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* Department of Soil Quality, Wageningen University, PO Box 8005, 6700 EC Wageningen, the Netherlands
Department of Animal Sciences, Wageningen University, PO Box 338, 6700 AH Wageningen, the Netherlands
1 Corresponding author: erwin.temminghoff{at}wur.nl
| ABSTRACT |
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Key Words: dietary adjustment dairy cow manure composition ammonia volatilization
| INTRODUCTION |
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Changing the CP content or the digestibility of the feed will affect both the N content and the N composition of manure slurry, because, in both cases, urinary N excretion is affected more than fecal excretion of N (Kebreab et al., 2002). Lowering the CP content of diets, especially when CP is fed above protein requirements (as is usually the case), will not only decrease the amount of N excreted by dairy cattle, but will also reduce the short-term N availability of manure, making it less susceptible to leaching and volatilization (Paul et al., 1998). Sørensen et al. (2003) observed an increase in the concentration of N in feces dry matter when the digestibility of the diets increased. Nitrogen utilization efficiency increased when lactating dairy cows were fed grass silage diets enriched with a low-degradable starch source instead of a high-degradable starch source (Castillo et al. 2001).
Excessive N is mainly excreted by the cow as urea via the urinary tract (Vérité and Delaby, 2000; Børsting et al., 2003). After contact with the enzyme urease, which is present in feces, urea is rapidly degraded into NH3, which is susceptible to volatilization. Ammonia is considered an important source of acidifying gaseous N emissions. Furthermore, NH3 can act as a source of N in low-nutrient ecosystems and it can react with atmospheric acids to form particulates, which can be spread over a wide area (Sommer and Hutchings, 2001; Webb et al., 2005). In Europe, about 75% of the NH3 emitted to the atmosphere can be attributed to livestock production, and measures restricting NH3 emissions from the livestock sector are considered the most effective approach to reduce the impact of NH3 on the environment (Webb et al., 2005). Besides the total ammoniacal nitrogen (TAN) concentration [TAN = NH4+ + NH3,aq (aqueous)] in manure slurry, the pH and the DM content of the slurry are the most important parameters determining the NH3 volatilization potential (Jarvis and Pain, 1990; Sommer et al., 2003). Paul et al. (1998), in 2 feeding trials, observed decreases in NH3 emissions from manure slurry when the dietary CP content decreased. In one experiment, CP levels were lowered from 16.4 to 12.3%, which reduced NH3 emissions by 40%, whereas in the other experiment, CP levels were reduced from 18.3 to 15.3%, which reduced NH3 emissions by 20%. Similar decreases in NH3 emissions with decreasing protein content of the feeds were reported by James et al. (1999) and Külling et al. (2001).
The aim of this research was to investigate how manure composition was affected by dietary changes. The slurries were produced in a feeding trial in which nonlactating cows were fed specific diets that varied in protein and energy content (Reijs et al., 2007). The effect of feeding strategy on manure composition was studied by measuring total as well as direct available (free) nutrient concentrations (N, P, K, Ca, Mg, and Na) in different manure slurries. In addition, the effects of diet composition and manure characteristics on NH3 volatilization were investigated.
| MATERIALS AND METHODS |
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Before the slurry samples were analyzed for total nutrient concentrations, the samples were first dried for 3 d in a drying oven (Heraeus 6060, Kendro Laboratory Products, Hanau, Germany) at 70°C. After drying, the samples were ground (<1 mm) using a Culatti MFC-type Micro Hammer Mill (Culatti AG, Zürich, Switzerland).
Next, the slurry samples were digested by microwave digestion with HNO3, H2O2, and HF (Novozamsky et al., 1996) to determine total nutrient concentrations of Mg, Ca, K, and Na. Furthermore, the dried and ground manure slurry samples were digested using H2SO4, salicylic acid, H2O2, and selenium (Novozamsky et al., 1983) to determine total P concentrations in the manure samples. Potassium, Mg, Na, and Ca concentrations were determined by inductively coupled plasma atomic emission spectrometry (Varian (Vista-pro), Palo Alto, CA). Total P was measured by segmented-flow analysis (Skalar, Breda, the Netherlands). Total C was measured in the dried slurry samples on a CHN-analyzer (EA 1108, Fisons Instruments Milan, Italy), and total N was measured in fresh slurry samples using the Kjeldahl method (method ISO5983; ISO, 1979). Carbon losses during drying were minimized by using a forced-air drying oven. The C/N ratios of the slurries were calculated from the total C and total N data.
Determination of Free Nutrient Concentrations
The Donnan membrane technique manure cell consists of an acceptor solution separated from manure slurry by 2 negatively charged cation exchange membranes (Van der Stelt et al., 2005). The membranes allow transport of positively charged cations, whereas transport of neutral and negative ions is restricted. Within 5 d, (Donnan) equilibrium is reached between free cation concentrations in manure slurry and free cation concentrations in the acceptor solution.
Before starting the experiment, each manure slurry was homogenized, after which 10 kg of slurry was transferred into a plastic container (206 mm height, 11.3 L; Fisher Scientific, Waltham, MA), and 3 Donnan membrane technique cells were immersed in each slurry. The containers were closed with lids that contained a small opening into which a stirrer was placed. During the experiment, the slurries were continuously mixed to prevent settling of the solid phase. At different times (0, 7, 10, and 14 d), samples were taken of both the acceptor solution (3 mL) and the manure slurry (~250 mL).
No pretreatments were required to measure free nutrient concentrations in the sampled acceptor solutions, because only free positively charged ions can pass the membrane. Free K, Ca, Mg, and Na concentrations were determined by inductively coupled plasma atomic emission spectrometry. Subsamples of the acceptor solution were taken, diluted 200 times with ultrapure water, and measured by segmented-flow analysis to determine the free ammonium (NH4+) concentration present in manure slurry. The measured potassium data were used to correct for differences in ionic strength between acceptor solution and manure slurries in accordance with Van der Stelt et al. (2005). The ammonia (NH3,aq) concentrations and the TAN concentrations of the slurries were calculated by the speciation program Ecosat (Keijzer and van Riemsdijk, 2002), using the equilibrium reactions of the different species in combination with the measured pH and NH4+ concentrations. Because nutrient concentrations were constant during the experiment, mean nutrients concentrations have been presented (Table 3
).
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where G represents the (relative) amount of NH3 volatilized at time t (d) after start of the incubation; A represents the (relative) asymptotic gas production (mmol of NH3/mol of TAN); B denotes the time (d) required for half of the amount of gas produced to be formed; and constant C determines the curvature and, thereby, the position of the point of inflection. For C
1, the profile has no point of inflection (t
0).
Statistical Analysis
The SPSS program was used for statistical analysis of the data (SPSS Inc., 2003). Differences in manure composition caused by different feeding strategies were analyzed by ANOVA. Correlations were made between feed characteristics and the chemical composition of manures. The effects of dietary changes in protein and energy content on manure composition were tested for the 4 groups (1 to 4) described earlier, using the model: y = protein + energy + protein x energy + rep (protein x energy). Analysis of the effects of feed characteristics on ammonia volatilization was performed using repeated measurement analyses. Data were transformed when necessary to achieve equality of variances.
| RESULTS AND DISCUSSION |
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Increasing the energy content from 5,050 to 6,840 kJ/ kg of DM (and simultaneously improving the digestibility of the feed; Table 1
) reduced the DM content of the manure slurries. This result agrees with results reported by Broderick (2003), who observed a decrease in fecal DM quantity, when the digestibility of the feed increased. Moreover, at a greater energy content of the diet, more feed (and N) was consumed by the animals in this experiment, adding to the excess of N (discussed in the next section). Excess N will be mostly excreted via the urinary tract, which will decrease the DM content of the slurry. On average, the DM content of the slurries was 14% less when the energy content of the feeding regimens was 35% greater. The C:N ratios of the manure slurries were, on average, 17% less when the digestibility of the organic matter was approximately 17% greater.
Total Nutrient Content
The total DMI of the animals (forage + concentrates) ranged from 1.4% (LPLEb) to 2.9% (HPHEa and HPHEb) of the mean BW, which is similar to the range reported for nonlactating cows in the standard of the American Society of Agricultural Engineers (0.7–2.2%; ASAE, 2005).
The total K content of the slurries ranged from 26 to 80 g/kg of DM (Table 3
) and was, except for the straw-based feeding regimens (LPLEb and HPLEb), similar to the normal K content found in dairy slurries produced in the Netherlands (±59 g/kg of DM; Blgg, 2005).
The amount of K consumed by cows that were fed straw-based diets was approximately half that consumed by the other cows. Subsequently, K content in the LPLEb and HPLEb slurries was approximately 50% lower than in the other slurries. The total Na content of the slurries varied between 1.8 and 6.3 g/kg of DM (Table 3
). The Na content of all tested slurries was lower than the mean Na content found in dairy slurries (±7 g/kg of DM). This suggests that the feeding regimens contained low amounts of Na. Nevertheless, minimum daily Na intakes required by cows (7 g/d; CVB, 2003) were met for all feeding regimens (Table 1
) except for the LPHEb treatment, from which slightly less Na was consumed (6 g/d) than required.
The Ca content of the slurries varied considerably between the different diets (SEM = 0.7 g/kg of DM). The least total Ca content was found for the HPHEa slurry (8.6 g/kg of DM) and the greatest Ca content was found for slurry LPLEb (14.1 g/kg of DM). However, the mean daily amounts of Ca excreted were almost equal for the these 2 extremes [e.g., 43 g/cow per day for HPHEa and 44 g/cow per day for LPLEb], which shows that, in addition to the content, the absolute amount of manure excreted is also important. For all feeding regimens, the mean daily Ca excretion was 44 ± 7 g/cow per day.
Total Mg content of the slurries varied from 5.9 g/ kg of DM for the HPLEb treatment to 9.4 g/kg of DM for the HPHEb treatment. For all feeding regimens, the mean daily amount of Mg excreted was 31 ± 7 g/cow per day. All slurries except HPHEb had Mg content comparable to the mean Mg content found in dairy slurries (Table 3
), whereas total Mg content of the HPHEb slurry was approximately 34% less. The Mg content of the slurries was positively correlated with the total K content of the slurries (Pearson = 0.744; P < 0.001). A greater K content in manure slurries is the result of an increase in the dietary K content. A high K content in the feed has a negative effect on the digestibility of Mg (Schonewille et al., 1999; Weiss, 2004), leading to an increase in the amount of Mg excreted by the animal.
The total P content of the slurry based on the highly digestible grass silage treatment (HPHEb; 14 g/kg of DM) was greater than the mean total P content found in dairy slurry (8.2 g/kg of DM; t-test; P < 0.05; Anonymous 2005a). The P content of the other treatments varied from 5.9 (LPLEb) to 10.3 g/kg of DM (HPHEa).
The total N content of slurries produced by dry cows fed diets containing high protein and high energy contents (regimens HPHEa and HPHEb) were approximately 54% greater than the mean N content found in dairy slurries (Table 3
). All other treatments had total N content comparable to the mean N content found in dairy slurries, except for the LPLEa slurry, which was approximately 32% lower than the mean N content. The total N content of slurries produced by nonlactating cows fed diets containing a high protein content or a high energy content were, on average, 56 and 27% greater (CP: P < 0.001; NEL: P < 0.01) than the N content of slurries produced by cows fed diets with low protein or low energy contents. In contrast, Broderick (2003) observed a decrease in total N excreted in manure slurry of lactating dairy cows, when the energy content of the feed increased. These contradictory observations are likely to be related to the lesser efficiency of N utilization of nonlactating cows used in this experiment compared with the lactating cows used by Broderick (2003). In the case of nonlactating cows (in the present experiment), no N was converted into milk N protein, and N requirements for maintenance were lower. Consequently, feeding extra CP or energy to the cows will result in greater amounts of excreted N than for lactating cows.
Similar to the total N content, the total P content of the slurries increased with greater protein (48%) or energy content (39%), or both, of the feeding regimens (P < 0.01). The N:P ratios of the slurries varied from 5.4 to 9.0 and were on average 10% greater than the mean N:P ratio found in manure slurries (6.1; Table 3
). The N:P ratio required by crops is about 8:1 (Lefcourt and Meisinger, 2001). Because manure application is primarily based on N requirements of plants, a greater N:P ratio of slurry manure will decrease the amount P applied (in excess) to the soil, which will reduce the risk of P loading of soils. Total P present in manure slurry was positively related to the Mg and TAN content of manure slurry, which might relate to the potential presence of minerals (e.g., struvite) in manure slurry (Van der Stelt et al., 2005).
Free Nutrient Content
Almost all Na present in manure slurry existed as free ions (73 to 100%), whereas only small amounts of the divalent cations Ca and Mg (1 to 10% and 0 to 19%, respectively) were present in manure slurry as free ions, as can be derived from Table 3
. The relative free Na content in the slurries correlates (Pearson = 0.714; P < 0.05) with the Na content of the feed (Table1), which indicates that Na supply was sufficient during the feeding trial. The low free Ca and Mg contents are most likely caused by precipitation of minerals [e.g., CaCO3 (calcite) and MgNH4PO4H2O (struvite)] or adsorption to organic matter (Sommer and Husted, 1995).
Changes in the protein content or in the energy content/digestibility of the feed did not significantly affect the relative free nutrient content of Na, Ca, and Mg. Total ammoniacal N accounted for 52 to 77% of the total N content present in manure slurry. Both the TAN content and the organic N content of the slurries were greater (P < 0.01) with greater CP content of the feed. However, the increase in TAN was 3 times greater than the increase in organic N, indicating that more N is excreted via the urinary tract with greater CP content of the feed. Similar observations were reported by Broderick (2003). In contrast to the observations of Broderick (2003), however, the TAN content in our experiment was greater for the high-energy diets (~32%; P < 0.001). This discrepancy is related to the greater N intake of the cows receiving the high-energy diets, in combination with the physiological status of the cows. Unlike lactating cows, nonlactating cows are not able to use this extra N uptake efficiently through the production of milk. Therefore, the extra N uptake is excreted in urine, causing a greater TAN content in the slurry.
Both the free Ca2+ and the free Mg2+ contents were negatively correlated to the TAN content present in manure slurry (Ca2+: Pearson = –0.462, P < 0.05; Mg2+: Pearson = –0.514, P < 0.05). This is probably related to the exchange of Ca2+ and Mg2+ from the liquid phase with NH4+ adsorbed to organic matter, which was described previously by Sommer et al. (2003).
Ammonia Volatilization
The chemical composition of the (diluted) manure slurries used in the ammonia volatilization experiment is given in Table 2
. The ionic strengths of the slurries were greater when the feeding regimens contained either more energy or proteins, ranging from 0.17 M in case of the straw based regimen with a low protein content (LPLEb) to 0.36 M for the regimens high in energy and high in protein content (treatments HPHEa and HPHEb). The ionic strengths of the slurries are within the range (e.g., 0.1 to 0.4 M) previously reported by Sommer et al. (2003). The pH values of the manure slurries at the start of the experiment ranged from 7.2 to 7.6 for the feeding regimens low in protein and from 7.6 to 8.4 for the regimens high in protein. Similarly, both Külling et al. (2001) and Paul et al. (1998) measured higher slurry pH values when dairy cattle were fed more CP. Slurry pH values were lower when slurries were obtained from feeding regimens containing a high energy content. At greater dietary energy content, more feed is taken in by the animal per unit of time (Table 1
) and hence, the passage rate of the feeds through the animal is greater. Feeding energy-rich diets will stimulate volatile fatty acid formation in the hindgut, which will decrease slurry pH, as was shown to occur for energy-rich diets in feeding trials with lactating cows (Reynolds et al., 2001).
The NH3,aq content in manure slurries produced from feeding regimens with a high CP content were, during the complete experiment, considerably greater than the NH3,aq content in slurries produced from regimens with a low CP content (on average 10 times greater). Moreover, the range in NH3,aq content was variable for the slurries based on feeds containing a high CP content; for example, varying from 0.8 to 4.2 g of N/ kg of DM. Comparable differences in slurry NH3,aq content were calculated for slurries studied in feeding trials by Paul et al.(1998), where the NH3,aq content was more than 4 times greater when the feed contained 15.3% instead of 12.3% CP. The NH3,aq content of the slurries were barely affected by changes in the energy content of the feed. The NH3,aq content of both straw-based treatments (HPLEb and LPLEb) were 2 times greater than the other treatments containing a similar amount of protein in the feed. The greater NH3,aq content for the straw treatments are most likely caused by the high carbon content of the slurries (Table 2
), which stimulated the ammonification process (Külling et al., 2001) and because of the higher pH, which shifted the NH4+/ NH3,aq equilibrium in favor of NH3,aq.
Figure 1a
shows the mean cumulative NH3 amounts volatilized per day from the different manure slurries incubated at 12°C for 32 d. The absolute NH3 amounts volatilized are expressed per cow per day to correct for differences in amounts of manure slurry produced per treatment. The amounts of NH3 volatilized per cow per day varied, for the low CP treatments, between 0.13 and 0.21 g of NH3 and for the high CP treatments between 0.93 and 1.41 g of NH3. Compared with previous studies the amounts of NH3 volatilized in 32 d were low. Misselbrook et al. (2005) reported that similar amounts of NH3 were volatilized from cattle slurry surfaces in 50 h of incubation. Under normal conditions, NH3 emissions from manure slurries are the combined results of diffusion and convectional processes occurring at the surfaces of slurries (Sommer and Hutchings, 2001). In most laboratory studies, NH3 volatilization is simulated by transporting air over the slurry surface (as in the study by Misselbrook et al., 2005). In our experiment, active transport of air was minimized, and thus, NH3 emissions due to convectional processes should be minimized. Hence, lesser amounts of NH3 will volatilize per unit of time. Extrapolating the measured data to conditions in which both diffusional and convectional processes occur is problematic because diffusion is determined mainly by the concentration gradient (e.g., solubility of NH3), whereas convection is determined mainly by air velocity and temperature. However, our method is suited to compare NH3 volatilization from different treatments relatively and to assess the effects of dietary changes on NH3 volatilization.
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The effects of changing dietary CP or energy content on NH3 emissions from the manure slurries became clearer when the (cumulative) NH3 amounts volatilized were expressed in proportion to the amount of slurry produced (Figure 1b
), or in proportion to the TAN content of the slurries (Figure 1c
). Expressed per kilogram of wet manure slurry, the NH3 amounts volatilized from slurries based on low-CP regimens (108 g/kg of DM) were, on average, 78% lower than the NH3 amounts volatilized from slurries based on high-CP regimens (190 g/kg of DM). Külling et al. (2001) reported a 69% decrease in the rate of NH3 emissions when cows were fed 125 g of CP/kg of DM instead of 175 g/kg. At high CP content, on average, 66% more NH3 was volatilized from manure slurries based on low energy feeds. The differences in amounts of slurry excreted led to similar NH3 emissions at low energy content when NH3 is expressed as milligrams of NH3-N per kilogram of manure (e.g., HPLEa, HPLEb; 32 and 41 L/d), whereas the difference became more evident for the slurries at high energy content (e.g., HPHEa and HPHEb; 54 and 43 L/d). At low CP content, no effects of energy content of the feed on the amount of NH3 emitted per kilogram of manure slurry were observed and amounts of NH3 volatilized increased in the order: LPLEa
LPHEb < LPHEa
LPLEb.
When NH3 emissions are expressed as a proportion of the TAN content of the slurries (Figure 1c
), the order of the NH3 emissions reflects the 4 dietary groups. However, at low CP content, no statistical differences (P < 0.05) in amounts of NH3 volatilized were observed between slurries LPHEa and LPLEa. Again, NH3 emissions are much lower when the CP content of the feeding regimens was lower (71%), and increasing the energy content of the regimens resulted in lower NH3 emissions, both at high (86%) and low (33%) CP contents.
Dietary changes to improve manure quality and reduce environmental losses are primarily based on reducing CP content and increasing the fiber content (i.e., lowering the net energy content of diets). Our data confirm that lowering dietary CP content can be an effective way to reduce N emissions. In contrast, the effects of increasing the fiber content of the feeds on NH3 volatilization from manure slurry are not as well defined. Increasing the fiber content of the diet will, in general, decrease the OM content, which is fermented in the rumen. Dry matter intake and the passage rate of OM will be less, which will reduce the efficiency of microbial N synthesis in the rumen. Hence, more N in the rumen will be transformed into NH3, which will subsequently be transformed into urea and (partly) excreted via the urinary tract.
| CONCLUSIONS |
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| ACKNOWLEDGEMENTS |
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Received for publication July 17, 2006. Accepted for publication August 4, 2008.
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