Transfer of CO2, N2O and CH4 to butyl rubber (polyisobutylene) septa during storage

Greenhouse gases are more sampled than ever because of environmental interests. Gas samples are often inserted into vials with gas tight butyl rubber septa before concentration analysis. Little is known on the global transfer property of butyl rubber septa for CO2, N2O and CH4. Sorption kinetics were measured by injecting CO2, N2O or CH4 into glass vials with either one of four butyl rubber septa types and stored during 90 days. CO2 and N2O concentrations decreased during storage depending upon septa type and initial concentration, with the highest linear rate being 0.023 for CO2 and 0.0015 mg L(-3) day(-1) for N2O. When a low concentration was injected, CH4 concentration changes over time were small and did not differ between septa types. Sorption isotherms were measured using nine concentrations and stored during 45 days. CO2 sorption isotherms ranged from 0 to 3.7 x 10(-3) m(3) m(-2) and N2O from 0.3 to 1.4 x 10(-3) m(3) m(-2). Examples of errors associated with the use of these butyl rubber septa are given.     

Emissions of N2O and CH4 during the Composting of Liquid Swine Manure

Composted organic wastes have been shown to reduce emissions of N2O and CH4, but little is known about the release of these gases during the composting process. This research examined the emissions of N2O and CH4 during the composting of liquid swine manure and wheat straw at two operations, one with forced aeration and the other without. The lack of aeration increased CH4 emissions to 24 times that of composting with aeration, but had no significant effect on N2O production. When total N2O and CH4 emissions from composting were compared with liquid swine manure emissions, aerated composting was found to reduce emissions to as low as 30% of those from liquid manure storage, while non-aerated composting elevated emissions up to an estimated 330% of liquid manure storage.     

Determination of CH4, CO2 and N2O in air samples and soil atmosphere by gas chromatography mass spectrometry, GC-MS

A method for determination of the climate gases CH4, CO2 and N2O in air samples and soil atmosphere was developed using GC-MS. The method uses straightforward gas chromatography (separation of the gases) with a mass spectrometric detector in single ion mode (specific determination). The gases were determined with high sensitivity and high sample throughput (18 samples h(-1)). The LOD (3sigma) for the gases were 0.10 micro L L(-1) for CH4, 20 microL L(-1) for CO2 and 0.02 microL L(-1) for N2O. The linear range (R2 = 0.999) was up to 500 microL L(-1) for CH4, 4000 microL L(-1) for CO2 and 80 microL L(-1) for N2O. The samples were collected in 10 mL vials and a 5 microL aliquot was injected on column. The method was tested against certified gas references, the analytical data gave an accuracy within +/-5% and a precision of +/-3%. The presence of < or = 10% by volume of C2H2 (often used experimentally to prevent N2 formation from N2O) did not interfere with detection for the targeted trace gases.     

北京大气CH4、CO2、TOC日变化规律及垂直分布的自动连续观测

提出了一种能自动连续监测CH4、CO2、TOC日变化及垂直分布的系统,利用该系统监测了2002年冬季CH4、CO2、TOC垂直分布的日变化的变化趋势.结果发现,距地面高度增加,受湍流扩散的影响,CH4、CO2、TOC浓度降低.冬季CH4浓度的日变化呈现明显的单峰周期变化,CO2日变化呈双峰形分布,TOC日变化没有明显的特征,其日变化受机动车尾气排放的影响很大.根据2002年冬季CO2浓度与2000年以前的对比结果发现,北京市冬季燃煤排放的污染物已处于一个相对稳定期,而随着北京市机动车保有量迅速增加,尾气排放成为影响某些大气微量气体日变化的主要因素.     

The effect of atmospheric pressure on CH4 and CO2 emission from a closed landfill site in Manchester, UK

A time series study was conducted to ascertain the effect of barometric pressure on the variability of CH₄ and CO₂ concentrations in a closed landfill site. An in situ data of methane/carbon dioxide concentrations and environmental parameters were collected by means of an in-borehole gas monitor, the GasClam (Ion Science, UK). Linear regression analysis was used to determine the strength of the correlation between ground-gas concentrations and barometric pressure. The result shows CH₄ and CO₂ concentrations to be variable with weak negative correlations of 0.2691 and 0.2773, respectively, with barometric pressure over the entire monitoring period. Although the R ² was slightly improved by considering their concentration over single periods of rising and falling pressure, single periods of rising pressure and single periods of falling pressure, their correlations remained insignificant at 95 % confidence level. The result revealed that atmospheric pressure—the acclaimed major control on the variability of ground-gas concentration—is not always so. A case was made for the determination of other possible controls such as changes in temperature, soil permeability, landfill water depth, season, and geology of the borehole and also how much of control each factor would have on the variability/migration of CH₄ and CO₂ concentrations from the studied landfill.     

Formation and Emission of N2O and CH4 from Compost Heaps of Organic Household Waster

Composting can be a source of N₂O andCH₄ production. In this investigation, differentcompost heaps of organic household waste weremonitored with the focus on potential formation ofCH₄ and N₂O in the heaps and emission ofthese gases from the heaps. The studied compost heapshad different compost ages, turning intervals andcompost sizes. The analysed compost gases containedbetween 1–3421 L of N₂O-N L^-1 and 0–470 mL of CH₄ L^-1. The emission rates ofN₂O and CH₄ from the compost heaps werebetween 1–1464 mg N₂O m^-2 day^-1 and0–119 000 mg CH₄ m^-2 day^-1. These verylarge differences in compost gas composition andemission indicate the importance of compostmanagement. The results also give an understanding ofwhere in the composting process an increasing emissionof N₂O and CH₄ can occur.     

Long-term spatiotemporal patterns of CH4 and N2O emissions from livestock and poultry production in Turkey

This study quantified spatiotemporal patterns of CH₄ and N₂O emissions from livestock and poultry production in Turkey between 1961 and 2007. CH_4(enteric) (from enteric fermentation), CH_4(manure) (from manure management), and N₂O_(AWM) (from animal waste management) emissions in Turkey were estimated at 1,164, 216, and 55 Gg in 1961 and decreased to 844, 187, and 39 Gg in 2007, contributing a share of roughly 2% to the global livestock-related CH₄ emissions and %1.5 to the global N₂O_(AWM) emissions, respectively. Total CO₂-eq emissions were estimated at 50.7 Tg in 1961 and declined from a maximum value of 60.7 Tg in 1982 to a minimum value of 34.5 Tg in 2003, with a mean emission rate of 48 Tg year^???1 due to a significant reduction in the number of ruminant livestock. The highest mean share of emissions belonged to West Black Sea (14% and 16%) for CH_4(enteric) and CH_4(manure) and to North East Anatolia (12% and %13) for N₂O_(AWM) and total CO₂-eq emissions, respectively. The highest emission density was 1.7 Mg km^???2 year^???1 for CH_4(enteric), 0.3 Mg km^???2 year^???1 for CH_4(manure), and 0.07 Mg km^???2 year^???1 for the total CO₂-eq emissions in the West and North East Anatolia regions and 0.09 Mg km^???2 year^???1 for N₂O_(AWM) in the East Marmara region. Temporal and spatial variations in CH_4(enteric), CH_4(manure), and N₂O_(AWM) emissions in Turkey were estimated using regression models and ordinary kriging at a 500-m resolution, respectively.     

Spatial and Temporal Performance of the MiniFACE (Free Air CO2 Enrichment) System on Bog Ecosystems in Northern and Central Europe

The Bog Ecosystem Research Initiative (BERI) projectwas initiated to investigate, at five climaticallydifferent sites across Europe, the effects of elevatedCO₂ and N deposition on the net exchange ofCO₂ and CH₄ between bogs and the atmosphere,and to study the effects of elevated CO₂ and Ndeposition on the plant biodiversity of bogcommunities. A major challenge to investigate theeffects of elevated CO₂ on vegetation andecosystems is to apply elevated CO₂concentrations to growing vegetation without changingthe physical conditions like climate and radiation.Most available CO₂ enrichment methods disturb thenatural conditions to some degree, for instance closedchambers or open top chambers. Free Air CO₂Enrichment (FACE) systems have proven to be suitableto expose plants to elevated CO₂ concentrationswith minimal disturbance of their natural environment.The size and spatial scale of the vegetation studiedwithin the BERI project allowed the use of a modifiedversion of a small FACE system called MiniFACE. Thispaper describes the BERI MiniFACE design as well asits temporal and spatial performance at the five BERIfield locations. The temporal performance of theMiniFACE system largely met the quality criteriadefined by the FACE Protocol. One minute averageCO₂ concentrations measured at the centre of thering stayed within 20% of the pre-set target for morethan 95% of the time. Increased wind speeds werefound to improve the MiniFACE system's temporalperformance. Spatial analyses showed no apparentCO₂ gradients across a ring during a 4 day periodand the mean differences between each sampling pointand the centre of the ring did not exceed 10%.Observations made during a windy day, causing aCO₂ concentration gradient, and observations madeduring a calm day indicated that short term gradientstend to average out over longer periods of time. On aday with unidirectional strong winds, CO₂concentrations at the upwind side of the ring centrewere higher than those made at the centre and at thedownwind side of the ring centre, but the bell-shapeddistribution was found basically the same for thecentre and the four surrounding measurement points,implying that the short term (1 sec) variability ofCO₂ concentrations across the MiniFACE ring isalmost the same at any point in the ring. Based on gasdispersion simulations and measured CO₂concentration profiles, the possible interferencebetween CO₂-enriched and control rings was foundto be negligible beyond a centre-to-centre ringdistance of 6 m.     

Determination of O3, NO2, SO2, CO and PM10 measured in Belgrade urban area

O(3), NO(2), SO(2), CO and PM(10) concentrations, simultaneously determined for the first time in Belgrade urban area in the autumnal period of 2005, are presented. The obtained results display similar behaviour of SO(2), NO(2), CO, PM(10) opposite from that of O(3). The weekend effect was also investigated showing diminution of average daily concentrations of SO(2), NO(2), PM(10) and CO for 72, 40, 37 and 42% respectively, and increase of the average daily concentration of O(3) for 56%. Influence of meteorological conditions on observed concentration levels was studied, too. The observed influence of wind speed on the O(3) nightly concentration levels was analyzed pointing to the phenomena of O(3) transport during episodic measurements. To make an identification of possible pollution sources and analyse the influence of meteorological parameters on pollution levels, air back trajectories for high level concentrations episodes were calculated and analysed. A multivariate receptor modelling (Principal Component Analysis, Cluster Analysis) has been applied to a set of data in order to determine the contribution of different sources. It was found that the main principal components, extracted from the air pollution data, were related to gasoline combustion, oil combustion and ozone transport.     

Influence of Meteorological Factors NO2, SO2, CO and PM10 on the Concentration of O3 in the Urban Atmosphere of Eastern Croatia

Ozone, NO₂, SO₂, CO, PM₁₀ and meteorological parameters were measured simultaneously during the summer?Cautumn season 2007 in Osijek??the eastern, flat, agricultural part of Croatia. Fourier analysis confirms the existence of variation in ozone volume fractions with periods ranging from the usual semi-daily and daily to 7 and 28 daily cycles. The relationships between O₃ and other variables were modelled in three ways: principal component analysis, multiple linear regression and principal component regression. The results of the principal component analysis detected underlying relationships among ozone concentrations and meteorological variables. An extremely simple meteorological model is suitable for the prediction of ozone levels. The meteorological factors, temperature and cloudiness played a main role in the MLR model (R ²?=?0.83). The application of the principal component regression approach confirmed that the original variables associated with the valid principal components were meteorological variables (R ²?=?0.82).     

Laboratory study of the emission of NO and N2O from some Belgian soils

The NO, NO₂ and N₂O emission was measured, upon application of nitrate, ammonium and both, to four Belgian soils with different characteristics. The addition of NH ₄ ⁺ caused higher NO and N₂O emissions than the addition of no nitrogen, or the addition of NO ₃ ^– . In contrast to the two soils with a pH of approximately 8 the two soils with a pH around 6 showed a considerable delay in production of both NO and N₂O upon the application of the ammonium, probably due to the lag-period of nitrification. The soils with a pH of 8 gave higher emissions on the application of NH ₄ ⁺ than the soils with a pH of 6. The emission of NO₂ was found to be considerably lower than the NO emission from the soils. The NO/NO₂ ratio varied between 5–25 at considerable NO emissions (>50 nmol kg^–1). In the controls of soil 1 and soil 2, which showed very low NO emissions ratios of <1 were observed. The N₂O/NO ratios varied between 5–20 when NO emissions were considerable (>50 nmol kg^–1). Soil 3 and 4 gave lower N₂O/NO ratios than soil 1 and 2. In the controls of soil 1 and soil 2, at low NO emissions, N₂O/NO ratios of >300 were observed. Soil 3 and 4 gave higher NO/NO₂ and lower N₂O/NO ratios than soil 1 and 2.     

Seasonal characteristics of SO2, NO2, and CO emissions in and around the Indo-Gangetic Plain

Anthropogenic emissions of sulfur dioxide (SO₂), nitrogen dioxide (NO₂), and carbon monoxide (CO) exert significant influence on local and regional atmospheric chemistry. Temporal and spatial variability of these gases are investigated using surface measurements by the Central Pollution Control Board (India) during 2005–2009 over six urban locations in and around the Indo-Gangetic Plain (IGP) and supported using the satellite measurements of these gases. The stations chosen are Jodhpur (west of IGP), Delhi (central IGP), Kolkata and Durgapur (eastern IGP), Guwahati (east of IGP), and Nagpur (south of IGP). Among the stations studied, SO₂ concentrations are found to be the highest over Kolkata megacity. Elevated levels of NO₂ occur over the IGP stations of Durgapur, Kolkata, and Delhi. Columnar NO₂ values are also found to be elevated over these regions during winter due to high surface concentrations while columnar SO₂ values show a monsoon maximum. Elevated columnar CO over Guwahati during pre-monsoon are attributed to biomass burning. Statistically significant correlations between columnar NO₂ and surface NO₂ obtained for Delhi, Kolkata, and Durgapur along with very low SO₂ to NO₂ ratios (≤0.2) indicate fossil fuel combustion from mobile sources as major contributors to the ambient air over these regions.     

Monitoring of allethrin, deltamethrin, esbiothrin, prallethrin and transfluthrin in air during the use of household mosquito repellents

Three types of mosquito repellent [two different mosquito coils containing allethrin 0.1% w/w and transfluthrin 0.03% w/w, an aerosol sample containing a combination of two pyrethroid molecules (deltamethrin 0.02% w/w + allethrin 0.13% w/w) and two different mosquito mats containing esbiothrin 2.0% w/w and prallethrin 1.5% w/w as active ingredients] were individually subjected to use in a closed room. Air samples from the room were drawn at different time intervals (15, 30 and 45 min, and 1, 2, 4, 6 and 8 h) uniformly from three different positions in the room (top, middle and bottom) with the pyrethroid contents analysed using gas chromatography-electron capture detection (GC-ECD). Analysis of air samples showed maximum concentrations of the pyrethroid residues allethrin (0.0120 ppm), transfluthrin (0.0134 ppm), deltamethrin (0.0057 ppm), allethrin (0.080 ppm), esbiothrin (0.015 ppm) and prallethrin (0.0138 ppm) within 30-45 min of use. The drop in residue content was significant with time. At the end of a 6 h period, most of the residues had dissipated to below 0.0001 ppm. Further significant differences were observed in the residue contents tested at different points within the room. Studies were compared with the experimental results obtained when the mosquito repellents were tested with air circulation in the room.     

Application of a compact all solid-state laser system to the in situ detection of atmospheric OH,HO2, NO and IO by laser-induced fluorescence

A tuneable, high pulse-repetition-frequency, solid state Nd:YAG pumped titanium sapphire laser capable of generating radiation for the detection of OH, HO2, NO and IO radicals in the atmosphere by laser induced fluorescence (LIF) has been developed. The integration of the laser system operating at 308 nm into a field measurement apparatus for the simultaneous detection of hydroxyl and hydroperoxy radicals is described, with detection limits of 3.1 x 10(5) molecule cm(-3) (0.012 pptv in the boundary layer) and 2.6 x 10(6) molecule cm(-3) (0.09 pptv) achieved for OH and HO2 respectively (30 s signal integration, 30 s background integration, signal-to-noise ratio = 1). The system has been field tested and offers several advantages over copper vapour laser pumped dye laser systems for the detection of atmospheric OH and HO2 radicals by LIF, with benefits of greater tuning range and ease of use coupled with reduced power consumption, instrument footprint and warm-up time. NO has been detected in the atmosphere at approximately 1 ppbv by single photon LIF using the Alpha 2Sigma+ <-- Chi 2Pi1/2 (0,0) transition at 226 nm, with absolute concentrations in good agreement with simultaneous measurements made using a chemiluminescence analyser. With some improvements in performance, particularly with regard to laser power, the theoretical detection limit for NO is projected to be approximately 2 x 10(6) molecule cm(-3) (0.08 pptv). Whilst operating at 445 nm, the laser system has been used to readily detect the IO radical in the laboratory, and although it is difficult to project the sensitivity in the field, an estimate of the detection limit is < 1 x 10(5) molecule cm(-3) (< 0.004 pptv), well below previously measured atmospheric concentrations of IO.     

Prediction models of CO, SPM and SO2 concentrations in the Campo de Gibraltar Region, Spain: a multiple comparison strategy

The 'Campo de Gibraltar' region is a very industrialized area where very few air pollution studies have been carried out. Up to date, no model has been developed in order to predict air pollutant levels in the different towns spread in the region. Carbon monoxide (CO), Sulphur dioxide (SO(2)) and suspended particulate matter (SPM) series have been investigated (years 1999-2000-2001). Multilayer perceptron models (MLPs) with backpropagation learning rule have been used. A resampling strategy with two-fold crossvalidation allowed the statistical comparison of the different models considered in this study. Artificial neural networks (ANN) models were compared with Persistence and ARIMA models and also with models based on standard Multiple Linear Regression (MLR) over test sets with data that had not been used in the training stage. The models based on ANNs showed better capability of generalization than those based on MLR. The designed procedure of random resampling permits an adequate and robust multiple comparison of the tested models. Principal component analysis (PCA) is used to reduce the dimensionality of data and to transform exogenous variables into significant and independent components. Short-term predictions were better than medium-term predictions in the case of CO and SO(2) series. Conversely, medium-term predictions were better in the case of SPM concentrations. The predictions are significantly promising (e.g., d (SPM 24-ahead) = 0.906, d (CO 1-ahead) = 0.891, d (SO2 1-ahead) = 0.851).     

Water quality and dissolved inorganic fluxes of N,P, SO<Subscript>4</Subscript>, and K of a small catchment river in the Southwestern Coast of India

The southwestern coast of India is drained by many small rivers with lengths less than 250 km and catchment areas less than 6,500 km². These rivers are perennial and are also the major drinking water sources in the region. But, the fast pace of urbanization, industrialization, fertilizer intensive agricultural activities and rise in pilgrim tourism in the past four to five decades have imposed marked changes in water quality and solute fluxes of many of these rivers. The problems have aggravated further due to leaching of ionic constituents from the organic-rich (peaty) impervious sub-surface layers that are exposed due to channel incision resulting from indiscriminate instream mining for construction-grade sand and gravel. In this context, an attempt has been made here to evaluate the water quality and the net nutrient flux of one of the important rivers in the southwestern coast of India, the Manimala river which has a length of about 90 km and catchment area of 847 km². The river exhibits seasonal variation in most of the water quality parameters (pH, electrical conductivity, dissolved oxygen, total dissolved solids, Ca, Mg, Na, K, Fe, HCO₃, NO₂-N, NO₃-N, P _\text-inorg_{\rm \text{-}inorg}, P _\text-tot_{\rm \text{-}tot}, chloride, SO₄, and SiO₂). Except for NO₃-N and SiO₂, all the other parameters are generally enriched in non-monsoon (December–May) samples than that of monsoon (June–November). The flux estimation reveals that the Manimala river transports an amount of 2,308 t y^− 1 of dissolved inorganic nitrogen, 87 t y^− 1 dissolved inorganic phosphorus, and 9246 t y^− 1 of SO₄, and 1984 t y^− 1 K into the receiving coastal waters. These together constitute about 23% of the total dissolved fluxes transported by the Manimala river. Based on the study, a set of mitigation measures are also suggested to improve the overall water quality of small catchment rivers of the densely populated tropics in general and the south western coast in particular.     

Monitoring and validating the temporal dynamics of interday streamflow from two upland head micro-watersheds with different vegetative conditions during dry periods of the growing season in the Bohemian Massif,Czech Republic

At present, dynamic land use, climate change, and growing needs for fresh water are increasing the demand on the ecosystem effects of forest vegetation. Mountainous areas are at the forefront of scientific interest in European forest ecology and forest hydrology. Although uplands cover a significant area of the Czech Republic and other countries and are often covered with forest formations, they do not receive an appropriate amount of attention. Therefore, two experimental upland head micro-watersheds in the Bohemian Massif were selected for study because they display similar natural conditions, but different vegetative conditions (forest versus meadow). During the 2011 growing season, short-term streamflow measurements were carried out at the discharge profiles of both catchments and were evaluated in relation to climatic data (rainfall and temperature). The basic premise was that the streamflow in a forested catchment must exhibit different temporal dynamics compared to that in treeless areas and that these differences can be attributed to the effects of woody vegetation. These conclusions were drawn from measurements performed during dry periods lasting several days. A decreasing streamflow trend during the day part of the day (0900–1900 hours) was observed in both localities. The decrease reached approx. 44 % of the initial morning streamflow (0.24 dm³ s^?1 day^?1) in the treeless catchment and approx. 20 % (0.19 dm³ s^?1 day^?1) in the forested catchment. At night (1900–0900 hours), the streamflow in the forested catchment increased back to its initial level, whereas the streamflow in the treeless catchment stagnated or slowly decreased. We attribute these differences to the ecosystem effects of woody vegetation and its capacity to control water loss during the day. This type of vegetation can also function as a water source for the hydrographic network during the night.     

Analyzing SO 2 concentrations and wind directions during a short monitoring campaign at a site far from the industrial pole of La Plata, Argentina

This article presents and discusses SO2 air quality concentrations (ppbv) together with wind velocities and directions measurements carried out between September 1st and December 21st 2005 at a site located 8.5 km away from the Industrial Pole of La Plata area. As the city and its surroundings have no official monitoring network, the current work enlarges the air quality information available from the zone and sets some initial considerations to the future siting of monitoring stations. The statistical analysis of the data was performed using techniques of tests for outliers and trends, dissimilarity measures and robust regression. In relation to SO2 concentrations, low values were found during this short campaign considering daily averages (with a maximum of 8.5 ppbv) and hourly averages (with a maximum of 25.9 ppbv); World Health Organization guidelines were never surpassed. Nevertheless, a strong dependence between wind directions carrying air pollutants from the Industrial Pole and hourly concentration peaks were found. Due to low monthly SO2 concentrations and because a decreasing time trend was found, the authors propose, as an example, the implementation of an alternative discontinuous method to the continuous analyzer used in the current campaign. Our results state that sampling every 7 days at 13:00-13:59 hours (local time) would be enough to get representative values of the air quality. As a general remark it is possible to highlight that longer and systematic studies should be encouraged to confirm the seasonal wind pattern and to evaluate the air quality.