Atmospheric Environment 46 (2012) 248e255 Contents lists available at SciVerse ScienceDirect Atmospheric Environment journal homepage: www.elsevier.com/locate/atmosenv A model for inventory of ammonia emissions from agriculture in the Netherlands G.L. Velthof a, *, C. van Bruggen b, C.M. Groenestein c, B.J. de Haan d, M.W. Hoogeveen e, J.F.M. Huijsmans f a Alterra, Part of Wageningen UR, P.O. Box 47, 6700 AA Wageningen, The Netherlands Statistics Netherlands (CBS), Postbus 24500, 2490 HA Den Haag, The Netherlands c Wageningen UR Livestock Research, P.O. Box 135, 6700 AC Wageningen, The Netherlands d PBL Netherlands Environmental Assessment Agency, PO Box 303, 3720 AH Bilthoven, The Netherlands e LEI, Part of Wageningen UR, PO Box 29703, 2502 LS The Hague, The Netherlands f Plant Research International, Part of Wageningen UR, P.O. Box 616, 6700 AP Wageningen, The Netherlands b a r t i c l e i n f o a b s t r a c t Article history: Received 18 May 2011 Received in revised form 16 September 2011 Accepted 28 September 2011 Agriculture is the major source of ammonia (NH3). Methodologies are needed to quantify national NH3 emissions and to identify the most effective options to mitigate NH3 emissions. Generally, NH3 emissions from agriculture are quantified using a nitrogen (N) flow approach, in which the NH3 emission is calculated from the N flows and NH3 emission factors. Because of the direct dependency between NH3 volatilization and Total Ammoniacal N (TAN; ammoniumeN þ N compounds readily broken down to ammonium) an approach based on TAN is preferred to calculate NH3 emission instead of an approach based on total N. A TAN-based NH3-inventory model was developed, called NEMA (National Emission Model for Ammonia). The total N excretion and the fraction of TAN in the excreted N are calculated from the feed composition and N digestibility of the components. TAN-based emission factors were derived or updated for housing systems, manure storage outside housing, manure application techniques, N fertilizer types, and grazing. The NEMA results show that the total NH3 emission from agriculture in the Netherlands in 2009 was 88.8 Gg NH3eN, of which 50% from housing, 37% from manure application, 9% from mineral N fertilizer, 3% from outside manure storage, and 1% from grazing. Cattle farming was the dominant source of NH3 in the Netherlands (about 50% of the total NH3 emission). The NH3 emission expressed as percentage of the excreted N was 22% of the excreted N for poultry, 20% for pigs, 15% for cattle, and 12% for other livestock, which is mainly related to differences in emissions from housing systems. The calculated ammonia emission was most sensitive to changes in the fraction of TAN in the excreted manure and to the emission factor of manure application. From 2011, NEMA will be used as official methodology to calculate the national NH3 emission from agriculture in the Netherlands. Ó 2011 Elsevier Ltd. All rights reserved. Keywords: Ammonia Agriculture Inventory Manure Total ammoniacal nitrogen (TAN) Netherlands 1. Introduction Agriculture contributes to about 80% of the total ammonia emission in Europe (http://www.emep.int). The major NH3 sources from agriculture are related to the excretion of urine by livestock, i.e. livestock housing (Groenestein, 2006; Monteny, 2000), manure storage, grazing (Bussink, 1994), and application of manure (Huijsmans et al., submitted for publication). Moreover, application of urea containing fertilizers and application of ammonium (NHþ 4) based mineral N fertilizers on calcareous soils are sources of NH3 * Corresponding author. Tel.: þ31 317 486503; fax: þ31 317 419000. E-mail addresses: [email protected] (G.L. Velthof), [email protected] (C. van Bruggen), [email protected] (C.M. Groenestein), bronno.deHaan@ pbl.nl (B.J. de Haan), [email protected] (M.W. Hoogeveen), jan. [email protected] (J.F.M. Huijsmans). 1352-2310/$ e see front matter Ó 2011 Elsevier Ltd. All rights reserved. doi:10.1016/j.atmosenv.2011.09.075 (Bouwman et al., 2002). Ammonia may form secondary particulate matter in the atmosphere (Erisman and Schaap, 2003), which may have adverse effects on human health (Moldanová et al., 2011). When NH3 is deposited to soil, it can cause soil acidification (Van Breemen et al., 1983) and eutrophication of natural aquatic and terrestrial ecosystems. This results in loss of plant biodiversity (Bobbink et al., 1998). Moreover, NH3 is a so-called indirect source of the greenhouse gas nitrous oxide (N2O; IPCC, 1996). The Gothenburg Protocol of the UN Convention on Long-range Transboundary Air Pollution (UNECE, 1999) and the EU National Emission Ceiling Directive (European Commission, 2001) have set limits to NH3 emissions. Therefore countries have to report their NH3 emissions to the UNECE and/or the European Commission. Moreover, countries have to report their NH3 emissions as a basis for their N2O emission calculation to the UNFCCC. Refinement of the projections of NH3 emission are needed to find effective options to mitigate NH3 emissions. G.L. Velthof et al. / Atmospheric Environment 46 (2012) 248e255 A guidebook has been made for inventories of emissions of air pollutants, including NH3 (EMEP/EEA, 2009). It has been designed for countries that have to report NH3 emission to the UNECE and/or European Commission. Generally, NH3 emissions from agriculture are quantified using a nitrogen (N) flow approach. In such approach, the NH3 emission is calculated from the N flows and NH3-emission factors. Several studies describe models and emission factors used in different countries, e.g. Denmark (Hutchings et al., 2001), France (Gac et al., 2007), Ireland (Hyde et al., 2003), Germany (Dämmgen et al., 2006), Switzerland (Reidy et al., 2008b), The Netherlands (Luesink and Kruseman, 2007), UK (Webb and Misselbrook, 2004), and USA (Faulkner and Shaw, 2008). Manure is a mixture of feces and urine. N in feces is mainly organically bound. The urine of mammals consist mainly of urea N and the urine of poultry of uric acid. Urea rapidly hydrolyses into NHþ 4 through the enzyme urease, by which slurries do not contain urea. The degradation of uric acid is much slower, especially in dried manure in which microbial activity is low. Solid poultry manure may still contain uric acid when applied to the soil (Nicholson et al., 1996). AmmoniumeN and N compounds which are readily broken down to NHþ 4 , such as urea and uric acid, are referred to as Total Ammoniacal N (TAN; EMEP/EEA, 2009). Accurate projections of NH3 emissions from agriculture require methods that are closely linked to the processes controlling NH3 emission. An approach to calculate NH3 emission using emission factors based on TAN instead of total N is a step closer to a processbased NH3-emission model and is preferred to calculate NH3 emission (EMEP/EEA, 2009; Reidy et al., 2008a). There are several benefits of using a TAN-based approach instead of an approach based on total N. Firstly, NH3 is produced from NHþ 4 (at high pH levels) by which the relation between NH3 emission and TAN content is more direct than between NH3 emission and total N content (e.g. Elzing and Monteny, 1997; Velthof et al., 2005). Secondly, changes in feed composition may not only change the total N excretion, but also the portion of TAN in the total N excretion (Canh et al., 1998; Valk, 1994). Thirdly, the emission factors for manure application in the Netherlands are based on the TAN content of the applied manure (Huijsmans et al., submitted for publication). Effects of changes in feed composition and manure management in housing may affect the TAN content of manure, and thus affect the NH3 emission from manure applied to soil. These effects can be quantified using a TAN-based flow model. A TANbased approach requires information on the N digestibility of the N compounds in the feed to calculate the TAN excretion. Moreover, the N mineralization of organic N into TAN and immobilization of TAN into organic N during the storage of manure have to be quantified. This paper describes a TAN-based NH3-inventory model (National Emission Model for Ammonia; NEMA), which will be used for calculating NH3 emission from agriculture in the Netherlands (Van der Maas et al., 2011). In the current paper, the NEMA model is described and the NH3 emissions from agriculture in the Netherlands are quantified for the year 2009. Scenario analyses are carried out to get quantitative insight in the effect of changes of model parameters on the total NH3 emission, including changes in the TAN excretion, types of housing systems, types of manure application techniques, and emission factors for housing, manure storage, grazing and manure application. 2. Materials and methods 2.1. Description of the NEMA model The NEMA model is a deterministic TAN-based N flow model, which calculates the total NH3 emission from agriculture in the 249 Netherlands on annual basis. It calculates NH3 emission from housing, manure storage outside housing, manure application to soil, grazing, and mineral N fertilizer, based on the flow of TAN (Fig. 1) and TAN-based NH3-emission factors. 2.2. Excretion of total N and TAN The total N and TAN excretion is calculated yearly for 35 livestock categories, using statistical data of the type and composition of animal feed for the different livestock categories (CBS, 2009). The N excreted is calculated as the difference between the intake of N and retention of N in animal products, using standard N balance calculation methods (e.g. Canh et al., 1998; Valk, 1994; Wilkerson et al., 1997). The fraction of TAN in the N excretion is calculated as the excretion of urine-N which is the digested part of the N in feed not converted into animal products (Groenestein et al., submitted for publication). The undigested N is excreted as fecal N. The content of crude protein of the feed is generally known. However, the digestibility of N in the feed changes, because feeding compounds in the feed change over time. Bikker et al. (2011) developed an optimization model to calculate feed compositions based on the crude protein content of the feed, season, prices of the feed compounds of the specific year and market developments. The calculated average N digestibility of the feed is then used to calculate the TAN excretion of pigs, poultry, cattle, horses, sheep and goats. For some small livestock categories, like rabbits, data of feed composition are not available. For these animals, the TAN fraction of the N excretion is estimated at 70%. 2.3. Emission from housing, manure storage, manure application, grazing, and fertilizer The NH3 emission from housing systems is calculated from the number of livestock per category, the total N excretion during housing, the fraction of TAN in the excreted N, the N nett mineralization and immobilization of manure during storage, and the NH3-emission factor for housing systems. Most NH3-emission factors for housing systems are based on measurements on commercial farms or experimental stations (e.g. Aarnink, 1997; Groenestein, 2006; Groot Koerkamp, 1998; Ogink et al., 2008; and Monteny, 2000). Groenestein et al. (submitted for publication) reason that based on studies of Beline et al. (1998), Sommer et al. (2007), Sørensen et al. (2003), 10% of organic N in slurry is mineralized during storage. In solid manure, N may be immobilized, but quantification of immobilization is uncertain and studies show large variations in immobilization (Chadwick et al., 2000; Petersen et al., 1998; Kirchmann, 1991). Therefore they assumed 25% of the TAN in solid manure to be immobilized during storage, and that the N is not released during a later stage of storage. For dried poultry manure they assume no net mineralization or immobilization, because drying inhibits the hydrolysis of uric acid in poultry manure into ammonium. Part of the produced manure is stored outside the livestock building. The total amount of manure TAN stored outside was calculated for each manure type from the TAN excretion, N mineralization in the housing and N immobilization, multiplied with the fraction of manure stored outside. In order to calculate the amount TAN applied to the field, the gaseous emissions of other N compounds (N2, N2O, and NOx) during housing and manure storage have to be calculated. The emission factor for N2O is derived from IPCC (1996), that of NOx is set equal to N2O, and that of N2 ranges from 1 to 10%. It was assumed that no N is lost by leaching during manure storage, because in the Netherlands slurries have to be stored in covered basins with concrete floors. The total amount of TAN applied as slurry and solid manure to soil is calculated from the TAN excreted and mineralized or immobilized in housing and outside storage, corrected for the total gaseous N 250 G.L. Velthof et al. / Atmospheric Environment 46 (2012) 248e255 Excretion livestock Total N (484 Gg N) TAN (319 Gg TAN) NH3: 46 Gg N N2, N2O, NOx :12 Gg N Grazing on natural grasslands 8 Gg TAN Excretion in housing 269 Gg TAN Housing + manure storage Mineralisation: 8 Gg TAN Export and treatment of manure: 48Gg TAN Mineral fertilizer 238 Gg N Slurry and solid manure 82 Gg TAN NH3 11 Gg N NH3 8 Gg N Arable land Slurry and solid manure 89 Gg TAN NH3 22 Gg N Grazing 43 Gg TAN NH3 1 Gg N Grassland Fig. 1. General set-up of NEMA model. The arrows indicate the flows of TAN and N. The grey boxes with clouds the location and type of the gaseous N emissions and the boxes with dotted lines the N sources. The numbers indicate the flows of TAN and N and the gaseous emissions in Gg N per year. emissions in housing and outside storage. This amount is corrected for the manure exported, imported, and processed (i.e. the N that is removed from agriculture), and for changes in the amount of stored manure between years. The total amount of manure is divided over grassland and arable land, based on the N and P application standards in the Netherlands. The implementation of the manure application techniques were derived from statistics (CBS, 2009). The NH3-emission factors for manure application techniques were based on field experiments, and ranged between 2% of the TAN applied for slurry injection on arable land to 74% for broadcast surface spreading on grassland (Huijsmans et al., submitted for publication). The NH3-emission factor for grazing by cattle was based on the results of studies of Bussink (1992, 1994), as described by Huijsmans et al. (submitted for publication). The NH3-emission factor for grazing in 2009 was 2.7% of the TAN excreted. The NH3-emission factors for the different fertilizer types were calculated using the regression equations of Bouwman et al. (2002). Information about the fertilizer type, application method, soil pH, soil Cation Exchange Capacity (CEC), and climate, were used to derive the emission factors for the different N fertilizers (Huijsmans et al., submitted for publication). The emission factors ranged from 0% for nitrate fertilizers to 14.3% for urea. The emission factor for calcium ammonium nitrate, the most common mineral N fertilizer in the Netherlands, was 2.5%. 2.4. Total ammonia emission The total NH3 emission from agriculture was calculated as the sum of the NH3 emissions of housing, manure storage outside housing, manure application to soil, grazing, and mineral N fertilizer. In this paper the results for 2009 are presented, i.e. the year with most up-to-date inventory data. 2.5. Scenario analyses The effect of changes of several input parameters of the NEMA model on the total NH3 emission were calculated: The assumption of mineralization in stored slurry (10% of excreted organic N) is uncertain. The effect of a nett mineralization of 0 and 20% of the organic N in slurry on the total NH3 emission was quantified. The effect of changes in TAN excretion was assessed by assuming that the TAN fraction in the N excretion of all livestock categories was 10% smaller and larger, relative to the default value for 2009. There are indications that the NH3-emission factor for cubicle housing systems for dairy cattle is underestimated, because of larger air inlets (Smits and Huis in ’t Veld, 2007). The effect of a higher emission factor of relative 20% higher than the default emission factor for dairy housing systems on NH3 emission was quantified. Management and housing systems of pigs, poultry, and cattle evolve during the years, which can change emissions. In this calculation, the effect of a 20% smaller and larger emission factor on NH3 emission relative to the default emission factor was assessed for pig, poultry, and beef cattle systems. The emission factors for N2, N2O and NO are poorly quantified because measurements are lacking. The effect on NH3 emission of a 50% smaller and larger emission factor relative to the default emission factors was quantified. Huijsmans et al. (submitted for publication) show that the NH3-emission factor for shallow injected slurry on grassland has increased since the nineties. It has been suggested that this increase was (partly) due to less careful slurry application. The G.L. Velthof et al. / Atmospheric Environment 46 (2012) 248e255 251 Table 1 Number of animals and excretion of total N and TAN in 2009. Animal category Cattle Pigs Poultry Other Dairy cattle Young cattle Veal calves Beef cattle Fattening pigs Sows Other pigs Layers (>18 weeks) Broilers Other poultry Sheep and goats Horses Fur animals Number of animals Total N excretion 106 kg N TAN-excretion þ N mineralization in stored manure 106 kg N TAN excreted and mineralized, % of total excreted N 1489071 1237222 894248 347058 5872351 985244 260361 35293716 43285129 20497031 769369 144924 910701 189 68 14 22 75 30 4 27 23 13 11 7 2 484 120 47 9 14 53 20 3 21 17 9 7 5 1 327 63 69 64 64 71 67 75 78 74 69 64 71 50 68 Total effect on NH3 emission of 20% smaller and larger emission factors for all slurry application techniques relative to the default emission factors was assessed. The emission factors for application of poultry manure are equal to those of slurry. However, it is known that part of the excreted uric acid by poultry is not hydrolyzed during storage, especially when the manure is dried (Nicholson et al., 1996). The fate of uric acid of poultry manure after application to the soil and its effect on NH3 emission are not well quantified. If soil-applied uric acid does not contribute to NH3 emission, the use of a NHþ 4 based emission factor in an approach with calculated TAN excretion (i.e. the sum of NHþ 4 and uric acid) may lead to an overestimation of the NH3 emission. The effect of an emission factors for poultry manure which were 50% smaller than the default emission factors on NH3 emission was quantified. The implementation of the manure application techniques are derived from statistics, but in practice an application technique may be applied in a different way. In this calculation it is assumed that the share of cattle slurry application to grassland with narrow band application increases from 23 to 50% and that the share of shallow injection of cattle slurry grassland decreases from 56 to 29%. Differences in the distribution of manure over grassland and arable land may affect NH3 emission, because the emission factors differ between slurry application methods on grassland and arable land. It was assumed that the distribution of manure N of grazing livestock (cattle, sheep, goat, horses) between grassland and arable land differs 20% relative to that for 2009. The emission factor for grazing is 2.7% of the TAN excreted during grazing in 2009 (Huijsmans et al., submitted for publication). The effects on total NH3 emission of an emission factor of 10% (the default emission factor in the guidebook of EMEP/EEA, 2009) and 4.5% of the TAN excreted (the emission factor for grazing derived by Bussink (1994) at a N application of 250 kg N per ha) was assessed. or immobilization, was 63e69% for cattle, 67e75% for pigs, 69e78% for poultry, and 50e71% for other livestock categories (Table 1). The distribution of the housing systems and manure systems for major livestock categories is presented in Table 2. Slurry-based systems are the most common systems in the Netherlands. The majority of dairy cows (95% in 2009) were held in common cubicle housing systems and only 5% of the dairy cows are kept in housing systems with low NH3 emission, like tied stalls. During summer, most of the dairy cattle grazed during the day and were kept in housing at night (about 54%); 24% of the dairy cattle were kept in zero grazing systems and 22% in day and night grazing systems (not shown). About 40% of the pigs were kept in housing systems with low NH3 emission in 2009 (Table 2). There is a large diversity in type housing systems for poultry: battery, floor housing and aviary (Table 2). Almost 27% of cattle slurry, 15% of pig slurry, and 88% of poultry slurry is stored outside the housing. Shallow injection is by far the most common slurry application technique for grasslands (Table 3), followed by narrow band application. On arable land, most of the slurry is injected or surface spread followed by direct incorporation into the soil (Table 3). Nearly all solid manure is surface spread to arable land, after which it is incorporated in the soil in a second track. The total N excretion by livestock in housing was 269 Gg TAN and during grazing 51 Gg TAN from which 8 Gg TAN was deposited on natural grasslands and 43 Gg TAN on managed grasslands (Fig. 1). The NH3 emissions from natural grassland are recorded for the national emission inventory, but these emissions are not reported as agricultural emissions. About 48 Gg TAN of the produced Table 2 Share of housing systems and manure storage systems for major animal categories in 2009. Animal category Housing system Share, % Dairy cows Cubicle house Low emission Tie stall Common Low emission Common Low emission Battery cages Floor housing; common Floor housing; low emission Aviary house; common Aviary house; low emission Other Common Low emission 95 1 4 61 39 57 43 43 17 7 8 20 5 82 18 Fattening pigs Sows including piglets 3. Results Layers >18 weeks 3.1. N excretion and activity data The total N excretion by livestock in the Netherlands in 2009 was 484 Gg N, from which 61% excreted by cattle, 22% by pigs, 13% by poultry, and 4% by other livestock categories (Table 1). The fraction of TAN in percentage of the total N excreted, including net mineralization Broilers 252 G.L. Velthof et al. / Atmospheric Environment 46 (2012) 248e255 changed the total NH3 emission with 6.6 Gg NH3eN. Other factors that had a relatively large effect were changes in the emission factors of housing systems, mineralization of organic N in slurry, and the emission factor for grazing (Fig. 2). Table 3 Implementation rates of manure application techniques in the Netherlands in 2009. Land use Application method Grassland Shallow injection Partly shallow injected and partly band applied Narrow band application Surface application Injection Shallow injection Narrow band application Partly shallow injected and partly band applied Surface spreading and incorporation in two tracks Surface spreading and incorporation in one track Broadcast surface spreading Arable land 56% 12% 23% 9% 61% 8% 6% 7% 3% 11% 4% 4. Discussion A method was developed to calculate both the total N excretion and the percentage of TAN in the N excretion, using information of the feed composition and crude protein digestibility. Decreasing the protein content in animal feed may both decrease the N excretion and the percentage of TAN in the N excretion. Van Bruggen et al. (2011) calculated the TAN excretion of livestock in the Netherlands from 1990. The total N excretion of dairy cows in 1991 was 155 kg N per cow per year, with an average TAN fraction of 0.75. The total N excretion in 2009 was 127 kg N per cow per year, with an average TAN fraction of 0.60. Both the N excretion and TAN fraction decreased, which is mainly due to a decrease in N application rates to grassland resulting in lower N content in roughage. The TAN fraction in N excretion of fattening pigs decreased from 72% in 1991 to 68% in 2009, which was due to changes in N contents of the feed. The changes in TAN fraction for poultry are much smaller. For example, the TAN fraction in the N excretion of layers remained stable; 77% in 1991 to 78% in 2009. Approaches based on calculated TAN excretion using feed composition have more potential to quantify the effects of feeding strategies on ammonia emission than approaches using a fixed TAN fraction or total N. However, the calculation of TAN requires detailed information about the composition of the feed, which is often not available. The calculations show that a relative change in the fraction of TAN in the excreted N by 10% (for all livestock categories) changed the total calculated NH3 emission from agriculture in the Netherlands by about 8%. Thus, the sensitivity of the NEMA model for the TAN fraction is high, which is due to the fact that the TAN fraction affects NH3 emission in all parts of the manure management systems, i.e. housing, manure storage outside, grazing, and manure application. The TAN content of manure is also affected by mineralization and immobilization during storage. The results of the calculations show that the total NH3 emission in the Netherlands changes with 3.2 Gg N (or 3.5%; Fig. 2) if the net N mineralization of the organic N in slurry during storage changes with 10%. There is little information about mineralization and immobilization of NHþ 4 in manure during storage. This is mainly because such measurements are manure is not applied to agricultural soils, but removed by manure processing, and exported to other countries. The amount of manure applied to grassland (89 Gg TAN) is somewhat higher than that applied to arable land (82 Gg TAN; Fig. 1). The total amount of mineral N fertilizer applied was 238 Gg N in 2009. Calcium ammonium nitrate was by far the most common mineral N fertilizer in the Netherlands, i.e. 65% of the total mineral N use in 2009. 3.2. Ammonia emission in 2009 The total NH3 emission from agriculture in the Netherlands in 2009 was 88.8 Gg NH3eN, from which 50% from housing, 37% from manure application, 9% from mineral N fertilizer, 3% from outside manure storage, and 1% from grazing (Table 4). Cattle farming was the dominant source of NH3 emission in the Netherlands (about 50% of the total NH3 emission). The NH3 emission expressed as percentage of the total excreted N decreased in the order poultry (22% of the excreted N), pig (20%), cattle (15%), and other livestock (12%). The NH3 emission expressed as percentage of the excreted and mineralized TAN was 34% for poultry, 32% for pigs, 23% for cattle, and 23% for other livestock. On average, 18% of N excreted by livestock (or 26% of the TAN excreted and mineralized in manure storage) in the Netherlands in 2009 volatilized as NH3 to the atmosphere. 3.3. Scenario analyses Changing the TAN fraction in N excretion with 10% had a large effect on the total NH3 emission: 7.5 Gg NH3eN (Fig. 2). Changes in the NH3-emission factor for manure application with 20% Table 4 Ammonia emission from agriculture in the Netherlands in 2009. NH3 emission in 106 g N Source of NH3 Cattle Pigs Poultry Other Dairy cattle Young cattle Veal calves Beef cattle Total Fattening pigs Sows and other pigs Total Layers Poultry for meat production Total Sheep and goats Horses and ponies Fur animals Total Total manure Mineral N fertilizers Total agriculture NH3 emission in Housing Manure storage Grazing Manure application Total % of excreted N % of excreted TAN 11.0 3.6 1.7 1.2 17.4 10.9 4.6 15.5 6.2 4.0 10.2 0.4 0.4 0.2 1.0 44.1 0.4 0.2 0.0 0.1 0.7 0.2 0.1 0.3 1.0 0.2 1.2 0.1 0.1 0.0 0.1 2.3 0.5 0.4 0.0 0.1 1.0 0.0 0.0 0.0 0.0 0.0 0.0 0.1 0.1 16.9 5.0 0.7 1.5 24.2 3.8 2.0 5.8 0.3 1.5 1.9 0.6 0.4 0.1 1.1 33.0 28.7 9.2 2.5 2.9 43.3 14.9 6.7 21.6 7.6 5.7 13.2 1.2 1.0 0.3 2.4 80.5 8.3 88.8 15 14 18 14 15 20 20 20 28 16 21 10 13 15 12 17 24 19 27 21 23 28 29 28 36 22 28 17 20 22 19 25 0.2 1.2 G.L. Velthof et al. / Atmospheric Environment 46 (2012) 248e255 253 EF grazing 10% 3.1 EF grazing 4.5% 0.8 Manure to grassland: +20% 2.0 Manure to grassland: -20% -2.0 Increase narrow band manure application on grassland 1.7 EF application poultry manure -50% -1.2 EF manure application +20% 6.6 EF manure application -20% -6.6 EF N2, N2O, NOX +50% -0.3 EF N2, N2O, NOX -50% 0.3 EF housing pigs and poultry +20% 4.6 EF housing pigs and poultry -20% -4.6 EF housing dairy cows +20% 1.7 TAN fraction all manures +10% (relative) TAN fraction all manures -10% (relative) 7.5 -7.5 3.2 Mineralisation 20% of excreted organic N in slurry Mineralisation 0% of excreted organic N in slurry -3.2 -10 -5 0 5 10 Fig. 2. Effects of changing parameters on total calculated NH3eN emission in the Netherlands in 2009 using NEMA model see Materials and methods for description of the scenarios. EF is emission factor. The total calculated NH3 emission was 88.8 Gg N (see Table 4). difficult, as the NHþ 4 contents in the manure are not only affected by NH3 emission, but also by emissions of NO, N2O and N2 of which the latter is very difficult to measure. The few studies in literature show a large variation in N mineralization ranging from less than 10% to more than 50%, depending on factors such as temperature and type of manure (e.g. Sommer et al., 2007; Sørensen et al., 2003; and Beline et al., 1998). In the approach of Dämmgen and Hutchings (2008), it is assumed that 10% of organic N in cattle slurry and solid cattle manure is mineralized during storage. For solid cattle manures, it is assumed that 40% of the excreted TAN is immobilized during storage. The model of Webb and Misselbrook (2004) also assumes 10% mineralization of organic N in slurry storage. Moreover, it was assumed that 1 kg TAN is immobilized per 150 kg added straw in solid manures, which was about 47% of TAN remaining in the manure after NH3 emission in a scenario equated in Reidy et al. (2009). In the NEMA model it is assumed that 10% of the organic N of animal slurry mineralizes during storage in housing. Because of the large uncertainties, no mineralization in the manure storage outside is calculated, assuming that most of the easily mineralizable organic N is already mineralized in the housing. For solid manure, it is assumed that 25% of the TAN is immobilized during storage. Clearly, the mineralization (and immobilization) of manure during storage is poorly quantified. For manure from mammals, urea and easy degradable urine-N will þ be rapidly converted into NHþ 4 , thus TAN equals NH4 . However, the calculated TAN fraction of poultry after storage, before application includes both NHþ 4 and uric acid, especially when the manure is dried. Indeed, Van Faassen and Van Dijk (1987) measured NH4 and uric acid contents for layers of 15% and 57% of total N respectively, summing up to a total TAN fraction of 72%. NEMA calculated an average TAN fraction for layer manure of 71% for slurry and 74% for solid manure (not shown), which is close to these findings. Also for broilers, the 254 G.L. Velthof et al. / Atmospheric Environment 46 (2012) 248e255 total TAN fraction was 72% in the study of Van Faassen and Van Dijk (1987), of which 12% was NHþ 4 eN and 60% uric acid N. The calculated average TAN fraction in broiler manure was 66% according to NEMA. After application to the soil, the uric acid is degraded within about 10 days (Kirchmann, 1991). The NH3-emission factor for manure applied to the soil is based on the measured NHþ 4 content of the manure (Huijsmans et al., submitted for publication) The fate of uric acid of poultry manure after application to the soil and its effect on NH3 emission are not well quantified. If soil-applied uric acid does not contribute to NH3 emission, the use of a NHþ 4 based emission factor in an approach with calculated TAN excretion (i.e. the sum of NHþ 4 and uric acid) may lead to an overestimation of the NH3 emission. The calculations showed that decreasing the emission factor of application of poultry manure by 50% relative to the default emission factor, decreased the total NH3 emission in the Netherlands by 1.2 Gg N (about 1%). There is a need of quantification of the effect of uric acid in poultry manure on NH3 emission, because the TAN-based models relate NH3 emission to the TAN content, while measured NH3 emissions are generally related to measured NHþ 4 contents in the manure. Cattle farming, both dairy and beef, is the dominant source of NH3 emission in the Netherlands. However, when the NH3 emission for each livestock categories is expressed as percentage of excreted N, the NH3 emission decreases in the order poultry (22% of the excreted N), pig (20%), cattle (15%), and other livestock (12%). This effect is mainly due to the differences in housing systems and application techniques. The emission factors for housing systems are generally highest for poultry housing, and especially the solid manures. Furthermore, the solid poultry manure cannot be (shallow) injected or directly incorporated, resulting in higher emissions after application. The higher emission per kg excreted N for pigs than for cattle is due to a combination of higher emission factors for pig housing systems and the fact that part of the manure of dairy cattle is excreted during grazing (resulting in low NH3 emission). The results of the calculations suggest that the total NH3 emission from agriculture in the Netherlands can vary by several millions kg NH3eN (Fig. 2). The parameters that have largest effect on the total emission are the TAN excretion and the emission factors for manure application. Housing systems are the largest source of ammonia in the Netherlands (Table 4). Manure application is also major source of NH3 emission in the Netherlands (Table 4), even though all manures have to be applied with techniques with a low NH3 emission. Other factors that may significantly contribute to the variation of the calculated NH3 emission include the estimate of N mineralization during slurry storage, and the emission factors for housing systems and grazing. NEMA includes the major NH3 sources in agriculture, which are related to manure management and fertilizer use. Other potential sources of NH3 are not yet included, such as emissions during ripening of crops or from crop residues (e.g. De Ruijter et al., 2010; Holtan-Hartwig and Bøckmann, 1994; Sommer et al., 2004). Moreover NH3 emission during manure transport or temporal storage of manure during transport of manure from livestock farm to an arable farm are not included. The NEMA model is developed for the national scale, but the NEMA methodology has also been implemented in a tool which is be used to calculate farm specific N excretion of dairy cows and NH3 emission for dairy farming (Sebek, personal communication). From 2011, NEMA will be used as official methodology to calculate the national NH3 emission from agriculture in the Netherlands (Van der Maas et al., 2011). Acknowledgements The NEMA model was developed in a project of the Scientific Committee of the Manure Act (CDM), financed by the Ministry of Economic Affairs, Agriculture and Innovation in the Netherlands (projects BO-05-007 and WOT-04-003-008). 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