Methane mass balance at three landfill sites: What is the efficiency of capture by gas collection systems?

Many developed countries have targeted landfill methane recovery among greenhouse gas mitigation strategies, since methane is the second most important greenhouse gas after carbon dioxide. Major questions remain with respect to actual methane production rates in field settings and the relative mass of methane that is recovered, emitted, oxidized by methanotrophic bacteria, laterally migrated, or temporarily stored within the landfill volume. This paper presents the results of extensive field campaigns at three landfill sites to elucidate the total methane balance and provide field measurements to quantify these pathways. We assessed the overall methane mass balance in field cells with a variety of designs, cover materials, and gas management strategies. Sites included different cell configurations, including temporary clay cover, final clay cover, geosynthetic clay liners, and geomembrane composite covers, and cells with and without gas collection systems. Methane emission rates ranged from -2.2 to >10,000 mg CH(4) m(-2) d(-1). Total methane oxidation rates ranged from 4% to 50% of the methane flux through the cover at sites with positive emissions. Oxidation of atmospheric methane was occurring in vegetated soils above a geomembrane. The results of these studies were used as the basis for guidelines by the French environment agency (ADEME) for default values for percent recovery: 35% for an operating cell with an active landfill gas (LFG) recovery system, 65% for a temporary covered cell with an active LFG recovery system, 85% for a cell with clay final cover and active LFG recovery, and 90% for a cell with a geomembrane final cover and active LFG recovery.     

Improving the aeration of critical fine-grained landfill top cover material by vegetation to increase the microbial methane oxidation efficiency

The natural methane oxidation potential of methanotrophic bacteria in landfill top covers is a sustainable and inexpensive method to reduce methane emissions to the atmosphere. Basically, the activity of methanotrophic bacteria is limited by the availability of oxygen in the soil. A column study was carried out to determine whether and to what extent vegetation can improve soil aeration and maintain the methane oxidation process. Tested soils were clayey silt and mature compost. The first soil is critical in light of surface crusting due to vertical erosion of an integral part of fine-grained material, blocking pores required for the gas exchange. The second soil, mature compost, is known for its good methane oxidation characteristics, due to high air-filled porosity, favorable water retention capacity and high nutrient supply. The assortment of plants consisted of a grass mixture, Canadian goldenrod and a mixture of leguminous plants. The compost offered an excellent methane oxidation potential of 100% up to a CH₄-input of 5.6 l CH₄ m⁻² h⁻¹. Whereas the oxidation potential was strongly diminished in the bare control column filled with clayey silt even at low CH₄-loads. By contrast the planted clayey silt showed an increased methane oxidation potential compared to the bare column. The spreading root system forms secondary macro-pores, and hence amplifies the air diffusivity and sustain the oxygen supply to the methanotrophic bacteria. Water is produced during methane oxidation, causing leachate. Vegetation reduces the leachate by evapotranspiration. Furthermore, leguminous plants support the enrichment of soil with nitrogen compounds and thus improving the methane oxidation process. In conclusion, vegetation is relevant for the increase of oxygen diffusion into the soil and subsequently enhances effective methane oxidation in landfill cover soils.     

Investigating the performance of aerobic,semi-aerobic,and anaerobic bioreactor landfills for MSW management in developing countries

Three different laboratory bioreactors, each duplicated, with dimensions 0.5 × 0.5 × 1 m were set up and monitored for 160 days. Municipal Solid Wastes with an organic content of ~80 % and a density of 550 kg/m³ were placed in bioreactors. Fresh leachate collected from waste collection vehicles was used with a recirculation rate of 28 L/day. Aerobic bioreactors were aerated at a rate of 0.15–0.24 L/min/kg of waste. Almost the same level of treatment was observed in terms of chemical oxygen demand reduction of leachate, which was in the range of 91–93 %. However, for anaerobic bioreactor, it took almost twice the time, 160 vs. 76 days, to reach the same level of treatment and stabilization. The behavior of semi-aerobic bioreactor was somewhere between the aerobic and anaerobic ones. Total biogas production for anaerobic bioreactors was 90 L/kg of waste, which contained 57–63 % methane. Methane concentration measured in semi-aerobic bioreactor was below 5 %. The main advantage of aerobic bioreactor was the fast rate of the process, while for semi-aerobic bioreactor, it was the elimination of the need for energy to maintain aerobic conditions, and for anaerobic bioreactor it was the production of biogas and potential energy recovery.     

Simulation model for gas diffusion and methane oxidation in landfill cover soils

Landfill cover soils oxidize a considerable fraction of the methane produced by landfilled waste. Despite many efforts this oxidation is still poorly quantified. In order to reduce the uncertainties associated with methane oxidation in landfill cover soils, a simulation model was developed that incorporates Stefan-Maxwell diffusion, methane oxidation, and methanotrophic growth. The growth model was calibrated to laboratory data from an earlier study. There was an excellent agreement between the model and the experimental data. Therefore, the model is highly applicable to laboratory column studies, but it has not been validated with field data. A sensitivity analysis showed that the model is most sensitive to the parameter expressing the maximum attainable methanotrophic activity of the soil. Temperature and soil moisture are predicted to be the environmental factors affecting the methane oxidizing capacity of a landfill cover soil the most. Once validated with field data, the model will enable a year-round estimate of the methane oxidizing capacity of a landfill cover soil.     

Effect of leachate irrigation on methane oxidation in tropical landfill cover soil

The effect of leachate irrigation on methanotrophic activity in sandy loam-based landfill cover soil with vegetation was investigated. Laboratory-scale experiments were conducted to investigate the methane oxidation reaction in cover soil with and without plants (tropical grass). The methane oxidation rate in soil columns was monitored during leachate application at different organic concentrations and using different irrigation patterns. The results showed that the growth of plants on the final cover layer of landfill was promoted when optimal supplement nutrients were provided through leachate irrigation. The vegetation also helped to promote methane oxidation in soil, whereas leachate application helped increase the methane oxidation rate in nonvegetated cover soil. Intermittent application of leachate (once every 4 days) improved the methane oxidation activity as compared to daily application. Nevertheless, the adverse effects of organic overloading on methane oxidation rate and plant growth were also observed.     

Construction and evaluation of simulated pilot scale landfill lysimeter in Bangladesh

This research concentrates the design, construction and evaluation of simulated pilot scale landfill lysimeter at KUET campus, Khulna, Bangladesh. Both the aerobic and anaerobic conditions having a base liner and two different types of cap liner were simulated. After the design of a reference cell, the construction of landfill lysimeter was started in January 2008 and completed in July 2008. In all construction process locally available civil construction materials were used. The municipal solid waste (MSW) of 2800–2985 kg having the total volume of 2.80 m³ (height 1.6 m) and moisture content of 65% was deposited in each lysimeter by applying required compaction energy. In contrast, both the composition in terms of methane (CH₄), carbon dioxide (CO₂) and oxygen (O₂) as well as the flow rate of landfill gas (LFG) generated from MSW in landfill lysimeter were measured and varied significantly in relation to the variation of lysimeter operational condition. Moreover, anaerobic lysimeter-C shows the highest composition of LFG in compare to the anaerobic lysimeter-B due to the providing of lower compaction of cap liner in anaerobic lysimeter-C. Here, it is interesting to note that in absence of compacted clay liner (CCL) and hence percolation of rainwater that facilitates rapid degradation of MSW in aerobic lysimeter-A has resulted in the highest settlement than that of anaerobic landfill lysimeter-B and C. Moreover, in case of anaerobic lysimeter-B and C, the leachate generation was lower than that of aerobic lysimeter-A due to the providing of cap liner in anaerobic lysimeter-B and C, played an important role to reduce the percolation of rainwater. The study also reveals that the leachate pollution index (LPI) has decreased in relation to the increasing of elapsed period as well as the LPI for collection system of aerobic lysimeter-A was higher than that of the collection system of anaerobic lysimeter-B and C. Finally, it can be depicted that LPI for lysimeter was significantly high and proper treatment will be necessary before discharging the lysimeter leachate into the water bodies.     

Spatial variability of soil gas concentration and methane oxidation capacity in landfill covers

In order to devise design criteria for biocovers intended to enhance the microbial oxidation of landfill methane it is critical to understand the factors influencing gas migration and methane oxidation in landfill cover soils. On an old municipal solid waste landfill in north-western Germany soil gas concentrations (10, 40, 90 cm depth), topsoil methane oxidation capacity and soil properties were surveyed at 40 locations along a 16 m grid. As soil properties determine gas flow patterns it was hypothesized that the variability in soil gas composition and the subsequent methanotrophic activity would correspond to the variability of soil properties. Methanotrophic activity was found to be subject to high spatial variability, with values ranging between 0.17 and 9.80 g CH₄ m⁻² h⁻¹_. Considering the current gas production rate of 0.03 g CH₄ m⁻² h⁻¹, the oxidation capacity at all sampled locations clearly exceeded the flux to the cover, and can be regarded as an effective instrument for mitigating methane fluxes. The methane concentration in the cover showed a high spatial heterogeneity with values between 0.01 and 0.32 vol.% (10 cm depth), 22.52 vol.% (40 cm), and 36.85 vol.% (90 cm). The exposure to methane raised the oxidation capacity, suggested by a statistical correlation to an increase in methane concentration at 90 cm depth. Methane oxidation capacity was further affected by the methanotroph bacteria pH optimum and nutrient availability, and increased with decreasing pH towards neutrality, and increased with soluble ion concentration). Soil methane and carbon dioxide concentration increased with lower flow resistance of the cover, as represented by the soil properties of a reduced bulk density, increase in air capacity and in relative ground level.     

Mitigating methane emissions and air intrusion in heterogeneous landfills with a high permeability layer

Spatially variable refuse gas permeability and landfill gas (LFG) generation rate, cracking of the soil cover, and reduced refuse gas permeability because of liquid addition can all affect CH₄ collection efficiency when intermediate landfill covers are installed. A new gas collection system that includes a near-surface high permeability layer beneath the landfill cover was evaluated for enhancing capture of LFG and mitigating CH₄ emissions. Simulations of gas transport in two-dimensional domains demonstrated that the permeable layer reduces CH₄ emissions up to a factor of 2 for particular spatially variable gas permeability fields. When individual macrocracks formed in the cover soil and the permeable layer was absent, CH₄ emissions increased to as much as 24% of the total CH₄ generated, double the emissions when the permeable layer was installed. CH₄ oxidation in the cover soil was also much more uniform when the permeable layer was present: local percentages of CH₄ oxidized varied between 94% and 100% across the soil cover with the permeable layer, but ranged from 10% to 100% without this layer for some test cases. However, the permeable layer had a minor effect on CH₄ emissions and CH₄ oxidation in the cover soil when the ratio of the gas permeability of the cover soil to the mean refuse gas permeability ?0.05. The modeling approach employed in this study may be used to assess the utility of other LFG collection systems and management practices.     

The influence of air inflow on CH4 composition ratio in landfill gas

When landfill gas is collected, air inflow into the landfill can reduce CH₄ productivity. The decline of CH₄ content in landfill gas (LFG) negatively affects energy projects. We studied air inflow rates and LFG characteristics from 699 vertical collection facilities (VCFs) in the 2nd landfill at the Sudokwon Landfill in South Korea. We first determined whether or not N₂ was an effective indicator of air inflow at this site using argon assays. The results of this analysis showed that the denitrification processes could be disregarded and that N₂ was an effective indicator of air inflow. Using the composition of N₂ in LFG samples, we found that air inflow occurred at 73.6 % of the VCFs, and 25.6 % of samples from these facilities showed more than 80 vol% of air inflow. In addition, we observed that the O₂ consumption rate was more than 70 % of the volume in all samples. $ R_{{{\text{CH}}_{ 4} }} $ , which is the ratio of CH₄ to the sum of CH₄ and CO₂, decreased with increasing air inflow. Finally, we found that, as air inflow increased, the variation in $ R_{{{\text{CH}}_{ 4} }} $ values for samples with equal air inflow ratios also increased due to differences in air inflow routes.     

Leachate generation and biogas energy recovery in the Jebel Chakir municipal solid waste landfill,Tunisia

A survey was conducted between 2006 and 2008 in order to identify municipal solid waste (MSW) composition and its influence on leachate generation and to assess the amount of biogas yield from the Jebel Chakir landfill in Tunis City. The organic fraction was the predominant compound in the MSW, followed by paper, fine, plastic, leather, rubber, metal, textile, glass and ceramic. The average MSW moisture content varies from 60 % in the wet season to 80 % in the dry one. The recognised MSW composition is well representative if compared to that of cities in developing countries. A large leachate quantity is produced in the landfill of Jebel Chakir, despite the negative water balance of the site. Based on the annual MSW landfilled quantities and using the LandGEM model, the expected peak landfill gas (LFG) production is estimated to occur 1 year after the landfill closure with a rate of 3.53 × 10⁷ m³/year. The analysis of the potential conversion of LFG to electric energy shows it at a total LFG-to-electricity energy of around 257 GWh with a heating value of 4,475 kcal/m³ based on an LFG collection efficiency of 33 % and energy efficiency of 33 % giving an economic feasibility for a 10 MW power plant.     

Methanotrophs and methanotrophic activity in engineered landfill biocovers

The dynamics and changes in the potential activity and community structure of methanotrophs in landfill covers, as a function of time and depth were investigated. A passive methane oxidation biocover (PMOB-1) was constructed in St-Nicéphore MSW Landfill (Quebec, Canada). The most probable number (MPN) method was used for methanotroph counts, methanotrophic diversity was assessed using denaturing gradient gel electrophoresis (DGGE) fingerprinting of the pmoA gene and the potential CH₄ oxidation rate was determined using soil microcosms. Results of the PMOB-1 were compared with those obtained for the existing landfill cover (silty clay) or a reference soil (RS). During the monitoring period, changes in the number of methanotrophic bacteria in the PMOB-1 exhibited different developmental phases and significant variations with depth. In comparison, no observable changes over time occurred in the number of methanotrophs in the RS. The maximum counts measured in the uppermost layer was 1.5 × 10⁹ cells g dw^?1 for the PMOB-1 and 1.6 × 10⁸ cells g dw^?1 for the RS. No distinct difference was observed in the methanotroph diversity in the PMOB-1 or RS. As expected, the potential methane oxidation rate was higher in the PMOB-1 than in the RS. The maximum potential rates were 441.1 and 76.0 μg CH₄ h^?1g dw^?1 in the PMOB and RS, respectively. From these results, the PMOB was found to be a good technology to enhance methane oxidation, as its performance was clearly better than the starting soil that was present in the landfill site.     

Enhanced methane recovery by food waste leachate injection into a landfill in Korea

The current food waste leachate (FWL) disposal practice in Korea warrants urgent attention and necessary action to develop an innovative and sustainable disposal strategy, which is both environmentally friendly and economically beneficial. In this study, methane production by FWL injection into a municipal solid waste landfill with landfill gas (LFG) recovery facility was evaluated for a period of more than 4 months. With the target of recovering LFG with methane content ~50%, optimum LFG extraction rate was decided by a trial and error approach during the field investigation in five different phases. The results showed that, upon FWL injection, LFG extraction rate of ~20 m(3)/h was reasonable to recover LFG with methane content ~58%. Considering the estimated methane production potential of 31.7 m(3) CH(4) per ton of FWL, methane recovery from the landfill was enhanced by 14%. The scientific findings of this short-term investigation indicates that FWL can be injected into the existing sanitary landfills to tackle the present issue and such landfills with efficient liner and gas collection facility can be utilized as absolute and sustainable environmental infrastructures.     

Greenhouse gas emissions from biogenic waste treatment: options and uncertainty

A simplified life cycle assessment was conducted to estimate greenhouse gas (GHG) emissions and energy production from each component of biogenic waste treated in an open dumping site, and by composting, anaerobic digestion, and incineration employed with additional options. The impact of uncertainties and sensitivities of the parameters in the treatment methods were investigated. We conducted a sensitivity analysis to identify the most sensitive parameters, and we discussed the relationship between uncertainty and sensitivity. Our results revealed that the moisture content of food waste and the biomass-derived carbon and methane concentration of the landfill gas of biogenic waste subjected to open dumping are the most sensitive parameters across all the treatment methods. The net GHG emissions from food waste treated in an open dumping site ranged over ten times (0.30 ? 3.67 Gg CO₂ eq/Gg). In addition, by employing additional options for the open dumping site, including soil cover, a landfill gas collection system, shifting to a semi-aerobic condition, and energy conservation by using a gas engine, we found that the net GHG emissions could be reduced by 10, 27.9, 37.4 %, and up to 56.7 %, respectively. Shifting to a semi-aerobic system is the most effective method for reducing GHG emissions, followed by landfill gas collection.     

Above- and below-ground methane fluxes and methanotrophic activity in a landfill-cover soil

Landfills are a major anthropogenic source of the greenhouse gas methane (CH(4)). However, much of the CH(4) produced during the anaerobic degradation of organic waste is consumed by methanotrophic microorganisms during passage through the landfill-cover soil. On a section of a closed landfill near Liestal, Switzerland, we performed experiments to compare CH(4) fluxes obtained by different methods at or above the cover-soil surface with below-ground fluxes, and to link methanotrophic activity to estimates of CH(4) ingress (loading) from the waste body at selected locations. Fluxes of CH(4) into or out of the cover soil were quantified by eddy-covariance and static flux-chamber measurements. In addition, CH(4) concentrations at the soil surface were monitored using a field-portable FID detector. Near-surface CH(4) fluxes and CH(4) loading were estimated from soil-gas concentration profiles in conjunction with radon measurements, and gas push-pull tests (GPPTs) were performed to quantify rates of microbial CH(4) oxidation. Eddy-covariance measurements yielded by far the largest and probably most representative estimates of overall CH(4) emissions from the test section (daily mean up to ～91,500μmolm(-2)d(-1)), whereas flux-chamber measurements and CH(4) concentration profiles indicated that at the majority of locations the cover soil was a net sink for atmospheric CH(4) (uptake up to -380μmolm(-2)d(-1)) during the experimental period. Methane concentration profiles also indicated strong variability in CH(4) loading over short distances in the cover soil, while potential methanotrophic activity derived from GPPTs was high (v(max)～13mmolL(-1)(soil air)h(-1)) at a location with substantial CH(4) loading. Our results provide a basis to assess spatial and temporal variability of CH(4) dynamics in the complex terrain of a landfill-cover soil.     

Bio-tarp alternative daily cover prototypes for methane oxidation atop open landfill cells

Final landfill covers are highly engineered to prevent methane release into the atmosphere. However, methane production begins soon after waste placement and is an unaddressed source of emissions. The methane oxidation capacity of methanotrophs embedded in a “bio-tarp” was investigated as a means to mitigate methane release from open landfill cells. The bio-tarp would also serve as an alternative daily cover during routine landfill operation.Evaluations of nine synthetic geotextiles identified two that would likely be suitable bio-tarp components. Pilot tarp prototypes were tested in continuous flow systems simulating landfill gas conditions. Multilayered bio-tarp prototypes consisting of alternating layers of the two geotextiles were found to remove 16% of the methane flowing through the bio-tarp. The addition of landfill cover soil, compost, or shale amendments to the bio-tarp increased the methane removal up to 32%. With evidence of methane removal in a laboratory bioreactor, prototypes were evaluated at a local landfill using flux chambers installed atop intermediate cover at a landfill. The multilayered bio-tarp and amended bio-tarp configurations were all found to decrease landfill methane flux; however, the performance efficacy of bio-tarps was not significantly different from controls without methanotrophs. Because highly variable methane fluxes at the field site likely confounded the test results, repeat field testing is recommended under more controlled flux conditions.     

BMP estimation of landfilled municipal solid waste by multivariate statistical methods using specific waste parameters: case study of a sanitary landfill in Turkey

The main objective of this study was to determine whether methane potential of waste could be estimated more easily by a limited number of waste characterization variables. 36 samples were collected from 12 locations and 3 waste depths in order to represent almost all waste ages at the landfill. Actual remaining methane potential of all samples was determined by the biochemical methane potential (BMP) tests. The cumulative methane production of closed landfill (cLF) samples reached 75–125 mL at the end of experiment duration, while the samples from active landfill (aLF) produced in average 216–266 mL methane. The average experimental k and L ₀ values of cLF and aLF were determined by non-linear regression using BMP data with first-order kinetic equation as 0.0269 day^?1–30.38 mL/g dry MSW and 0.0125 day^?1–102.1 mL/g dry MSW, respectively. The principal component analysis (PCA) was applied to analyze the results for cLF and aLF along with BMP results. Three PCs for the data set were extracted explaining 72.34 % variability. The best MLR model for BMP prediction was determined for seven variables (pH–Cl–TKN–NH4–TOC–LOI–Ca). R ² and Adj. R ² values of this best model were determined as 80.4 and 75.3 %, respectively.     

Stabilisation of biodried municipal solid waste fine fraction in landfill bioreactor

The biodrying process of solid waste is a pre-treatment for the bio-stabilisation of the municipal solid waste. This study aims to investigate the fate of the municipal solid waste fine fraction (MSWFF) resulting from a biodrying treatment when disposed in landfills that are operated as bioreactors. Biodried MSWFF was apparently stable due to its low moisture content that slows down the microbial activity. The lab-scale anaerobic bioreactors demonstrated that a proper moisture content leads to a complete biodegradation of the organic matter contained in the biodried MSWFF. Using a pilot-scale landfill bioreactor (LBR), MSWFF stabilisation was achieved, suggesting that the leachate recirculation could be an effective approach to accomplish the anaerobic biodegradation and biostabilisation of biodried MSWFF after landfilling. The biostabilisation of the material resulting from the LBR treatment was confirmed using anaerobic and aerobic stability indices. All anaerobic and aerobic indices showed a stability increase of approximately 80% of the MSWFF after treatment in the LBR. The similar values of OD7 and BMP stability indices well agree with the relationship between the aerobic and anaerobic indices reported in literature.     

Characterization of trace constituents in landfill gas and a comparison of sites in Asia

Because landfill gas (LFG) contains an abundance of methane, the utilization of LFG as a renewable energy source is becoming popular in many countries. LFG, however, contains various trace constituents, some of which may pose problems during utilization. For example, siloxanes and halogenated volatile organic compounds (VOCs) can cause difficulties when present in the fuel of gas engines. In addition, many VOCs and mercury have harmful effects on human health, especially on the health of workers at landfill sites and people living near the landfills. Energy recovery from LFG is expected to make great progress in the near future, particularly in Asia, but we found little information on the trace constituents of LFG in this region. Therefore, we sought to characterize the trace components in LFG generated in two landfill sites in China and one site in Japan, to determine the typical concentrations of these trace components in LFG, and to compare their concentrations among landfill sites in Asia. We concluded that the trace components in LFG at the sites studied were mainly siloxanes generated from sewage sludge and harmful benzene, toluene, ethylbenzene, and xylene compounds from petroleum products.     

Methane oxidation in a landfill cover with capillary barrier

The methane oxidation potential of a landfill cover with capillary barrier was investigated in an experimental plant (4.8 m x 0.8 m x 2.1m). The cover soil consisted of two layers, a mixture of compost plus sand (0.3 m) over a layer of loamy sand (0.9 m). Four different climatic conditions (summer, winter, spring and fall) were simulated. In and outgoing fluxes were measured. Gas composition, temperature, humidity, matrix potential and gas pressure were monitored in two profiles. CH4 oxidation rate within the investigated top cover ranged from 98% to 57%. The minimum was observed for a short time after irrigation. Temperature distribution, gas concentration profiles and lab-scaled batch experiments indicate that before irrigation the highest oxidising activity took place in a depth of about 30 cm. After irrigation the oxidising horizon seemed to migrate upwards since methanotrophic bacteria develop better there due to an adequate supply with oxygen. It can be assumed that the absence of oxygen is one of the most important limiting factors for the CH4 oxidation process. Abrupt cross-overs between horizons of different soil material may lead to zones of increased water saturation and decreased soil respiration.     

SEASONAL AND DIURNAL METHANE EMISSIONS FROM A LANDFILL AND THEIR REGULATION BY METHANE OXIDATION

Rates of methane emission from a Swedish landfill, measured by chamber technique and permanent frames, ranged between 0.034 and 20 mmol CH₄m⁻². h⁻¹on average. The emissions followed a seasonal pattern, with the highest fluxes occurring between September and May. Methane concentrations in soil also followed a seasonal pattern, with a marked decrease during summers. Using the means of methane emission rates from frost-free periods, a stepwise regression model was made, that could explain 95% of the variation. Soil temperature turned out to be the dominating factor, explaining 85% when transformed to a second-degree function. Methane emissions were negatively correlated with soil temperature, which strongly suggests that biological methane oxidation is an important regulating factor. The activity of methane-oxidizing microorganisms was greatest around 0.5–0.6 m depth in the soil profile, and moisture at this level enhanced emissions. The tendency for methane emissions to be higher at night was probably due to the inhibitory influence of low soil temperatures on methane-oxidizing microorganisms.