Surface measurements of trace gases in the tropical region near hyderabad

Surface air samples were collected near Hyderabad during the period of 12–27 March 1985. These samples were analysed for CFC-11, CFC-12, CFC-114, CFC-12B1, CH₄ and CO using gas Chromatographic techniques. Results show lower mixing ratios of these halogenated hydrocarbons near Hyderabad compared with concentrations observed at other places in the tropical/extratropical regions. However, the concentration of methane observed near Hyderabad is the same as the annual average observed in the same latitude region as well as the global average. This indicates that there is no significant regional source of these species in the Hyderabad region.     

Latitudinal distributions of trace gases in and above the boundary layer

Statistical analyses of global atmospheric concentrations provide evidence that C₂Cl₄, CHCl₃ and CH₃CCl₃ (methylchloroform) are more abundant in the tropical boundary layer than above it (α ? 0.09) by 27% (±27%), 21% (?21%, +12%) and 6.4% (±6%) respectively. The air samples on which these results are based were collected by cryogenic techniques during the June 1978 project GAMETAG flights and analyzed soon afterwards by gas chromatography (EC/GC and GC/FID), thus providing latitudinal concentrations of CO, CH₄, CCl₃F, CCl₂F₂, CH₃CCl₃ and light C₂-hydrocarbons, both in and above the boundary layer. In August 1980, after further development of analytical techniques, the stored air samples were re-analyzed to establish the latitudinal distributions of CH₃I, CHCl₃, C₂Cl₄, C₂F₃Cl₃ (F-113) and CHClF₂ (F-22) in and above the boundary layer. Stability studies, spanning a year, show that the concentrations of these gases do not change in the flasks.     

Measurements of primary trace gases and NOY composition in Houston,Texas

Concentrations of CO, SO₂, NO, NO₂, and NO_Y were measured atop the University of Houston's Moody Tower supersite during the 2006 TexAQS-II Radical and Aerosol Measurement Project (TRAMP). The lowest concentrations of all primary and secondary species were observed in clean marine air in southerly flow. SO₂ concentrations were usually low, but increased dramatically in sporadic midday plumes advected from sources in the Houston Ship Channel (HSC), located NE of the site. Concentrations of CO and NO_x displayed large diurnal variations in keeping with their co-emission by mobile sources in the Houston Metropolitan Area (HMA). CO/NO_x emission ratios of 5.81 ± 0.94 were observed in the morning rush hour. Nighttime concentrations of NO_x (NO_x = NO + NO₂) and NO_Y (NO_Y = NO + NO₂ + NO₃ + HNO₃ + HONO + 21N₂O₅ + HO₂NO₂ + PANs + RONO₂ + p-NO₃^? + …) were highest in winds from the NNW-NE due to emission from mobile sources. Median ratios of NO_x/NO_Y were approximately 0.9 overnight, reflecting the persistence and/or generation of NO_Z (NO_Z = NO_Y ? NO_x) species in the nighttime Houston boundary layer, and approached unity in the morning rush hour. Daytime concentrations of NO_x and NO_Y were highest in winds from the HSC. NO_x/NO_Y ratios reached their minimum values (median ca 0.63) from 1300 to 1500 CST, near local solar noon, and air masses often retained enough NO_x to sustain additional O₃ formation farther downwind. HNO₃ and PANs comprised the dominant NO_Z species in the HMA, and on a median basis represented 17–20% and 12–15% of NO_Y, respectively, at midday. Concentrations of HNO₃, PANs, and NO_Z, and fractional contributions of these species to NO_Y, were at a maximum in NE flow, reflecting the source strength and reactivity of precursor emissions in the HSC. As a result, daytime O₃ concentrations were highest in air masses with HSC influence. Overall, our findings confirm the impact of the HSC as a dominant source region within the HMA. A comparison of total NO_Y measurements with the sum of measured NO_Y species (NO_Yi = NO_x + HNO₃ + PANs + HONO + p-NO₃^?) yielded excellent overall agreement during both day ([NO_Y](ppb) = ([NO_Yi](ppb)11.03 ± 0.16) ? 0.42; r² = 0.9933) and night ([NO_Y](ppb) = ([NO_Yi](ppb)11.01 ± 0.16) + 0.18; r² = 0.9975). A similar comparison between NO_Y–NO_x concentrations and the sum of NO_Zi (NO_Zi = HNO₃ + PANs + HONO + p-NO₃^?) yielded good overall agreement during the day ([NO_Z](ppb) = ([NO_Zi](ppb)11.01 ± 0.30) + 0.044 ppb; r² = 0.8527) and at night ([NO_Z](ppb) = ([NO_Zi](ppb)11.12 ± 0.69) + 0.16 ppb; r² = 0.6899). Median ratios of NO_Z/NO_Zi were near unity during daylight hours but increased to approximately 1.2 overnight, a difference of 0.15–0.50 ppb. Differences between NO_Z and NO_Zi rarely exceeded combined measurement uncertainties, and variations in NO_Z/NO_Zi ratios may have resulted solely from errors in conversion efficiencies of NO_Y species and changes in NO_Y composition. However, nighttime NO_Z/NO_Zi ratios and the magnitude of NO_Z ? NO_Zi differences were generally consistent with recent observations of ClNO₂ in the nocturnal Houston boundary layer.     

Atmospheric trace gases: Possibility of sources in the southern hemisphere

When measurements of globally distributed trace gases establish their existence in the southern hemisphere, it is not always clear whether their presence is due to transport from the northern hemisphere or partly from significant sources in the southern hemisphere. In this paper a simple criterion is developed whereby one can determine if significant southern hemisphere sources exist for a given trace gas. Despite the limitations of the model, there are strong indications that C₂ hydrocarbons (C₂H₂, C₂H₄, C₂H₆), CO and CH₄ have significant southern hemisphere sources.     

Correction for water vapor in the measurement of atmospheric trace gases

The presence of water vapor in a sample of air reduces the concentration of a trace gas measured from the sample. We present a methodology to correct for this effect for those cases when the concentration of the trace gas has already been measured from a wet sample. The conversion or correction factor that takes the wet mole fraction to a dry mole fraction is determined by the mixing ratio of water vapor inside the sampling canister. For those samples where the water vapor is saturated inside the canister, the water vapor mixing ratio is largely determined by laboratory conditions; for the unsaturated samples, the mixing ratio is determined by station conditions. If the meteorology at the sampling station is known, the equations presented here can be used directly to calculate the appropriate correction factor. For convenience, we use climatological data to derive average monthly correction factors for seven common global sampling sites: Barrow, AK, US (71 degrees N, 157degrees W); Cape Meares, OR, US (45 degrees N, 124 degrees W); Mauna Loa, HI, US (19 degrees N, 155 degrees W); Ragged Point, Barbados (13 degrees N, 59 degrees W); American Samoa (14 degrees S, 171 degrees W); Cape Grim, Tasmania, Australia (41 degrees S, 145 degrees E); South Pole (90 degrees S). These factors adjust wet mole fractions upwards within a range of 0.002% for the South Pole to over 0.8% for saturated sites. We apply the correction factors to wet nitrous oxide (N2O) mole fractions. The corrected data are more consistent with our understanding of N2O sources.     

Biodegradation of trace gases in simulated landfill soil cover systems

The attenuation of methane and seven volatile organic compounds (VOCs) was investigated in a dynamic methane and oxygen counter gradient system simulating a landfill soil cover. The VOCs investigated were: Tetrachloromethane (TeCM), trichloromethane (TCM), dichloromethane (DCM), trichloroethylene (TCE), vinyl chloride (VC), benzene, and toluene. Soil was sampled at Skellingsted landfill, Denmark. The soil columns showed a high capacity for methane oxidation, with oxidation rates up to 184 g/m2/d corresponding to a 77% reduction of inlet methane. Maximal methane oxidation occurred at 15-20 cm depth, in the upper part of the column where there were overlapping gradients of methane and oxygen. All the chlorinated hydrocarbons were degraded in the active soil columns with removal efficiencies higher than 57%. Soil gas concentration profiles indicated that the removal of the fully chlorinated compound TeCM was because of anaerobic degradation, whereas the degradation of lower chlorinated compounds like VC and DCM was located in the upper oxic part of the column. Benzene and toluene were also removed in the active column. This study demonstrates the complexity of landfill soil cover systems and shows that both anaerobic and aerobic bacteria may play an important role in reducing the emission of trace components into the atmosphere.     

Climatic effect of observed changes in atmospheric trace gases at Antarctica

The seasonal decline in ozone in the Antarctic atmosphere has been termed the ‘Antarctic ozone hole’. Possibly this hole is caused by upper atmospheric wind, due to resumption of high solar activity after the polar night which produces large amounts of ozone-destroying nitric oxide or due to unusual chlorine chemistry at extreme cold temperatures and associated polar stratospheric clouds. Of particular concern is that the observed changes in ozone could be linked to the observed increases in the gases that affect ozone such as methane, nitrous oxide, etc. All these gases affect the climate of the Earth through their so-called ‘greenhouse’ action. We have examined the nature of the greenhouse effect on polar climate due to observed changes in atmospheric trace gases in Antarctica which are reported here.     

Scavenging of soluble trace gases by falling rain droplets in inhomogeneous atmosphere

We analyze non-isothermal absorption of trace gases by the rain droplets with internal circulation which is caused by interfacial shear stresses. It is assumed that the concentration of soluble trace gases and temperature in the atmosphere varies in a vertical direction. The rate of scavenging of soluble trace gases by falling rain droplets is determined by solving heat and mass transfer equations. In the analysis we accounted for the accumulation of the absorbate in the bulk of the falling rain droplet. The problem is solved in the approximation of a thin concentration and temperature boundary layers in the droplet and in the surrounding air. We assumed that the bulk of a droplet, beyond the diffusion boundary layer, is completely mixed and concentration of the absorbate and temperature are homogeneous and time-dependent in the bulk. By combining the generalized similarity transformation method with Duhamel's theorem, the system of transient conjugate equations of convective diffusion and energy conservation for absorbate transport in liquid and gaseous phases with time-dependent boundary conditions is reduced to a system of linear convolution Volterra integral equations of the second kind which is solved numerically. Calculations are performed using available experimental data on concentration and temperature profiles in the atmosphere.It is shown than if concentration of a trace gas in the atmosphere is homogeneous and temperature in the atmosphere decreases with height, beginning from some altitude gas absorption is replaced by gas desorption. Neglecting temperature inhomogenity in the atmosphere described by adiabatic lapse rate leads to essential overestimation of the trace gas concentration in a droplet on the ground.     

Sulfate and nitrate mixing ratios in the vicinity of the tropopause

Measurements of sulfate and nitrate in filter samples made during the Global Atmospheric Sampling Program (GASP) from aircraft flying near the tropopause over a period of 28 months beginning in early 1976 are presented. Sulfate and nitrate mixing ratios show a peak near or just above the tropopause during the winter-spring seasons. No peak is evident for sulfate during the summer-fall seasons. The sulfate mixing ratios show a constant average level in 1977–1978 of 0.12 ± 0.04 ppbm above the tropopause and 0.05 ± 0.04 ppbm below the tropopause with higher levels in the spring. Nitrate levels are similar but exhibit greater variability. Correlations between sulfate and nitrate (r = 0.78) and between sulfate and nitrate, on ozone (r = 0.80, 0.78) suggest a predominately stratospheric source for these species.     

Dissolved trace element biogeochemistry of a tropical river, Southwestern India

River Swarna, a small tropical river originating in Western Ghats (at an altitude of 1,160 m above mean sea level) and flowing in the southwest coast of India discharges an average of 54 m³s^?1 of water into the Arabian Sea, of which significant part is being discharged during the monsoon. No studies have been made yet on the water chemistry of the Swarna River basin, even as half a million people of Udupi district use it for domestic and irrigational purposes. As large community in this region depends on the freshwater of Swarna River, there is an urgent need to study the trace element geochemistry of this west flowing river for better water management and sustainable development. The paper presents the results on the biogeochemistry of dissolved trace elements in the Swarna River for a period of 1 year. The results obtained on the trace elements show seasonal effect on the concentrations as well as behavior and thus forming two groups, discharge driven (Li, Be, Al, V, Cr, Ni, Zr, In, Pb, Bi and U) and base flow driven (groundwater input; Mn, Fe, Co, Cu, Ga, Zn, As, Se, Rb, Sr, Ag, Cd, Cs, Ba and Tl) trace elements in Swarna River. The biogeochemical processes explained through Hierarchical Cluster Analysis show complexation of Fe, Ga and Ba with dissolved organic carbon, redox control over Mn and Tl and biological control over V and Ni. Also, the water quality of Swarna River remains within the permissible limits of drinking water standards.     

Estimating source regions of European emissions of trace gases from observations at Mace Head

A technique is described for identifying probable source locations for a range of greenhouse and ozone-depleting trace gases from the long-term measurements made at Mace Head, Ireland. The Met. Office's dispersion model NAME is used to predict concentrations at Mace Head from all possible sources in Europe, then source regions identified as those which consistently lead to elevated concentrations at Mace Head. Estimates of European emissions and their distribution are presented for a number of trace gases for the period 1995–1998. Estimated emission patterns are realistic, given the nature and varied applications of the species considered. The results indicate that whilst there are limitations, useful information about source distribution can be extracted from continuous measurements at a remote site. It is probable that much improved estimates could be derived if observations were available from a number of sites. The ability to assess emissions has obvious implications in monitoring compliance with internationally agreed quota and protocols.     

Measurements of the streaming potential of clay soils from tropical and subtropical regions using self-made apparatus

The streaming potential has been wildly used in charged parallel plates, capillaries, and porous media. However, there have been few studies involving the ζ potential of clay soils based on streaming potential measurements. A laboratory apparatus was developed in this study to measure the streaming potential (ΔE) of bulk clay soils’ coupling coefficient (C) and cell resistance (R) of saturated granular soil samples. Excellent linearity of ΔE versus liquid pressure (ΔP) ensured the validity of measurements. The obtained parameters of C and R can be used to calculate the ζ potential of bulk soils. The results indicated that the ζ potentials measured by streaming potential method were significantly correlated with the ζ potentials of soil colloids determined by electrophoresis (r ²?=?0.960**). Therefore, the streaming potential method can be used to study the ζ potentials of bulk clay soils. The absolute values of the ζ potentials of four soils followed the order: Ultisol from Jiangxi?>?Ultisol from Anhui?>?Oxisol from Guangdong?>?Oxisol from Hainan, and this was consistent with the cation exchange capacities of these soils. The type and concentration of electrolytes affected soil ζ potentials. The ζ potential became less negative with increased electrolyte concentration. The ζ potentials were more negative in monovalent than in divalent cationic electrolyte solutions because more divalent cations were distributed in the shear plane of the diffuse layer as counter-cations on the soil surfaces than monovalent cations at the same electrolyte concentration.     

Agriculture's share in the emission of trace gases affecting the climate and some cause-oriented proposals for sufficiently reducing this share

This paper discusses agriculture's share in the world-wide emissions of climate-affecting gases and in the global warming potential (GWP). Proposals also are presented to reduce these emissions adequately, using a cause-oriented approach. Largely due to the fertilization and cultivation of agriculture as well as the burning of biomass, agriculture has a very high share in the anthropogenic emissions of NH(3), N(2)O, CH(4) and CO at >95%, 81%, 70% and 52%, respectively, while its share in the NO(x) and CO(2) emissions is relatively small at 35% and 21%. The GWP of agriculture, based on annually 16.1 x 10(9) tons of CO(2), approaches 63% of the GWP of the energy sector or 80% of the GWP of its CO(2) emissions. At 34% and 32%, respectively, the main originators in the GWP of agriculture would seem to be CO(2) (changing land use) and CH(4) (animal husbandry/rice cropping/biomass burning) followed at 15% by NO(2) (technical and biological N fixation/(cultivation and recultivation/biomass burning) and 10% and 9% by CO and NO(x). The GWP of 3 German dairy cows corresponds with 13.2 tonnes CO(2) per year the GWP of two average German automobiles. However, the ozone-destroying effect of N(2)O and the climate-relevant effects of NH(3) are not yet included here. As with the therapy for other 'modern' boundary-crossing environmental damages, such as acidification or eutrophication, global climate change therapy likewise needs a therapy for the respective effects of reactive compounds of carbon, nitrogen, phosphorous, and sulfur also emitted by agriculture. Proposals for reducing these emissions within the agricultural sector include need-oriented plant, animal and human nutrition, more efficient external and internal nutrient recycling, the cessation of further clearing by burning, along with intensified afforestation mainly in the tropics, targeted measures to reduce nutrient losses/emissions, and measures for more efficient use of nutrients in plant, animal and human nutrition. These measures would at best result in reduced pollution of the global environment but not put it to an end. Decisive, therefore, is both the tolerable extent of mankind and its long-term sustainable way of life.     

Geochemical behaviour of dissolved trace elements in a monsoon-dominated tropical river basin,Southwestern India

The study presents a 3-year time series data on dissolved trace elements and rare earth elements (REEs) in a monsoon-dominated river basin, the Nethravati River in tropical Southwestern India. The river basin lies on the metamorphic transition boundary which separates the Peninsular Gneiss and Southern Granulitic province belonging to Archean and Tertiary–Quaternary period (Western Dharwar Craton). The basin lithology is mainly composed of granite gneiss, charnockite and metasediment. This study highlights the importance of time series data for better estimation of metal fluxes and to understand the geochemical behaviour of metals in a river basin. The dissolved trace elements show seasonality in the river water metal concentrations forming two distinct groups of metals. First group is composed of heavy metals and minor elements that show higher concentrations during dry season and lesser concentrations during the monsoon season. Second group is composed of metals belonging to lanthanides and actinides with higher concentration in the monsoon and lower concentrations during the dry season. Although the metal concentration of both the groups appears to be controlled by the discharge, there are important biogeochemical processes affecting their concentration. This includes redox reactions (for Fe, Mn, As, Mo, Ba and Ce) and pH-mediated adsorption/desorption reactions (for Ni, Co, Cr, Cu and REEs). The abundance of Fe and Mn oxyhydroxides as a result of redox processes could be driving the geochemical redistribution of metals in the river water. There is a Ce anomaly (Ce/Ce*) at different time periods, both negative and positive, in case of dissolved phase, whereas there is positive anomaly in the particulate and bed sediments. The Ce anomaly correlates with the variations in the dissolved oxygen indicating the redistribution of Ce between particulate and dissolved phase under acidic to neutral pH and lower concentrations of dissolved organic carbon. Unlike other tropical and major world rivers, the effect of organic complexation on metal variability is negligible in the Nethravati River water.     

Organic trace gas composition of the marine boundary layer over the northwest Indian Ocean in April 2000

In April 2000 atmospheric trace gas measurements were performed on the western Indian Ocean on a cruise of the Dutch research vessel Pelagia from the Seychelles (5°S, 55°E) to Djibouti (12°N, 43°E). The measurements included analysis of dimethyl sulfide (DMS), acetone and acetonitrile every 40 s using PTR-MS (proton-transfer-reaction mass spectrometry) and gas chromatographic analyses of C₂–C₇ hydrocarbons in air samples taken during the cruise. The measurements took place at the end of the winter monsoon season and the sampled air masses came predominantly from the Southern Hemisphere, resulting in low concentrations of some long-lived hydrocarbons, halocarbons, acetone (350 pptv) and acetonitrile (120 pptv). On three consecutive days a diurnal cycle in DMS concentration was observed, which was used to estimate the emission of DMS (1.5±0.7×10¹³ molecules m⁻² s⁻¹) and the 24 h averaged concentration of hydroxyl (OH) radicals (1.4±0.7×10⁶ molecules cm⁻³). A strongly increased DMS concentration was found at a location where upwelling of deeper ocean waters took place, coinciding with a marked decrease in acetone and acetonitrile. In the northwestern Indian Ocean a slight increase of some trace gases was noticed showing a small influence of pollution from Asia and from northeast Africa as indicated with back trajectory calculations. The air masses from Asia had elevated acetonitrile concentrations showing some influence of biomass burning as was also found during the 1999 Indian Ocean Experiment, whereas the air masses from northeast Africa seemed to have other sources of pollution.     

Production of boundary layer ozone from tropical American Savannah biomass burning emissions

Boundary layer ozone and carbon monoxide were measured at a savannah site in the Orinoco river basin, during the dry and wet seasons. CO and O₃ concentrations recorded around noontime show a good linear correlation, suggesting that the higher ozone levels observed during the dry season are photochemically produced during the oxidation of reactive hydrocarbons in the presence of NO_x both emitted by biomass burning. The rate of photochemical ozone production in the boundary layer ozone by biomass burning calculated from the production ratio ΔO₃/ΔCO (0.17±0.01 v : v) and the amount of CO produced by fires (0.26–1.3 mole m⁻² dry season⁻¹), ranges from 0.6 to 2.6 ppbv h⁻¹ for 8 h of daylight. This O₃ production rate is in fairly good agreement with the value derived from RO₂ radical measurements made in the Venezuelan savannah during the dry season. The net boundary layer production of O₃ from all tropical America savannah fires is estimated to range between 0.28 and 0.36 Tmol O₃ per year, which is about 3 times higher than the O₃ produced from pollution sources in the eastern United States during the summer. An extrapolation to all of the world's savannah would indicate a net boundary layer ozone production of about 1.2 Tmol yr⁻¹. This is discussed in the context of the overall global budget of tropospheric ozone.     

Uncertainties in the current knowledge of some atmospheric trace gases associated with U.S. agriculture: a review

Approximately 80 different crop species are grown in the United States in widely differing geographic areas, climatic and edaphic conditions, and management practices. Although the majority of cultivated acreage in the United States is planted with only about 10 primary crops, uncertainties associated with trace gas emissions arise from: (1) limited data availability, (2) inaccurate estimates because of large temporal and spatial variability in trace gas composition and magnitude of trace gas emissions from agricultural activities, (3) differing characteristics of pollutant emissions from highly dispersed animal feed-lots, and (4) limited understanding of the emissions of semi-volatile organic compounds (SVOCs) associated with agriculture. Although emission issues are of concern, so also is atmospheric deposition to cropping systems, including wet and dry nitrogen, minerals, and organic compounds. These can have feedback effects on trace gas emissions. Overall, the many gaps in our understanding of these aspects of agricultural systems deserve serious attention.     

The role of precursor gases and meteorology on temporal evolution of O3 at a tropical location in northeast India

South Asia, particularly the Indo-Gangetic Plains and foothills of the Himalayas, has been found to be a major source of pollutant gases and particles affecting the regional as well as the global climate. Inventories of greenhouse gases for the South Asian region, particularly the sub-Himalayan region, have been inadequate. Hence, measurements of the gases are important from effective characterization of the gases and their climate effects. The diurnal, seasonal, and annual variation of surface level O₃ measured for the first time in northeast India at Dibrugarh (27.4° N, 94.9° E, 111 m amsl), a sub-Himalayan location in the Brahmaputra basin, from November 2009 to May 2013 is presented. The effect of the precursor gases NO _x and CO measured simultaneously during January 2012–May 2013 and the prevailing meteorology on the growth and decay of O₃ has been studied. The O₃ concentration starts to increase gradually after sunrise attaining a peak level around 1500 hours LT and then decreases from evening till sunrise next day. The highest and lowest monthly maximum concentration of O₃ is observed in March (42.9?±?10.3 ppb) and July (17.3?±?7.0 ppb), respectively. The peak in O₃ concentration is preceded by the peaks in NO _x and CO concentrations which maximize during the period November to March with peak values of 25.2?±?21.0 ppb and 1.0?±?0.4 ppm, respectively, in January. Significant nonlinear correlation is observed between O₃ and NO, NO₂, and CO. National Atmospheric and Oceanic Administration Hybrid Single-Particle Lagrangian Integrated Trajectory back-trajectory and concentration weighted trajectory analysis carried out to delineate the possible airmass trajectory and to identify the potential source region of NO _x and O₃ concentrations show that in post-monsoon and winter, majority of the trajectories are confined locally while in pre-monsoon and monsoon, these are originated at the Indo-Gangetic plains, Bangladesh, and Bay of Bengal.