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.     

Relationship between CH₄ and N₂O flux from soil and their ambient mixing ratio in a riparian rice-based agroecosystem of tropical region

Temporal variations of the ambient mixing ratio of greenhouse gas (CH(4) and N(2)O) in a riparian rice-based agro-ecosystem of tropical region were studied during 2005-2006 in coastal Odisha. The endeavour was made with the hypothesis that the ambient mixing ratio of CH(4) and N(2)O depends on the changes in the flux of CH(4) and N(2)O from the rice fields in the riparian rice ecosystems. A higher ambient mixing ratio of CH(4) was recorded during the tillering to grain filling stages of the rice crop, during both dry and wet seasons. The higher ambient mixing ratio of CH(4) during the wet season may attribute to the higher CH(4) emission from the rice field. The average mixing ratio of CH(4) was recorded as 1.84 ± 0.05 ppmv and 1.85 ± 0.06 ppmv during 2005 and 2006, respectively. The ambient CH(4) mixing ratio was recorded negatively correlated with the average ambient temperature. The N(2)O mixing ratio ranged from 261.57 to 399.44 ppbv with an average of 330.57 ppbv during 2005. However, the average mixing ratio of N(2)O was recorded as 318.83 ± 20.00 ppbv during 2006. The N(2)O mixing ratio was recorded to be negatively correlated with rainfall and average ambient temperature. Significant negative correlation (r = -0.209) of N(2)O with sunshine hours may attribute to the photochemical break down of N(2)O. The temporal variation of N(2)O flux from the rice field does not affect the ambient mixing ratio of N(2)O in the same way as in the case of the ambient mixing ratio of CH(4). However, the higher mixing ratio of N(2)O during the fallow period of the post monsoon period may attribute to the N(2)O flux from soil. Results indicate that intensively cultivated coastal ecosystems can be a major source of ambient greenhouse gas.     

Atmospheric aerosol concentration level and chemical characteristics of water-soluble ionic species in wintertime in Beijing,China

Total suspended particulate (TSP) samples were collected during wintertime from November 24, 1998 to February 12, 1999 in Beijing. Ionic species including Cl-, NO3(-), SO4(2-), Na+, NH4(+), K+, Mg2+ and Ca2+ were determined by Ion Chromatography (IC). The sum average concentration of all the determined ions accounted for 18.9% of the TSP concentration, and SO4(2-) appeared the dominant ion with an average concentration of 30.84 microg m(-3); the sum mass concentration of SO4(2-), NO3(-), Ca2+ and NH4(+) accounted for about 83.2% of all the eight ions measured. The study indicated that the chemical form of sulfate and ammonium varies with TSP concentration levels. During heavy pollution periods, the average TSP concentration was 0.66 mg m(-3), and the NH4(+)/SO4(2-) molar ratio was low (0.58). It indicated that sulfate may present as CaSO4 and (NH4)2SO4 x CaSO4 x 2H2O. When TSP concentration (average 0.186 mg m(-3)) was relatively low, the NH4(+)/SO4(2-) molar ratio was 1.94, close to the theoretical ratio of 2 of (NH4)2SO4. Under this condition (NH4)2SO4 is expected to exist as the major form of sulfate. When the TSP concentration level was medium (average 0.35 mg m(-3)), the NH4+/SO4(2-) molar ratio appeared an average value (1.27), (NH4)2SO4, (NH4)2SO4 x CaSO4 x 2H2O and CaSO4 are expected to be present in those aerosol particles. Meteorological conditions including wind speed and wind direction were related to the TSP concentration level.     

太湖流域近地表主要温室气体本底浓度特征

根据2003年1月-2005年6月太湖流域近地表大气中主要温室气体CO2、CH4和N2O本底浓度的监测资料,研究了该流域近地表大气主要温室气体浓度的变化特征.结果表明,在观测时段内,该流域近地表大气CO2浓度呈上升趋势;CH4浓度呈逐年递减趋势;N2O浓度呈先减后增趋势.3种气体主要与人类活动、工农业生产和交通运输业发展有关,CO2浓度的季节变化明显,冬春季高,夏秋季低,最高值在12月,最低值在8月;CH4浓度由春至夏升高,由夏至秋至冬递减,最高值在7月,最低值在2月;N2O浓度没有明显的季节变化,它们主要受源汇强度变化影响.CO2浓度的日变化基本呈双峰态,是源汇强度变化和边界层稳定程度相互作用的原因,CH4浓度无明显日变化规律,N2O浓度日变化中的最高值总体呈现是夏、秋、春至冬逐渐延迟的状态.     

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.     

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.     

Analysis of the air pollution climate at a background site in the Po valley

The Po valley in northern Italy is renowned for its high air pollutant concentrations. Measurements of air pollutants from a background site in Modena, a town of 200 thousand inhabitants within the Po valley, are analysed. These comprise hourly data for CO, NO, NO(2), NO(x), and O(3), and daily gravimetric equivalent data for PM(10) from 1998-2010. The data are analysed in terms of long-term trends, annual, weekly and diurnal cycles, and auto-correlation and cross-correlation functions. CO, NO and NO(2) exhibit a strongly traffic-related pattern, with daily peaks at morning and evening rush hour and lower concentrations over the weekend. Ozone shows an annual cycle with a peak in July due to local production; notwithstanding the diurnal cycle dominated by titration by nitrogen oxide, the decreasing long term trend in NO concentration did not affect the long term trend in O(3), whose mean concentration remained steady over the sampling period. PM(10) shows a strong seasonality with higher concentration in winter and lower concentration in summer and spring. Both PM(10) and ozone show a marked weekly cycle in summer and winter respectively. Regressions of PM(10) upon NO(x) show a consistently greater intercept in winter, representing higher secondary PM(10) in the cooler months of the year. There is a seasonal pattern in primary PM(10) to NO(x) ratios, with lower values in winter and higher values in summer, but the reasons are unclear.     

温室效应气体及其监测方法

本文就CO_2、N_2O、CH_4及氟里昂等几种主要温室效应气体之最新监测动向进行综述,引述文献28篇.     

Spatial and temporal variations of SPM, RPM, SO2 and NOx concentrations in an opencast coal mining area

A study for assessment and management of air quality was carried out in the Ib Valley area of the Ib Valley coalfield in Orissa state, India. The 24 h average concentrations of suspended particulate matter (SPM), respirable particulate matter (RPM), sulfur dioxide (SO(2)) and oxides of nitrogen (NO(x)) were determined at regular intervals throughout one year at twelve monitoring stations in residential areas and six monitoring stations in mining/industrial areas. The 24 h average SPM and RPM concentrations were 124.6-390.3 microg m(-3) and 25.9-119.9 microg m(-3) in residential areas, and were 146.3-845.2 microg m(-3) and 45.5-290.5 microg m(-3) in industrial areas. During the study period, 24 h and annual average SPM and RPM concentrations exceeded the respective standards set in the Indian national ambient air quality standard (NAAQS) protocol as well as USEPA, EU, WHO and World Bank standards at most of the residential and industrial areas. However, concentrations of SO(2)(annual average: 24.6-36.1 microg m(-3) and 24 h average: 17.0-46.3 microg m(-3)) and NO(x)(annual average: 23.6-40.9 microg m(-3) and 24 h average: 18.3-53.6 microg m(-3)) were well within the prescribed limit of the NAAQS and international standards in both residential and industrial areas. The temporal variations of SPM and RPM fitted polynomial trends well and on average in the mining area 31.91% of the SPM was RPM. The linear regression correlation coefficients between SPM and RPM and between NO(x) and SO(2) were 0.94 (+/-0.04) and 0.66 (+/-0.10), respectively. The optimum interpolation technique, kriging, determined that maximal concentrations of SPM and RPM occurred within the mining site. Highest concentrations of particulate matter were observed during the winter season followed by summer, autumn and rainy seasons. An action plan is formulated for effective control of air pollution at source, and mitigative measures should include implementation of green belts around the sensitive areas where the concentration of air pollutants exceeds the standard limit.     

乌鲁木齐市2种主要温室气体浓度水平

利用2010年乌鲁木齐市近地面大气主要温室气体的自动监测数据,分析了CO2和CH4浓度的分布特征和时间变化规律.结果表明,乌鲁木齐市CO2小时浓度在(349.1～605.0)×10-6之间;采暖期浓度高,平均浓度为438.1 ×10-6,非采暖期浓度低,平均浓度为375.0×10-6.CH4浓度日变化明显,昼间低、夜间...     

Seasonal evaluation of outdoor/indoor air quality in primary schools in Lisbon

The aim of this study was to evaluate the indoor (I) and outdoor (O) levels of NO?, speciated volatile organic compounds (VOCs) and carbonyls at fourteen primary schools in Lisbon (Portugal) during spring, autumn and winter. Three of these schools were also selected to be monitored for comfort parameters, such as temperature and relative humidity, carbon dioxide (CO?), carbon monoxide (CO), total VOCs, and both bacterial and fungal colony-forming units per cubic metre. The concentration of CO? and bioaerosols greatly exceeded the acceptable maximum values of 1800 mg m?3 and 500 CFU m?3, respectively, in all seasons. Most of the assessed VOCs and carbonyls occurred at I/O ratios above unity in all seasons, thus showing the importance of indoor sources and building conditions in indoor air quality. However, it has been observed that higher indoor VOC concentrations occurred more often in the colder months, while carbonyl concentrations were higher in the warm months. In general, the I/O NO? ratios ranged between 0.35 and 1, never exceeding the unity. Some actions are suggested to improve the indoor air quality in Lisbon primary schools.     

Chemical characteristics of aerosols and trace gas distribution over North and Central India

A field campaign on aerosol chemical properties and trace gases measurements was carried out along the Delhi-Hyderabad-Delhi road corridor (spanning about 3,200 km) in India, during February 1-29, 2004. Aerosol particles were collected on quartz and cellulose filters using high volume (PM(10)) sampler at various locations along the route (i.e., urban, semi-urban, rural, and forest areas) and have been characterized for major cations (Na(+), Ca(2+), Mg(2+), K(+), and NH (4) (+)), anions (Cl(-), NO (3)(-), and SO (4)(2-)), and heavy metals (Cu, Cd, Fe, Zn, Mn, and Pb). Simultaneously, we measured NO(2) and SO(2) gases. These species show large spatial and temporal variations. The ambient PM(10) concentration has been observed to be the highest (55 ± 4 μg m(-3)) near semi-urban areas followed by forest areas (48 ± 2 μg m(-3)) and in rural areas (44 ± 22 μg m(-3)). The concentrations of NO( x ) (NO(2)+NO) and SO(2) ranged from 16 to 69 μg m(-3) and 4 to 11 μg m(-3), respectively. Among anions, NO(3)(-) and SO(4) (2-) are the major constituents of PM(10). The urban and semi-urban sites showed enhanced concentrations of Fe, Zn, Mn, Cd, and Pb. This study provide information about atmospheric concentrations of various species in the northern to central India, which may be important for policy makers to better understand the air quality of the region.     

Global and Regional Distribution of Carbon Monoxide from MOPITT: Seasonal Distribution at 700 hPa

The Measurement of Pollution in the Troposphere (MOPITT) instrument is an eight-channel gas correlation radiometer, which was launched on the Earth Observing System (EOS) Terra satellite in 1999. Carbon monoxide (CO) is one of the important trace gases because its concentration in the troposphere directly influences the concentrations of tropospheric hydroxyl (OH), which controls the lifetimes of tropospheric trace gases. CO traces the transport of global and regional pollutants from industrial activities and large scale biomass burning. The global and regional distributions of CO were analyzed using the MOPITT data for East Asia, which were compared with the ozone distributions. In general, seasonal CO variations are characterized by a peak in the spring, which decrease in the summer. This work also revealed that the seasonal cycles for CO are at a maximum in the spring and a minimum in the summer, with average concentrations ranging from 118 to 170 ppbv. The monthly average for CO shows a similar profile to that for O3. This fact clearly indicates that the high concentration of CO in the spring is possibly due to one of two causes: the photochemical production of CO in the troposphere, or the transport of the CO into East Asia. The seasonal cycles for CO and O3 in East Asia are extensively influenced by the seasonal exchanges of different air mass types due to the Asian monsoon. The continental air masses contain high concentrations of O3 and CO, due to the higher continental background concentrations, and sometimes to the contribution from regional pollution. In summer this transport pattern is reversed, where the Pacific marine air masses that prevail over Korea bring low concentrations of CO and O3, which tend to give the apparent summer minimums.     

Estimating residential air pollution exposure among citizens in Oslo 1974-1998 using a geographical information system

Annual concentration fields of SO2 and NOx for the period 1974-1998 are calculated for a 22 x 18 km2-grid in Oslo. In a study of lung cancer and air pollution in Oslo, 16209 men living in Oslo have been followed from 1972/73 to 1998. This paper presents a method for estimating their annual residential air pollution exposure for SO2 and NOx. In the exposure assessment the National Population Register provided information on home addresses. Each participant was given an annual average air pollutant concentration outdoors of the address he lived the largest part of that year. Persons living close to streets with high traffic were given an additional concentration, and persons who moved outside Oslo were given a region value for each year. Due to regulations of the sulfur content in fuel oil and a general change of local heating systems to electricity or distant heating, the SO2-concentrations in Central Oslo were reduced during the period from about 60 microg m(-3) in 1974-75 to about 4 microg m(-3) in 1997-98. Due to the increasing traffic the NOx-concentrations have increased slowly, from about 40 microg m(-3) in 1974-84 to about 60 microg m(-3) in 1989. After the introduction of catalyst cars the concentrations were reduced to about 45 microg m(-3) in 1997-98.     

Characteristics of malodor pollutants and aromatic VOCs around an urban valley in Korea

In this study, the environmental behavior of malodor pollutants (MPs) [including reduced sulfur compounds (RSCs)] and aromatic volatile organic compounds (AVOCs) were investigated around urban valley areas during several field campaigns (February through December 2006). The MPs measured in the study area include the RSCs (H(2)S, CH(3)SH, DMS, and DMDS), ammonia (NH(3)), and styrene (STY); the AVOCs include benzene (BEN), toluene (TOL), ethylbenzene (EB), m,p-xylene (MPX), and o-xylene (OX). The variation of most MP concentrations (except for DMDS) was found to be larger than that of AVOCs. It was found that STY (2,346 +/- 4,867 ppbv) was the most dominant MP followed by NH(3) (447 +/- 285), CH(3)SH (16 +/- 41), and the others (<8). The magnitude of AVOCs was found in the following descending order: TOL (1.4 +/- 2.2 ppbv), EB (1.0 +/- 2.1), MPX (0.9 +/- 2.0), and the others (<0.8). The concentration levels of most MPs on industrial (I) and downwind (D) sites were up to an order of magnitude higher than those at non-industrial (N) and upwind (U) sites. For most AVOCs, the former was ~3 times higher than the latter. For malodor intensity in RSCs, CH(3)SH was the dominant contributor. The concentration difference in target compounds between the sites/periods is likely to be caused by the combined effects such as emission sources, geographical features (e.g., semi-closed topography), and meteorological conditions (e.g., wind directions) in and outside the urban valley.     

Long-term relationships between SO2 and NOx emissions and SO4(2-) and NO3- concentration in bulk deposition at the Hubbard Brook Experimental Forest, NH

A highly significant second-order polynomial relation between SO(2) emissions and SO(4)(2-) concentrations during 1970-2000 (r(2)= 0.80, p= <0.001), and a linear relation between NO(x) and NO(3)(-) concentrations during 1991-2000 (r(2)= 0.67, p= 0.004) in bulk precipitation were found for the Hubbard Brook Experimental Forest, NH based on emissions from a 24 h, back-trajectory determined source area. Earlier periods (1965-1980) for SO(2)ratio SO(4)(2-) and longer periods (1965-2000) for NO(x)ratio NO(3)(-) had poorer linear relations, r(2)= 0.03, p= 0.51 and r(2)= 0.22, p= 0.004, respectively. Methodology by the US Environmental Protection Agency for calculating emissions data during this period has changed significantly and frequently, making trend analysis difficult. Given the large potential for errors in estimating emissions and to a lesser extent, deposition, the robust relations between SO(2) emissions and SO(4)(2-) concentrations in bulk precipitation at the Hubbard Brook Experimental Forest show that careful, long-term measurements from a single monitoring site can provide sound and reasonable data on trends in air pollution.     

CO and NO2 pollution in a long two-way traffic road tunnel: investigation of NO2/NOx ratio and modelling of NO2 concentration

The CO, NO and NO2 concentrations, visibility and air flow velocity were measured using continuous analysers in a long Norwegian road tunnel (7.5 km) with traffic in both directions in April 1994 and 1995. The traffic density was monitored at the same time. The NO2 concentration exceeded Norwegian air quality limits for road tunnels 17% of the time in 1994. The traffic through the tunnel decreased from 1994 to 1995, and the mean NO2 concentration was reduced from 0.73 to 0.22 ppm. The ventilation fan control, based on the CO concentration only, was unsatisfactory and the air flow was sometimes low for hours. Models for NO2 concentration based on CO concentration and absolute air flow velocity were developed and tested. The NO2/NOx ratio showed an increase for NOx levels above 2 ppm; a likely explanation for this phenomenon is NO oxidation by O2. Exposure to high NO2 concentrations may represent a health risk for people with respiratory and cardiac diseases. In long road tunnels with two-way traffic, this study indicates that ventilation fan control based on CO concentration should be adjusted for changes in vehicle CO emission and should be supplemented by air flow monitoring to limit the NO2 concentration.     

Mann–Kendall trend of pollutants,temperature and humidity over an urban station of India with forecast verification using different ARIMA models

The purpose of the present research is to identify the trends in the concentrations of few atmospheric pollutants and meteorological parameters over an urban station Kolkata (22° 32′ N; 88° 20′ E), India, during the period from 2002 to 2011 and subsequently develop models for precise forecast of the concentration of the pollutants and the meteorological parameters over the station Kolkata. The pollutants considered in this study are sulphur dioxide (SO₂), nitrogen dioxide (NO₂), particulates of size 10-μm diameters (PM₁₀), carbon monoxide (CO) and tropospheric ozone (O3). The meteorological parameters considered are the surface temperature and relative humidity. The Mann–Kendall, non-parametric statistical analysis is implemented to observe the trends in the data series of the selected parameters. A time series approach with autoregressive integrated moving average (ARIMA) modelling is used to provide daily forecast of the parameters with precision. ARIMA models of different categories; ARIMA (1, 1, 1), ARIMA (0, 2, 2) and ARIMA (2, 1, 2) are considered and the skill of each model is estimated and compared in forecasting the concentration of the atmospheric pollutants and meteorological parameters. The results of the study reveal that the ARIMA (0, 2, 2) is the best statistical model for forecasting the daily concentration of pollutants as well as the meteorological parameters over Kolkata. The result is validated with the observation of 2012.     

Ammonia Monitoring in Switzerland with Passive Samplers: Patterns, Determinants and Comparison with Modelled Concentrations

Gaseous ammonia (NH3) is an important form of N deposition to ecosystems, but it is not being routinely monitored in Switzerland. Therefore, a study was conducted to estimate annual means and seasonal patterns of NH3 concentrations for different site types in Switzerland, and to compare annual measured and modelled NH3 concentrations. NH3 concentrations were measured using the 'Zürcher' passive sampler, a Palmes type sampler with an acidic solution as absorbent. Twenty-four sampling sites were run for one year, and 17 for two years. The samplers were changed fortnightly or monthly. Spatial emission patterns were mapped by combining information on (1) the location of emission sources, (2) national statistics on NH3-emitting activities and (3) activity-specific emission factors. The spatial resolution was one hectare. The mean annual NH3 concentration in the ambient air of the 41 sites was 2.5+/-0.3 microg m(-3) (mean+/-standard error). It ranged from 0.4 to 7.5 microg m(-3). The site type and the season were the most important factors explaining the variation in the seasonal mean concentration. NH3 concentrations were highest in intensively used agricultural areas and in cities, and lowest in Alpine sites remote from emission sources. At 39 out of 41 sites, the NH3 concentrations were higher in summer (3.1+/-0.3 microg m(-3)) than in winter (2.0+/-0.3 microg m(-3)). Modelled NH3 concentrations did not systematically deviate from measured concentrations (r2 = 0.69). With the combined monitoring and modelling approach, it is now possible to obtain a reasonable and consolidated picture of the overall NH3 situation in Switzerland.     

Effects of temperature and soil moisture on methyl halide and chloroform fluxes from drained peatland pasture soils

A series of laboratory-based incubations using a stable isotope tracer technique was applied to measure the net and gross fluxes of CH(3)Cl and CH(3)Br as well as the net fluxes of CHCl(3) from surface soils of the Sacramento-San Joaquin Delta of California. Annually averaged flux measurements show that these mineral/oxidized peat soils are a net source of CH(3)Cl (140 ± 266 nmol m(-2) d(-1)) and CHCl(3) (258 ± 288 nmol m(-2) d(-1)), and a net sink of CH(3)Br (-2.3 ± 4.5 nmol m(-2) d(-1)). Gross CH(3)Cl and CH(3)Br fluxes are strongly influenced by both soil moisture and temperature: gross production rates of CH(3)Cl and CH(3)Br are linearly correlated with temperature, whereas gross consumption rates exhibit Gaussian relationships with maximum consumption at soil moisture levels between 20 and 30% volumetric water content (VWC) and a temperature range of 25 to 35 °C. Although soil moisture and soil temperature strongly affect consumption rates, the range of gross consumption rates overall is limited (-506 ± 176 nmol m(-2) d(-1) for CH(3)Cl and -12 ± 4 nmol m(-2) d(-1) for CH(3)Br) and is similar to rates reported in previous studies. CHCl(3) fluxes are not correlated with methyl halide fluxes, temperature, or soil moisture. The annual emission rates of CHCl(3) from the Sacramento-San Joaquin Delta are found to be a potentially significant local source of this compound.