CAN SURFACE-APPLIED ZEOLITE REDUCE AMMONIA LOSSES

FROM FEEDYARD MANURE? A LABORATORY STUDY

H. M. Waldrip, R. W. Todd, N. A. Cole

ABSTRACT. Ammonia (NH3) emission from beef cattle feedyard manure results in losses of nitrogen (N), which may nega-
tively affect air, soil, and water quality. The magnitude and rate of NH3 volatilization from feedyards partially depends on
the amount of urinary urea excreted and dissociation of ammonium (NH4+) into NH3 following urea hydrolysis. Zeolite
clinoptilolite is a naturally occurring, porous aluminosilicate mineral that can sorb and sequester cations within its nega-
tively charged framework structure. Zeolite has been used to mitigate NH3 losses and improve fertilizer value of compost,
sewage sludge, and manure in livestock barns; however, few studies have evaluated its efficacy on open-lot beef cattle
feedyards. Zeolite application to pen surfaces could be a practical and cost-effective means of reducing NH3 losses. Ob-
jectives of this study were to (1) characterize NH4+ sorption by zeolites with differing physicochemical properties and
(2) evaluate zeolite effects on rates and cumulative losses of NH3 following application of artificial urine to feedyard ma-
nure. Batch incubation studies with four commercially available zeolites revealed that NH4+ sorption by zeolite was rapid
(1 to 2 h) with large differences in sorption potential largely related to zeolite pH. Maximum sorption ranged from 28 to
97 cmol NH4+-N kg-1 zeolite. Effects of zeolite application rate [0.5% to 10.0% of manure dry matter (DM)] on sorption
and desorption characteristics in a manure/artificial urine matrix were highly variable but tended to be proportional to
zeolite application rate: as little as 0.5% zeolite increased NH4+-N recovery by up to 19%. In flow-through chamber stud-
ies, higher rates of zeolite did not reduce cumulative NH3 emissions, as 1.0% zeolite reduced cumulative NH3 emission by
42% and 5.0% zeolite reduced N losses by only 18% compared to unamended manure. Surface application of zeolite has
potential for mitigating feedyard NH3 losses, but specific zeolite properties influenced its effectiveness. Further studies are
warranted to evaluate effects of repeated zeolite application, co-application of zeolite and urease inhibitors, and
cost:benefit ratios of zeolite application at commercial feedyards.
Keywords. Ammonia, Ammonium, Beef cattle, Feedyard, Manure, Sorption, Zeolite.

E
mission of ammonia (NH3) from concentrated
animal feeding operations, such as open-lot beef
cattle feedyards, results in losses of agronomical-
ly important nitrogen (N), which may negatively
affect both human health and the environment (Paerl, 1997;
Lippmann, 1998; Hristov, 2011). Researchers estimate that
approximately 43% to 48% of total anthropogenic NH3
emissions originate from cattle manure (both beef and
dairy) (Battye et al., 1994; NRC, 2003; USEPA, 2005).
Beef production operations were estimated to be responsi-
ble for about 55% of cattle manure-derived NH3 emitted in
the U.S. in 2002 (USEPA, 2005). Practical, low-cost meth-
ods to decrease NH3 emissions, such as surface application
of naturally occurring compounds such as zeolite clinop-
Submitted for review in September 2014 as manuscript number PAFS
10965; approved for publication by the Plant, Animal, and Facility
Systems Community of ASABE in December 2014.
Mention of trade names or commercial products in this manuscript is
solely for the purpose of providing specific information and does not
imply recommendation or endorsement by the USDA. The USDA is an
equal opportunity provider and employer.
The authors are Heidi M. Waldrip, Research Soil Scientist, Richard
W. Todd, Soil Scientist, and N. Andy Cole, Supervisory Research
Animal Scientist, USDA-ARS Conservation and Production Research
Laboratory, Bushland, Texas. Corresponding author: Heidi M. Waldrip,
USDA-ARS CPRL, P.O. Drawer 10, Bushland, TX 79012; phone: 806-
356-5764; e-mail: heidi.waldrip@ars.usda.gov.
tilolite, could potentially mitigate feedyard N losses.
The majority of feedyard NH3 is derived from urinary
urea [NH2(CO)NH2)], which is the principal nitrogenous
compound in bovine urine and can comprise from 24% to
71% of total N excretion (feces and urine) by finishing cat-
tle (Waldrip et al., 2013). Urea hydrolysis is a two-step
process (Kaminskaia and Kostic, 1997). In the first step,
one molecule of urea is hydrolyzed to one molecule each of
ionic ammonium (NH4+) and carbamic acid [NH2(CO)OH]
(eq. 1). Carbamic acid is unstable and is converted into
another molecule of NH4+ and CO2 in the second step of the
process (eq. 2). Therefore, the hydrolysis of urea results in
the production of two NH4+ molecules according to:
NH2(CO)NH2 + H2O → NH4+ + NH2(CO)OH (1)
+
NH2(CO)OH → NH4 + CO2 (2)
Following urea hydrolysis, the resultant NH4+ is in equi-
librium with dissolved NH3 in manure according to the
reaction:
NH4+ + OH- ↔ NH3 + H2O (3)
which can proceed in either direction. The proportion of
each ammoniacal species (NH3 vs. NH4+) present in manure
is determined by the dissociation constant, which depends
on manure pH, temperature, and ionic strength (Arogo et

Transactions of the ASABE

Vol. 58(1): 137-145 2015 American Society of Agricultural and Biological Engineers ISSN 2151-0032 DOI 10.13031/trans.58.10965 137
al., 2003). At a constant temperature, higher pH favors lites with differing chemical compositions in a manure-
formation of NH3 and increases the potential for volatiliza- artificial urine matrix, and (2) evaluated the effects of zeo-
tion (Sawyer and McCarty, 1978). lite addition on cumulative losses of NH3 following appli-
In a study by Cole et al. (2009), concentrations of total cation of artificial urine to feedyard manure in enclosed
ammoniacal nitrogen (TAN), which includes both NH3 and chambers.
NH4+, under urine spots on feedyard surfaces averaged
6,755 mg N kg-1, or 52.0 cmol N kg-1. Although the rate
and magnitude of NH3 volatilization from feedyards vary MATERIALS AND METHODS
with seasonal temperatures and animal diet, anywhere from ZEOLITES
27% to 72% of dietary N can be lost from manure as NH3 Four regionally available zeolite clinoptilolites were ob-
(Swensson, 2003; Todd et al., 2006, 2008, 2011). Reported tained from commercial vendors and designated zeolite A
per capita NH3 emission rates for feedyard-finished beef and B (Zeomax 1430T and Zeomax 4080T, respectively;
cattle in the Southern High Plains ranged from 68 to 149 g Zeotech Corp., Fort Worth, Tex.), zeolite C (American Ab-
NH3-N head-1 d-1 (Todd et al., 2008, 2011), which translates sorbents Natural Products, Inc., Lago Vista, Tex.), and zeo-
into daily N losses of 1,360 to 2,980 kg NH3-N d-1 for a lite D (St. Cloud Mining Co., Winston, N.M.). Chemical
typical 20,000-head feedyard. This loss reduces manure analyses of the zeolites was performed by Servi-Tech La-
fertilizer value and limits the sustainability of feedyard beef boratories in Amarillo, Texas. Zeolite pH was determined
production. Thus, it is important from environmental, so- with a 1:1 ratio of zeolite to water using a pH meter with a
cial, and economic standpoints to identify cost-effective combination glass electrode (Accumet 30, Fisher Scientific,
and practical management practices that reduce NH3 emis- Hampton, N.H.), and electrical conductivity (EC) was de-
sions from large-scale beef feeding operations. termined with a TetraCon 325 standard conductivity cell
Zeolite clinoptilolite [(Na4K4)(Al8Si40)O96⋅24H2O] is a and EC meter (WTW, Wissenschaftlich-Technische
naturally occurring, abundant, porous aluminosilicate min- GmbH, Wilheim, Germany). Total Kjeldahl N (TKN),
eral found in igneous, sedimentary, and metamorphic de- TAN, and nitrate (NO3-) were determined colorimetrically
posits throughout the world. Zeolite has a high cation ex- on an 8000 Series Lachat QuikChem FIA+ (Lachat Instru-
change capacity (CEC) and affinity for ionic NH4+ due to ments, Loveland, Colo.) with Standard Method 4500-NH3
its framework structure consisting of layers of interlinked (TAN) and EPA Method 353.2 (NO3--N). Acid-peroxide
four- and five-tetrahedral rings, creating ion sieving chan- digestion followed by inductively coupled plasma atomic
nels with a selectivity sequence of K+ > NH4+ > Na+ > Ca2+ emission spectroscopy (ICP-AES) was used to quantitate
> Mg2+ (Ames, 1967). Zeolite has been investigated as a total Ca2+, Mg2+, K+, and Na+. Mehlich-3 P (Mehlich, 1984)
means of reducing NH3 losses during composting (Bernal was determined with the Lachat FIA+ previously de-
et al., 1993; Kithome et al., 1999), from dairy slurry scribed. Selected properties of the zeolite samples are pre-
(Lefcourt and Meisinger, 2001), from duck and layer hen sented in table 1.
manure (Li et al., 2008; Wang et al., 2012), and in poultry
houses (Koelikker et al., 1978). However, very little work
has been conducted to evaluate the efficacy of surface-
applied zeolite for mitigating NH3 losses from open-lot
beef cattle feedyards. In one 14-day laboratory study, Cole Table 1. Chemical composition of the four regionally available zeolites
et al. (2007) reported that zeolite application at 0.6%, 1.1%, used in this study.[a]
and 2.2% dry matter (DM) basis to simulated feedyard sur- Zeolite
faces in flow-through chambers reduced cumulative NH3-N Parameter A B C D
pH[b] 8.5 9.0 8.2 8.0
losses by 53%, 49%, and 67%, respectively. Similarly, CEC (cmolc kg-1) 61 62 51 60
Lefcourt and Meisinger (2001) reported that application of EC (mmho cm-1) 0.12 0.73 1.09 <0.05
2.5% and 6.25% zeolite to dairy slurry decreased cumula- Exchangeable cations (mg kg-1)
tive NH3 losses by 22% and 47%, respectively. When ap- Ca2+ 1639 398 3376 4166
Mg2+ 181 55 99 110
plied to soil, the NH4+ retained by zeolite should be slowly K +
1891 4627 4559 5309
released following cation exchange and nitrification pro- Zn+ 0.2 0.8 0.5 0.5
cesses (Kithome et al., 1998). Therefore, manure amended Na+ 618 11,080 4976 5570
with zeolite could serve as a source of slow-release fertiliz- Total N (mg kg-1) 62 58 51 79
Nitrate-N (mg kg-1) 12 1 1 1
er for crop production, decreasing reliance on chemical Total ammoniacal N (mg kg-1) 6 6 1 ND
fertilizers and improving the sustainability of agricultural [c]
Phosphorus (mg kg ) -1
7 4 3 4
systems (Gholamhoseini et al., 2013). Organic matter (%) 1.4 1.0 0.7 0.7
Zeolite application has potential as a method to se- Clinoptilolite content (%) 65 65 NA 95
Total surface area (mg g-1) 40 to 65 40 to 65 NA <800
quester NH4+ following cattle urination and subsequent Pore diameter (angstroms) 4 to 7 4 to 7 NA 4 to 7
urea hydrolysis, resulting in a value-added manure product [a]
CEC = cation exchange capacity, EC = electrical conductivity, Ca2+ =
and reduced feedyard NH3 emission. The objectives of this calcium, Mg2+ = magnesium, K+ = potassium, Zn+ = zinc, Na+ = sodi-
study were to evaluate the efficacy of surface-applied zeo- um, N = nitrogen, ND = not detected, and NA = not available. Zeolite
lite clinoptilolite to mitigate NH3 emissions from beef cattle properties provided by commercial distributors and Servi-Tech Indus-
tries in Amarillo, Texas.
manure. Specifically, we (1) conducted batch equilibration [b]
1:1 ratio of zeolite to water.
experiments to quantify the NH4+ sorption potential of zeo- [c]
Mehlich-3 phosphorus.

138 TRANSACTIONS OF THE ASABE

CHARACTERISTICS OF AMMONIUM SORPTION Table 2. Selected chemical and physical characteristics of beef
feedyard manures used in this study. Data are presented as averages
AND DESORPTION BY ZEOLITES
±standard deviations (n = 3).
Sorption experiments were based on the work of Fer- Parameter Feedyard A Feedyard E
nando et al. (2005) and Waldrip et al. (2012). Briefly, 2.0 g pH[a] 7.5 ±0.0 7.7 ±0.1
zeolite was placed into 50 mL polypropylene centrifuge Electrical conductivity (dS m-1) 6.6 ±0.4 7.0 ±0.2
tubes with 20 mL of a (NH4)2SO4/0.01 M CaCl2 solution Moisture (%) 17.1 ±3.2 14.1 ±1.7
that contained 3.6 cmol N L-1 as NH4+. The CaCl2 supplied Organic matter (g kg-1)[b] 630 ±27 645 ±37
competing exchangeable cations intended to mimic the Major nutrients (g kg-1)[c]
Total Kjeldahl N 24.4 ±2.5 24.5 ±0.9
ionic strength effects of urine on NH4+ sorption. Chloro- Total ammoniacal N 2.9 ±0.7 3.1 ±0.3
form (100 μL) was added to each tube to inhibit microbial NO3--N 0.01 ±0.00 0.01 ±0.00
growth. To determine time required to reach maximum Total P 11.0 ±0.4 8.7 ±0.2
sorption, samples were shaken for 0.1, 0.2, 0.4, 1.0, 2.0, Total S 6.2 ±0.7 6.1 ±0.2
4.0, and 6.0 h at 180 rpm in an Innova 42 controlled- C:N ratio 15.1 ±0.9 15.3 ±0.8
Exchangable cations (g kg-1)
temperature shaker-incubator (New Brunswick Scientific, K+ 20.0 ±2.0 17.4 ±1.0
Edison, N.J.) at 22°C. Following incubation, supernatants Ca2+ 33.4 ±0.7 38.0 ±1.9
were collected by centrifuging the tubes at 4300 × g for Mg 2+
7.7 ±0.3 6.4 ±0.2
20 min and decanting the supernatant with a pipette. The Na+ 5.4 ±0.6 5.4 ±0.1
zeolites were then stored at 4°C until use in desorption Sum of exchangeable cations 66.5 ±3.2 67.2 ±3.1
[a]
Manure:water = 1:10.
studies (less than one week). [b]
Concentrations presented on a dry matter basis.
After incubation, solution pH and EC were determined [c]
N = nitrogen, NO3- = nitrate, P = phosphorus, S = sulfur, C = carbon,
as previously described. Concentrations of TAN and NO3- K+ = potassium, Ca2+ = calcium, Mg2+ = magnesium, Na+ = sodium.
were quantified colorimetrically with a Lachat flow injec-
tion analyzer (Hach Co., Loveland, Colo.). The amount of within the sampled pens (five pens per feedyard) had been
NH4+-N sorbed by the zeolites was calculated as the differ- in the pens for over 100 days and were near finishing
ence between the initial and final solution concentrations, weight (500 to 600 kg). The animals were fed a steam-
and included correction for background TAN in the zeo- flaked corn-based diet that contained 13.0% to 14.5% crude
lites. protein (DM basis). Pen manure was collected by gently
The potential for desorption and recovery of sorbed scraping loose, unconsolidated material from five locations
NH4+ was determined by subjecting NH4+-loaded zeolites in the pens, which was combined to provide one composite
from the sorption study to a series of five 30 min extrac- sample per feedyard (two feedyards, five pens per feedyard,
tions with 20 mL of 2.0 M KCl. Extraction conditions, su- five samples per pen). Manure samples were assumed rep-
pernatant collection, and TAN analysis were as previously resentative of the majority of the pen surface; however, wet
described for the sorption potential portion of the study. areas (e.g., urine spots and near water troughs) and recently
The total amount of TAN that was desorbable from the voided feces were avoided during sampling for this study.
zeolites was calculated as the sum of TAN in the five se- The feedyard manures were sieved (4 mm) to remove
quential extracts. large aggregates but received no further processing. Ma-
To examine the effects of increasing NH4+ concentration nure moisture content was determined gravimetrically after
on sorption by zeolite, solutions of (NH4)2SO4/0.01 M drying to a constant weight at 105°C for 24 h. Selected
CaCl2 containing 0, 0.7, 1.8, 3.6, 7.2, 14.5, or 28.0 cmol manure properties are presented in table 2. Manure pH and
NH4+-N L-1 were equilibrated with the four zeolites for 4 h EC were determined using a 1:10 ratio of manure to water.
at a 1:10 ratio of zeolite to solution (2.0 g zeolite and Other chemical and physical analyses of manure were per-
20 mL solution), based on the procedure of Fernando et al. formed by Servi-Tech Laboratories in Amarillo, Texas, as
(2005) and Waldrip et al. (2012). Chloroform (100 μL) was previously described.
added to inhibit microbial growth. The equilibration condi- For sorption and desorption studies, zeolites were added
tions, supernatant collection, TAN analysis, and EC and pH to manure (3.0 g DM) at rates of 0%, 0.5%, 1.0%, 2.5%,
determination were as previously described. 5.0%, and 10.0% of manure DM in 50 mL centrifuge tubes
with 30 mL of 14 cmol NH4+-N L-1 as (NH4)SO4/0.01 M
AMMONIUM SORPTION BY ZEOLITE IN A CaCl2. Sorption and desorption studies were then per-
MANURE/ARTIFICIAL URINE MATRIX formed as previously described.
Manure samples were collected in October 2012 from
two open-lot commercial beef cattle feedyards, designated EFFECT OF ZEOLITE ON AMMONIA EMISSIONS
feedyard A and feedyard E, located in the Southern High FROM FEEDYARD MANURE
Plains in Deaf Smith County, Texas (34° 53′ N, 102° To evaluate the effects of zeolite application on NH3
30′ W). The average temperature in the area ranges from emissions from simulated feedyard pen surfaces, we con-
5.6°C to 27.3°C, and annual precipitation is about 500 mm ducted a four-day flow-through chamber study according to
(NCDC, 2000). The feedyards were typical of beef opera- the basic procedure of Shi et al. (2001) and Parker et al.
tions in the region and contained approximately 13,000 (2005). In brief, unconsolidated beef cattle manure (200 g
(feedyard A) and 20,000 (feedyard E) finishing cattle at a DM) was placed into plastic containers (12.7 cm × 12.7 cm
stocking density of approximately 15 m2 head-1. The cattle × 15.2 cm deep), and zeolite C was surface applied at rates

58(1): 137-145 139

of 0%, 0.5%, 1.0%, and 5.0% of manure DM. Zeolite C
was selected for testing because it exhibited the greatest
sorption potential of the four zeolites evaluated. There were
three replicate containers per treatment, and a blank (no
manure or zeolite) was included to correct for background
atmospheric NH3 concentration. Artificial urine was pre-
pared according to Kool et al. (2006) and contained 8.2 g N
L-1 urea, 0.81 g N L-1 hippuric acid, 14.0 g L-1 KHCO3,
10.5 g L-1 KCl, 0.4 g L-1 CaCl2⋅2H2O, 1.2 g L-1
MgCl⋅5H2O, and 3.7 g L-1 Na2SO4 and was adjusted to pH
8.0 with NaOH. In order to simulate NH3 emissions from a
recently deposited urine spot, 80 mL of artificial urine was Figure 1. Sorption of ammonium (NH4+) by zeolites equilibrated with
3.6 cmol L-1 NH4+-N for up to 6 h at 22°C. Error bars represent aver-
applied to bring the gravimetric moisture content to 40%, ages ±standard deviations.
which was the typical moisture content of urine spots in
commercial feedyard pens in the Southern High Plains equilibrated with swine effluent containing 5.6 cmol L-1
(Cole et al., 2009). The artificial urine was thoroughly NH4+-N (Penn et al., 2010), wastewater (Nguyen and Tanner,
mixed with the manure and zeolite in each container. Each 1998), and during composting (Bernal et al., 1993). After 6 h
container was connected by propylene tubing to an NH3 of equilibration, 66% (zeolite D) to 100% (zeolite C) of the
collection trap containing 100 mL 0.5 M H2SO4, which was added NH4+ was retained by zeolite. During equilibration,
then connected to a large manifold. The manifold was at- solution pH was slightly lower with zeolite D (average pH
tached to a Gilmont Accucal flowmeter (Gilmont Instru- 8.4) than with zeolites A, B, and C (average pH 8.8; p <
ments, Barrington, Ill.) connected to a vacuum pump (mod- 0.001) and did not change significantly with equilibration
el D-75, Precision Scientific, Winchester, Va.). The total time (p > 0.05) (fig. 2a). In general, a higher pH would in-
airflow rate was 41.6 L min-1 (~3.2 L min-1 per container), crease the degree of negative surface charge, thus increasing
and flow rates from individual containers were measured CEC and potential for NH4+ sorption (van Raij and Peech,
daily with a Bios DryCal DC-Lite primary flowmeter (Bios 1972). However, at a higher pH there should also be a great-
International Corp., Butler, N.J.). Acid in the traps was er proportion of TAN present as NH3 relative to NH4+ (Saw-
changed every 24 h for a total of 4 d, and samples were yer and McCarty, 1978), which could limit the degree of
stored at -20°C prior to analysis for TAN content, which NH4+ retention. There was a tendency for solution EC to
was quantified using an indophenol method (Keeney and decrease over time with all zeolites except for zeolite C,
Nelson, 1982) in a 96-well microplate format on a Synergy which increased slightly over time (fig. 2b); however, no
2 microplate reader (BioTek Instruments, Inc., Winooski,
Vt.). Final manure TAN content was determined colorimet-
rically following extraction with 2.0 M KCl for 1 h at 22°C.

STATISTICAL ANALYSIS
All experiments were arranged in a randomized design
with three sample replicates per treatment. Single-factor
analysis of variance (ANOVA) with a pairwise t-test was
used to determine the significance of differences in NH4+
sorption and desorption characteristics, NH3 emissions, and
solution chemistries among the zeolites and zeolite-
amended manure. Relationships between variables were
evaluated with correlation analysis and Pearson-moment
correlation coefficients. All statistical analyses were con- (a)
ducted with Systat version 13.0 (Systat Software, Inc., Chi-
cago, Ill.).

RESULTS AND DISCUSSION

AMMONIUM SORPTION AND DESORPTION
CHARACTERISTICS OF ZEOLITES
Sorption of NH4+ by zeolites exposed to 3.6 cmol L-1
NH4+-N was rapid and did not change significantly (p >
0.05) after about 1 h of equilibration (fig. 1). There were
large differences in the quantity of NH4+ sorbed among the (b)
four zeolites, ranging from 24 (zeolite D) to 44 (zeolite C) Figure 2. Changes in (a) solution pH and (b) electrical conductivity
cmol NH4+-N kg after 6 h of equilibration. Zeolite sorption (EC) over time when zeolites were equilibrated with 3.6 cmol L-1
values were within the range previously reported for zeolites NH4+-N for up to 6 h at 22°C. Error bars represent averages
±standard deviations.

140 TRANSACTIONS OF THE ASABE

significant relationship was observed between solution EC
and NH4+ sorption (r = 0.116; p > 0.05).
Correlation analysis revealed that sorption was positive-
ly related to solution pH (r = 0.708; p < 0.001) and zeolite
CEC (r = 0.718; p < 0.001). Penn et al. (2010) also found
that zeolite CEC was positively related to NH4+ sorption in
swine manure; however, the zeolites investigated by these
researchers had CEC values that ranged from 65 to
127 cmolc kg-1; whereas the zeolites in the current study
had lower CEC values within a much narrower range (50 to
62 cmolc kg-1; table 1). Other researchers have reported that
NH4+ sorption by zeolite was rapid, with equilibrium
reached within 1 to 2 h with reaction rate coefficients rates
that ranged from 0.13 to 0.19 min-1 (Bernal and Lopez-
Real, 1993; Kithome et al., 1998; Penn et al., 2010). Penn
et al. (2010) conducted batch equilibration studies with
different zeolites and found that peak NH4+ and K+ ex-
change occurred within 100 s of addition of swine effluent,
which was followed by a slower sorption up to about
50 min. These researchers proposed that the slowed re-
sponse later in the equilibration was likely the result of
diffusion of NH4+ into zeolite micropores and accumulation
of reaction products. Kithome et al. (1998) saw that NH4+
sorption by zeolite was increased when pH was raised from
6 to 7, likely due to the formation of new sorption sites and
decreased ionic competition at a higher pH. In the current
study, it is possible that the slightly lower pH of zeolite D
during equilibration resulted in the reduced sorption by this
particular zeolite compared to the other zeolites tested.
In general, the rate of ion exchange for a substance de-
pends on the quantity of exchangeable cations present
(Sparks, 2003). Ames (1967) reported that the lyotropic
series for ion removal from simulated wastewater by zeolite
was K+ > NH4+ > Na+ > Ca2+ > Mg2. In theory, significant
amounts of soluble K+ or other cations could displace or
compete with NH4+ for binding sites during equilibration.
However, the zeolite that sorbed the most NH4+ (zeolite C)
contained only slightly less K+, Ca2+, Mg2+, and total ex-
changeable cations than did the zeolite that sorbed the least
(zeolite D) (table 1). On the other hand, there was a signifi-
cant negative relationship between zeolite Ca2+ content and
NH4+ sorption (r = -0.221; p < 0.05).
Sorption and desorption characteristics of the zeolites
are presented in figure 3. Extraction of the NH4+-loaded
zeolites with five consecutive 30 mL aliquots of 2.0 M KCl
Figure 3. Effects of equilibration time on ammonium (NH4+) sorption
and desorption properties of zeolites. Error bars represent averages
±standard deviations.
58(1): 137-145
revealed that the majority (average of 82%) of sorbed NH4+
was readily removed with the first extraction (data not
shown). Five extractions removed from 59% to 100% of
sorbed NH4+ from the zeolites that had been equilibrated
for 6 h (fig. 3). The most NH4+ was desorbed from zeolite
C, which was 88%, 144%, and 134% more than zeolites A,
B, and D, respectively. Length of equilibration time did not
affect recovery of NH4+ from zeolites A or C; however,
recovery was 37% lower from zeolite B and 36% higher
from zeolite D when equilibration time was increased from
1 to 6 h. Similar to sorption characteristics, the quantity of
desorbable NH4+-N recovered from the zeolites was posi-
tively related to solution pH (r = 0.584; p < 0.001) and EC
(r = 0.339; p < 0.01), and zeolite CEC (r = 0.580; p <
0.001).
In two similar studies, Penn et al. (2010) and Kithome et
al. (1998), evaluated sorption and desorption characteristics
of natural zeolites and found that 65% to 95% of sorbed
NH4+ could be removed with a single 2.0 M KCl extraction.
Kithome et al. (1998) observed a biphasic trend in desorp-
tion of NH4+ from zeolite characteristic of a diffusion-
controlled process, with rapid desorption within the first
20 min that slowed over time. These researchers reported
that the desorption characteristics of zeolite provided evi-
dence of the potential utility of zeolite as a controlled-
release NH4+ fertilizer. The findings from the current study
support those of Kithome et al. (1998) and Penn et al.
(2010). However, this work also provided evidence that
there are large differences in sorption and desorption char-
acteristics of zeolites due to differing physicochemical
properties. Thus, it cannot be assumed that zeolites from
different sources would be equivalent at mitigating
feedyard NH3 losses.
To determine the effects of NH4+ concentration on zeo-
lite sorption and desorption characteristics, we chose an
equilibration time of 4 h based on the results from the ki-
netic sorption study (fig. 1). Results revealed that NH4+
sorption by zeolite increased with higher NH4+ concentra-
tions, up to maximum values of 97.3 ±2.2 cmol kg-1 (zeo-
lite C) when equilibrated with 14.5 cmol L-1 NH4+-N
(fig. 4). There was no significant difference (p > 0.05) in
sorption by zeolite A, B, or C when equilibrated with
28 cmol L-1 NH4+-N. Average sorption of the three zeolites
was 80 cmol kg-1, which corresponded to retention of 29%
of the NH4+-N added from the 28 cmol L-1 NH4+-N solu-
Figure 4. Ammonium (NH4+) sorption potential of zeolites when equil-
ibrated with 0 to 28.0 cmol L-1 NH4+-N. Error bars represent averages
±standard deviations.
141
tion. Sorption by zeolite D was significantly lower (p <
0.05) than the other three zeolites at solution concentrations
greater than 1.8 cmol L-1, with retention of only 32 cmol
kg-1 NH4+-N after equilibration with 28.0 cmol L-1 NH4+-N.
Sorption with 28.0 cmol L-1 NH4+-N was positively related
(r = 0.65; p < 0.05) to pH during equilibration, but there
was no relationship between solution EC (p > 0.05) and
sorption of NH4+ by zeolite. It should be noted that ob-
served maximum sorption exceeded the theoretical maxi-
mum sorption based on zeolite CEC (table 1); however, the
calculated CEC values for these zeolites were lower than
those reported in other studies, where clinoptilolite CEC (a)
ranged from 66 to 127 cmolc kg-1 (Nguyen and Tanner,
1998; Penn et al., 2010). It is likely that the calculation
method of estimating CEC did not provide a good estimate
of the available cation exchange sites of the zeolites in this
study, as it has been shown that a longer period (~4 weeks)
is required for complete NH4OAc saturation and cation
release from zeolites than from clay and other soil constitu-
ents (Kitsopoulos, 1999).

EFFECTS OF ZEOLITE APPLICATION RATE ON

AMMONIUM SORPTION AND DESORPTION IN
A MANURE/ARTIFICIAL URINE MATRIX
The effects of zeolite application rate on sorption of NH4+ (b)
when equilibrated in a manure/artificial urine matrix were
highly variable, and no clear trend was evident for any ma-
nure, zeolite, or rate of zeolite application (figs. 5a and 5b).
In the absence of zeolite (Control), manures from feedyards
A and E sorbed 36.7 ±3.0 and 32.7 ±0.9 cmol kg-1 NH4+-N,
respectively. In a previous study, Waldrip et al. (2012) found
that manure from the same feedyards sorbed 20 (feedyard A)
and 21 (feedyard E) cmol kg-1 NH4+-N when equilibrated
with 3.6 cmol L-1 NH4+-N. Furthermore, isotherm studies
indicated that these manures could sorb up to 199 (feed-
yard A) and 227 (feedyard E) cmol kg-1 NH4+-N when equil-
ibrated with 36 cmol L-1 NH4+-N (Waldrip et al., 2012). In (c)
the current study, there was increased sorption with applica-
tion rates of 1.0% (zeolite B, feedyard A), 0.5% (zeolites A
and D, feedyard E), and 5.0% (zeolites A and C, feedyard E);
however, sorption with 10.0% zeolite was not significantly
(p > 0.05) greater than Control for any zeolite or feedyard
manure, and was actually lower than Control with zeolite D
(feedyard A) and zeolites A and B (feedyard E) (figs. 5a and
5b).
Despite inconsistency in effects of zeolite on NH4+ sorp-
tion, there was increased recovery of NH4+ in desorption
studies, where desorbable NH4+-N was relatively propor-
tional to zeolite application rate (figs. 5c and 5d). The con- (d)
centrations of desorbed NH4+-N exceeded the amount
Figure 5. Effect of rate of zeolite application on (a, b) sorption and
sorbed by as much as 2-fold due to co-extraction of sorbed (c, d) desorption of ammonium (NH4+) from feedyard manure. Con-
and manure-derived NH4+. Similar to the findings of trol (no zeolite) is presented as the horizontal bar. Error bars repre-
Waldrip et al. (2012), the majority (65% ±6%) of NH4+-N sent averages ±standard deviations.
was readily removed by the first KCl extraction (data not
shown). Application of as little as 0.5% zeolite to feed- A and feedyard E, respectively. These results indicate that
yard E manure increased the amount of desorbable NH4+-N the NH4+-N held by zeolites would be available for plant
by 14% and 19% for zeolites C and D, respectively. The growth if zeolite-amended manure was applied to crop or
application of zeolite C at 10.0% DM increased desorbable pasturelands, resulting in improved fertilizer value of
NH4+ recovery by 18% and 33% for manures from feedyard feedyard manure.

142 TRANSACTIONS OF THE ASABE

EFFECT OF ZEOLITE APPLICATION RATE
ON AMMONIA EMISSIONS
In a four-day chamber study in which zeolite C was
added to manure from feedyard A at rates of 0, 0.5%, 1.0%,
and 5.0% DM, it was observed that emissions of NH3 from
the chambers were highly variable over time (fig. 6); how-
ever, zeolite at 1.0% and 5.0% of manure DM reduced NH3
losses during the first two days of incubation by as much as
48% compared to Control (no zeolite). At day 3, there was
no significant difference (p < 0.05) in NH3 emissions
among the treatments, but at day 4 there was a flush of NH3
release from both Control (no zeolite) and manure that con-
tained 5.0% zeolite. Other researchers have also reported
that zeolite reduces initial NH3 from manure with eventual
release of sorbed NH3 (Kithome et al., 1999; Li et al.,
2008). Kithome et al. (1999) proposed that this could be
due to decreased NH3 in the headspace air that led to
changes in the equilibria between gaseous and soluble NH3
and NH4+ sorbed on the zeolite. However, it remains un-
clear why there was a flush of NH3 release from unamend-
ed manure at the same time and of the same magnitude as
manure amended with 10.0% zeolite.
Irrespective of fluctuations over time, cumulative emis-
sions were significantly reduced (p < 0.001) by 18% (5.0%
zeolite) to 42% (1.0% zeolite) compared to manure that did
not contain zeolite (fig. 7 and table 3). The cumulative
NH3-N loss from unamended manure/artificial urine (Con-
Figure 6. Rates of ammonia nitrogen (NH3-N) volatilization from
feedyard manure/artificial urine amended with zeolite at rates from 0
(Control) to 5.0% of manure dry matter.
Figure 7. Cumulative ammonia nitrogen (NH3-N) losses from
feedyard manure/artificial urine amended with zeolite at rates of 0
(Control) to 5.0% of manure dry matter.
58(1): 137-145
Table 3. Effects of zeolite application on cumulative ammonia
nitrogen (NH3-N) losses from feedyard manure. Data are means of
three replications per treatment, standard deviation (SD), percentage
of urine N added to manure, and percentage of NH3-N loss compared
to Control (no zeolite). Values followed by different letters are
significantly different (p < 0.05).
Cumulative NH3-N Emission
% of
Mean SD Urine N % of
Treatment (mg) (mg) Added Control
Blank 0.46 0.04 - -
Control 73.6 a 18.9 10.5 a 100
0.5% Zeolite 59.4 b 12.7 8.5 b 80.7
1.0% Zeolite 42.9 c 6.1 6.1 c 58.3
5.0% Zeolite 60.2 b 5.7 8.6 b 81.8
trol) over four days was 73.6 mg, equivalent to 37 mg NH3-
N kg-1 manure. Cumulative losses were most reduced by
the application of zeolite at a rate of 1.0% manure DM.
During the early portion of the experiment (days 1 to 3),
there were no significant differences (p > 0.05) among cu-
mulative NH3 losses from chambers that contained una-
mended manure and zeolite at 0.5% DM. However, by
day 4, the chambers that contained 0.5% zeolite had lost an
average of 14 mg less NH3-N than unamended manure,
indicating that low rates of zeolite application could effec-
tively reduce feedyard NH3 emissions.
Despite lower cumulative NH3 emissions from manure
amended with zeolite, it remains unclear if zeolite applica-
tion would be a cost-effective means of mitigating N losses
from commercial feedyards. Other studies have evaluated
the effects of surface amendments such as alum
[Al2(SO4)3], calcium chloride (CaCl2), humic substances,
and urease inhibitors [N-(n-butyl)thiophosphoric triamide
(NBPT)] on NH3 losses from feedyard manure (Shi et al.,
2001; Parker et al., 2012). While these amendments re-
duced cumulative NH3-N losses by 26% to 98%,
cost:benefit ratios indicated that most were not cost-
effective, and the expense may be prohibitive for most pro-
ducers. As feces and urine are being continually deposited
and mixed within feedyard pens, zeolite would need to be
applied at regular intervals to be effective. Further field and
laboratory studies are warranted to determine the applica-
tion rate and frequency required for zeolite to be economi-
cally feasible in regard to zeolite cost and manure fertilizer
value gain. Study is also needed to identify if co-
application of zeolite with other amendments, such as
NBPT, improves zeolite performance and NH4+ retention,
as reported by Cole et al. (2007). Another issue is that ap-
plication of powdered or very fine-mesh zeolite to com-
mercial feedyards could cause excessive nuisance dust that
causes respiratory issues for both cattle and feedyard per-
sonnel; thus, a thorough evaluation of the practicality of
zeolite application at the feedyard scale is required prior to
recommendation of zeolite as a method for mitigating NH3
losses.
CONCLUSIONS
In this study, sorption of NH4+ by zeolites with differing
physicochemical properties was rapid and complete within
1 to 2 h. The maximum concentration of NH4+-N retained
143
by the zeolites ranged from 28 to 97 cmol kg-1 and was
related to solution pH and zeolite CEC. The majority (aver-
age 65%) of sorbed NH4+ was removed by a single 2.0 M
KCl extraction, indicating that sorbed NH4+ would be
available for plant uptake. Application of as little as 0.5%
zeolite increased NH4+ recovery by 19%, and 10.0% zeolite
increased recovery by 33%. Cumulative NH3 emissions
from manure/artificial urine amended with 1.0% zeolite
were reduced by 42%; however, reduced NH3 losses were
not proportional to zeolite application rate, and emission
with 5.0% zeolite was only reduced by 18%. Further study
is warranted at both field and lab scale to evaluate the eco-
nomic feasibility and practicality of zeolite as a method of
mitigating feedyard NH3 losses.
ACKNOWLEDGEMENTS
This project was partially supported by funding from
Texas Cattle Feeders Association for Grant Project 58-
6209-2-072: Controlling feedyard ammonia emissions with
surface-applied natural zeolite clinoptilolite. The authors
thank Heather Robbe (USDA-ARS, Bushland, Texas) and
Ricky Perry (formerly of West Texas A&M University,
Canyon, Texas) for their technical assistance on this pro-
ject.
REFERENCES
Ames Jr., L. L. (1967). Zeolite removal of ammonium ions from
agricultural and other waste waters. In Proc. Pacific Northwest
Ind. Waste Conf. (pp. 135-152). Pullman, Wash.: Washington
State University Technical Extension Service.
Arogo, J., Westerman, P. W., & Liang, Z. S. (2003). Comparing
ammonium ion dissociation constant in swine anaerobic lagoon
liquid and deionized water. Trans. ASAE, 46(5), 1415-1419.
http://dx.doi.org/10.13031/2013.15441.
Battye, R., Battye, W., Overcash, C., & Fudge, S. (1994).
Development and selection of ammonia emission factors: Final
Report. EPA Contract No. 68-D3-0034. Washington, D.C.:
USEPA, Office of Research and Development.
Bernal, M. P., & Lopez-Real, J. M. (1993). Natural zeolites and
sepiolite as ammonium and ammonia adsorbent materials.
Bioresource Tech., 43(1), 27-33. http://dx.doi.org/10.1016/0960-
8524(93)90078-P.
Bernal, M. P., Lopez-Real, J. M., & Scott, K. M. (1993).
Application of natural zeolites for the reduction of ammonia
emissions during the composting of organic wastes in a
laboratory composting simulator. Bioresource Tech., 43(1), 35-
39. http://dx.doi.org/10.1016/0960-8524(93)90079-Q.
Cole, N. A., Todd, R. W., & Parker, D. B. (2007). Use of fat and
zeolite to reduce ammonia emissions from beef cattle feedyards.
In Proc. Intl. Symp. Air Quality and Waste Management for
Agriculture. St. Joseph, Mich.: ASABE.
Cole, N. A., Mason, A. M., Todd, R. W., Rhoades, M., & Parker, D.
B. (2009). Chemical composition of pen surface layers of beef
cattle feedyards. Prof. Animal Sci., 25, 541-552.
Fernando, W. A., Xia, K., & Rice, C. W. (2005). Sorption and
desorption from liquid swine waste in soils. SSSA J., 69(4),
1057-1065. http://dx.doi.org/10.2136/sssaj2004.0268.
Gholamhoseini, M., Ghalavand, A., Khodaei-Joghan, A.,
Dolatabadian, A., Zakikhani, H., & Farmanbar, E. (2013).
Zeolite-amended cattle manure effects on sunflower yield, seed
quality, water use efficiency, and nutrient leaching. Soil Tillage
Res., 126, 193-202.
144
Hristov, A. N. (2011). Technical note: Contribution of ammonia
emitted from livestock to atmospheric PM2.5 in the United
States. J. Dairy Sci., 94(6), 3130-3136.
http://dx.doi.org/10.3168/jds.2010-3681.
Kaminskaia, N. V., & Kostic, N. M. (1997). Kinetics and
mechanism of urea hydrolysis catalyzed by palladium (II)
complexes. Inorganic Chem., 36(25), 5917-5926.
http://dx.doi.org/10.1021/ic961500p.
Keeney, D. R., & Nelson, D. W. (1982). Nitrogen: Inorganic forms.
In A. L. Page, R. H. Miller, & D. R. Keeney (Eds.), Methods of
Soil Analysis: Part 2. Chemical and Microbiological Properties
(pp. 643-698). Madison, Wisc.: ASA and SSSA.
Kithome, M., Paul, J. W., Lavkulich, L. M., & Bomke, A. A.
(1998). Kinetics of ammonium adsorption and desorption by the
natural zeolite clinoptilolite. SSSA J., 62(3), 622-629.
http://dx.doi.org/10.2136/sssaj1998.03615995006200030011x.
Kithome, M., Paul, J. W., & Bomke, A. A. (1999). Reducing
nitrogen losses during simulated composting of poultry manure
using adsorbents or chemical amendments. J. Environ. Qual.,
28(1), 194-201.
http://dx.doi.org/10.2134/jeq1999.00472425002800010023x.
Kitsopoulos, K. P. (1999). Cation-exchange capacity (CEC) of
zeolitic volcaniclastic materials: Applicability of the ammonium
acetate saturation (AMAS) method. Clays and Clay Minerals,
47(6), 688-696. http://dx.doi.org/10.1346/CCMN.1999.0470602.
Koelikker, J. K., Hellickson, M. L., Miner, J. R., & Nakane, H. S.
(1978). Improving poultry house environments with zeolite.
ASAE Paper No. 784044. St. Joseph, Mich.: ASAE.
Kool, D. M., Hoffland, E., Abrahamse, S., & van Groenigen, J. W.
(2006). What artificial urine composition is adequate for
simulating soil N2O fluxes and mineral N dynamics? Soil Biol.
Biochem., 38(7), 1757-1763.
http://dx.doi.org/10.1016/j.soilbio.2005.11.030.
Lefcourt, A. M., & Meisinger, J. J. (2001). Effect of adding alum or
zeolite to dairy slurry on ammonia volatilization and chemical
composition. J. Dairy Sci., 84(8), 1814-1821.
http://dx.doi.org/10.3168/jds.S0022-0302(01)74620-6.
Li, H., Xin, H., Liang, Y., & Burns, R. T. (2008). Reduction of
ammonia emissions from stored laying hen manure through
topical application of zeolite, Al+Clear, Ferix-3, or poultry litter
treatment. J. Appl. Poultry Res., 17(4), 421-431.
http://dx.doi.org/10.3382/japr.2007-00076.
Lippmann, M. (1998). The 1997 USEPA standards for particulate
matter and ozone. In R. E. Hester, & R. M. Harrison (Eds.), Air
Pollution and Health (pp. 75-100). Issues in Environmental
Science and Technology. London, U.K.: Royal Society of
Chemistry.
Mehlich, A. (1984). Mehlich 3 soil test extractant: A modification
of the Mehlich-2 extractant. Comm. Soil Sci. Plant Anal., 15(12),
1409-1416. http://dx.doi.org/10.1080/00103628409367568.
NCDC. (2000). Monthly station normals of temperature,
precipitation, and heating and cooling degree days.
Climatography of the United States No. 81. Asheville, N.C.:
National Climatic Data Center. Retrieved from http://hurricane.
ncdc.noaa.gov/climatenormals/clim81/TXnorm.pdf.
Nguyen, M. L., & Tanner, C. C. (1998). Ammonium removal from
wastewaters using natural New Zealand zeolites. New Zealand J.
Agric. Res., 41(3), 427-446.
NRC. (2003). Air Emissions from Animal Feeding Operations:
Current Knowledge, Future Needs. Washington D.C.: National
Research Council.
Paerl, H. W. (1997). Coastal eutrophication and harmful algal
blooms: Importance of atmospheric deposition and groundwater
as new nitrogen and other nutrient sources. Limnol. Oceanogr.,
42(5, pt. 2), 1154-1165.
http://dx.doi.org/10.4319/lo.1997.42.5_part_2.1154.
TRANSACTIONS OF THE ASABE
Parker, D. B., Pandrangi, S., Greene, L. W., Almas, L. K., Cole, N.
A., Rhoades, M. B., & Koziel, J. A. (2005). Rate and frequency
of urease inhibitor application for minimizing ammonia
emissions from beef cattle feedyards. Trans. ASAE, 48(2), 787-
793. http://dx.doi.org/10.13031/2013.18321.
Parker, D. B., Rhoades, M. B., Cole, N. A., & Sambana, V. P.
(2012). Effect of urease inhibitor application rate and rainfall on
ammonia emissions from beef manure. Trans. ASABE, 55(1),
211-218. http://dx.doi.org/10.13031/2013.41248.
Penn, C. J., Warren, J. G., & Smith, S. (2010). Maximizing
ammonium nitrogen removal from solution using different
zeolites. J. Environ. Qual., 39(4), 1478-1485.
http://dx.doi.org/10.2134/jeq2009.0324.
Sawyer, C. N., & McCarty, P. L. (1978). Chemistry for
Environmental Engineering (3rd ed.). New York, N.Y.:
McGraw-Hill.
Shi, Y., Parker, D. B., Cole, N. A., Auvermann, B. W., &
Mehlhorn, J. E. (2001). Surface amendments to minimize
ammonia emissions from beef cattle feedlots. Trans. ASAE,
44(3), 677-682.
Sparks, D. L. (2003). Environmental Soil Chemistry. San Diego,
Cal.: Academic Press.
Swensson, C. (2003). Relationship between content of crude protein
in rations for dairy cows, N in urine, and ammonia release.
Livestock Prod. Sci., 84(2), 125-133.
http://dx.doi.org/10.1016/j.livprodsci.2003.09.009.
Todd, R. W., Cole, N. A., & Clark, R. N. (2006). Reducing crude
protein in beef cattle diet reduces ammonia emissions from
artificial feedyard surfaces. J. Environ. Qual., 35(2), 404-411.
http://dx.doi.org/10.2134/jeq2005.0045.
Todd, R. W., Cole, N. A., Clark, R. N., Flesch, T. K., Harper, L. A.,
& Baek, B. H. (2008). Ammonia emissions from a beef cattle
feedyard on the Southern High Plains. Atmos. Environ., 42(28),
6797-6805. http://dx.doi.org/10.1016/j.atmosenv.2008.05.013.
Todd, R. W., Cole, N. A., Rhoades, M. B., Parker, D. B., & Casey,
K. D. (2011). Daily, monthly, seasonal, and annual ammonia
emissions from Southern High Plains cattle feedyards. J.
Environ. Qual., 40(4), 1090-1095.
58(1): 137-145
http://dx.doi.org/10.2134/jeq2010.0307.
USEPA. (2005). National Emission Inventory: Ammonia emissions
from animal agricultural operations. Revised draft report, April
22. Washington D.C.: U.S. Environmental Protection Agency.
Van Raij, B., & Peech, M. (1972). Electrochemical properties of some
oxisols and alfisols of the tropics. Proc. SSSA, 36(4), 587-593.
http://dx.doi.org/10.2136/sssaj1972.03615995003600040027x.
Waldrip, H. M., Todd, R. W., & Cole, N. A. (2012).
Characterization of ammonium sorption by beef feedyard
manure. Trans. ASABE, 55(4), 1609-1619.
http://dx.doi.org/10.13031/2013.42236.
Waldrip, H. M., Todd, R. W., & Cole, N. A. (2013). Prediction of
nitrogen excretion by beef cattle: A meta-analysis. J. Animal
Sci., 91(9), 4290-4302. http://dx.doi.org/10.2527/jas.2012-5818.
Wang, J. Z., Hu, Z. Y., Zhou, X. Q., An, Z. Z., Gao, J. F., Liu, X.
N., Jiang, L. L., Lu, J., Kan, X. M., Li, M., Hao, Y. B., &
Kardol, P. (2012). Effects of reed straw, zeolite, and
superphosphate amendments on ammonia and greenhouse gas
emissions from stored duck manure. J. Environ. Qual., 41(4),
1221-1227. http://dx.doi.org/10.2134/jeq2011.0373.
NOMENCLATURE
ANOVA = analysis of variance
CEC = cation exchange capacity
DM = dry matter
EC = electrical conductivity
ICP-AES = inductively coupled plasma-atomic emission
spectroscopy
N = nitrogen
NH3 = ammonia
NH4+ = ammonium
NO3- = nitrate
TAN = total ammoniacal nitrogen
TKN = total Kjeldahl nitrogen
145