Short-term Distributions of Reduced Sulfur Compounds in the Ambient Air Surrounding a Large Landfill Facility

In order to explore the environmental behavior of reduced sulfur compounds (RSC) as malodorous components emitted from diverse source processes, the distribution characteristics of four sulfur (S) compounds - hydrogen sulfide (H₂S), methyl mercaptan (CH₃SH), dimethyl sulfide (DMS: (CH₃)₂S), and dimethyl disulfide (DMDS: (CH₃)₂S₂) – were investigated in a municipal landfill area. In the course of this study, their ambient concentration levels were measured during two time periods from 13 individual spots selected as a function of distance from the center of the landfill site. The results generally indicated the absolute dominance of H₂S over the other S compounds investigated (up to 5 km radius) such that their mean values were found as 1415 (H₂S), 148 (DMS), 20.6 (CH₃SH), and 14.4 ppt (DMDS). When our data were compared in terms of either varying distance from the source or relationship with meteorological conditions, the H₂S data sets were most evident to reflect the potential effects of strong source processes in the landfill environment, relative to other S gases (or to volatile organic compounds measured concurrently). The results of this study further indicated the relatively good correspondence between the measured H₂S concentration level and humans' intuitive sensory of odor and nuisance.     

Odour emission characteristics of 22 recreational rivers in Nanjing

The odour emission characteristics of 22 recreational rivers in Nanjing were investigated and analysed. Eight odorous compounds (ammonia (NH₃), hydrogen sulphide (H₂S), sulphur dioxide (SO₂), carbon disulphide (CS₂), nitrobenzene (C₆H₅NO₂), aniline (C₆H₅NH₂), dimethylamine (C₂H₇N), and formaldehyde (HCHO)) were measured in odour emission samples collected using a custom-made emission flux hood chamber. The results showed that all odorants were detected in all monitoring rivers. NH₃ was the main odorant, with emission rates ranging from 4.86 to 15.13 μg/min m². The total odour emission rate of the Nan River, at 1 427.07 OU/s, was the highest of the all investigated rivers. H₂S, NH₃ and nitrobenzene were three key odour emission contributors according to their contributions to the total odour emission. A correlation analysis of the pollutants showed there was a significant positive correlation between the emission rate of NH₃ and the concentration of ammonia nitrogen (NH₄ ⁺-N) and total nitrogen (TN). The H₂S and SO₂ emission rates had a significant positive correlation with sulphides (S^2?) and available sulphur (AS) in the water and sediment. The content of TN, NH₄ ⁺-N, S^2? and AS in the water and sediment affected the concentration of H₂S, SO₂ and NH₃ in the emission gases. NH₄ ⁺-N, S^2? and AS are suggested as the key odour control indexes for reducing odours emitted from these recreational rivers. The study provides useful information for effective pollution control, especially for odour emission control for the recreational rivers of the city. It also provides a demonstrate example to show how to monitor and assess a contaminated river when odour emission and its control need to be focused on.     

A Study of Sorptive Loss Patterns for Reduced Sulfur Compounds in the Use of the Bag Sampling Method

In this work, the basic properties of the bag sampling method were examined and characterized in terms of recovery rate with respect to four reduced sulfur compounds (RSC) including H₂S, CH₃SH, DMS, and DMDS. For this comparative study, two types of calibration approaches were performed to evaluate the relative RSC loss due to bag sampling. As a reference calibration tool, a syringe dilution (SD) method was applied. The working standards prepared by diluting the primary standard in a gas-tight syringe (as a mixing chamber) were injected to the GC/PFPD through a loop-injection system to yield a background calibration information. In contrast, the target calibration was performed based on a bag dilution (BD) method. To this end, working standards for multiple calibration points were prepared by two different bag types (Tedlar bag (TB) and polyester bag (PB)). These standards were then drawn by the same syringe and injected into the GC/PFPD via loop. On the basis of these comparative analyses, both absolute and relative differences in RSC recovery rates (RR) were evaluated (e.g., comparison of wall-loss effect). The results indicate that TB has a mean RR of 87% for the four RSC with their values ranging from 82 (CH₃SH) to 91% (DMDS). On the other hand, the results of PB generally exhibited slightly reduced RR with their mean values of 77% (range: 73% of H₂S to 83% of DMS). The results of this study generally suggest that the losses of RSC samples, while inevitable with the bag sampling method, exhibit certain patterns between different RSCs and between different grab sampling materials.     

Inspection of non-CO2 greenhouse gases from emission sources and in ambient air by Fourier-transform-infrared-spectrometry: Measurements with FTIS-MAPS

Infrared spectrometry is a versatile basis to analyse greenhouse gases in the atmosphere. A multicomponent air pollution software (MAPS) was developed for retrieval of gas concentrations from radiation emission as well as absorption measurements. Concentrations of CO, CH₄, N₂O, and H₂O as well as CO₂, NO, NO₂, NH₃, SO₂, HCl, HCHO, and the temperature of warm gases are determined on-line. The analyses of greenhouse gases in gaseous emission sources and in ambient air are performed by a mobile remote sensing system using the double-pendulum interferometer K300 of the Munich company Kayser-Threde. Passive radiation measurements are performed to retrieve CO, N₂O, and H₂O as well as CO₂, NO, SO₂, and HCl concentrations in smoke stack effluents of thermal power plants and municipal incinerators and CO and H₂O as well as CO₂ and NO in exhausts of aircraft engines. Open-path radiation measurements are used to determine greenhouse gas concentrations at different ambient air conditions and greenhouse gas emission rates of diffusive sources as garbage deposits, open coal mining, stock farming together with additional compounds (e.g. NH₃), and from road traffic together with HCHO. Some results of measurements are shown. A future task is the verification of emission cadastres by these inspection measurements.     

Entrapping of organic wastes by coordination clathrates

The feasibility of the Hofmann clathrates Ni(CN)₂(NH₃)·G(G=guest molecule) and the octahedral Werner-type complexes Ni(X)₂(L)₄ (X=NCS, NCO, CH₃CO₂, C₆H₅CO₂; L=Py, 4-Mepy) as a scavenger for organic substrates in a polluted aqueous or organic medium is dependent on the complex lability, thermal stability and reversibility in solvent trapping which can be conveniently studied by thermogravimetric means. Besides the parent monomeric octahedral complexes, all the thermal decompositional intermediates, namely, monomeric tetrahedral, dimeric octahedral and polymeric octahedral, are also potential scavengers for selected organic substances though they operate via a cycle of bond-making and bond-breaking processes.     

Gastro-enteric methane versus sulphate and volatile fatty acid production

The breakdown of low digestible components present in food during passage through the human and animal gastro-intestinal (GI) tract is performed by the highly diverse microbial community present in this ecosystem. Fermentation of these substances yields, besides CO₂ and volatile fatty acids, H₂, which is used as a substrate by three different H₂-consuming bacteria. Sulphate-reducing bacteria (SRB) use H₂ to reduce SO _inf4 ^sup2- to H₂S, hydrogenotrophic methane-producing bacteria (MPB) use H₂ to reduce CO₂ to CH₄ and reductive acetogens (RAC) use H₂ to reduce CO₂ to CH₃COOH. A competition between these three bacterial groups exists for the common H₂ substrate. This results generally in the dominance of one group above the other two.     

A mathematical model to estimate errors associated with closed flux chambers

Errors associated with the closed flux chamber technique, used to measure surface emissions from landfills, were investigated by using a combination of numerical modeling and laboratory studies. A transient-state, advective–dispersive–reactive model was developed and used in conjunction with its steady-state version to quantify the errors associated with closed flux chambers. In developing the model, all four major gases, CH₄, O₂, CO₂, and N₂, and the oxidation of CH₄ to CO₂ were considered. Laboratory experiments were conducted on a monolayered as well as a two-layered landfill cover system to calibrate and verify the model. The model was used to develop a plot of the percentage errors associated with closed flux chambers of different dimensions and surface flux rates.     

城市绿地温室气体通量监测与减排研究

采用LGR-密闭式动态通量箱法对城市绿地生态系统温室气体(CO₂、CH₄)通量的日变化、季节变化特征及其影响因子等进行了较为系统的研究。城市绿地花草CO₂通量有明显的日变化和季节变化特征,白天通量值为负,是CO₂的净吸收汇;夜晚为正值,是CO₂的净释放源;7:00左右由源转为汇,17:00左右由汇转为源,不同花卉24 h总通量有正负2种结果。冬季草坪作为源的时间延长,而作为汇的时间缩短。光强和温度是影响CO₂通量日变化和季节变化的主要因素。城市绿地CH₄通量较小,不足以对温室气体总量产生显著影响。从减少温室气体排放的角度对城市绿地花草的选择提出了建议。     

Empirical gas emission and oxidation measurement at cover soil of dumping site: example from Malaysia

Methane (CH₄) is one of the most relevant greenhouse gases and it has a global warming potential 25 times greater than that of carbon dioxide (CO₂), risking human health and the environment. Microbial CH₄ oxidation in landfill cover soils may constitute a means of controlling CH₄ emissions. The study was intended to quantify CH₄ and CO₂ emissions rates at the Sungai Sedu open dumping landfill during the dry season, characterize their spatial and temporal variations, and measure the CH₄ oxidation associated with the landfill cover soil using a homemade static flux chamber. Concentrations of the gases were analyzed by a Micro-GC CP-4900. Two methods, kriging values and inverse distance weighting (IDW), were found almost identical. The findings of the proposed method show that the ratio of CH₄ to CO₂ emissions was 25.4 %, indicating higher CO₂ emissions than CH₄ emissions. Also, the average CH₄ oxidation in the landfill cover soil was 52.5 %. The CH₄ and CO₂ emissions did not show fixed-pattern temporal variation based on daytime measurements. Statistically, a negative relationship was found between CH₄ emissions and oxidation (R ²?=?0.46). It can be concluded that the variation in the CH₄ oxidation was mainly attributed to the properties of the landfill cover soil.     

Greenhouse gas emissions from forestry,land-use changes,and agriculture in Tanzania

The purpose of the study was to identify and quantify anthropogenic sources and sinks of greenhouse gases from forestry, land-use changes and agriculture in Tanzania. The 1990 inventory revealed that, in the land-use sector, methane (CH₄) and carbon dioxide (CO₂) are the primary gases emitted. Enteric fermentation in livestock production systems is the largest source of CH₄. Although deforestation results in greenhouse gas emissions, the managed forests of Tanzania are a major CO₂ sink.     

气质联用法测固定污染源中三氟甲烷、四氟甲烷、六氟乙烷和六氟化硫

建立了固定污染源排气中三氟甲烷、四氟甲烷、六氟乙烷和六氟化硫的采样和气质联用分析方法,检出限分别为0.06、0.15、0.21、0.71 mg/m3,精密度在3.2%以下,相关系数大于0.999 6,并对浙江省内2家典型企业排放的温室气体进行了监测,实际样品监测结果表明,该方法能够满足废气中4种温室气体的监测要求。     

31P-NMR evaluation of organophosphorus pesticides degradation through metal ion promoted hydrolysis

The degradation of some organophosphorus pesticides (OPPs) in the presence of metal ions was studied by ³¹P-NMR spectroscopy. Both ³¹P-NMR and gas chromatography/mass spectroscopy results were used in order to determine the nature of metabolites formed after degradation. The degraded organophosphorus pesticide were investigated for chlorpyrifos and phoxim in the presence of several metal ions including Hg²⁺, Cu²⁺, Cd²⁺, Ni²⁺, Pb²⁺, and Ag⁺. ³¹P-NMR results indicated Ag⁺ and Hg²⁺ ion promoted degradation of OPPs and other metal ions formed complex with OPPs and cannot degrade OPPs. We found that the degradation of chlorpyrifos and phoxim with Ag⁺ or Hg²⁺ led to the formation of O,O-diethyl-O-methyl phosphorothionate, (C₂H₅O)₂(CH₃O)PS, at metal ion/pesticide mole ratios ≤1.0 and completely decomposed at a higher mole ratio of 10. Finally, the method was successfully applied to the degradation study of a number of technical and formulated pesticides in the presence of Ag⁺ ion at a metal ion/pesticide mole ratio of 10.     

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.     

Methane emissions from natural wetlands

Methane is considered one of the most important greenhouse gases in the atmosphere. Because of the strict anaerobic conditions required by CH₄-generating microorganisms, natural wetland ecosystems are one of the main sources of biogenic CH₄. The total natural wetland area is estimated to be 5.3 to 5.7 × 10¹² m², making up less than 5% of the Earth's land surface. However, natural wetland plays a disproportionately large role in CH₄ emissions. Wetlands are likely the largest natural sources of CH₄ to the atmosphere, accounting for about 20% of the current global annual emission. Out of the total amount of CH₄ emitted, northern wetlands contribute 34%, temperate wetlands 5%, and tropical systems about 60%.Because of the unique characteristics and high productivity, wetland ecosystems are important in the global carbon cycle. Natural wetlands are permanently or temporarily saturated. Strict anaerobic conditions consequently develop, which allows methanogenesis to occur. But the thin oxic layer and the oxic plant rhizophere promote activity of CH₄-oxidizing bacteria or methanotrophs. Thus, both CH₄ formation and consumption in wetland systems are microbiological processes and are controlled by many factors. Eight of the controlling factors, including carbon supply, soil oxidation-reduction status, pH, temperature, vegetation, salinity and sulfate content, soil hydrological conditions and CH₄ oxidation are discussed in this paper.     

Seasonal Differences in the Levels of Gaseous Air Pollutants in the Vicinity of a Waste Dump

Hydrogen sulphide, ammonia, nitrogen dioxide, mercaptans and sulphur dioxide (H₂S, NH₃, NO₂, R-SH, SO₂) concentrations were measured at the location in the vicinity of the waste dump to determine the air pollution level of these pollutants prior to the operation of the Mobile Thermal Treatment Plant. Samples were collected over one year period. Seasonal differences, and the influence of meteorological parameters (temperature, relative humidity, pressure and wind direction) on the air pollution levels were studied. Results show relatively low concentrations of H₂S, NO₂, R-SH and SO₂, while NH₃ levels were higher compared to the guideline values. Good weather conditions (high air pressure and low relative humidity) are connected to long range transport of NO₂, while higher temperatures result in elevated NH₃ and R-SH concentrations. Because of the predominant northeast wind direction (the same as the waste dump direction), the contribution of air pollution from the direction of the waste dump at the measuring site is significant, but that does not necessarily mean that the pollutants originated from that source.     

Greenhouse gas emission inventory for Senegal, 1991

The first greenhouse gas (GHG) emission estimates for Senegal, for the year 1991, were produced according to the draft IPCC/OECD guidelines for national inventories of GHGs. Despite certain discrepancies, nonavailability of data, the quality of some of the data collected, and the methodology, the estimates provide a provisional basis for Senegal to fulfill its obligations under the UN Framework Convention on Climate Change. This inventory reveals that GHG emissions in Senegal, like those in many developing countries, can mainly be attributed to the use of biomass for energy, land-use change and forestry, and savanna burning. Taking into account the direct global warming potential of the main GHGs (CO₂, CH₄, and N₂O), Senegal's emissions are estimated at 17.6 Tg ECO₂. The major gases emitted are CO₂ (61% of GHG emissions), followed by CH₄ (35%) and N₂O (4%). Energy accounts for 45% of total emissions (12% from fossil energy and 33% from traditional biomass energy); land-use change and forests, 18%; agriculture, 24%; waste, 12%; and industry, 1%.     

Determination of Ni(CO)4, Fe(CO)5, Mo(CO)6, and W(CO)6 in sewage gas by using cryotrapping gas chromatography inductively coupled plasma mass spectrometry

Evidence for the occurrence of Ni(CO)4 in addition to Mo(CO)6 and W(CO)6 in fermentation gases from a municipal sewage treatment plant is presented for the first time. The gases were sampled at the top of the sewage sludge digester using Tedlar bags, and were analysed using cryotrapping followed by gas chromatography coupled with inductively coupled mass spectrometry (GC-ICP-MS). The use of an ICP-MS as an element-specific detector gives sufficiently low detection limits for metals and was coupled to a packed column gas chromatograph. This method provides information about the speciation of volatile transition metals in contrast to previously used methods for the determination of Ni(CO)4 in gas samples. The element-specific detection of three different isotopes (m/z 58, 60, 62) and the correspondence of the samples' retention times with those of the standard provided convincing evidence that Ni(CO)4 is present in the fermentation gas. The concentrations found were in the sub-ppb level, which is at least one order of magnitude lower than the threshold level of 1 ppb (v/v). In addition, Mo(CO)6 and W(CO)6 were also measured in the sub-ppb range in contrast to the absence of Fe(CO)5. The stabilities of Ni(CO)4, Fe(CO)5, and Mo(CO)6 were tested in a carbon monoxide atmosphere. In the presence of distilled water, the following order of stability was found after 11 weeks: Fe(CO)5 < Ni(CO)4 < Mo(CO)6. In the presence of an aqueous solution containing nickel, molybdenum, tungsten and iron, however, only Fe(CO)5 was significantly decomposed (< 0.3% recovery); Ni(CO)4 and Mo(CO)6 were stable after 11 weeks. No W(CO)6 was formed. The low stability of Fe(CO)5 in the presence of water could be the reason why no volatile iron compound was found in sewage gas. This study showed that GC-ICP-MS can be employed to identify species-specific traces of metal carbonyls in process gases such as sewage gas.     

Detection of sulphur dioxide in the air using Scotch pine needles

Air quality is especially important in surface layers, for it is this layer that provides the living components of environment with the needed oxygen and carbon dioxide. Various air polluting gases penetrate cells affecting and contaminating them. Chloroplast shell of some pine species, for instance, doubles under the impact of carbon dioxide which is followed by tillacoids swelling and reduction.Literature provides opinions of some authors, who consider Scotch pine needle to be a biological indicator of sulphur dioxide. Others object to it basing on the observations of physiological development.The property of a Scotch pine as that of biological indicator manifests in SO₂ absorption by its needles. The analysis of total content of SO₂ in the needles shows an increase of SO₂ concentration.Sulphur in the needles is found in the form of organically bound sulphur, aminoacids, hormones as well as in the form of sulphates.Basing on our previous analysis we have generalized the data on the correlation concentrations of sulphur dioxide in the air and general concentrations of sulphur in the needles. We have supplemented the observations with the analyses of organically bound sulphur and concentrations of nonorganic sulphur. According to research data, needles contain a characteristic and rather stable quantity of organically bound sulphur.So we may state that the SO _inf4 ^sup2– concentration and the amount of SO₂ absorbed from the air are interdependent.Some authors state that SO _inf4 ^sup2– content in the soil doesn't affect sulphur content in pine needles. That is why we studied the affect of SO _inf4 ^sup2– content in the soil on sulphur content in Scotch pine needles.We could prove this statement by means of various kinds of analyses only partially. The ion transport is affected by the presence of other ions, pH and a lot of other factors.What may be said for sure is that different qualities of soils gave only minor and insignificant deviations.Hence our assumption about the SO₂ contamination from air, proved by its effect on the soils, turns to suit approximate measurements.     

Characterization of hydrocarbon contaminated areas by multivariate statistical analysis: Case studies

Analysis of soil gases is a relatively rapid and inexpensive method to delineate and measure hydrocarbon contamination in the subsurface caused by diesel or gasoline. Techniques originally developed for petroleum exploration have been adapted to tracking hydrocarbons which have leaked or spilled at or below the earth's surface.Discriminant analysis (a multivariate statistical technique) is used to classify soil gas samples of C₁ to C₇ hydrocarbons as biogenic (natural soil gases) or thermogenic (contaminant hydrocarbons). Map plots of C₁ to C₇ total interstitial hydrocarbons, C₂ to C₇ interstitial hydrocarbons, and C₁/C _n rations are used to further delineate and document the extent and migration of contamination.Three case studies of the technique are presented: each involves leakage of hydrocarbons from underground storage tanks. Soil gas analysis clearly defines the spread of contamination and can serve as the basis for the correct placement of monitoring wells. The method proved to be accurate, rapid, and cost-effective; it therefore has potential for widespread application to the identification of soil and groundwater contaminated by hydrocarbons.