Quantification of multiple methane emission sources at landfills using a double tracer technique

A double tracer technique was used successfully to quantify whole-site methane (CH₄) emissions from Fakse Landfill. Emissions from different sections of the landfill were quantified by using two different tracers. A scaled-down version of the tracer technique measuring close-by to localized sources having limited areal extent was also used to quantify emissions from on-site sources at the landfill facility, including a composting area and a sewage sludge storage pit. Three field campaigns were performed. At all three field campaigns an overall leak search showed that the CH₄ emissions from the old landfill section were localized to the leachate collection wells and slope areas. The average CH₄ emissions from the old landfill section were quantified to be 32.6 ± 7.4 kg CH₄ h⁻¹, whereas the source at the new section was quantified to be 10.3 ± 5.3 kg CH₄ h⁻¹. The CH₄ emission from the compost area was 0.5 ± 0.25 kg CH₄ h⁻¹, whereas the carbon dioxide (CO₂) and nitrous oxide (N₂O) flux was quantified to be in the order of 332 ± 166 kg CO₂ h⁻¹ and 0.06 ± 0.03 kg N₂O h⁻¹, respectively. The sludge pit located west of the compost material was quantified to have an emission of 2.4 ± 0.63 kg h⁻¹ CH₄, and 0.03 ± 0.01 kg h⁻¹ N₂O.     

环境中的药物——LC-MS/MS分析地表水和地下水

成百上千的活性物质正被用于人药和兽药处方中.由于药物的广泛应用,它们的残留物可通过多种途径进入环境.虽然主要通过尿和粪便的排泄,但是药品生产中的排放也应被考虑.当抗生素用于水产业,就会产生更直接的影响.污水处理设备不能完全除去药物,因此药物会出现在地表和地下水样品中.近年来,人们对环境中药物的兴趣正在增加,需要建立一种快速、灵敏、有选择性的方法来分析水样.     

Gas production, composition and emission at a modern disposal site receiving waste with a low-organic content

AV Miljø is a modern waste disposal site receiving non-combustible waste with a low-organic content. The objective of the current project was to determine the gas generation, composition, emission, and oxidation in top covers on selected waste cells as well as the total methane (CH₄) emission from the disposal site. The investigations focused particularly on three waste disposal cells containing shredder waste (cell 1.5.1), mixed industrial waste (cell 2.2.2), and mixed combustible waste (cell 1.3). Laboratory waste incubation experiments as well as gas modeling showed that significant gas generation was occurring in all three cells. Field analysis showed that the gas generated in the cell with mixed combustible waste consisted of mainly CH₄ (70%) and carbon dioxide (CO₂) (29%) whereas the gas generated within the shredder waste, primarily consisted of CH₄ (27%) and nitrogen (N₂) (71%), containing no CO₂. The results indicated that the gas composition in the shredder waste was governed by chemical reactions as well as microbial reactions. CH₄ mass balances from three individual waste cells showed that a significant part (between 15% and 67%) of the CH₄ generated in cell 1.3 and 2.2.2 was emitted through leachate collection wells, as a result of the relatively impermeable covers in place at these two cells preventing vertical migration of the gas. At cell 1.5.1, which is un-covered, the CH₄ emission through the leachate system was low due to the high gas permeability of the shredder waste. Instead the gas was emitted through the waste resulting in some hotspot observations on the shredder surface with higher emission rates. The remaining gas that was not emitted through surfaces or the leachate collection system could potentially be oxidized as the measured oxidation capacity exceeded the potential emission rate. The whole CH₄ emission from the disposal site was found to be 820 ± 202 kg CH₄ d⁻¹. The total emission rate through the leachate collection system at AV Miljø was found to be 211 kg CH₄ d⁻¹. This showed that approximately ¼ of the emitted gas was emitted through the leachate collections system making the leachate collection system an important source controlling the overall gas migration from the site. The emission pathway for the remaining part of the gas was more uncertain, but emission from open cells where waste is being disposed of or being excavated for incineration, or from horizontal leachate drainage pipes placed in permeable gravel layers in the bottom of empty cells was likely.     

Release and fate of fluorocarbons in a shredder residue landfill cell: 2. Field investigations

The shredder residues from automobiles, home appliances and other metal containing products are often disposed in landfills, as recycling technologies for these materials are not common in many countries. Shredder waste contains rigid and soft foams from cushions and insulation panels blown with fluorocarbons. The objective of this study was to determine the gas composition, attenuation, and emission of fluorocarbons in a monofill shredder residue landfill cell by field investigation. Landfill gas generated within the shredder waste primarily consisted of CH₄ (27%) and N₂ (71%), without CO₂, indicating that the gas composition was governed by chemical reactions in combination with anaerobic microbial reactions. The gas generated also contained different fluorocarbons (up to 27 μg L^?1). The presence of HCFC-21 and HCFC-31 indicated that anaerobic degradation of CFC-11 occurred in the landfill cell, as neither of these compounds has been produced for industrial applications. This study demonstrates that a landfill cell containing shredder waste has a potential for attenuating CFC-11 released from polyurethane (PUR) insulation foam in the cell via aerobic and anaerobic biodegradation processes. In deeper, anaerobic zones of the cell, reductive dechlorination of CFCs to HCFCs was evident, while in the shallow, oxic zones, there was a high potential for biooxidation of both methane and lesser chlorinated fluorocarbons. These findings correlated well with both laboratory results (presented in a companion paper) and surface emission measurements that, with the exception from a few hot spots, indicated that surface emissions were negative or below detection.     

Mitigation of methane emission from Fakse landfill using a biowindow system

Landfills are significant sources of atmospheric methane (CH₄) that contributes to climate change, and therefore there is a need to reduce CH₄ emissions from landfills. A promising cost efficient technology is to integrate compost into landfill covers (so-called “biocovers”) to enhance biological oxidation of CH₄. A full scale biocover system to reduce CH₄ emissions was installed at Fakse landfill, Denmark using composted yard waste as active material supporting CH₄ oxidation. Ten biowindows with a total area of 5000 m² were integrated into the existing cover at the 12 ha site. To increase CH₄ load to the biowindows, leachate wells were capped, and clay was added to slopes at the site. Point measurements using flux chambers suggested in most cases that almost all CH₄ was oxidized, but more detailed studies on emissions from the site after installation of the biocover as well as measurements of total CH₄ emissions showed that a significant portion of the emission quantified in the baseline study continued unabated from the site. Total emission measurements suggested a reduction in CH₄ emission of approximately 28% at the end of the one year monitoring period. This was supported by analysis of stable carbon isotopes which showed an increase in oxidation efficiency from 16% to 41%. The project documented that integrating approaches such a whole landfill emission measurements using tracer techniques or stable carbon isotope measurements of ambient air samples are needed to document CH₄ mitigation efficiencies of biocover systems. The study also revealed that there still exist several challenges to better optimize the functionality. The most important challenges are to control gas flow and evenly distribute the gas into the biocovers.     

Release and fate of fluorocarbons in a shredder residue landfill cell: 1. Laboratory experiments

The shredder residues from automobiles, home appliances and other metal-containing products are often disposed in landfills, as recycling technologies for these materials are not common in many countries. Shredder waste contains rigid and soft foams from cushions and insulation panels blown with fluorocarbons. The objective of this study was to use laboratory experiments to estimate fluorocarbon release and attenuation processes in a monofill shredder residue (SR) landfill cell. Waste from the open SR landfill cell at the AV Miljø landfill in Denmark was sampled at three locations. The waste contained 1–3% metal and a relatively low fraction of rigid polyurethane (PUR) foam particles. The PUR waste contained less blowing agent (CFC-11) than predicted from a release model. However, CFC-11 was steadily released in an aerobic bench scale experiment. Anaerobic waste incubation bench tests showed that SRSR produced significant methane (CH₄), but at rates that were in the low end of the range observed for municipal solid waste. Aerobic and anaerobic batch experiments showed that processes in SRSR potentially can attenuate the fluorocarbons released from the SRSR itself: CFC-11 is degraded under anaerobic conditions with the formation of degradation products, which are being degraded under CH₄ oxidation conditions prevailing in the upper layers of the SR.     

Release of fluorocarbons from insulation foam in home appliances during shredding

It is a current practice that refrigerators and freezers in many countries are shredded after the end of useful lives. The shredder residue is deposited in landfills. During the shredding process a significant fraction of blowing agent (BA) in the insulation foam may be released into the atmosphere. The objective of this study is to determine the fraction of BA released from foam during shredding, by comparing the BA content in insulation foam of refrigerator units before shredding with the BA content of shredded foam. All foam samples analyzed were manufactured with trichlorofluoromethane [CFC-11 (CCl3F)] as BA. The average content of BA in the insulation foam from eight U.S. refrigerator units manufactured before 1993 was found to be 14.9% +/- 3.3% w/w. Several refrigerator units also identified as being manufactured before 1993 were stockpiled and shredded at three shredder facilities, of which one was operated in both wet and dry modes. The selected shredder facilities represent typical American facilities for shredding automobiles, refrigerators, freezers, and other iron containing waste products. Shredded material was collected and separated on location into four particle size categories: more than 32 mm, 16-32 mm, 8-16 mm, and 0-8 mm. Adjusting for sample purity, it was found that the majority (>81%) of the foam mass was shredded into particles larger than 16 mm. The smallest size fraction of foam (0-8 mm) was found to contain significantly less BA than the larger size categories, showing that up to 68% +/- 4% of the BA is released from these fine particles during the shredding process. Because only a minor fraction of the foam is shredded into particles smaller than 8 mm, this has a minor impact on the end result when calculating the total BA release from the shredding process. Comparing BA content in shredded samples from the three shredder facilities with the measured average BA content of the eight refrigerator units, it was found that on average 24.2% +/- 7.5% of the initial BA content is released during the shredding process.     

Cross-sectional biomonitoring study of pesticide exposures in Queensland,Australia, using pooled urine samples

A range of pesticides are available in Australia for use in agricultural and domestic settings to control pests, including organophosphate and pyrethroid insecticides, herbicides, and insect repellents, such as N,N-diethyl-meta-toluamide (DEET). The aim of this study was to provide a cost-effective preliminary assessment of background exposure to a range of pesticides among a convenience sample of Australian residents. De-identified urine specimens stratified by age and sex were obtained from a community-based pathology laboratory and pooled (n = 24 pools of 100 specimens). Concentrations of urinary pesticide biomarkers were quantified using solid-phase extraction coupled with isotope dilution high-performance liquid chromatography–tandem mass spectrometry. Geometric mean biomarker concentrations ranged from <0.1 to 36.8 ng/mL for organophosphate insecticides, <0.1 to 5.5 ng/mL for pyrethroid insecticides, and <0.1 to 8.51 ng/mL for all other biomarkers with the exception of the DEET metabolite 3-diethylcarbamoyl benzoic acid (4.23 to 850 ng/mL). We observed no association between age and concentration for most biomarkers measured but noted a “U-shaped” trend for five organophosphate metabolites, with the highest concentrations observed in the youngest and oldest age strata, perhaps related to age-specific differences in behavior or physiology. The fact that concentrations of specific and non-specific metabolites of the organophosphate insecticide chlorpyrifos were higher than reported in USA and Canada may relate to differences in registered applications among countries. Additional biomonitoring programs of the general population and focusing on vulnerable populations would improve the exposure assessment and the monitoring of temporal exposure trends as usage patterns of pesticide products in Australia change over time.     

Tracer method to measure landfill gas emissions from leachate collection systems

This paper describes a method developed for quantification of gas emissions from the leachate collection system at landfills and present emission data measured at two Danish landfills with no landfill gas collection systems in place: Fakse landfill and AV Miljø. Landfill top covers are often designed to prevent infiltration of water and thus are made from low permeable materials. At such sites a large part of the gas will often emit through other pathways such as the leachate collection system. These point releases of gaseous constituents from these locations cannot be measured using traditional flux chambers, which are often used to measure gas emissions from landfills. Comparing tracer measurements of methane (CH₄) emissions from leachate systems at Fakse landfill and AV Miljø to measurements of total CH₄ emissions, it was found that approximately 47% (351 kg CH₄ d^?1) and 27% (211 kg CH₄ d^?1), respectively, of the CH₄ emitting from the sites occurred from the leachate collection systems. Emission rates observed from individual leachate collection wells at the two landfills ranged from 0.1 to 76 kg CH₄ d^?1. A strong influence on emission rates caused by rise and fall in atmospheric pressure was observed when continuously measuring emission from a leachate well over a week. Emission of CH₄ was one to two orders of magnitude higher during periods of decreasing pressure compared to periods of increasing pressure.