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Predicting Greenhouse Gas Emissions from Beef Cattle Feedyard Manure Heidi M. Waldrip, 1 Kenneth D. Casey, 2 Richard W. Todd, 1 and N. Andy Cole 1 1 USDA-Agricultural Research Service (USDA-ARS),Conservation and Production Research Laboratory, Bushland, Texas 2 Texas A&M AgriLife Research, Amarillo, Texas Table 1. Summary statistics. Correlation coefficients (R; n = 79) were used to identify primary variables related to GHG emissions. Asterisks indicate significance at: P < 0.05 (*), 0.01 (**), 0.0001 (***). NS, not significant. Most of the variables investigated were related to measured N 2 O fluxes (P < 0.01), and nitrate concentration had the highest R value. In contrast, few significant relationships were identified for CH 4 flux: only OD254 nm, which indicates organic matter complexity, was significant (P < 0.001). INTRODUCTION The Texas Panhandle is the largest beef feeding area in the US, producing approximately 20% to 30% of finished beef. Beef cattle feedyards are sources of greenhouse gases (GHG), most notably enteric methane (CH 4 ) and manure-derived nitrous oxide (N 2 O) and CH 4 . However, little information exists on the magnitude of feedyard GHG emissions or the factors that influence their production. Valid prediction methods are needed to inventory feedyard GHG and assess the impact of beef production on the environment. Most biochemical process-based models to predict GHG rely on information derived from studies on soil, which may, or may not, be valid for manure in open lot systems. The limited study on manure-derived feedyard GHG indicates that fluxes of both N 2 O and CH 4 are highly variable in space and time. Improved understanding of factors related to manure- derived GHG could help refine process-based models and produce useful empirical models for predicting the environmental footprint of feedyard beef. In turn, this could lead to more accurate inventory calculation techniques for regulatory agencies. OBJECTIVES: Determine factors related to production and volatilization of N 2 O and CH 4 from manure in beef cattle feedyard pens Develop empirical models to predict GHG emissions based on manure physicochemical properties MATERIALS AND METHODS GHG flux data and manure samples were collected during 8 four-day non- flow-through, non-steady-state (NFT-NSS) chamber studies conducted in 2012 and 2013 on two Texas Panhandle feedyards (Feedyard A and Feedyard C; Fig. 1). Each pen contained 10 NFT-NSS chamber bases inserted into pack manure (Fig. 2a and b). Chambers were located in specific areas (e.g., near feedbunk and water trough areas, back of pen, middle of pen, etc.) and contained sensors to record manure temperature. After fitting the base with a chamber cap, headspace was sampled with a disposable syringe at 0, 10, and 30 min. Concentrations of N 2 O and CH 4 were quantified with gas chromatography (Fig. 3). See the presentation of Casey et al. (Mon. 1:00, Paper: 96-1) for specific details Figure 1. Aerial views of Feedyard-A (left; 22,000 head capacity) and Feedyard-C (right; 55,000 head capacity). Figure 2. a) NFT-NSS chamber with top installed, and b) two rows of five NFT-NSS chambers installed in a pen at Feedyard-C. Physicochemical properties of the dense pack fraction of pen manure are presented in Table 1. There were a total of 79 GHG measurements and manure samples. Water-extractable manure organic matter [WEOM; 1:100 (wt:vol)] was analyzed for dissolved organic carbon (DOC), total dissolved carbon (DC), and total dissolved nitrogen (DN). Ultraviolet-visible (UV-vis) spectral characteristics of WEOM were evaluated between the wavelengths of 200 and 700 nm. Absorbance at 254 nm (OD254), and ratios of E2/E6 (proportion of humified to non-humified material) and E4/E6 (degree of humification, molecular weight, aromaticity) were calculated based on absorbances at 254, 280, 472, and 664 nm. Mixed modeling (Proc MIXED) was used to develop empirical equations to predict manure-derived N 2 O emissions. Study was set as a random variable. Models were evaluated by regression and measures of difference (Willmott et al., 1982) and compared to two randomly chosen subsets ( n = 20) of the original dataset. Reference: Willmott, C.J. 1982. Bull. Am. Met. Soc. 63:1309-1313. Figure 3. Emissions of (a) nitrous oxide (N 2 O) and (b) methane (CH 4 ) from manure in two commercial Texas feedyards. Gas fluxes were determined using NFT-NSS chambers (10 chambers per sampling date, designated Chambers 1-10) and gas chromatography. Emissions of both GHG were highly variable due to environmental conditions and locations of chambers within pens. Average fluxes were 1.1 + 2.2 and 1.9 + 4.3 mg m -2 h -1 for N 2 O and CH 4 , respectively. CONCLUSIONS Emissions of both GHG were highly variable due to environmental conditions and locations of chambers within pens. Average fluxes were 1.1 + 2.2 and 1.9 + 4.3 mg m -2 h -1 for N 2 O and CH 4 , respectively (Fig. 3a and b). Most of the variables investigated were related to measured N 2 O fluxes (P < 0.01), and nitrate concentration had the highest R value. In contrast, few significant relationships were identified for CH 4 flux: only OD254 nm, which indicates organic matter complexity, was significant (P < 0.001) (Table 1). N 2 O flux tended to increase with manure NO 3 - (Fig. 4a) and was highest at ~ 10% and 30% water content (Fig. 4b). Predicted N 2 O flux from empirical models developed in this study had 70% to 80% agreement with measurements, and the models adequately simulated both high and low values (Table 2). Inclusion of UV-vis spectral characteristics (Model 3) improved model predictions somewhat: regression analyses for the two data subsets and Model 3 predictions produced R 2 values of 0.74 to 0.80 with intercepts near O and slope near 1 (Fig. 5). Further work is required to evaluate these models against an independent dataset and develop equations for predicting manure- derived CH 4 emission. ACKNOWLEDGEMENTS The authors thank Heather Robbe, Beverly Meyer, and Will Willis for technical assistance with manure analyses for this study. Figure 4. Relationships between manure a) NO 3 - -N and b) water content (% w/w) and N 2 O fluxes. N 2 O flux tended to increase with manure NO 3 - and were highest at ~ 10% and 30% water content. Variable Mean + Standard Deviation Range R CH 4 R N 2 O Nitrous oxide (mg m -2 h -1 ) 1.12 + 2.17 0 - 8.46 NS -- Methane (mg m -2 h -1 ) 1.91 + 4.27 0 - 25.5 -- NS Moisture (%) 28.6 + 8.9 9.1 - 48.7 0.219 0.319** Surface temperature ( o C) 20.1 + 11.6 1.8 - 39.8 0.164 0.314** Organic matter (% DM) 69.9 + 7.4 44.4 - 83.3 0.241 -0.327** Ammonia/ammonium-N (g kg -1 ) 3.05 + 2.31 0.35 - 10.9 NS -0.396*** Nitrate/nitrite-N (mg kg -1 ) 6.87 + 16.3 0 - 106 NS 0.580*** Dissolved organic C (mg g -1 ) 28.4 + 5.2 18.3 - 45.2 NS -0.413*** Dissolved total C (mg g -1 ) 31.4 + 5.9 20.6 - 50.1 NS -0.419*** Dissolved N (mg g -1 ) 9.52 + 3.60 2.66 - 18.2 NS -0.466*** OD254 nm 0.758 + 0.139 0.538 - 1.18 0.408*** NS E2/E6 66.4 + 20.6 21.2 - 127 NS -0.324** E4/E6 5.00 + 0.98 2.45 - 8.32 NS -0.266* 0 2 4 6 8 10 N 2 0 (mg m -2 h -1 ) 1 2 3 4 5 7 8 9 10 Chamber: a) 0 10 20 30 CH 4 (mg m -2 h -1 ) b) 04/29/13 09/22/13 10/13/13 10/21/13 Feedyard A Feedyard C a) b) 0 4 8 12 0 25 50 75 100 N 2 O (mg m -2 h -1 ) NO 3 - -N (mg kg -1 ) a) 0 4 8 12 0 10 20 30 40 50 Water (%) b) 11/09/12 11/27/12 11/09/12 11/27/12 12/10/12 12/10/12 03/25/13 04/29/13 03/25/13 09/22/13 10/13/13 10/21/13 RESULTS A number of empirical models were developed to predict feedyard manure- derived N 2 O emissions that were based on manure properties. Models were evaluated against two subsets of the original dataset (Subset 1 and Subset 2) and are as follows (Fig. 5): Model 1: Predicted N 2 O flux (N2O, mg m -2 h -1 ) as a function of manure NO 3 - - N concentration (NO3, mg kg -1 ) N2O = 0.599 + NO3(0.077) Subset 1 Subset 2 Model 2: Predicted N 2 O flux as a function of NO3, water content (W, proportion), temperature (T, o C), and water-extractable C content (DC, mg g -1 ) N2O = 2.77 + NO3(0.066) + W(0.5988) + T(0.032) + DC(-0.092) Subset 1 Subset 2 Model 3: Predicted N 2 O flux as a function of NO3, W, T, DC, and UV-vis spectral characteristics (OD254, E2/E6, E4/E6) N2O = 9.08 + NO3(0.060) + W(5.46) + T(0.029) + DC(-0.377) + E2/E6(-3.55) + E4/E6(0.171) + OD254(10.26) Subset 1 Subset 2 Measure of difference Model 1: f(NO3) Model 2: f(NO3, W, T, DC) Model 3: f(NO3, W, T, DC, OD254, E2/E4, E4/E6) MBE (mg m -1 h -1 ) -0.001 0.014 0.0002 RMSE (mg m -1 h -1 ) 1.78 1.63 1.39 MAE (mg m -1 h -1 ) 1.19 1.10 0.97 Index of Agreement (%) 69.8 76.3 85.6 0 2 4 6 8 10 0 5 10 15 20 Event Regression results: R 2 =0.70 y=0.85x + 0.51 0 2 4 6 8 10 0 5 10 15 20 N 2 O (mg m -1 h -1 ) Event N2O=f(NO3) Observed Regression results: R 2 =0.77 y=0.80x + 0.62 0 2 4 6 8 10 0 5 10 15 20 N 2 O (mg m -2 h -1 ) Event N2O=f(NO3, W, T, DC) Observed Regression results: R 2 =0.79 y=0.83x + 0.65 0 2 4 6 8 10 0 5 10 15 20 Event Regression results: R 2 =0.70 y-intercept=0.97x + 0.59 0 2 4 6 8 10 0 5 10 15 20 Event Regression results: R 2 =0.74 y=1.11x + 0.011 0 2 4 6 8 10 0 5 10 15 20 N 2 O (mg m -2 h -1 ) Event N2O=f(NO3, W, T, DC, OD254, E2/E6, E4/E6) Observed Regression results: R 2 =0.80 y=0.91x + 0.013 Table 2. Statistical evaluation of model performance with measures of difference (MBE, Mean bias error; RMSE, Root mean square error; MAE, mean absolute error). Model evaluation indicated 70% to 86% agreement of predictions with measurements with very low bias estimates. Measures of error decreased and model agreement increased when UV-vis spectral characteristics were used to model N 2 O emission.

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Page 1: Predicting Greenhouse Gas Emissions from Beef …...Predicting Greenhouse Gas Emissions from Beef Cattle Feedyard Manure Heidi M. Waldrip,1 Kenneth D. Casey,2 Richard W. Todd,1 and

Predicting Greenhouse Gas Emissions

from Beef Cattle Feedyard Manure Heidi M. Waldrip,1 Kenneth D. Casey,2 Richard W. Todd,1 and N. Andy Cole1

1USDA-Agricultural Research Service (USDA-ARS),Conservation and Production Research Laboratory, Bushland, Texas 2Texas A&M AgriLife Research, Amarillo, Texas

Table 1. Summary statistics. Correlation coefficients (R; n = 79) were used to

identify primary variables related to GHG emissions. Asterisks indicate significance

at: P < 0.05 (*), 0.01 (**), 0.0001 (***). NS, not significant. Most of the variables

investigated were related to measured N2O fluxes (P < 0.01), and nitrate

concentration had the highest R value. In contrast, few significant relationships

were identified for CH4 flux: only OD254 nm, which indicates organic matter

complexity, was significant (P < 0.001).

INTRODUCTION The Texas Panhandle is the largest beef feeding area in the US, producing

approximately 20% to 30% of finished beef. Beef cattle feedyards are

sources of greenhouse gases (GHG), most notably enteric methane (CH4)

and manure-derived nitrous oxide (N2O) and CH4. However, little

information exists on the magnitude of feedyard GHG emissions or the

factors that influence their production. Valid prediction methods are needed

to inventory feedyard GHG and assess the impact of beef production on the

environment. Most biochemical process-based models to predict GHG rely

on information derived from studies on soil, which may, or may not, be valid

for manure in open lot systems. The limited study on manure-derived

feedyard GHG indicates that fluxes of both N2O and CH4 are highly variable

in space and time. Improved understanding of factors related to manure-

derived GHG could help refine process-based models and produce useful

empirical models for predicting the environmental footprint of feedyard beef.

In turn, this could lead to more accurate inventory calculation techniques for

regulatory agencies.

OBJECTIVES: Determine factors related to production and volatilization of N2O

and CH4 from manure in beef cattle feedyard pens

Develop empirical models to predict GHG emissions based on

manure physicochemical properties

MATERIALS AND METHODS GHG flux data and manure samples were collected during 8 four-day non-

flow-through, non-steady-state (NFT-NSS) chamber studies conducted in

2012 and 2013 on two Texas Panhandle feedyards (Feedyard A and Feedyard

C; Fig. 1). Each pen contained 10 NFT-NSS chamber bases inserted into

pack manure (Fig. 2a and b). Chambers were located in specific areas (e.g.,

near feedbunk and water trough areas, back of pen, middle of pen, etc.) and

contained sensors to record manure temperature. After fitting the base with a

chamber cap, headspace was sampled with a disposable syringe at 0, 10, and

30 min. Concentrations of N2O and CH4 were quantified with gas

chromatography (Fig. 3). See the presentation of Casey et al. (Mon. 1:00,

Paper: 96-1) for specific details

Figure 1. Aerial views of Feedyard-A (left; 22,000 head capacity)

and Feedyard-C (right; 55,000 head capacity).

Figure 2. a) NFT-NSS chamber with top installed, and b) two

rows of five NFT-NSS chambers installed in a pen at Feedyard-C.

Physicochemical properties of the dense pack fraction of pen manure are

presented in Table 1. There were a total of 79 GHG measurements and

manure samples. Water-extractable manure organic matter [WEOM; 1:100

(wt:vol)] was analyzed for dissolved organic carbon (DOC), total dissolved

carbon (DC), and total dissolved nitrogen (DN).

Ultraviolet-visible (UV-vis) spectral characteristics of WEOM were evaluated

between the wavelengths of 200 and 700 nm. Absorbance at 254 nm

(OD254), and ratios of E2/E6 (proportion of humified to non-humified material)

and E4/E6 (degree of humification, molecular weight, aromaticity) were

calculated based on absorbances at 254, 280, 472, and 664 nm.

Mixed modeling (Proc MIXED) was used to develop empirical equations to

predict manure-derived N2O emissions. Study was set as a random variable.

Models were evaluated by regression and measures of difference (Willmott et

al., 1982) and compared to two randomly chosen subsets (n = 20) of the

original dataset. Reference: Willmott, C.J. 1982. Bull. Am. Met. Soc. 63:1309-1313.

Figure 3. Emissions of (a) nitrous oxide (N2O) and (b) methane (CH4) from manure

in two commercial Texas feedyards. Gas fluxes were determined using NFT-NSS

chambers (10 chambers per sampling date, designated Chambers 1-10) and gas

chromatography. Emissions of both GHG were highly variable due to environmental

conditions and locations of chambers within pens. Average fluxes were 1.1 + 2.2 and

1.9 + 4.3 mg m-2 h-1 for N2O and CH4, respectively.

CONCLUSIONS Emissions of both GHG were highly variable due to environmental

conditions and locations of chambers within pens. Average fluxes were

1.1 + 2.2 and 1.9 + 4.3 mg m-2 h-1 for N2O and CH4, respectively (Fig. 3a

and b).

Most of the variables investigated were related to measured N2O fluxes

(P < 0.01), and nitrate concentration had the highest R value. In

contrast, few significant relationships were identified for CH4 flux: only

OD254 nm, which indicates organic matter complexity, was significant (P

< 0.001) (Table 1).

N2O flux tended to increase with manure NO3- (Fig. 4a) and was highest

at ~ 10% and 30% water content (Fig. 4b).

Predicted N2O flux from empirical models developed in this study had

70% to 80% agreement with measurements, and the models adequately

simulated both high and low values (Table 2).

Inclusion of UV-vis spectral characteristics (Model 3) improved model

predictions somewhat: regression analyses for the two data subsets and

Model 3 predictions produced R2 values of 0.74 to 0.80 with intercepts

near O and slope near 1 (Fig. 5).

Further work is required to evaluate these models against an

independent dataset and develop equations for predicting manure-

derived CH4 emission.

ACKNOWLEDGEMENTS The authors thank Heather Robbe, Beverly Meyer, and Will Willis for technical

assistance with manure analyses for this study.

Figure 4. Relationships between manure a) NO3--N and b) water content (% w/w) and

N2O fluxes. N2O flux tended to increase with manure NO3- and were highest at ~ 10%

and 30% water content.

Variable

Mean +

Standard

Deviation

Range R

CH4

R

N2O

Nitrous oxide (mg m-2 h-1) 1.12 + 2.17 0 - 8.46 NS --

Methane (mg m-2 h-1) 1.91 + 4.27 0 - 25.5 -- NS

Moisture (%) 28.6 + 8.9 9.1 - 48.7 0.219 0.319**

Surface temperature (oC) 20.1 + 11.6 1.8 - 39.8 0.164 0.314**

Organic matter (% DM) 69.9 + 7.4 44.4 - 83.3 0.241 -0.327**

Ammonia/ammonium-N (g kg-1) 3.05 + 2.31 0.35 - 10.9 NS -0.396***

Nitrate/nitrite-N (mg kg-1) 6.87 + 16.3 0 - 106 NS 0.580***

Dissolved organic C (mg g-1) 28.4 + 5.2 18.3 - 45.2 NS -0.413***

Dissolved total C (mg g-1) 31.4 + 5.9 20.6 - 50.1 NS -0.419***

Dissolved N (mg g-1) 9.52 + 3.60 2.66 - 18.2 NS -0.466***

OD254 nm 0.758 + 0.139 0.538 - 1.18 0.408*** NS

E2/E6 66.4 + 20.6 21.2 - 127 NS -0.324**

E4/E6 5.00 + 0.98 2.45 - 8.32 NS -0.266*

0

2

4

6

8

10

N20 (

mg m

-2 h

-1) 1 2 3

4 5 7

8 9 10

Chamber: a)

0

10

20

30

CH

4 (

mg

m-2

h-1

)

b)

04/2

9/1

3

09/2

2/1

3

10/1

3/1

3

10/2

1/1

3

Feedyard A Feedyard C

a) b) 0

4

8

12

0 25 50 75 100

N2O

(m

g m

-2 h

-1)

NO3--N (mg kg-1)

a)

0

4

8

12

0 10 20 30 40 50Water (%)

b)

11

/09

/12

11

/27

/12

11

/09

/12

11

/27

/12

12/1

0/1

2

12/1

0/1

2

03/2

5/1

3

04/2

9/1

3

03/2

5/1

3

09/2

2/1

3

10/1

3/1

3

10/2

1/1

3

RESULTS A number of empirical models were developed to predict feedyard manure-

derived N2O emissions that were based on manure properties. Models were

evaluated against two subsets of the original dataset (Subset 1 and Subset 2)

and are as follows (Fig. 5):

Model 1: Predicted N2O flux (N2O, mg m-2 h-1) as a function of manure NO3--

N concentration (NO3, mg kg-1)

N2O = 0.599 + NO3(0.077)

Subset 1 Subset 2

Model 2: Predicted N2O flux as a function of NO3, water content (W,

proportion), temperature (T, oC), and water-extractable C content (DC,

mg g-1) N2O = 2.77 + NO3(0.066) + W(0.5988) + T(0.032) + DC(-0.092)

Subset 1 Subset 2

Model 3: Predicted N2O flux as a function of NO3, W, T, DC, and UV-vis

spectral characteristics (OD254, E2/E6, E4/E6)

N2O = 9.08 + NO3(0.060) + W(5.46) + T(0.029) + DC(-0.377)

+ E2/E6(-3.55) + E4/E6(0.171) + OD254(10.26)

Subset 1 Subset 2

Measure of

difference

Model 1:

f(NO3)

Model 2:

f(NO3, W, T, DC)

Model 3:

f(NO3, W, T, DC,

OD254, E2/E4,

E4/E6)

MBE (mg m-1 h-1) -0.001 0.014 0.0002

RMSE (mg m-1 h-1) 1.78 1.63 1.39

MAE (mg m-1 h-1) 1.19 1.10 0.97

Index of Agreement (%) 69.8 76.3 85.6

0

2

4

6

8

10

0 5 10 15 20Event

Regression results:

R2=0.70

y=0.85x + 0.51

0

2

4

6

8

10

0 5 10 15 20

N2O

(m

g m

-1 h

-1)

Event

N2O=f(NO3)

Observed

Regression results:

R2=0.77

y=0.80x + 0.62

0

2

4

6

8

10

0 5 10 15 20

N2O

(m

g m

-2 h

-1)

Event

N2O=f(NO3, W, T, DC)

Observed

Regression results:

R2=0.79

y=0.83x + 0.65

0

2

4

6

8

10

0 5 10 15 20Event

Regression results:

R2=0.70

y-intercept=0.97x + 0.59

0

2

4

6

8

10

0 5 10 15 20

Event

Regression results:

R2=0.74

y=1.11x + 0.011

0

2

4

6

8

10

0 5 10 15 20

N2O

(m

g m

-2 h

-1)

Event

N2O=f(NO3, W, T, DC,OD254, E2/E6, E4/E6)

ObservedRegression results:

R2=0.80

y=0.91x + 0.013

Table 2. Statistical evaluation of model performance with measures of difference (MBE,

Mean bias error; RMSE, Root mean square error; MAE, mean absolute error). Model

evaluation indicated 70% to 86% agreement of predictions with measurements with

very low bias estimates. Measures of error decreased and model agreement increased

when UV-vis spectral characteristics were used to model N2O emission.