Picea sitchensis (Bong.) Carr) saplings were exposed to control, 10 or 100 microg l(-1) solutions of TCA applied twice weekly to foliage only or soil only over two consecutive 5-month growing seasons. At the end of each growing season similar elevated TCA concentrations (approximate range 200-300 ng g(-1) dwt) were detected in both foliage and soil-dosed saplings exposed to 100 microg l(-1) TCA solutions showing that TCA uptake can occur from both exposure routes. Higher TCA concentrations in branchwood of foliage-dosed saplings suggest that atmospheric TCA in solution is taken up indirectly into conifer needles via branch and stemwood. TCA concentrations in needles declined slowly by only 25-30% over 6 months of winter without dosing. No effect of TCA exposure on sapling growth was measured during the experiment. However at the end of the first growing season needles of saplings exposed to 10 or 100 microg l(-1) foliage-applied TCA showed significantly more visible damage, higher activities of some detoxifying enzymes, lower protein contents and poorer water control than needles of saplings dosed with the same TCA concentrations to the soil. At the end of each growing season the combined TCA storage in needles, stemwood, branchwood and soil of each sapling was <6% of TCA applied. Even with an estimated half-life of tens of days for within-sapling elimination of TCA during the growing season, this indicates that TCA is eliminated rapidly before uptake or accumulates in another compartment. Although TCA stored in sapling needles accounted for only a small proportion of TCA stored in the sapling/soil system it appears to significantly affect some measures of sapling health.     

The distinctive isotopic signature of plant-derived chloromethane: possible application in constraining the atmospheric chloromethane budget

Chloromethane (CH(3)Cl) is the most abundant halocarbon in the atmosphere. Although largely of natural origin it is responsible for around 17% of chlorine-catalysed ozone destruction. Sources identified to date include biomass burning, oceanic emissions, wood-rotting fungi, higher plants and most recently tropical ferns. Current estimates reveal a shortfall of around 2 million ty(-1) in sources versus sinks for the halocarbon. It is possible that emissions from green plants have been substantially underestimated. A potentially valuable tool for validating emission flux estimates is comparison of the delta13C value of atmospheric CH(3)Cl with those of CH(3)Cl from the various sources. Here we report delta13C values for CH(3)Cl released by two species of tropical ferns and show that the isotopic signature of CH(3)Cl from pteridophytes like that of CH(3)Cl from higher plants is quite different from that of CH(3)Cl produced by biomass burning, fungi and industry. delta13C values for CH(3)Cl produced by Cyathea smithii and Angiopteris evecta were respectively -72.7 per thousand and -69.3 per thousand representing depletions relative to plant biomass of 42.3 per thousand and 43.4 per thousand. The characteristic isotopic signature of CH(3)Cl released by green plants should help constrain their contribution to the atmospheric burden when reliable delta13C values for all other major sources of CH(3)Cl are obtained and a globally averaged delta13C value for atmospheric CH(3)Cl is available.     

Direct VUV photolysis of chlorinated methanes and their mixtures in a nitrogen stream

The gas-phase decomposition of CCl(4), CHCl(3) and CH(2)Cl(2) and their binary mixtures was studied in a flow-type reactor in a nitrogen gas stream, using a low-pressure mercury vapour lamp covered with a high-purity silica quartz sleeve. The 184.9 nm vacuum-ultraviolet (VUV) light emitted is able to rupture the C-Cl bond in these target substances. For H-containing compounds, the decomposition takes place not only by direct photolysis, but also by H abstraction by .Cl formed during the direct photolysis of the target substances. The relative contributions of direct photolysis and .Cl-sensitized reactions to the decomposition were estimated at different initial concentrations. The addition of CCl(4) to CHCl(3) or CH(2)Cl(2) increased their decomposition rates via increase of the .Cl concentration, whereas the addition of CH(2)Cl(2) to CHCl(3) decreased its degradation rate, suggesting that CH(2)Cl(2) acts as a .Cl radical scavenger. The variation of the product distribution confirms the effect of the composition of the irradiated gas mixtures on the relative contributions of .Cl-sensitized reactions and direct photolysis.     

Effect of land-use change on CH4 and N2O emissions from freshwater marsh in Northeast China

The wetlands play an important role in global carbon and nitrogen storage, and they are also natural sources of greenhouse gases such as methane (CH₄) and nitrous oxide (N₂O). Land-use change is an important factor affecting the exchange of greenhouse gases between wetlands and the atmosphere. However, few studies have investigated the effect of land-use change on CH₄ and N₂O emissions from freshwater marsh in China. Therefore, a field study was carried out over a year to investigate the seasonal changes of the emissions of CH₄ and N₂O at three sites (Deyeuxia angustifolia marsh, dryland and rice field) in the Sanjiang Plain of Northeast China. Marsh was the source of CH₄ showing a distinct temporal variation. Maximum fluxes occurred in June and the highest value was 20.69 ± 2.57 mg CH₄ m^?2 h^?1. The seasonal change of N₂O fluxes from marsh was not obvious, consisted of a series of emission pulses. The marsh acted as a N₂O sink during winter, while became a N₂O source in the growing season. The results showed that gas exchange between soil/snow and the atmosphere in the winter season contributed greatly to the annual budgets. The winter season CH₄ flux was about 3.24% of the annual flux and the winter uptake of N₂O accounted for 13.70% of the growing-season emission. Conversion marsh to dryland resulted in a shift from a strong CH₄ source to a weak sink (from 199.12 ± 39.04 to ?1.37 ± 0.68 kg CH₄ ha^?1 yr^?1), while increased N₂O emissions somewhat (from 4.07 ± 1.72 to 4.90 ± 1.52 kg N₂O ha^?1 yr^?1). Conversion marsh to rice field significantly decreased CH₄ emission from 199.12 ± 39.04 to 94.82 ± 9.86 kg CH₄ ha^?1 yr^?1 and N₂O emission from 4.07 ± 1.72 to 2.09 ± 0.79 kg N₂O ha^?1 yr^?1.     

Episodic release of methane bubbles from peatland during spring thaw

Methane (CH(4)) flux into the atmosphere during spring thaw was investigated in a small ombrotrophic peatland (141 degrees 48'E, 43 degrees 19'N, Japan) using the conventional chamber method. More than 50 chamber deployments on top of the snow cover were carried out and continued for more than 165h until the surface snow and underlying ice cover on top of the peat layer had thawed completely. Methane emissions were almost absent in the presence of snow cover. At the very moment the surface ice cover thawed, a large CH(4) flush (>10mgCH(4)m(-2)h(-1)) was recorded, which was on the same order of magnitude as episodic ebullition previously observed in the high-summer. Gas bubbles trapped in the ice layer on top of the waterlogged peat were preliminarily analyzed for the volumetric percentage in the total ice volume and their gas species compositions. Results showed that the bubbles occupied about 3.2% volume and that the mixing ratio of CH(4) in the bubbles was about 20%. The abundance of the bubble-form CH(4) was sufficient to explain the observed episodic CH(4) release during the thaw. Results of this study show that CH(4) emissions during the thaw season have great temporal variability; emission occurs as an episodic release of bubble-form CH(4) stored in the frozen layer. The results also imply the possibility that gas-phase CH(4) plays an important role, not only during the growing season but also in cold-season CH(4) dynamics in northern peatlands.     

Regeneration of a compost biofilter degrading high loads of ammonia by addition of gaseous methanol

The long-term stability of a biofilter loaded with waste gases containing NH3 concentrations larger than 100 ppmv was studied in a laboratory-scale compost reactor. At an empty bed residence time (tau) of 21 sec, elimination capacities of more than 300 g NH3/m3/day were obtained at elimination efficiencies up to 87%. Because of absorption and nitrification, almost 80% of the NH3-N eliminated from the waste gas could be recovered in the compost as NH4(+)-N or NO2-/NO3(-)-N. The high elimination capacities could be maintained as long as the NH4+/ NOX- concentration in the carrier material was less than 4 g NH4+/NOx(-)-N/kg wet compost. Above this critical value, osmotic effects inhibited the nitrifying activity, and the elimination capacity for NH3 decreased. To restore the biofilter performance, a carbon source (methanol) was added to reduce NH4+/NOx- accumulated in the compost. Results indicate that methylotrophic microorganisms did convert NH4+/NOx- into biomass, as long as the NO3- content in the compost was larger than 0.1 g NO3(-)-N/kg compost. Removal efficiencies of CH3OH of more than 90% were obtained at volumetric loads up to 11,000 g CH3OH/ m3/day. It is shown that addition of CH3OH is a suitable technique for regenerating the compost material from osmotic inhibition as a result of high NH3 loading. The biofilter was operated for 4 months with alternating load ing of NH3 and CH3OH.     

Geologic emissions of methane to the atmosphere

The atmospheric methane budget is commonly defined assuming that major sources derive from the biosphere (wetlands, rice paddies, animals, termites) and that fossil, radiocarbon-free CH4 emission is due to and mediated by anthropogenic activity (natural gas production and distribution, and coal mining). However, the amount of radiocarbon-free CH4 in the atmosphere, estimated at approximately 20% of atmospheric CH4, is higher than the estimates from statistical data of CH4 emission from fossil fuel related anthropogenic sources. This work documents that significant amounts of "old" methane, produced within the Earth crust, can be released naturally into the atmosphere through gas permeable faults and fractured rocks. Major geologic emissions of methane are related to hydrocarbon production in sedimentary basins (biogenic and thermogenic methane) and, subordinately, to inorganic reactions (Fischer-Tropsch type) in geothermal systems. Geologic CH4 emissions include diffuse fluxes over wide areas, or microseepage, on the order of 10(0)-10(2) mg m(-2) day(-1), and localised flows and gas vents, on the order of 10(2) t y(-1), both on land and on the seafloor. Mud volcanoes producing flows of up to 10(3) t y(-1) represent the largest visible expression of geologic methane emission. Several studies have indicated that methanotrophic consumption in soil may be insufficient to consume all leaking geologic CH4 and positive fluxes into the atmosphere can take place in dry or seasonally cold environments. Unsaturated soils have generally been considered a major sink for atmospheric methane, and never a continuous, intermittent, or localised source to the atmosphere. Although geologic CH4 sources need to be quantified more accurately, a preliminary global estimate indicates that there are likely more than enough sources to provide the amount of methane required to account for the suspected missing source of fossil CH4.