United States
             Environmental Protection
             Agency
            Robert S. Kerr Environmental Research EPA-600/2-80-066
            Laboratory           April 1980
            Ada OK 74820
             Research and Development
&EPA
Denitrification  as
Affected by
Irrigation  Frequency
of a Field  Soil

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                RESEARCH REPORTING SERIES

Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into nine series. These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology.  Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The nine series are:

      1.  Environmental Health Effects Research
      2.  Environmental Protection Technology
      3.  Ecological Research
      4.  Environmental Monitoring
      5.  Socioeconomic Environmental Studies
      6.  Scientific and Technical Assessment Reports (STAR)
      7.  Interagency Energy-Environment Research and Development
      8.  "Special" Reports
      9.  Miscellaneous Reports

This report has been assigned to the ENVIRONMENTAL PROTECTION TECH-
NOLOGY series. This series describes research performed to develop and dem-
onstrate instrumentation, equipment, and methodology to repair or prevent en-
vironmental degradation from point and non-point sources of pollution. This work
provides the new or improved technology required for the control and treatment
of pollution sources to meet environmental quality standards.
This document is available to the public through the National Technical Informa-
tion Service, .Springfield, Virginia  22161.

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                                       EPA-600/2-80-066
                                       April 1980
    DENITRIFICATION AS AFFECTED BY IRRIGATION
            FREQUENCY OF A FIELD SOIL
                       by
                Dennis E.  Rolston
               Andrew N.  Sharpley
                  Dianne W.  Toy
                David L.  Hoffman
              Francis E.  Broadbent
          Land, Air and Water Resources
            University of California
            Davis, California  95616
               Grant No. R-805550
                 Project Officer

                Arthur G. Hornsby
            Source Management Branch
Robert S. Kerr Environmental Research Laboratory
              Ada, Oklahoma 74820
ROBERT S. KERR ENVIRONMENTAL RESEARCH LABORATORY
      - OFFICE OF RESEARCH AND DEVELOPMENT
      U.S. ENVIRONMENTAL PROTECTION AGENCY
              ADA, OKLAHOMA  74820

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                                DISCLAIMER

     This report has been reviewed by the Robert S. Kerr Environmental
Research Laboratory, U.S. Environmental Protection Agency, and approved
for publication.  Approval does not signify  that the contents necessarily
reflect the views and policies of the U.S. Environmental Protection Agency,
nor does mention of trade names or commercial products constitute endorse-
ment or recommendation for use.
                                     ii

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                                 FOREWORD
     Environmental protection efforts dealing with agricultural and nonpoint
sources have received increased emphasis with the passage of the Clean Water
Act of 1977 and the subsequent implementation of the Rural Clean Water
Program.  As part of this Laboratory's research on the occurrence, movement,
transformation, fate, impact, and control of environmental contaminants, data
are developed to assess the causes and possible solutions of adverse environ-
mental effects of irrigated agriculture.

     This report addresses the denitrification process as it affects the
management of nitrogen and water in an agricultural production system.  An
understanding of the complete nitrogen cycle, including denitrification, is
required to make sound management decisions regarding nitrogen use- and water
use-efficiency in irrigated agricultural systems.  This research should
benefit environmental managers as they attempt to understand and solve pollu-
tion problems related to nitrogeneous compounds and wastes.
                                        William C. Galegar      M
                                        Director
                                        Robert S. Kerr Environmental
                                          Research Laboratory
                                    iii

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                                   ABSTRACT
     The amount  of nitrogen  (N)  as nitrate (NO^)  in irrigation return flow
waters is dependent upon  each of the components  of the N cycle in soils.   One
of those components for which absolute amounts and rates are not well known
is denitrification.  Volatile denitrification products, primarily nitrous
oxide  (NaO) and  dinitrogen  (N2), are evolved whenever anoxic sites develop
within the soil  and when  sufficient  carbon (C) is available.   Absolute
amounts and rates of denitrification from a Yolo  loam field profile at Davis,
California, were studied  in  relation to the influence of irrigation frequency
and soil incorporation of crop residue.   Field plots were intensely instru-
mented with soil atmosphere  samplers,  soil solution samplers, tensiometers,
neutron access tubes, and thermocouples.   Two different C treatments were
established by using plots to which  no crop residues had been incorporated
within one year  prior to  the experiment and plots to which 10 metric tons  ha *
of chopped barley straw were incorporated into the top 10 cm of soil two
months prior  to  fertilization.   Irrigation frequencies of three irrigations
per week, one irrigation  per week, and one irrigation every two weeks were
established on areas cropped with perennial ryegrass.  Fertilizer was applied
at the rate of 300 kg N ha"1 as  KN03 enriched with 56 to 58% 15N to 1-m2
plots.  The flux of volatile gases at the soil surface was measured from the
accumulation  of  N20 and  15N2 beneath airtight covers placed over the soil
surface for one  to four hours at several times immediately after irrigation
and at less frequent intervals as denitrification fluxes decreased.

     Small rates of total denitrification were measured in this well-drained
alluvial soil under normal cyclic applications of irrigation water.  For
plots without C  addition, the largest denitrification of only 1.5% of the
applied fertilizer was measured in the most frequently irrigated plot. For
the least frequently irrigated plot  of one irrigation every two weeks, only
0.7% of the fertilizer denitrified.   For plots to which C was added as straw,
denitrification  was greatly  increased over that  of the plots not receiving
straw.  The greatest denitrification also occurred for the most frequently
irrigated plots  with denitrification being between 5 and 6.5% of the fertil-
izer applied.  For the least frequently irrigated plot, only 1.8% of the
fertilizer was denitrified.   Denitrification rates decreased to near zero
values within one or two  days after  irrigation.   The amount of N2 produced
was much greater than N20.   The N20  flux at the soil surface varied between
5 and 27% of  the total denitrification over a 40  to 50 day period.  N20 mole
fractions tended to be smallest  Immediately after irrigation and increased as
the soil water redistributed and the soil profile became less anoxic.
                                      iv

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     The irrigation frequency of  three irrigations  per  week gave higher N03
concentrations as measured by both soil solution  and  soil  samples within the
root zone of the crop than those  of  the other  two frequencies.   Thus,  fre-
quent, small irrigations tended to result in less leaching losses than
frequent, large irrigations.

     Denitrification as measured  using the  15N enrichment  method compared
reasonably well with that determined using  the acetylene  (C2H2)  inhibition
method.  However, rates of denitrification  as  measured  by  the  two methods at
any one sampling time varied considerably due  to  the  lags  in reduction of N£0
to N£ and to possible development of organisms which  may reduce  ^0  in the
presence of acetylene.

     Denitrification of N03 fertilizer was  simulated  using a mathematical
model that included transport and plant uptake of water and N  in soil.   The
rate of denitrification was considered to be a function of N03 concentration,
available C concentration, degree of soil-water saturation,  and  temperature.
Available C concentrations were calculated  from initial amounts  of soil C
and additions of plant residues or animal manure.   The  consumption of  added
C in the soil system was assumed  to occur in two  or three  stages with  dif-
ferent rate constants for each stage and C  addition.  A QIQ  value of two was
used to correct the denitrification rate constant and C consumption  constants
for temperature.  Model simulations for total  denitrification were compared
with measured N2 plus %0 gas fluxes during NO^ leaching in field plots of
Yolo soil at different soil-water contents, C  additions, soil  temperature,
and irrigation frequencies.  Reasonable agreement was found between  measured
and calculated rates and total amounts of denitrification  for  all plots.

     This report was submitted in fulfillment  of  Grant  No.  R805550 by  the
University of California, Davis, under the  sponsorship  of  the U.S.
Environmental Protection Agency.  This report  covers  a  period from
January 1, 1978 to September 30,  1979 and work was  completed as  of January  31,
1980.

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                                  CONTENTS
Foreword	   ill
Abstract	    iv
Figures	viii
Tables	xiii
Abbreviations and Symbols 	   xiv
Acknowledgments	    xv

   1.  Introduction 	     1
   2.  Conclusions	     3
   3.  Recommendations	     6
   4.  Experimental Procedures	     7
            Field installation	     7
            Experimental procedures - field 	    10
            Analytical techniques 	    13
            Analytical quality control	    14
   5.  Results and Discussion	    15
            Plot characteristics	    15
            N2 and NgO surface fluxes	    21
            N20 mole fraction	    29
            Plant uptake	    33
            Soil solution N	    33
            Soil residual N	    35
            Mass balance of N	    40
            Denitrification simulation model	    41
            Model input data	    44
            Comparison of calculated and measured denitrification ...    45
            Management simulations	    53

References	    55
Publications	    57
                                    vii

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                                   FIGUKES


Number

  1   Schematic diagram of experimental location and the treatment
        layout.  The area for measuring denitrificatian by the
        CzS.z method did not contain wood borders placed in the
        soil to a depth of 60 cm 	
      Mean bulk density as a function of soil depth at.the experi-
        mental site	       10

      Mean percentage of organic C as a function of soil depth at
        the experimental site	   11

      Schematic diagram of the apparatus for measuring NjO evolved
        using the C2H^ inhibition method	   13

      Mean soil temperature at the 5-cm soil depth as a function
        of time during the experimental period.  The arrows and
        symbols on the graph indicate the time that fertilizer was
        applied to the various plots	   15
                                                             /
      O2 concentration as a function of soil depth for two to
        three sampling times after irrigation for each of the six
        plots	 .   16

      Soil-water content for the 15- and 60-cm soil depths as a
        function of time for Plots A and B.  The data points
        represent values determined from neutron moisture meter
        data.  The arrows on the figures indicate the times of
        irrigation	   18

      Soil-water content for the 15- and 60-cm soil depths as a
        function of time for Plot C.  The data points represent
        values determined from neutron moisture meter data.  The
        arrows on the figures indicate the times of irrigation ....   18
                                                              »•
      Soil-water content for the 15- and 60-cm soil depths as a
        function of time for Plots D and E.  The data points
        represent values determined from neutron moisture meter
        data.  The arrows on the figures Indicate the times of
        irrigation	   19
                                    viii

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Number                                                                 Page

 10   Soil-water content for the 15- and 60-cm soil depths as a
        function of time for Plot F.  The data points represent
        values determined from neutron moisture meter data.  The
        arrows on the figures indicate the times of irrigation. ...   19

 11   Soil-water pressure head at the 30- and 60-cm soil depths
        as a function of time for Plots A and B.  Each data
        point represents the mean from triplicate tensiometers
        at each depth.  Arrows give the times of irrigation	   20

 12   Soil-water pressure head at the 30- and 60-cm soil depths
        as a function of time for Plot C.  Each data point
        represents the mean from triplicate tensiometers at
        each depth.  Arrows give the times of irrigation	   21

 13   Soil-water pressure head at the 30- and 60-cm soil depths
        as a function of time for Plots D, E, and F.  Each data
        point represents the mean from triplicate tensiometers
        at each depth.  Arrows give the times of irrigation	   22

 14   The N20 and N2 flux at the soil surface as measured by the
        accumulation of gases beneath covers as a function of
        time for Plot A.  The open circles are for N2 and the
        closed circles are for N20.  The arrows give the times
        of irrigation	   23

 15   The N20 and N2 flux at the soil surface as measured by the
        accumulation of gases beneath covers as a function of
        time for Plot B.  The open circles are for N2 and the
        closed circles are for N.O.  The arrows give the times
        of irrigation	   23

 16   The N20 and N2 flux at the soil surface as measured by the
        accumulation of gases beneath covers as a function of
        time for Plot C.  The open circles are for N2 and the
        closed circles are for N20.  The arrows give the times
        of irrigation	   24

 17   The N'20 and N2 flux at the soil surface as measured by the
        accumulation of gases beneath covers as a function of
        time for Plot D.  The open circles are for N2 and the
        closed circles are for NaO.  The arrows give the times
        of irrigation ..... 	   24

 18   The N20 and N2 flux at the soil surface as measured by the
        accumulation of gases beneath covers as a function of
        time for Plot E.  The open circles are for N2 and the
        closed circles are for N20.  The arrows give the times
        of irrigation	   25
                                     ix

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Number                                                                 pagt

 19   The N20 and N2 flux at the soil surface as measured by the
        accumulation of gases beneath covers as a function of
        time for Plot F.  The open circles are for N2 and the
        closed circles are for N.20.  The arrows give the times
        of irrigation	   26

 20   Comparison of the denitrification flux as a function of
        time as measured by the   N and C2H2 inhibition methods
        for Plots A, B, C, G, H, and I.  The denitrification flux
        is the sum of N  plus N.20.  The broken lines and open
        circles are for the C2H2 method.  The closed circles and
        solid line are for the   15N method.  Arrows give the
        times of irrigation	   27

 21   The N20 mole fraction as a function of time for Plots A and
        G.  The solid lines give the N20 mole fraction using the
         15N method and the broken lines give the N 0 mole fraction
        using the C2H2 method	2	   30

 22   The N20 mole fraction as a function of time for Plots B and
        H.  The solid lines give the N.O mole fraction using the
        '15.                 "2                    "
          H method and the broken lines give the N20 mole fraction
        using the C2H2 method	   30

 23   The N20 mole fraction as a function of time for Plots C^and I.
        The solid lines give the N20 mole fraction using the   N
        method and the broken lines give the N20 mole fraction
        using the CaH? method	   31

 24   The N20 mole fraction as a function of time using the  l %
        method for Plot D.  The arrows give the times of irrigation  .   32

 25   The NzO mole fraction as a function of time using the 15N
        method for Plot E.  The arrows give the times of irrigation  .   33

 26   The N20 mole fraction as a function of time using the 15N
        method for Plot F.  The arrows give the times of irrigation  .   34

 27   Plant uptake of fertilizer N as a function of time after
        fertilizer addition for all six plots, except for Plot A
        for which no grass was harvested	   35

 28   Soil solution fertilizer N as a function of depth for Plots
        A, B, and C for a sampling time midway through the ex-
        perimental period (upper part of figure) and at the end
        of the experimental period (lower part of figure).  Plot
        A was not sampled at the end of the period.  The data
        points represent the mean-concentration from triplicate
        soil solution samplers	   36

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Number                                                               Pag<

 29   Soil solution fertilizer N as a function of depth for Plots
        D, E, and F for a sampling time midway through the experi-
        mental period (upper part of figure) and at the end of the
        experimental period (lower part of figure).  The data
        points represent the mean concentration from triplicate
        soil solution samplers	   37

 30   Labeled inorganic and organic N for Plots A, B, and C as a
        function of soil depth at the end (63 days for B and C,
        49 days for A) of the experimental period	   38

 31   Labeled inorganic and organic N for Plots D, E, and F as a
        function of soil depth at the end (36 days) of the ex-
        perimental period	   39

 32   Flow diagram giving the order of calculations in the simu-
        lation model	   42

 33   Measured and calculated surface fluxes of denitrification
        products (N2 + N20) as a function of time for two manure-
        amended plots maintained at two different values of soil-
        water pressure head, h	   45

 34   The dependence of the empirical water function, fy, (Eq. [1])
        on relative soil-water content (water content/saturated
        water content)	   48

 35   Measured and calculated surface fluxes of denitrification
        products (Na + NaO) as a function of time for plots with
        and without straw incorporation at an irrigation frequency
        of three irrigations per week.  The solid lines are simu-
        lations based on Eq. [1].  The broken lines simply connect
        measured data points.   Arrows indicate time of irrigation.
        Note that the scales of the ordinate are greatly different
        for the "no straw" and "straw" plots	   49

 36   Measured and calculated surface fluxes of denitrification
        products (N2 + NjiO) as a function of time for plots with
        and without straw incorporation for an irrigation frequency
        of one irrigation per week.  The calculated lines are simu-
        lations based on Eq. [1].  Arrows indicate time of irriga-
        tion.  Note that the scales of the ordinate are greatly
        different for the "no straw" and "straw" plots	   50
                                    xi

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Number                                                                Page

 37   Measured and calculated surface fluxes of denitrification
        products  (N2 + NzO) as a function of time for plots with
        and without straw incorporation for an irrigation frequency
        of one irrigation every two weeks.  The calculated lines
        are simulations based on Eq.  [1].  Arrows indicate time of
        irrigation.  Note that the scales of the ordinate are
        greatly different for the "no straw" and "straw" plots. . .    51

 38   Three hypothetical soil-water content versus time curves
        for an irrigation frequency of one irrigation per week
        for plots with straw incorporation	    52
                                     xii

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                                  TABLES

Number                                                               Pag(

  1     Labeling System for the Nine Plots at Three Different
          Irrigation Frequencies and Two Carbon Additions	   9

  2     Particle Size Distribution and Texture with Soil Depth ...   9

  3     Characteristics of 15N Plots	12

  4     Amount of Irrigation Water Applied and Estimated Evapo-
          transpiration for 10- or 11-Day Periods During the
          Experimental Period	17

  5     Amounts of N^O and N2 Produced During Denitrification of
          Added Fertilizer N as Measured by the C2H2 and 15N
          Methods	29

  6     Mass Balance of Fertilizer N in the Various Components of
          the N Cycle for Each of the Six 15N Plots.  Leaching was
          Determined by Difference From the Other Components ....  40

  7     Comparison of Measured and Calculated Denitrification From
          Constant Water Plots on Yolo Loam Soil.  A Value of kj
          of 1.68 x 10-* g Soil Day"1 (yg C)-1 was Used for the
          Manure and Uncropped Calculations.   A Value of kj of
          6 x 10" ** g Soil Day"1 (yg C)-1 was Used for the Cropped
          Calculations 	  47

  8     Total Denitrification (kg N ha"1) Calculated for Various
          Ways of Applying NO" Fertilizer During One Irrigation
          Cycle of Cropped Soil to Which Straw was Applied 43 days
          Prior to Fertilization.  Simulations Were Made for
          Approximately 40 days After Fertilization	53
                                  xiii

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                  LIST OF ABBREVIATIONS AND SYMBOLS
ABBREVIATIONS
cm
m
ml
°C
kg ha"

mg
ppm
SYMBOLS
NOs
N20
N2
ISN

C02
02
c
Na
Cu
H20
63Ni
A
x
h

6

e
— centimeter              ppmv
— meter
— milliliter              cm3
— degrees Centigrade      g
— kilograms (103 grams)   yg
   per hectare             hr
— milligram (10~3 grams)  ET
— parts per million on a  MT
   weight basis
acetylene gas
Nitrogen
Ammonium
Nitrite
Nitrate
Nitrous Oxide gas
Nitrogen gas
Nitrogen -isotope of
mass 15
Carbon dioxide gas
Oxygen gas
Carbon                  kj
Sodium
Copper
Sulfate                 cs
Chloride
Water
Nickel isotope of mass  t
63                      kg
Potassium
Angstrom
distance (cm)           gw
soil-water pressure
head (cm)               C^
soil-water content
(cm3 cm"3)
saturated soil-water    k^
content (cm3cm"3)
soil bulk density
(g cm"3)                ko
                                     N
                            w
                           f-T
parts per million on a
volume basis
cubic centimeters
gram
micro grams (10 6 grams)
hour
evapo transp irat ion
metric ton (103 kg)
sum of denitrification
gases (N2 + N20)
[ygN(g soil)-1]
concentration of NO3
[yg N (cm solution)"3]
concentration of water
soluble carbon  [yg C
(g soil)-1]
water function for de-
nitrification
temperature function
first-order denitrifica-
tion constant  [g soil
                                       concentration of total
                                       soil organic carbon
                                       [yg C(g soil)"1]
                                       time (day)
                                       first-order constant for
                                       soil carbon decomposition
                                       (day-1)
                                       water function for carbon
                                       decomposition
                                       concentration of total
                                       organic carbon from straw
                                       or manure  [yg C(g soil)"1]
                                       first-order constant for
                                       straw or manure carbon
                                       decomposition (day"1)
                                       zero-order denitrification
                                       constant [yg N day
                                       (yg cr1]
                                  xiv

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                               ACKNOWLEDGMENTS
     The authors gratefully acknowledge additional financial support  for  this
research from the National Science Foundation - RANN  (Grant No. G134733X) and
the University of California Agricultural Experiment  Station.  The laborato-
ries and mass spectrometer facilities of the Department of Land, Air  and
Water Resources provided strong support for this research.  The senior author
also gratefully acknowledges support by the Soil Science Department,  Univer-
sity of Florida, Gainesville, while on sabbatical leave.  The denitrification
part of the simulation model was developed at the University of Florida in
cooperation with J.M. Davidson, P.S.C. Rao, and R.E.  Jessup, during the
sabbatical leave of the senior author.

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                                  SECTION 1

                                INTRODUCTION
     The amount of N03 reaching the groundwater of irrigated  lands  is  depend-
ent upon each of the components of the N cycle in soils.   One of  the poten-
tial losses of N from the soil system for which absolute  amounts  and rates
are not well known is denitrification.  Volatile denitrification  products,
primarily N20 and N2, are evolved whenever anoxic sites develop within the
soil and when sufficient C as supplied by soil organic matter, plant
materials, and manure is available.

     Simulation models of the N balance in soil systems attempt to  predict
the amount and concentration of N03 in irrigation return  flow water as a
function of irrigation and cropping practices (Mehran and Tanji,  1974;
Donigian and Crawford, 1976; Shaffer et_ al., 197^; Tanji  and  Gupta,  1978-; and
van Veen, 1977).  In general, the denitrification component of the  various
mathematical models has not had adequate input data especially for  the rates
of denitrification.  Total denitrification of applied fertilizers is used
quite frequently such as 10 to 15% of the fertilizer N applied (Fried  et al.,
1976).

     Very few experiments have evaluated the absolute amounts and rates of
denitrification in the field.  Rolston e_t al. (1976) demonstrated that the
volatile gases from denitrification could be measured in  a field  profile.
Total denitrification from gas fluxes compared reasonably with denitrifica-
tion determined by difference for a small, intensely-instrumented field plot.
Total denitrification was determined by integrating with  time the flux of the
gaseous denitrification products as determined from measured  soil gaseous
diffusion coefficients and concentration gradients.  These studies  only
evaluated the amount of denitrification under one cropping or C input  system
and one soil-water content near saturation.  Rolston and  Broadbent  (1977),
Rolston e£ al. (1978, 1979) directly measured denitrification from  the fluxes
of N2 and N20 at the soil surface of small, intensely-instrumented  field
plots.  NO3 fertilizer was applied to plots which had a crop  growing on the
soil, to plots to which manure had.been added, and to uncropped plots  main-
tained at two different soil-water contents near saturation and at  two dif-
ferent temperatures (winter and summer).  These experiments were  conducted
for constant water content conditions over the entire period  that denitri-
fication measurements were made.  These experiments defined the range  over
which denitrification might occur and gave the potential  rates and  total
amounts that might be expected in field soils.  However,  the  continual main-
tenance of high water content conditions for long time periods in the  field
is generally not the normal practice which might occur during irrigation or
rainfall events.  The wetting and drying cycles which would take place under

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field situations, due to either rainfall or irrigation, may drastically
change the rates and total amounts of denitrification  that may  occur.  The
rate that a microbial population can increase  from  a relatively small biomass
in an air dry soil to a population which could effectively reduce N03, the
length of time that irrigation water is maintained  on  the soil, and  the  rate
of redistribution of applied irrigation water  within the soil profile would
all have a very dynamic effect on the denitrification  process.

     Ryden et_ al. (1979) directly measured denitrification in field  soils  of
the Santa Maria Valley of California using the C2H2 inhibition  technique.
The C^B.2 inhibition method is based upon evidence that C2B.2 completely blocks
the reduction of N20 to N2 in the denitrification sequence.  Thus, all deni-
trification yields N20 which is easy to measure without the use of 15N.

     The objectives of the research reported here were:

     A.  To directly measure fluxes of N2 and  N20 gases from a  field soil  as
influenced by three different irrigation frequencies and two levels  of
C.

     B.  To compare denitrification obtained directly  using  15N2 and N20 gas
fluxes from 15N enriched fertilizer with denitrification measured directly
using the C2H2 inhibition method.

     C.  To evaluate existing N simulation models to determine  if such models
could simulate the dynamic denitrification process  that occurs  during and
after normal irrigation cycles and  to develop  or Improve existing models to
adequately consider denitrification.

     The research was conducted on  small 1-m2  field plots because of the
large cost of NO^ fertilizer tagged with high  enrichments of the stable
isotope 15N.  The experiments were  conducted at three  different irrigation
frequencies of three irrigations per week, one irrigation per week,  and  one
irrigation every two weeks with the same, total amount  of water  applied  to
each plot.  The plots also had two  C levels; one in which no plant materials
(residues) were added to the soil for more than one year prior  to the experi-
ment and a second in which 10 metric tons per  hectare  (MT ha'1) of chopped
barley straw were added approximately two months prior to fertilization.

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                                  SECTION 2

                                 CONCLUSIONS


     The following major conclusions were obtained from  this research:

     1.  The results of this research demonstrate that denitrification  rates
and total amounts are generally small for normal irrigation practices in
fairly well-drained, alluvial soil.

     The greatest amount of fertilizer N lost through denitrification was
only 1.5% of the total N applied (300 kg N ha"1) for .the situation where
plant materials had not been incorporated into the soil  for greater  than one
year prior to the experiment.  For the plots to which straw was incorporated
two months prior to fertilization, the greatest denitrification loss was
still only 6.5% of the total fertilizer applied (300 kg  N ha'1).  It is
expected that these values would be similar for other well-drained, loam
soils of similar C levels.  Little denitrification is expected in sandy
soils.  Approximately two or three times the denitrification measured here
might be expected in clay soils.  The presence of hardpans, impeding layers,
textural discontinuities or high water tables in the soil profile would all
tend to increase the amount of denitrification over that given in this
report.

     2.  Denitrification rates were largest immediately  after the first irri-
gation and decreased for subsequent irrigations.

     Denitrification fluxes tended to decrease quickly within one to two days
after irrigation.  The soil-water pressure head values for one to two days
after irrigation corresponded fairly closely with those  from experiments of
Rolston et al. (1978) for constant water content plots.  This very rapid
decrease in denitrification fluxes soon after irrigation was most likely due
to rapid redistribution of the soil water deeper into the soil profile
resulting in oxygen (02) diffusing into the soil pores and a decrease in the
amount of anoxic soil volume.

     3.  The presence of added organic C greatly increases denitrification
rates and total amounts due to the availability of C derived from the added
crop materials.

     The effect of C in the denitrification process is very important,
especially that from crop or manure additions.  However, simulations using
the denitrification model indicate -that soil C levels or organic matter
levels can be increased by two or three times with only  slight increases in

-------
denitrification.   This is due to the fact that only a small proportion of the
total organic C is available for denitrification.

      4.   In general,  the plots irrigated frequently, with small amounts of
water,- resulted in the greatest amount of denitrification.

      Those plots receiving irrigation only once every two weeks resulted in
very  small amounts of denitrification and were much smaller than the more
frequently irrigated treatments.  This phenomenon of greatest denitrification
under the most frequently irrigated plots is partially due to the initial
distribution of the added N(>3 fertilizer during the first irrigation.  NOa
fertilizer was applied uniformly during the first irrigation so that the NO^
band  was  distributed over a much narrower depth interval for the frequently
irrigated experiments than that of the less frequently irrigated experiments.
Another important factor affecting the amount of denitrification for the
least frequent irrigations was the fact that the soil profile was fairly dry
at  the initiation of each irrigation.  There may have been some time lag in
the development of anoxic conditions and microbial activity.  However, the
water applied to the initially dry profiles redistributed very quickly with
little time available for the development of anoxic conditions conducive to
denitrification.

      5.   Total denitrification for plots without straw additions compared
reasonably well for the 15N and €2^2 inhibition methods, although the rates
measured  at any one day were very much different between the two methods of
directly  measuring denitrification gases.

      These differences in rates at any one time period were attributed to the
lag in reduction of %0 to N2 for the 15N method and possibly to the develop-
ment  of organisms which could reduce ^0 in the presence of
      6.   The NzO mole fraction was generally small immediately after irriga-
 tion and then increased as redistribution of soil water resulted in less
 anoxic conditions within the wetted soil zone.

      The mole fraction as measured by the 15N and C2H2 methods compared
 reasonably well.  There was some indication that the %(> mole fraction tended
'to decrease with subsequent irrigations possibly due to the effect of N03
 concentration on the inhibition of ^0 reduction.

      7.   The addition of plant materials such as barley straw resulted in a
 decrease in the N20 mole fraction over those experiments without the addition
 of barley straw.

      This again would be expected since greater anoxic conditions would
 develop in the plots to which straw was .added than those without straw,
 resulting in more favorable conditions for %(> reduction to N2»
      8.   The data on %() mole fraction demonstrate that the proportion of
     produced during denitrification was very dynamic and variable.

-------
     Mole fractions varied from  zero to one  for  treatments without  C addi-
tions and varied from nearly  zero  to 0.4 or  0.5  -for  plots with C additions.
The overall N2<3 mole fraction throughout all irrigation  cycles varied from
0.04 to 0.27.

     9.  The frequently irrigated  plots with small applications of  water re-
sulted in higher NO3 concentrations in the root  zone than those plots with
less frequent, larger applications of water.

     The most frequently irrigated plots also resulted in greater plant  up-
take of fertilizer N, most likely  due to higher  NO3  concentrations  in the
root zone, and soil-water contents potentially more  conducive  to plant
growth.  The most frequently irrigated plots also tended to  lose less fer-
tilizer by leaching than that in the least frequently irrigated plots.   A
water management program using small irrigations several times per  week  would
tend to increase denitrification.  However,  the  increase in  denitrification
may be more than compensated by less leaching and more plant uptake of
applied N.

    10.  The denitrification simulation model was able to reasonably predict
rates and total amounts of denitrification with  a minimum amount of model
calibration.

     First order kinetics with respect to NO3 concentration  gave the best
prediction of denitrification rates and total amounts for all  plots.   This
does not mean that denitrification per se followed first-order kinetics  due
to the fact that diffusion of N03  to anoxic  zones may be the primary
mechanism resulting in a better fit using first-order than zero-order
kinetics.  The model is very sensitive to soil-water content,  which is
expected as previous data indicated that the very dynamic nature of denitri-
fication is dependent upon the amount of water in the soil.  It may be better
to use an Q£ diffusion and consumption component to  directly describe the
anoxic volume development.  However, it is expected  that this  would also be  a
very sensitive parameter and the necessary input data to do  such a  calcula-
tion ss& complex and not available.  The amount of organic C  derived from
manure and straw additions, which  is available for denitrification,  is still
somewhat uncertain and needs to be researched.

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                                  SECTION 3

                               RECOMMENDATIONS
     The following recommendations for efficient management of water and
nitrogen under irrigated conditions can be proposed from this research:
     1.  To decrease potential M>3 leaching and pollution of groundwater,
small and frequent applications of irrigation water should be made instead
of larger, less frequent applications.  However, increased labor, equipment,
and energy costs must be considered before recommending this management
technique as a viable alternative to present irrigation practices.

     2.  To increase N-use efficiency of applied N fertilizers  (decrease
denitrif ication) , incorporation of organic materials should be made at least
two months prior to NO 3 additions.

     3.  Future research should be directed at understanding the dynamic
effects of C from crop and manure incorporation into the soil on denitrif ica-
tion rates and total amounts.  The addition of C greatly increases denitrif i-
cation, yet there is very little information on the proportion of the applied
crop or manure C which is available for denitrification as a function of time
after incorporation.

     4.  In simulation modeling of the denitrification process in field
soils, the use of a water function based on relative soil-water saturation is
the most useful and easily-determined parameter indirectly accounting for the
degree of anoxic soil development.  Some means of accounting for degree of
anoxic soil development is essential in simulation of denitrification.  The
applicability of the soil-water function developed in this report to other
soils needs further research.

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                                  SECTION 4

                           EXPERIMENTAL PROCEDURES
FIELD INSTALLATION

     Six plots for the 15N method and three plots for the C^^z method were
established on Yolo loam soil, a member of the fine-silty, mixed, non-acid,
thermic, Typic Xerorthents family, at Davis, California.  The Yolo loam soil
is a deep, well-drained, alluvial soil in the Sacramento Valley.  The soil is
similar to other soils of extensive acreage.  The schematic diagram of the
experimental location and the treatment layout is given in Figure 1.  Each of









1


Three Irrigations
per week
PLOT A
No Straw
I5N Method

PLOT D
10 Mt ho"'
Straw Added
I5N Method

1 	 -|
PLOT 6
No Straw
C2H2 Method
	
























One Irrigation
per week
PLOTB
No Straw
I5N Method

PLOT E
10 Mt ha"'
Straw Added
I5N Method

PLOTH
No Straw
C2H2 Method
	 1
























One Irrigation
per two weeks
PLOTC
No Straw
I5N Method

PLOTF
10 Mt ha"'
Straw Added
I5N Method

I~
PLOT I
No Straw
C,H- Method
Lll__J












Figure 1.  Schematic diagram of experimental location and the treatment lay-
           out.  The area for measuring denitrification by the C2H2 method
           did not contain wood borders placed in the soil to a depth of 60
           cm.

-------
the six, 1-m2 plots  (A through F) was established with  a 60-cm deep  redwood
barrier around the outside edges of  each undisturbed block  of  soil.   Redwood
barriers were installed by digging a trench  around  the  1-m2 areas, slipping
the redwood over the undisturbed block  of  soil,  and backfilling the  trench on
the outside of the redwood.  The space  between the  wood barrier and  the soil
on the inside was sealed by pouring  melted paraffin into the small crack be-
tween the soil and the wood.  Each of the  six plots was instrumented with
tensiometers, soil solution samplers, soil atmosphere samplers,  thermo-
couples, and a neutron access tube.  Triplicate  soil atmosphere samplers were
installed at the 2-, 5-, 15-, 45- and 60-cm  soil depths. Triplicate samplers
designed to function as tensiometers or solution extractors were installed at
30-, 45-, 60-, and 90-cm depths.  Duplicate  thermocouples were installed at
the 5-cm depth.  Soil solution samplers consisted of porous cups glued  to
polyvinyl chloride tubing.  Soil atmosphere  samplers consisted of 0.1 cm
inside diameter nylon tubing glued into a  5-cm long, 0.25-7-cm I.D. perforated
acrylic plastic tube.  For the deeper soil depths,  the  small diameter nylon
tubing was placed inside a 1.3 cm diameter polyvinyl chloride  tube and  the
nylon tubing was glued into a milled plastic tip.   For  all  samplers, the
volume of the sampling tubes was very small  (less than  1.0  cm?). Soil  solu-
tion samples were obtained by evacuating bottles connected  to  samplers.   Soil
atmosphere samples were obtained by  withdrawing  1 ml of gas with glass
syringes.  All gas samples were analyzed within  a few hours after sampling.

     In addition to  the six plots with  redwood barriers down to the  60-cm
depth, three plots were also established to  evaluate the C2H2  method for
directly measuring denitrification.

     The plots were  irrigated by three  different irrigation frequencies.
Irrigation frequencies were three irrigations per week, one irrigation  per
week, and one irrigation every two weeks.  All plots received  the same  amount
of water which was Intended to be 15% greater than  evapotranspiration (ET).
The plots were irrigated with a spray irrigation system which  consisted of
spray nozzles on a traveling boom.   The irrigation  system applied water at a
rate of 0.54 cm hr"1 to Plots A, D,  and G; 0.63  cm  hr"1 to  Plots B,  E,  and
H; and 0.71 cm hr"1  to Plots C, F, and  I.

     In order to establish different C  treatments within each  of the three
irrigation frequencies, three plots  were used for which no  C additions  such
as plant residues or weeds were incorporated for one year prior to the  ex-
periment.  Three plots of each irrigation  frequency had 10  ME  ha 1 of chopped
barley-straw added to the soil approximately two months prior  to the initia-
tion of denitrification experiments.  Chopped straw was mixed  in the top 10
cm of the soil surface.  All plots and  the surrounding  buffer  areas  were
planted with perennial ryegrass (Lolium perenne).   The  grass was planted on
the plots approximately two months prior to  the  initiation  of  denitrification
experiments.  The €2^-2 inhibition plots did  not  have straw  additions.   Table
1 gives the plot labeling system and the irrigation frequency  and C  treat-
ments for the plots.

     Particle size analyses and texture as a function of soil  depth  for the
Yolo loam soil are given in Table 2, and the average bulk density at the
field site is given  as a function of depth in Figure 2.  The bulk density was

                                       8

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     TABLE 1.  LABELING SYSTEM FOR THE NINE PLOTS AT THREE DIFFERENT
               IRRIGATION FREQUENCIES AND TWO CARBON ADDITIONS

Plot
A
B
C
D
E
F
G
H
I
Denitrification
method
15N
15N
15N
15N
15N
15N
^2^2
C2H2
C2H£
*
Carbon
addition
0
0
0
10 MT ha"1
10 MT ha'1
10 MT ha"1
0
0
0
Irrigation
frequency
3 per week
1 per week
1 per 2 weeks
3 per week
1 per week
1 per 2 weeks
3 per week
1 per week
1 per 2 weeks

Chopped barley straw incorporated into the top 10 cm of soil.
    TABLE 2.  PARTICLE SIZE DISTRIBUTION AND TEXTURE WITH SOIL DEPTH
Depth
0 -
15 -
30 -
60 -
90 -
120 -
150 -
15
30
60
90
120
150
180
Sand (%)
41
40
42
38
38
32
25
Silt (%)
37
37
38
42
42
46
51
Clay (%)
22
23
20
20
20
22
24
Texture
Loam
Loam
Loam
Loam
Loam
Silt Loam
Silt Loam

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                    1.10
  BULK DENSITY (g cm"3)
1.20       1.30       1.40
1.50
Figure 2.  Mean bulk  density  as  a function of soil depth at  the experimental
           site.
greatest near  the soil  surface  with a minimum at  the 120-cm depth.   Bulk
density was determined  on  triplicate 7.6  cm long,  7.6 cm diameter undisturbed
soil cores for  each depth.   The percentage of organic C as a function of soil
depth is given  by Figure 3.   Organic C was determined on soil samples taken
during the experiment conducted by Rolston ejt al.  (1978, 1979).

EXPERIMENTAL PROCEDURES -  FIELD

     After the  plots had gone through several irrigation cycles  and the
grass was well  established,  KNOs solution was applied uniformly  to  the plots
throughout one  complete irrigation.   Dry  NO^ fertilizer was also applied to
the surrounding border  area.  The total amounts of fertilizer and the 15N
enrichment of the fertilizer applied to each plot  are given in Table 3.

     Immediately after  irrigation,  an airtight cover was placed  over the
plots.  The cover consisted  of  a thick sheet of acrylic plastic  with rubber
tubing on the lower edge to  make an airtight seal  with the top of the red-
wood border.  Samples of the atmosphere beneath  the cover were taken after
two to four hours with  the lid  in place and analyzed for 15Na and N20.  Soil
atmosphere samples from within  the soil profile were also  taken  soon after

                                      10

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                             ORGANIC  CARBON (%)

           0    0.2   0.4   0.6    0.8    1.0    1.2    1.4    1.6    1.8


1
o
I
1-
Q.
UJ
O
-1
O
CO



w
20
40

60


80


100

i9n
1 1 1 1 1 1 1 1
/
/
\
xx/P
PX

Q
1
J
Q
o/
1 1 1 1 1 1 1 1
Figure 3.  Mean percentage of organic C as a function of soil depth at the
           experimental site.
applying the fertilizer.  Soil atmosphere samples were taken in 1-ml aliquots
and N20, Q^t SD-^- ®2 analyzed by gas chromatography in the laboratory.  An-
other 0.5 to 1 ml of gas was taken to determine *%2 with the mass spec-
trometer.  Gas samples from the profile and samples from.beneath the cover
were taken several times per day for a few days after irrigation and at less
frequent intervals until the next irrigation cycle.  The volume of the
chambers placed over the plots are also given in Table 3.  By using the
volume of the chambers, the 15N enrichment of the applied fertilizer, the
precision of measuring 15N£ by the mass spectrometer, and the time period
that covers remained over the plots for each sampling period, a minimum
detection limit for 15N2 of 0.1 to 0.2 kg N ha"1 day : was determined.  Thus,
for any flux smaller than this limit, it is uncertain whether those values
are real or not.  The minimum detection limit for N20 was at least two orders
of magnitude smaller than that for 15N2«

     For measurement of denitrification with the C2H2 inhibition method, the
three main plots (G, H, I) were divided into six sub-plots (0.05 m2) which
were bounded by 25 cm deep, acrylic plastic barriers, protruding 10 cm above
the soil surface.  The sub-plots were separated by at least two meters.
On three of the sub-plots C2H2 flowed slowly (one liter hr"1 for one hour)
into the soil profile through six, 1-m long, perforated, acrylic plastic
                                      11

-------
                   TABLE 3.  CHARACTERISTICS  OF  15N  PLOTS
                     Volume of       Fertilizer    %  15N excess      Starting
Plot    Area  (m2)    Chamber  (m3)      (kg N/ha)     of fertilizer      date
A
B
C
D
E
F
1.0
1.0
1.0
1.0
1.0
1.0
0.0289
0.316
0.276
0.0265
0.0269
0.0349
281
284
282
288
288
287
58.7
58.7
58.7
59.8
59.8
55.9
7/3/78
7/4/78
7/10/78
8/28/78
8/29/78
9/4/78

tubes.  The  chambers  for measuring N20 flux were placed over the soil one
hour after the  C2H2 flow had stopped.   The six sub-plots,  three with and
three without C2H2, were subjected to  the same three irrigation frequencies
as those plots  to which  15N was  applied.   (Table 1 and Figure 1.)

     After two  complete irrigation cycles, KN03 solution equivalent to 300 kg
N ha"1 were  uniformly applied as for the 15N method, to a 1-m2 area, en-
closing each plot.  Consequently,  NO^  fertilizer was also applied to the
surrounding  border area.   Six hours after applying the fertilizer solution,
an airtight  cover was placed over  the  plots and the enclosed air space (7.5
liters) above the soil was slowly  but  continuously_swept by drawing air
through the  chamber at a flow rate of  25 liters hr l for three hours.  The
gas swept from  the cover was passed through dehydrite and ascarite to remove
H20 and C02, respectively, and finally through a 5 A molecular sieve trap
which quantitatively  adsorbed N20  (Hahn,  1972; Ryden e£ al., 1979).  A
schematic diagram of  the apparatus for measuring N20 evolved using the C2H2
inhibition method is  given by Figure 4.  The recovery of N20 from the 5 A
molecular sieve was carried out  as described by Ryden e_t al. (197Q).  The
minimum detectable flux of N20 using the molecular sieve trap was approxi-
mately 0.005 kg N ha"*1 day"1.

     Soil solution samples were  taken  at two times during the experiment.
The grass of the plots was cut periodically and the total clippings were
dried for analyses.   Soil  .samples  were taken midway through the experimental
period and at the end of the experimental period for Plots A, B, and C.  Soil
samples were taken only at the end of  the experimental period for Plots D, E,
and F.  Soil samples  were  taken in 15-cm increments down to 120 cm.  The
samples consisted of  ten separate  holes taken with a Veihmeyer tube within
the 1-m2 plots.  The  samples were  combined to give two samples at each depth
for analyses.
                                      12

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                      COVER
 ACETYLENE
                                                                     ASCARITE
                                                                     DEHYDRITE
                           VACUUM
                            PUMP
                                                             5A MOLECULAR
                                                               SIEVE
Figure 4.  Schematic diagram of the  apparatus  for measuring  N20  evolved using
           the C2H2 inhibition method.
ANALYTICAL TECHNIQUES

     Oxygen, N2, and C2H2 were analyzed by gas  chromatography with a thermal
conductivity detector.  The concentration of N20 in  the  gas  samples was
determined by chromatography using a hot 63Ni electron capture detector  as
described by Rasmus sen et al. (1976) .  The isotopic  composition of N in  gas
samples was determined on samples scrubbed for  02, C02,  and  H20 vapor and
directly injected into the mass spectrometer.   Details for determining iso-
topic composition of N by mass spectrometry is  given by  Rittenberg (1948).

     Soil samples were analyzed for extractable (inorganic)  and digestible
(organic) N and soil solution samples were analyzed  for  NH^,  NO 3,  and N02.
A soil sample was extracted with 1.0 N KC1 and  the solution  analyzed by  the
magnesium oxide-devarda alloy reduction technique.   The  extraction procedure
removed solution NHi^, N02, NOa, and exchangeable NH^.  The NH^ and N02 con-
centrations in all soil and soil solution samples were negligible.  The
KJeldahl method was used to determine the total digestible N in soil and
plant samples.  Two-gram  samples of soil were  digested  with 36 N  H2SOtf  and
salts (I&SO^, CuSOi}, and selenium) for approximately 17  hours to convert the
N to NHjj.  The same procedure was used for the  plant digests except that 0.25
                                      13

-------
g of plant material were used and the digestion time was 6 hours.  The N in
the digest was determined by titration of the NH^ liberated by distillation
of the digest with 40% NaOH.  Detailed procedures for determination of N in
soil, plant, and soil solution samples were given by Bremner  (1965).

     The soil for organic C determination was ground to pass  a 2mm sieve or
finer.  A subsample was then thoroughly ground with a pica mill to pass a 60
mesh sieve.  Approximately 0.2 grams of the soil sample were  placed in a
crucible to which a small amount of iron and tin accelerator  was added.  The
sample was covered with a single hole lid and placed into an  induction
furnace.  The C02 produced was collected in a Nesbit tower containing
ascarite.  The tower was weighed before and after the burn to determine the
amount of C02 trapped.  Detailed procedures for determination of organic C
in soil were given by Allison (1965).  There was no difference in the % C
between a soil sample that had been extracted with KC1 and a  sample that had
not been extracted.

ANALYTICAL QUALITY CONTROL

     To Insure accuracy of the results all analytical methods were checked
periodically with standard samples.  For gas chromatography and mass
spectrometer analyses, samples of standard gas were analyzed  at least every
twenty samples.  Chemical techniques for determining inorganic and organic N
in soil and soil solution samples and plant N were tested by  evaluating
standard samples at least every  30 samples.  In addition, duplicate soil,
soil solution, and plant samples were always used.  If one duplicate varied
by more than 5% from  the other,  samples were rerun.  Also, blanks  (deionized
water) were run every 15 samples to check for contamination.
                                       14

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                                  SECTION 5

                           RESULTS AND DISCUSSION
PLOT CHARACTERISTICS

     Temperatures at the 5-cm soil depth as a function of time during the
experimental period are given by  Figure 5.  The arrows indicate the time that
fertilizer was applied to particular plots.  Plots G, H, and I were conducted
at the same time as Plots A,  B, and C.  Soil temperature remained relatively
constant during most of the measurements on Plots A, B, C, 6, H, and I.  How-
ever, on Plots D, E, and F, the soil temperature tended to decrease with time
later in the summer.
                               40         60
                                TIME  (days)
too
Figure 5.  Mean soil temperature at the 5-cm soil depth as a function of time
           during the experimental.period.  The arrows and symbols on the
           graph indicate the time that fertilizer was applied to the various
           plots.

                                     15

-------
     The 62  concentration  as  a function of soil depth for two or three
sampling times  for  the six 15N plots,  are given in Figure 6.   These data
represent  typical measurements after irrigation.   It can be seen that for
                            02 CONCENTRATION (%)
                  10  15  20
15   20  25
                                                     • t • I hr
                                                     o t• 21hr
                                                       f39hr
 Figure 6.   02  concentration as a function of soil depth for two to three
            sampling times after irrigation for each of the six plots.
'Plots  A,  B,  and C (no C additions)  that 02 concentrations were relatively
high,  even within a few hours after irrigation.   Oxygen concentrations  did
not  decrease below 10% at any depth within the profile.  The effect of  the
straw  addition is demonstrated by the low 02 concentrations near the soil
surface  for  Plots D, E, and F.  The lowest 02 concentrations tended to  occur
immediately  after irrigation.  There was a slight increase in 02 concentra-
tion as  the  soil -profile drained and water was used by the crop.  The concen-
trations  of  02 in Plot F did not drop below 10%.   The small decrease in 02
was  probably due to the fact that irrigation was  made only every two weeks.
Therefore, the water infiltration and redistribution in the dry profile was
relatively rapid with little opportunity for depletion of 02 within the soil
profile.   Although 02 concentration within the soil profiles is not a good
indication of denitrification due to the fact that the samples are taken
primarily from large pore sequences, these data indicate that one should
                                      16

-------
expect more denitrification in Plots D, E, and F  than  in Plots  A,  B,  and C
due to the low Q£ concentrations for those plots'to which  straw had been
added.

     Table 4 gives the amount of irrigation water applied  and the  estimated
ET for 10 or 11 day periods during  the experiment.  The ET was  estimated from
pan evaporation data taken from a grassed area near the experimental  plots.
The crop ET was estimated from the pan evaporation data and a crop coeffi-
cient factor which was determined over many years of experiments relating pan
evaporation to ET of grass using lysimeters near  the experimental  site.   For
most time periods during the experiment, the amount of irrigation  water
applied was greater than the estimated ET.  The objective  was to apply
approximately 15% more water by irrigation than was evapotranspired.


TABLE 4.  AMOUNT OF IRRIGATION WATER APPLIED AND ESTIMATED EVAPOTRANSPIRATION
	FOR 10- OR 11-DAY PERIODS DURING THE EXPERIMENTAL PERIOD	

                              Irrigation                        Estimated
                                 water                     evapotranspiration

7/1
7/11
7/21
8/1
8/11
8/21
9/1
9/11
9/21
10/1

Dates
- 7/10
- 7/20
- 7/31
- 8/10
- 8/20
- 8/31
- 9/10
- 9/20
- 9/30
- 10/10
Total
applied (cm)
5.7
5.7
6.0
6.0
6.0
5.2
4.6
4.0
4.0
4.0
51.2
(cm)
5.0
4.8
4.9
5.3
5.6
4.1
3.3
5.2
3.2
3.0
44.4

     The soil-water content, 9 (cm3cm"3), for the 15- and 60-cm depths of the
six 15N plots are given as a function of time in Figures 7, 8, 9, and 10.
Zero time is initiation of irrigation.  The water content data for Plots A
and B, Plot C, Plots D and E, and Plot F are given by Figures 7, 8, 9, and
10, respectively.  The arrows on each figure indicate the time of irrigation


                                     17

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     .42

      .38
   §  .34
-'  .30

-------
   .38

   .36
 '§.34
 £.32
 (D

 H .40
 1
 a: .38
 Hi
 I .36
   .32 -
         i    i   i   i    r
                                        •—• I5cm
                                        o—o 60cm
                                                           V:
                                      I
                                             Plot E
                                             •—• 15cm
                                             o-~-o 60cm
                                                            I
                                                               J_
Figure 9.
 4   6   8   10   12   14  16   18  20  22  24  26  28  30  32   3'4  36  38
                      TIME (days)
Soil-water content for the 15- and 60-cm soil depths as a  function
of time for Plots D and E.  The data points  represent values  de-
termined from neutron moisture meter data.   The arrows  on  the
figures indicate the times of irrigation.
      .42
    6
    o
     '.36
     I

     |.34


     i .32
    =1.28
    O
    
-------
for each treatment.  As  expected,  the water content at the 15-cm depth was
greatly dependent upon rate of drainage, ET, and irrigation application.  The
water content  at  the 15-cm depth increases immediately after irrigation to
nearly the saturated water content value and then slowly decreases due to
drainage and crop use until the next irrigation.  As expected, the water
content of the 60-cm depth was less variable and remained fairly constant
with slight increases in water content after each irrigation.  The magnitude
and rate of change  of 6  at the 15-cm depth was strongly dependent upon irri-
gation frequency  as shown in the figures.

     The soil-water pressure head, h (cm of water), at the 30- and 60-cm
depths as a function of  time are given for Plots A and B, Plot C, and Plots
D, E, and F, by Figures  11, 12, and 13, respectively.  The arrows on each
figure indicate the time of irrigation.  The 30- and the 60-cm tensiometers
    u
    UJ
    X
    K
    CO
    in
    bJ
    K
    0.
    K
    111

    I
      -2OO -
       -240 -
                         8  10   \Z  14
                           TIME (days)
16   18  20  22  24  26  28  30  32  34  36
 Figure 11.  Soil-water pressure head at the 30- and 60-cm soil depths as a
             function of time for Plots A and B.  Each data point represents
             the mean from triplicate tensiometers at each depth.  Arrows give
             the times of irrigation.


 responded fairly quickly to each irrigation for Plot A  (irrigated three times
 per week).  The 30-cm depth tensiometer did not decrease below h = -40 cm
 during the measurement period.  For Plots B and C, however, the 30-cm
 tensiometers dropped down to h - -240 cm and h = -600 cm, respectively.
 Plots D, E, and F did not show as great a decrease in soil-water pressure
 head due most likely to decreasing ambient temperatures resulting in less
                                       20

-------
     100
  x"
  u
  ~  -100
    -200
  IU
  ct
  Q.
  UJ
  i
  o
  CO
-300


-400


-500


-600
                4
                         10   12  14   16   18   20  22  24   26   28  30
                                TIME (doys)
Figure 12.  Soil-water pressure head at  the 30- and 60-cm soil depths as a
            function of  time  for Plot C.   Each data point represents the mean
            from  triplicate tensiometers at each depth.   Arrows give the
            times of irrigation.


ET than that anticipated.  The experiments described by  Rolston et al.  (1978,
1979) demonstrated for Yolo loam soil, that denitrification became very small
after soil-water pressure heads became less than -70 cm  of water.   Thus, one
would expect from the data in Figures 11,  12,  and 13 for h vs.  time for all
six plots, that denitrification would generally occur for only one or two
days after irrigation when h  was greater than  -70 cm. The soil water re-
distributes rather rapidly in this well-drained,  alluvial soil resulting in
decreases in h within a  few days after irrigation.   Thus, one would expect
that the amount of time  available for denitrification is relatively small
compared to the entire cropping season as  long as restrictive layers do not
result in a buildup of water  at some depth.  There is a  limited amount  of h
data for Plot F because  all tensiometers were  switched over to soil solution
extractors in order to get a  sample  of the soil solution before the end of
the experimental period.

N2 AND N20 SURFACE FLUXES

     The N20 and N2 fluxes at the soil surface as measured by the  accumula-
tion of gases beneath the covers are given as  a function of time for the six
15N plots in Figures 14, 15,  16, 17,  18, and 19.   The N2 flux is given  by the
open circles and broken  lines, whereas the N20 flux is given by the solid
circles and solid lines.  It  is apparent that  many of the data points for N2
                                      21

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                                               PlotE
                                               •   •30cm
                                               o—o 60cm
                          4   6
8   10   12   14
 TIME (days)
18   20
Figure 13.  Soil-water pressure head at the 30- and 60-cm soil depths as a
            function of  time  for Plots  D,  E,  and F.   Each data point repre-
            sents the mean  from triplicate tensiometers at each depth.
            Arrows give  the times  of irrigation.


flux fall below the minimum detection limit of 0.1 to 0.2 kg N ha"1 day"1
for Figures 14, 15, and  16.   Thus,  the  %  flux is highly uncertain for the
three plots (A, B, C) which did not receive C additions.  Due to an unfortu-
nate accident with Plot  A,  within  one day  after fertilizer application, the
cover over the plots was left unshaded  and high temperatures built up beneath
the cover with considerable damage to the  grass.  ET and water movement for
Plot A was thus expected to be much different from that of the other plots.
                                      22

-------

                                                0
                                       ^r     1   \
                                                    PLOT A
                                                      oN,
                1
1
                                                              i
                                                                  i
                      8   10   12   14
16   18   20
 TIME (days)
                                                 22   24  26  28  30  32  34  36
Figure 14.  The N£0 and N£ flux at the soil surface as measured by the  accu-
            mulation of gases beneath covers  as  a function of time for  Plot
            A.  The open circles are for N2 and  the closed circles are  for
                   The arrows give the times of irrigation.

.40
.35
.30
.25
.IS

.10
.OS
o
1 1 1
-
-
-
-
•

M

1 1 t 1


f.
\ i
1
1
yfl.
/V>
i i i i i i i i i i i i i i i i i i
PLOT B
\ ' N.°
\
I 1 l \ I '
N |li A h
\ \ o.
-------
   0.8




   0.6

   as

   0.4

   0.3

   0.2

    0.1
  I   I

  PLOT C
  o Nt
  .N,0
 I
 M
A
                   8   10  12  14  16
Figure  16.   The N20 and N2 flux at the soil surface as measured by  the accu-
             mulation of gases beneath covers as a function of  time  for Plot
             C.   The open circles  are for N2 and the closed circles  are for
             N20.  The arrows give the times of irrigation.
    2.4
                                                           Plot D
                                                           o—o N.
        i      I I
        '°-4

        i  v  i T V   »   »   »    y   v   v    yvy    yvv    »   »  _
                                    16   18  ZO
                                   TIME (days)
                         26  26  30  32   34  36  38
Figure 17.   The N20 and N2 flux at  the  soil surface as measured by  the  accumu-
             lation of gases beneath covers as a function of time for Plot D.
             The open circles are  for N2 and the closed circles are  for  N20.
             The arrows give the times of irrigation.
                                        24

-------
      12
      10 T
    x
    <
    o
    LU
    O
I
 'I
I-'1
  /
 1
 O
        +
        I
        I
                                                        Plot E
                                                        o	° N,
                                                            N20
I            1
       ll   I-1.
                                                   JL
                                               _L
J.
           6   8   10   12  14   16   18  20   22  24  26  28  30
                            TIME (days)
                                                                 32  34  36
Figure 18.  The N20  and N2  flux at  the soil surface as measured by the accumu-
            lation of  gases beneath covers as a function of time for Plot E.
            The open circles  are for N2 and the closed circles are for N20.
            The arrows give the times of irrigation.


NO3 was apparently leached  from the top part of Plot A by 22 days (Figure 14)
with the result that denitrification essentially ceased by Day 22.  For Plots
B and C, however, small amounts of  denitrification were measured up to between
40 and 50 days after .fertilizer application, although rates were very small as
irrigation progressed.  In  general,  the flux of N2 was much greater than the
flux of N20.

     The N2 and N20  flux  for  Plots  D, E, and F was greatly increased over that
of Plots A, B, and C due  to the addition of barley straw.  There was a tend-
ency for denitrification  to approach zero much sooner for Plots D, E, and F
than that for the plots which did not receive C.  This may be due to differ-
ences in the amount  of water  movement through the soil profile with leaching
of NO3 from the upper  part  of the-soil profile where low 02 and high C values
were maintained.  Even with the addition of a relatively large amount of crop
residue into the soil  profile,  the  denitrification rates were relatively small
compared to rates observed  by Rolston et a.1. (1978) for plots maintained
uniformly wet for long time periods.

     A comparison of the  total denitrification gas flux as a function of time
measured by the 15N  and C2H2  methods is given by Figure 20.  The total
                                       25

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                                  14  16   18  20 22  24  26  28  30
                                     TIME (days)
32  34
 Figure 19.   The N20 and N2 flux at the soil surface as measured by the accumu
             lation of gases beneath covers as a function of time for Plot F.
             The open circles are for N£ and the closed circles are for
             The arrows give the times of irrigation.
 denitrification gas flux for the 15N method is the sum of 15N2 and N20 gas
 fluKes.   The total denitrification gas flux for the C2H2 method is only ^0
 flux since reduction of N20 to N2 was inhibited.  The denitrification flux
 plotted in Figure 20 is the total of N2 and ^0 for Plots A, B, C, G, H, and
 I at any sampling time.  The pattern of gas flux produced during denitrifica-
 tion was similar for both methods with peak flux occurring shortly after
•application of water.  It was observed, however, that denitrification at any
 one time during the repeated irrigation cycles was not equal for both methods.
 For Plots B and H the flux of gas produced during denitrification as measured
 by the C^2 method was initially greater than that measured by the 15N method.
 For example, 0.42, 0.66, and 0.46 kg N ha 1 of denitrification gas was evolved
 in the presence of C2H2 and 0.26, 0.52, and 0.27 kg N ha'1 of denitrification
 gases were evolved in the absence of C2H2 using the 15N method during the
 first three days after irrigation for the first three applications, respec-
 tively.   Following this, however, the opposite was true when only 0.1 and 0.06
 kg N ha 1 of denitrification gases were evolved in' the presence of C2H2 and
 0.28 and 0.19 kg N ha"1 of denitrification gases were evolved in the absence
 of C2H2 by the 15N method in the first two days after the fifth and sixth
 irrigation applications, respectively.  For Plots A and G, the amounts of
 denitrification gases evolved in the first two days after the initial
                                       26

-------
                                                          C2H2 method
                                                          H    metho(j
                              14    18    22   26
                                 TIME  (days)
                                           30   34    38   42
Figure 20.
Comparison of the denitrification flux as a function of time as
measured by the 15N and C2H2 inhibition methods for Plots A, B,
C, G, H, and I.  The denitrification flux is the sum of N2 plus
N20.  The broken lines and open circles are for the C2H2 method.
The closed circles and solid line are for the 15N method.  Arrows
give the times of irrigation.
irrigation in the presence and absence of C2H2 were 0.93 and 0.72 kg N ha *,
respectively.  In the same time period, after the tenth irrigation,  the
amounts of denitrification gases evolved in the presence and absence of C2H2
were 0.12 and 0.33 kg N ha~*, respectively.  For Plots C and I,  the  amounts of
denitrification gases evolved in the first two days after the initial irriga-
tion in the presence and absence of C2H2 were 0.82 and 0.61 kg N ha  *, re-
spectively.  For a two day period after the third irrigation, the amounts of
denitrification gases evolved in Plots C and I in the presence and absence of
C2H2 were 0.35 and 0.43 kg N ha"1, respectively.

     The .data of Figure 20 suggest that the production of denitrification
gases during the initial stages of denitrification can be increased  by the
presence of C2H2.  This increase results from the fact that N20  was  converted
to N2 in the absence of C2H2 leading to a delay in evolution of  N2 compared
to N20 from the field soil.  Furthermore, after a certain period of  time, the
presence of C2H2 can result in a decrease in production of N20- compared to
N20 and 15N2 in the absence of C2H2-.  Part of the reason for this behavior may
be that 02 concentrations were slightly reduced in the presence  of C2H2.   Also
                                      27

-------
 Yeomans and Beauchamp (1978) using soil incubation studies, reported  that C2H2
 is effective in inhibiting N20 reduction for a limited  time only in the con-
 tinued presence of C2H2 such that N20 could eventually  be converted to N2.
 It is possible that several applications of C2H2 at the same site in  the field
 soil in order to measure variations in N20 flux at frequent intervals could
 facilitate the growth of organisms capable of reducing  N20 in the presence of
 C2H2.  The results of the present study indicate that such a population may
 have developed when N20 flux in the presence of C2H2 became lower than that of
 N20 and N2 in the absence of C2H2.  This occurred in Plots G, H, and  I after
 13, 15, and 17 C2H2 applications, respectively.  The differences between
 treatments may have resulted from the increased variation in the soil moisture
 content as irrigation frequency decreased, with a subsequent decrease in soil
 microbial activity.

      It is interesting to note for the denitrification  flux comparisons of
 Figure 20 for Plots A and G that the fluxes were comparable at 22 days.
 However, it would be expected that fluxes would not be  the same for the 15N
 and C2H2 methods since the grass of Plot A was not transpiring, whereas in
 Plot G the grass was transpiring.  One would possibly expect differences in
 water movement and differences in the residence time of NO^ in the active zone
 where denitrification was occurring for these two areas.  However, gas fluxes
 were similar indicating that the differences in residence time may not have
 been that different with or without the grass.

      The total amounts of gases produced during denitrification of applied
 fertilizer N as measured by the C2H2 and 15N methods are presented in Table 5.
 Although denitrification flux at any single time as measured by the two
 methods was greatly different, only a slightly different total amount of
 denitrification gases was measured by the two methods., The denitrification
 of fertilizer in the presence of C2H2 for the three treatments (1.4,  1.2, and
 1.0% for Plots G, H, and,!, respectively) was slightly  greater than that
 using 15N (1.5, 1.1 and 0.7% for Plots A, B, and C, respectively).

      The total denitrification as measured by the 15N method for Plots D, E,
 and F which had received straw are also given in Table  5.  It is obvious from
 Table 5 that the addition of the straw greatly increased denitrification over
 that without straw addition.  However, the total amount denitrified from the
,. straw treatments was still not very large compared to  the total amount of
 fertilizer N applied.  This indicates that denitrification fluxes under normal
 irrigated conditions where the soil profile was not kept continuously wet, is
 rather small, at least for deep, well-drained alluvial  soils such as Yolo.
 The data of Table 5 show that the least amount of denitrification occurred
 for the irrigation frequency of one irrigation every two weeks.  This small
 amount of denitrification is due primarily to the fact  that the soil  is
 relatively dry for an extended time period and that when irrigation water is
 applied, infiltration and redistribution of the soil water occurs rapidly
 resulting in only a very short time period when the soil is anoxic enough for
 denitrification to occur.  The effect of infrequent irrigation is also to move
 the fertilizer.N. into the lower part of the root zone,  resulting in less N©3
 in the upper part of the soil where high C and high water contents may occur
 simultaneously.  For the other two irrigation frequencies, the 15N and C2H2
 methods show that the largest amount of denitrification occurred for  the most

                                       28

-------
   TABLE 5.  AMOUNTS OF N20 AND N2 PRODUCED DURING  DENITRIFICATION OF ADDED
             FERTILIZER N AS MEASURED BY .THE C2H2 AND 15N METHODS

Denitrifi cation (kgN ha"1)
Plot
15N






C2H2



Method
A
B
C
D
E
F
Method.
G
H
I
N20

1.1
0.6
0.3
1.8
0.8
1.0

1.0
0.8
0.7
N2

3.0
2.6
1.6
13.1
17.6
4.0

3.5
2.6
2.0
Total

4.1
3.2
1.9
14.9
18.4
5.1

4.3
3.4
2.7
N20
(N20 + N2)

0.27
0.19
0.16
0.12
0.04
0.22

0.23
0.24
0.26
Loss of fert.
N as total
denit. (%)

1.5
1.1
0.7
5.2
6.4
1.8

1.4
1.2
1.0

frequently irrigated plot of three irrigations per week.  The soil was kept
fairly wet for long time periods and by adding small, frequent amounts of
water, the W^ tended to remain in the upper portion of the soil profile for
longer time periods resulting in more denitrification.  For Plots D and E,
the irrigation frequency of one irrigation per week (Plot E) gave the
greatest amount of denitrification.  However, the differences between Plots D
and E are small and there is some indication from the water content data
(Figure 9) that an impeding layer or a hardpan existed in Plot E which tended
to keep water contents higher in the profile for longer time periods creating
more anoxic conditions.  These results indicate that very frequent irriga-
tions tend to result in the largest amount of denitrification, whereas infre-
quent irrigations result in the least amount of denitrification.

N20 MOLE FRACTION

     The various proportions of N20 and N2 produced during denitrification is
of great interest due to the potential that N20 may be contributing to the
depletion of the ozone layer of the lower stratosphere.  Figures 21 through
26 give N20 mole fraction as a function of time for the nine plots of this
experiment.  Figures 21, 22, and 23 give the N20 mole fraction from both the
                                      29

-------
                                    T
                                          T
                                15
 CM
 N
     1.0
    0.8
    0.6
 CM 0.4
    0.2
                                  N method
                                C2H2 method
                                                    Plots A ond G
         Fll  v     y        v    v     v       v     v    v
                                                                    \
        0     2    4    6     8    10    12   14    16    18   20    22

                                  TIME (days)
Figure 21.   The N20 mole fraction as a function  of time for Plots A and 6.
            The solid lines give the N20 mole fraction using the 15N method,
            and the broken lines give the N20 mole fraction using the  C2H2
            method.
     1.0
4-
O.
0,0.6
    0.4
  M
    0.2
                                  • I5N method
                                  o C2H2 method
                                                      i       i      I

                                                         Plots B ond H
                                                   /
                            M.
                                   f:  1.
                                                             /i
10     15     20   25     30     35
              TIME  (days)
                                                            40
                                                                  45
Figure 22.   The N20 mole fraction as a function of  time for Plots B and H.
            The solid lines give the ^0 mole fraction using the 15N method
            and the broken lines give the N20 mole  fraction using the C2H2
            method.
                                    30

-------
   CM
      1.0
     0.8
     0.6
     0.2

       0
         I
Figure 23.

                                      1	
                                   N method
                               0 C2H2 method
                                                       Plots C and I
1
     I
                   1  -
                       10
                               15
        20
25
30
35
40
                                    TIME  (days)
            The N20 mole fraction as a function of time for Plots C and I.
            The solid lines give the N20 mole fraction using the 15N method,
            and the broken lines give the N20 mole fraction using the C2H2
            method.
15N2 and the C2H2 methods.  For the frequently irrigated plots (Plots A and
G) , the N20 mole fraction was quite dynamic due to the frequent irrigation
applications.  The N20 mole fraction varied from nearly zero to one during
different irrigation cycles.  The mole fraction as measured by the two dif-
ferent methods compared reasonably well.  For Plots B and H (Figure 22) there
was a general tendency for a decrease in the N20 mole fraction with increas-
ing time.  This may be due to the effects of high NO^ concentration initially
which tends to inhibit N20 reduction, and therefore, would result in high N20
mole fractions shortly after fertilizer application.  The C2H2 method
compared reasonably well with the 15N method except toward the end of the
sampling.  After the first two irrigation cycles, both sets of data indicate
that the mole fraction tended to be relatively small immediately after
irrigation and then increased as the soil profile dried or became less
anoxic.  This would be expected since under less anoxic conditions there is a
decreased potential for N20 reduction to N2.

     Similar behavior is demonstrated by the N20 mole fraction for Plots C
and I (Figure 23) demonstrating that the N20 mole fraction tended to increase
from the low value immediately after irrigation to higher values as the pro-
file dried.

     For Plots D, E, and F (Figures 24, 25, and 26), which were the plots to
which C was added as chopped barley straw, the N20 mole fractions tended to
                                     31

-------
  M
   *
      1.0
     0.8
                                                  I        I       T
                                                    Plot D
          ' »  V   VTV    T^T    VTV    TTV   W  »
                                   V
                         10
                                  15
                                  TIME  (days)
                                                                     V
20     20     30     35
Figure 24.
            The N20 mole fraction as a function of time using the 15N method
            for Plot D.  The arrows give the times of irrigation.
be much lower than those measured for the plots without C addition.   This
again would be expected since much more anoxic conditions developed  in plots
to which straw was added than those without straw resulting in better condi-
tions for N20 reduction to N2.  There does seem to be a general decrease in
N20 mole fraction with time for Plots D and F.  Plot E did not show  that be-
havior.  The data for Plot E, however, definitely showed the increase in N20
mole fraction within each irrigation cycle.  In fact, there is essentially no
NaO produced very shortly after irrigation to result in mole fractions near
zero.

     The data on N20 mole fraction demonstrate that the proportion of N20
produced during denitrification was a very dynamic and variable property.
Mole fractions varied all the way from zero to one for treatments without C
additions and varied from nearly zero to 0.4 or 0.5 for plots with C addi-
tions.  A time-averaged N20 mole fraction would be about 0.2 or 0.3  for  those
plots without C additions and approximately 0.1 for those plots with C addi-
tions.  The overall N20 mole fraction calculated from the data in Table  5
varied from 0.04 for Plot E to 0.27 for Plot A.
                                     32

-------
                                                       PLOT  E
      1.0
   CM
     0.8
         I          I
4
1          I
   CM
     0.6
                                                   I
                                  15     20     25
                                    TIME  (days)
                                             30      35
Figure 25.
The N20 mole fraction as a function of time using the 15N method
for Plot E.  The arrows give.the times of irrigation.
PLANT UPTAKE

     Figure 27 gives the plant uptake of fertilizer N as a function of time
after fertilizer addition for Plots B, C, D, E,  and F (no uptake for A).
Plots B and C for the experiments without C addition compared reasonably  well
in total uptake versus time.  In a similar fashion, Plots D,  E,  and F showed
similar N uptake.  The cooler temperatures later in the summer appeared to
have an effect on Plots D, E, and F with less uptake than that of Plots B and
C.  Plot D took up more N than the other two plots, most likely due to much
better water conditions from frequent small irrigations.

SOIL SOLUTION N

     The soil solution fertilizer N within the six 15N plots  for two sampling
times are given by Figures 28 and 29.  Figure 28 gives the data for Plots A,
B, and C for a sampling time midway through the experimental  period and for a
sampling time shortly before termination of the experiment.   Data for Plots
D, E, and F are given by Figure 29 for a sampling time midway through the
period and near the end of the experimental period.  Data points given here
are the mean soil solution NO^ concentrations derived from the fertilizer
from triplicate solution extractors at each depth for each plot.  Both
figures show that the two plots which received irrigation once per week and
once every two weeks had similar soil solution NO3 concentrations.   The two
                                     33

-------
 1.0

0.8

0.6
                                                          I        1
                                                       Plot  F
                                v
   M
      0.2
                                           i
                                            i
                          10
15     20     25
  TIME (days)
                                                   30
35
Figure 26.  The N20 mole fraction as a function of time using the 15N method
            for Plot E.  The arrows give the times of irrigation.


plots which received irrigation water three times per week, however, behaved
very differently with much higher concentrations of fertilizer remaining in
the upper part of the profile especially for the sampling midway through the
experimental period (the top part of both figures).  This demonstrates that
the frequent, small irrigations tended to keep the NO3 in the upper part of
the soil profile whereas the infrequent, large irrigations tended to move the
NOs deeper into the soil.  Part of this was due to the fact that the initial
distribution of the fertilizer was somewhat different due to the fact that
the fertilizer was applied uniformly during the first irrigation.  Therefore,
all the fertilizer was applied in a very small pulse for Plots A and D,
whereas for Plots C and F, all the fertilizer was applied in one large irri-
gation which would tend to distribute the fertilizer over a deeper depth.
These figures also show that, even for the sampling period midway through the
experiment, that fertilizer NO3 concentrations at the 90-cm depth were al-
ready quite high for Plots B, C, E, and F, indicating that probably large
amounts of fertilizer N would be leached below the grass root system for
these plots.  By the last sampling time near the end of the experiment, the
fertilizer N(>3 in the soil solution for Plot D began to decrease at the 30-cm
depth due to denitrification and continual leaching to deeper soil depths.

     As demonstrated by Rolston ^it al. (1979), the variability in the NOg
concentration of the triplicate samples at any particular soil depth was
quite high.  Standard deviations were sometimes as great as 150% of the mean,
with 60% of the mean being fairly common.
                                      34

-------
          60


          50
     i
      D
     2   40
      o>

     uj   30
     ^^
     ^f
     I-
     %   20

     \-
     _J
     Q_
          10
                          20            40           60
                                   TIME  (days)
80
Figure 27.  Plant uptake of fertilizer N as a function of time after fertil-
            izer addition for all six plots, except for Plot A for which no
            grass was harvested.
SOIL BESIDUAL N

     The labeled inorganic N (fertilizer derived N) for the six plots at the
end of the sampling period are given by Figures 30 and 31.  Each data point
represents the mean from ten Individual soil samples at each depth combined
to_two samples for analyses.  The labeled inorganic N represents primarily
NOa-N whereas the labeled organic N is simply organic N which had been
Immobilized by microorganisms or by live or dead plant roots.  The effect of
the three different irrigation frequencies are also demonstrated here on the
leaching of NO3 through the soil profile.  In Plot A, a. relatively high NOs
peak occurred between 60 and 75 cm after approximately 60 days.  Plot A
received small frequent irrigations.  For Plots B and C which received irri-
gations less frequently, the high peak did not occur and the NO3 concentra-
tions were relatively uniform with depth.  Relatively high concentrations
still existed at the 120-cm soil depth, indicating that substantial NO^ was
potentially leached below 120 cm.  The labeled organic N within the soil
profile was predominantly due to live or dead plant material.  The result of
extreme damage to the grass of Plot A was very low labeled organic N in the
upper part of the profile, whereas Plots B and C had high organic N in the
top 30 cm of soil.   However, the organic N values continued to be measurable
                                     35

-------
down to 120 cm in this profile,  indicating that roots extended fairly deep or
that there was some immobilization of added N by microorganisms.
                     SOIL  SOLUTION  FERTILIZER  N (ppm)

                     .0   20 40 60  80  100 120 140 160  180200
                                           Plots A,B,C
                                           • A- 24days
                                           oB- 37 days
                                           * C- 30 days
                                           Plots B,C
                                          ° B-51 days
                                          * C-44 days
                     ,-/    ,o
Figure 28.  Soil solution fertilizer N as a function of  depth for Plots A, B,
            and C for a sampling time midway through the experimental period
            (upper part of figure) and at the end of the experimental period
            (lower part of figure).  Plot A was not  sampled  at the end of the
            period.  The data points represent the mean  concentration from
            triplicate soil solution samplers.
                                     36

-------
                     SOIL SOLUTION  FERTILIZER N (ppm)

                     ^0  20  40 60  80  100  120 140 160 180 200
                E
                o
               Q.
               UJ
               Q
 10

20

30

40

50

60

70

80

90
 0

 10

20

30

40

50

60

70

80

90
Plots D, E, F
• D-17 days
o E-15days
*• F -15 days
                                          Plots D.E.F
                                          • D-31 days

                                          0 E - 29 days
                                          * F-31 days
Figure 29.  Soil solution fertilizer N  as  a function of depth for Plots D, E,
            and F for a sampling time midway through the experimental period
            (upper part of figure)  and  at  the end of the experimental period
            (lower part of figure).  The data points represent the mean con-
            centration from triplicate  soil solution samplers.


     A similar behavior of organic  and  inorganic N is demonstrated by Figure
31 for the plots receiving straw additions.   As for Plot A,  the plot receiv-
ing frequent,  small irrigations  (Plot D) demonstrated a peak in NO3 concen-
tration between 30 and 45 cm,  indicating less leaching of  the applied
                                     37

-------
                   LABELED INORGANIC N  (ju,q Ng"' soil)

                   0         10        20        30       40
                30
                60
            .-.  90
             E
             E 120
            Q.
            UJ
            O   0
            O
            Cfl
                30
                60
                90
               120
          I

        • Plot A
        o Plot B
         Plot C
                                                    T
                             I    I     I     I     I    I
        • Plot A
        o Plot B
        4 Plot C
                        I     I    I     I     i     I    I
                            10
20
30
                                                   -I
40
                     LABELED  ORGANIC N (>*g Ng  soil)
Figure 30.  Labeled inorganic and  organic N for Plots A, B, and C as a func
            tion of soil depth at  the end (63 days for B and C, 49 days for
   t         A) of the experimental period.
fertilizer through the profile than for  the other plots.  Aldfcugh a definite
NO^ peak occurred for both Plots A and D,  the magnitude of the peak was
greater in A than in D due to no plant uptake of N in A and very little de-
nitrification in A.  As was the case for Plots B and C, Plots E and F showed
very little difference In NO^ due  to irrigation treatment.  The labeled
organic N was similar for all three plots, with high, labeled organic N in
the top 15 cm and a rapid decrease to fairly low levels deeper in the profile.
                                     38

-------
                    LABELED  INORGANIC N  (/*g Ng 'soil)

                    0        10        20        30       40
                                               • Plot D
                                               o Plot E
                                                Plot F
                                               • Plot D
                                               o Plot E
                                                Plot F
                 120
                     0        10       20
                       LABELED  ORGANIC  N
30       40
  Ng  soil)
Figure 31.  Labeled inorganic and organic N for Plots D, E,  and F as  a  func-
            tion of soil depth at the end (36 days) of the experimental
            period.
     The labeled inorganic N values demonstrate that leaching of N03 was
decreased by small,  frequent irrigations.  However, as shown under the
section on gas fluxes,  the frequent, small irrigation treatments resulted in
the greatest amount  of  denitrification loss.  Thus, although NO^ leaching may
be less, frequent irrigations would result in more denitrification.  A bal-
ance would have to be drawn between denitrification losses and leaching
                                     39

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losses.  These data show that over  the  time period  of  this  experiment  that
although denitrification was increased  on  the  frequently irrigated plots, the
increased denitrification was not as great as  the leaching  that occurred in
the infrequently irrigated plots.   Thus, frequent small irrigations would
result In maintaining high NO3 in the upper part of the soil profile,  and
would, thus, be more accessible for plant uptake.

MASS BALANCE OF N

     Table 6 gives the amounts of fertilizer N for  the various components of
the N cycle.  The amount of fertilizer, the amount  remaining in the soil, the


TABLE 6.  MASS BALANCE OF FERTILIZER IN THE VARIOUS COMPONENTS OF THE  N CYCLE
          FOR EACH OF THE SIX 15N PLOTS.  LEACHING  WAS DETERMINED BY DIFFER-
          ENCE FROM THE OTHER COMPONENTS

Plots
Component
Fert. applied
Soil digests
Soil extracts
Plant uptake
Denitrification
Leaching
(by difference)
A

281.0
10.8
149.8
—
4.1
116.3
B

284.0
114.9
68.8
45.8
3.2
51.3
C

282.0
77.7
60.7
46.7
1.9
95.0
D
l-i -| — 1

288.0
95.3
82.3
21.0
14.9
74.5
E

288.0
65.7
54.4
11.9
18.4
137.6
E

287.0
82.9
77.9
13.0
5.1
108.1

amount  taken up by  the plant, and  denitrification were measured  directly.
Due to  the difficulties in estimating  the leaching  component even in  small
plots such as those used by Rolston  et al.  (1979),  leaching was  estimated by
difference from the other measured components.   The residual soil N in  the
upper 120 cm of soil was determined  with  reasonable accuracy.  There  could be
some question about the accuracy or  the ability  to  measure all of the deni-
trification gases produced.  However,  the C2H2 and  15N methods gave nearly
the same total denitrification indicating that the  flux of denitrification
gases below the borders of the 15N plots  was  insignificant. ; Thus, it seems
that although some  errors in denitrification  fluxes could easily have been
made, it appears that the numbers  given for denitrification are  reasonable.

     The determination of leaching by  difference in Table 6 shows that  con-
siderable N was lost below the 120-cm  depth for  these experiments.  These
data are somewhat confusing for Plot A since  the calculation gives greater
leaching for Plot A than for Plots B or C.  However, the soil solution  N03

                                     40

-------
values and the residual soil NOa values showed considerable NOs  remaining in
the soil profile for Plot A, whereas Plots B and.C had much less NOs  re-
maining in the upper 120 cm of soil.  Plant uptake was zero and  very  little
N remained in the soil as labeled organic N for Plot A.   Thus, the N  not
taken up by the plant and not immobilized as organic N was apparently avail-
able for leaching, resulting in 116 kg leached out of 281 kg applied.  For
Plots D, E, and F, however, Plot D, which was the frequent, small irrigations,
resulted in the least amount of leaching.  For Plot D, substantial N03 re-
mained in the upper 120 cm of the profile, considerable N was immobilized in
the organic fraction, and plant uptake of applied N was high.  Nearly one-
half of the applied N was leached from the plot with an irrigation frequency
of one irrigation per week, and something less than one-half was leached  from
the plot with an irrigation frequency of once every two weeks.

     This amount of leaching seems excessive if the amount of irrigation  was
no greater than 15% of the ET.  Evidence exists from the denitrification
modeling section that the amount of irrigation water applied was greater  than
115% of actual ET.  The plots may have been using less water than the esti-
mated ET due to frequent cuttings of the grass and the effect of placing
covers over the plots for two to four hours per day on each sampling  day.
This effect of more leaching than anticipated will be discussed  further in
the section on the denitrification simulation model.

DENITRIFICATION SIMULATION MODEL

     The mathematical equations used to describe  the transient behavior of
water and N in soils are similar to those presented by Davidson et al.
(1978).  The numerical procedures used to solve these equations, however,
were different in that plate theory rather than finite difference techniques
were employed.  The numerical scheme used in this report and verification  of
the model are also presented by Rao et^ al^, (1980).  A flow diagram giving  the
order of calculations in the simulation model is  given by Figure 32.

     To verify the denitrification portion of the N simulation model de-
scribed by Rao jet jal. (1980), the experimental results of Rolston et al.
(1978) and those of this report were used.  The field experiments used 15N
tagged NO 3 fertilizer to measure N2 and ^0 gas emission from the soil
surface during denitrification.  To simulate denitrification,  a first-order
reaction with respect to NO3 and C concentration was assumed.   It was also
assumed that the time required for the N2 and N20 gases to diffuse from the
site of production to the soil surface was small  relative to the time scale
of the experiments.  Thus, the model contained no gaseous diffusion component.
The effect of soil temperature on denitrification was accounted for by using
a Qio (temperature coefficient) value of 2.  The  effect of anoxic conditions
on denitrification was accounted for through a water function which was based
upon degree of soil-water saturation.   The rate of denitrification was
calculated from:


                 p f - ki 9 *v f T Sr <*
                                      41

-------
                         ROOT GROWTH
                  (Maximum Rooting Depth &
                   Root Density in Soil)
                    POTENTIAL E,T, DEW*)
                   (Penman Model or Input)
                   POTENTIAL NITROGEN UPTAKE
                   DEPWND  (Empirical)
                     PLANT WTER UPTAKE
                    (Holz-Remson Model)
                    N  TRANSFORWTIONS
                    MftNURE-N AND SOIL~N
                    Mineralization, Immobilization
                    Nitrification, Denitrification
PLANT NITROGEN UPTAKE
(Empirical Model)
   WTER TRANSPORT
(Semi-Empirical Approach)
  SOLUTE TRANSPORT
 AWONIIM-N AND NITRATC-N
 (Chromatographic-Plate Theory)
CARBON TRNfttWriONS
MANURE-C AND SOIL-C
(Calculate Available Carbon
 For Input Into Denitrification
 Model)
Figure 32.   Flow  diagram giving  the order  of calculations  in  the  simulation
               model.
                                                42

-------
where G is sum of denitrif ication  gases  (N2  + N20) ,  C  is the concentration
of NO^, (L.. is the concentration  of water-soluble carbon,  fy is the water
function, fT is  the temperature  function,  p  is the soil bulk density, 6 is
the volumetric soil-water content, and kj^  is the first order denitrif ication
rate constant.

     The water-soluble carbon, C^, in Eq.  [1]  has been shown by Burford and
Bremner (1975) to correlate  significantly  with denitrification.   For soil
organic matter,  the water extractable C was  calculated from the following
relationship (Burford and Bremner, 1976; Reddy et^ a^. ,  1979):

                 (^ = 24.5 +  0.0031 Cg                                   [2]


where C^ is water extractable C  concentration and Cg is total soil organic C
concentration.   The total soil organic C decomposition rate was  assumed to
be a first-order reaction:
where t is time, kg is the first-order constant  for  C  decomposition,  and &,
is a function describing relative respiration  as a function of  relative
soil-water content:

                gw = 1.67 (6/9s) for 0.1  <. (6/9s) <.  0.6                 [4a]


                gw = 1.75 -1.25  (9/0s) for 0.6 <. (9/6s)  <. 1.0           [4b]


adapted from Reddy et al. (1979) where 0g  is the saturated soil-water content
(cm3 cm"3) .  Equations [4a] and  [4b] are  specific for  the Yolo  soil but  may
be reasonable for other fine textured soils.   This function gives a maximum
decomposition (g^ = 1) at a soil-water potential of  0.33  bar (9/6  =  0.6).


     Relationships between water extractable C (or C available  for dentrifi-
cation) and total organic C in manure or plant residue are not  readily avail-
able.  Thus, it was assumed for  this study that  the  C  in  the manure or plant
residues could be divided into a portion which was readily decomposed
(Fraction I) and totally available for dentrif ication  and a portion which was
slowly decomposed (Fraction II) and only partially available.   The latter
portion was assumed to follow the same relationship  as that for soil  organic
C (Eq. [2]).  The percentages of C in Fractions  I and  II  and the rate con-
stants for various manures and plant residues  are presented by  Reddy  et al.
(1979).  The decomposition of manure or plant  residues can be described by:
                        5 k± % fT Ci

where the subscript i refers to Fraction I or II.  The value of  C.  for
Fraction I enters directly into the denitrification equation (Eq.  [1]).   The


                                     43

-------
value of C. for Fraction  II  is  considered to be the same as soil C and is
substitutes for Cg  into Eq.  [2],   Thus,  the total "soil" C for cases where
manure or plant residues  are added to  soil is the sum of Fraction II C from
the manure or  residue  and the soil C.   The decomposition of manure C of
Fraction I can be more adequately described by two subtractions, each having
different rate constants  (Reddy et_ aJL.,  1979).

MODEL INPUT DATA

     The input data for  the  denitrification model were obtained from Rolston
£t jl. (1978), and  the data  of  this report on Yolo loam soil at Davis,
California.  Rate constants  for the decomposition of C in soils are presented
by Reddy et_ al.  (1979).

     The field experiment of Rolston jjt al. (1978) consisted of six, 1-m2
field plots maintained at two soil-water contents near water saturation and
at three C levels established by applying manure (3.4 x 10** kg ha l in the
top  10 cm of soil)  to  some plots, cropping some plots with perennial ryegrass,
and  leaving some plots uhcropped.  These experiments were conducted during
the  summer and the  winter to obtain two temperature levels.  Steady state
soil-water contents were maintained in the soil profile during the denitri-
fication process by small but frequent irrigations each day.  These field
experiments by Rolston et al. (1978) will subsequently be referred to as
"constant water" plots throughout this report.  The constant water plots were
used to develop  the empirical water function, fw, in Eq. [1] by forcing the
calculated denitrification to be the same as that measured for the two plots
at different soil-water  contents.  The water function is further described in
the  "Comparison  of  Calculated and Measured Denitrification" section of this
report.  After the  water function was  developed and the denitrification rate
constant for the two plots determined,  the same water function and rate
constant k^ were used  to  calculate denitrification for the other ten constant
water experiments.   The  effect  of the  crop root system through the additional
C it added and 02 depletion  which resulted also increased denitrification.
The  rate constant required for  cropped plots was approximately four times
greater than that for  the uncropped plots.

     The water function  and  the denitrification rate constant determined from
the  constant water  plots  were subsequently used to calculate denitrification
for  field experiments  described in this report.  These plots will subsequent-
ly be referred to as the "irrigation frequency" plots in this report.

     Denitrification in  the  constant water plots and irrigation frequency
plots was determined by measuring the  flux of N20 and N2 gases at the soil
surface after  the addition of 15N03 fertilizer.  The uptake of 15N by the
grass as a function of time  was used as input data in the denitrification and
N transport model.

     Soil-water  content  and  pressure head were measured at frequent intervals
in all plots and these data  were used  to check the calculated soil-water
contents predicted  by  the model,  especially in the irrigation frequency
plots.  For the irrigation frequency plots, it became immediately apparent
that the predicted  soil-water contents  versus time after each irrigation

                                      44

-------
were smaller than those measured values.  For four plots,  it was necessary to
decrease the estimated ET by 50 to 85% in order to attain  a reasonable com-
parison of calculated and measured water contents within the soil profile.
The ET may have been underestimated due to placement  of  covers over the plots
for up to eight hours on some days and to decreased transpiration from short,
clipped grass.

     Soil-water characteristic curves at various depths  for the Yolo soil
were taken from Rolston and Broadbent (1977) and LaRue e_t  al.  (1968).  The
relationship between hydraulic conductivity and soil-water content was
taken from LaRue et al. (1968) for a Yolo loam field  site  within 100 m of
the plots used  for direct measurement of denitrification.

COMPARISON OF CALCULATED AND MEASURED DENITRIFICATION

     Comparisons of the measured and calculated denitrification flux as a
function of time for two constant water plots with manure  during the summer
(23°C) are given by Figure 33.  The solid circles are measured values of
          80
        2 50
        X40
           30
        O
         r-20

           10
            0
Total (kgNha-')10
  •   218
   — 206
•	209    8

             6
                  h= -15cm
         Summer
*        Manure
                 Tola I (kgN ha1)
      Measured   •  47
Calculated-1storder— 57
          -0*brder--50
                                                          70cm
             "024    6    8   10   12   14   16   18   20
                               TIME   (days)
Figure 33.   Measured  and calculated surface fluxes  of  denitrification
            products  (N£ + N£0) as a function of time  for two manure-amended
            plots maintained at two different values of soil-water pressure
            head, h.
                                    45

-------
the N2 and N20 flux, and  the solid  line  is  the  calculated  denitrification
flux assuming first-order kinetics  as  derived by Eq.  [1].   The rate  coeffi-
cient, klf used for the calculations in  Figure  33,  was  1.68 x ICT1* g soil
day 1 (ug C) 1.  Since N03 concentrations within the  soil  profile were gen-
erally large in all plots, it might be_assumed  that denitrification  followed
zero-order kinetics with  respect  to NO^  concentration rather than first-order
kinetics as given by Eq.  [1],  For  zero-order kinetics,  the denitrification
rate is given by:
Where ko is the  zero-order denitrification constant  and the other functions
and coefficients are  the  same  as  in Eq.  [1].   The broken line in Figure 33
is the calculated denitrification rate  assuming zero-order kinetics  (Eq.
[6]).  The zero-order rate coefficient,  kg, used for the calculations  in
Figure 33 was 0.046 ug N  day  l (ygC)  1.   The  zero-order model does not
predict the large denitrification rate  that occurred immediately after the
NOs was applied.  The first-order equation describes these large initial
rates better than does the zero order case.

     The calculated denitrification rates given in Figure 33 were developed
using the water  function, f,,,  in  Figure 34.   The water function was  developed
by forcing the calculated amounts of denitrification for the indicated period
in the two plots shown in Figure  33 to  be approximately equal to the mea-
sured values.  The water  function in Figure 34 is an empirical relationship
which explicitly implies  a relative degree of anoxic development for these
field plots.  The water function  provides a simple way of accounting for the
change in 02 diffusion and storage in the soil as the soil-water content
changes.  Denitrification becomes essentially zero below 80% of the  saturated
water content value.  The maximum potential for denitrification would  occur
at saturation where all pores  are completely  filled  with water, and  the
diffusion of 02  is limited to  diffusion through water.

     Total denitrification, as determined by  integrating the flux versus time
data, is also given in Figure  33.  Comparisons of total denitrification for
all 12 of the constant water plots are  given  in Table 7.  The same water
function presented in Figure 34 was used to calculate denitrification  for all
plots.  Also, the same denitrification  rate constant was used for all  plots
except those cropped  with grass.   The constant required to describe  denitri-
fication from plots cropped with  grass  was approximately 3.6 times greater
than that for the other plots  due to the effect of the root system in  con-
suming 02 and in adding soluble C to the soil.

     The denitrification  rate  constant  (6 x lo"1* g soil day"1 (ugC)""1),
determined for the cropped plots  of the constant water experiments and the
water function of Figure  34, were subsequently used  in calculating denitri-
fication for the six  irrigation frequency plots of this report.  Figure 35
gives the surface flux of N20  plus N2 for the plots  receiving three  irriga-
tions per week (1. 15  ET) .  The arrows at the  top of  the figure indicate when
the irrigation was made.  The  top and bottom  sections of Figure 35 are for
plots without and with added straw, respectively. Note that the scales of


                                      46

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TABLE 7.  COMPARISON OF MEASURED AND CALCULATED DENITRIFICATION FROM CONSTANT
          WATER PLOTS ON YOLO LOAM SOIL.   A VALUE OF kx  OF 1.68 x 10'^ g SOIL
          DAY"1 (ygC)"1 WAS USED FOR THE  MANURE AND UNCROPPED CALCULATIONS.
          A VALUE OF kx OF 6 x 10"^ g SOIL DAY'1 (ygC)"1 WAS USED FOR THE
          CROPPED CALCULATIONS

Denitrificatlon
Temperature
°C
23
23
23
23
23
23
8
8
8
8
8
8
Treatment
Manure, h = -15 cm
Manure, h = -70 cm
Cropped, h = -15 cm
Cropped, h = -70 cm
Uncropped, h = -15 cm
Uncropped, h = -70 cm
Manure, h = -8 cm
Manure, h = -50 cm
Uncropped, h = -8 cm
Uncropped, h = -50 cm
Cropped, h = -8 cm
Cropped, h = -50 cm
Measured
kg N
218
47
40
9
10
4
33
30
0.4
0.4
19
2
Calculated
ha""1
206
57
47
8
15
2
52
0
3
0
21
1
                                     47

-------
               1.0
            z
            O
            u°-6
            z
            o:
            ^ 0.2
                o
                 0.5     0.6     0.7     0.8    0.9     1.0
                   RELATIVE WATER CONTENT, Q/QS
Figure 34.  The dependence  of  the empirical water function,  fy,  (Eq. [1]) on
            relative soil-water content (water content/saturated water
            content).


the ordinate are greatly different for the top and bottom sections of the
figure (Figures 36 and 37 also).  It is also important  to recall that the
minimum detection limit for N£ flux was in the neighborhood  of 0.1 to 0.2 kg
N ha"1 day"1.  Thus, many of the data points for the top  section of each
figure are highly uncertain.   The data points are the measured denitrifica-
tion flux and the solid lines  are calculated denitrification rates using the
simulation model assuming first-order kinetics.  The total measured and
calculated denitrification  are also given in each section for each plot.-
The data in Figure 35  illustrate that both denitrification rate  and total
denitrification were described reasonably well using the  model.

     Figures 36 and 37 give the denitrification flux as a function of time
for the plots irrigated once per week and once every two  weeks,  respectively.
Again, the data in Figures  36  and 37 illustrate that the  calculated denitri-
fication compares reasonably well with measured rates and total  amounts of
denitrification.
                                    48

-------
  0.8

  0.7


  0.6


  05


  0.4


10.3

7ro
^0.2
D)
~ 0.1
x
il  0


^,4.0

  3.2

  2.4

   1.6

  OB
                   0
                       V V  vVV   V V V   VVV  YVV   vVv
                                              Plot A  Total(kgNha1)
                                              No Carbon added
                                         —•  Measured    4.1

                                           — Calculated    3D
                                             Plot D   Total (kgN ha'1)
                                             Straw added
                                           •  Measured    143

                                          —  Calculated    12.8
                     0       8        16       24
                               Time     (Days)
                                       32
40
Figure 35.  Measured and calculated surface  fluxes  of denitrification
            products (N2 + N20) as a function  of  time for plots with and
            without straw incorporation at an  irrigation frequency of  three
            irrigations per week.  The solid lines  are simulations based  on
            Eq.  [1].  The broken lines simply  connect measured data points.
            Arrows indicate time of irrigation.   Note that the scales  of  the
            ordinate are greatly different for the  "no straw" and "straw"
            plots.
                                       49

-------
                 O8
                 0.6
                 0.4
                 02
               O)
               x
                  0
                  10
                  8
                  6
       r~r
                                                                 r
   Rot B    Total (kgNha1)
   No Carbon added
 •  Measured      312
— Calculated     3.7
   -        •      •    1
   4-^	1	1	1	1	h
                                       1      I
   Plot E    Total (kgNhS1)
   Straw added
   Measured    ia4
   Calculated   22.3
0      8       16      24      32
            Time     (Days)
                                                         40
                     48
Figure 36.   Measured and  calculated surface  fluxes of denitrlfication
             products (N2  + N20) as a function of time; for plots with and
             without straw incorporation for  an irrigation frequency of one
             irrigation per week.  The calculated lines are simulations based
             on Eq. [1].   Arrows Indicate time of irrigation.  Note that the
             scales of the ordinate are greatly different for  the  "no straw"
             and "straw" plots.
                                        50

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 0.6


 0.5

 0.4


 Q3

 0.2


 0.1

  0
 6.0

 5.0
i

 4.0

 3.0
                 2.0
                  1.0
                                            Rot C      Total (kg N ha"1)
                                            No Carbon added
                                            Measured       1.9
                                            Calculated       20
                           •
                       H	H
                                                    1	1
                                            Plot F      Total (kgNha')

                                            Straw added

                                            Measured      5.1
                                            • Calculated      3.9
                                 A.
                           •.  •  . /•^.   ,«   i«   . ••«,
   0       8       16      24
                 Time   (Days)
                                                   32
40
48
Figure 37.   Measured and  calculated surface  fluxes of denitrification
             products (N2  + N£0)  as a function of time for plots with and
             without straw incorporation for  an irrigation frequency of one
             irrigation every two weeks.   The calculated  lines are simulations
             based on Eq.  [1].   Arrows indicate time of irrigation.  Note  that
             the scales of the  ordinate are greatly different for the "no
             straw" and "straw" plots.
                                        51

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     Simulations of denitrification were sensitive to the empirical water
function in Figure 34.   Figure 38 gives three hypothetical water content
(15 cm depth) versus  time  curves  for the one irrigation per week irrigation
frequency plot with straw  added.   Line B in Figure 38 is the soil-water
content calculated by the  model for Plot E (Figure 36).  Lines A and C are
0.01 cm3 cm"3 larger  or smaller,  respectively, than the soil-water content
represented by curve  B. For differences in soil-water content of 0.01
cm3 cm"3 (Figure 38), the  calculated denitrification was different by
approximately a factor of  two.
               'E
               u
               IE
               u
               o
               (J
               ro
0.42

0.40

0.38

0.36

Q34

0.32
                 9
                 TO
                 I
                 X  41
                 li.  3
                 q, 2
                    0
                           Total Denitrification
                                    kgNha-'
                               A  -   37
                               B  -   22
                               C  -   12
 Figure 38.  Three hypothetical  soil-water content versus time curves for an
             irrigation frequency  of  one irrigation per week for plots with
             straw incorporation.


      The sensitivity of denitrification to the soil-water function makes it
 difficult to accurately simulate  denitrification for field situations.
 Measured water contents in  the  field frequently vary by as much or more than
 the ± 0.01 cm3 cm"3 considered  in Figure 38.   For a site adjacent to the
 plots of Rolston et al. (1978)  and those of this report, Simmons et al.
                                       52

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 (1959) measured standard deviations of ±  0.02-0.03  cm3  cm"3  for 16  soil-
water content measurements  (at one depth) from a 1  ha field.   Thus,  it would
be desirable to have a function which accounted  for the degree of anoxic
development in the soil which was not as  sensitive  as the  empirical  water
function given in Figure 34.  On the other hand,  a  function  which accounted
for diffusion of 02 in the macropores and diffusion of  02  through water films
or into aggregates could be equally sensitive to  the diffusion rate  of 02 in
the water, the size of the microsites, and the consumption of  02 by  micro-
organisms and roots.  It is probable that the sensitivity  demonstrated in
this model due to the empirical water function is indeed real.   Therefore,
one would expect that denitrification would vary  substantially from  spot to
spot in a field.  In fact, the concept of microsites as  sites  of denitrifica-
tion requires that denitrification be sensitive  to  the  amount  of soil  water
and the diffusion of 02 to zones of high microbial  activity.   It is  not known
whether the water function developed for  these Yolo loam soil  field  sites can
be extrapolated to other soils.  Considerably more  research  is needed  on
other soil types to determine whether soil-water content or 02  diffusion is
the most sensitive and which procedure could be more easily extrapolated to
other situations.

MANAGEMENT SIMULATIONS

     The simulation model described and used in  this manuscript can  be used
to calculate potential denitrification losses for various  soil-water,  soil,
and crop management situations.  For example, total denitrification  for six
hypothetical cases involving the possibilities of applying NOs  fertilizer with
irrigation water are given in Table 8.  All input data  for the simulations


TABLE 8.  TOTAL DENITRIFICATION (kg N ha"1) CALCULATED  FOR VARIOUS WAYS OF
          APPLYING NOa FERTILIZER DURING  ONE IRRIGATION  CYCLE  OF CROPPED
          SOIL TO WHICH STRAW WAS APPLIED 43 DAYS PRIOR TO FERTILIZATION.
          SIMULATIONS WERE MADE FOR APPROXIMATELY 40 DAYS AFTER FERTILIZA-
	TION	

                              Fertilizer timing

                   Applied uniformly      Applied during      Applied  during
 Irrigation          during entire          1st 1/3 of          last 1/3 of
 frequency            irrigation            irrigation          irrigation


3 Irrigations            10.7                  13.8               14.3
  per week

1 Irrigation              4.6                   2.8                 5.4
  per two
  weeks
                                      53

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are the same as those used in Figures 35 and 37  (straw addition) with  the
exception of when the NO^ fertilizer was applied.   Simulations of  denitrifi-
cation were made for applying NOs fertilizer uniformly during the  entire
first irrigation, during the first one-third of  the first  irrigation,  and
during the last one-third of the first irrigation.   For each of  these  three
timings of fertilizer application during irrigation,  two irrigation  frequen-
cies of three irrigations per week and one irrigation every two weeks  were
used.  The calculations given in Table 8 demonstrate that  the fertilizer
application time did not affect denitrification  significantly for  the  fre-
quent irrigation system.  This was due primarily to the fact that  only small
amounts of water were applied at any one time  and the NO^  resided  at about
the same position in the soil profile regardless of whether it was applied
during the first one-third or the last one-third of the irrigation cycle.
Denitrification was calculated to be slightly  greater by applying  fertilizer
during one-third of the cycle than for the case  where the  fertilizer was
applied uniformly throughout the first irrigation period (Table  8).  This is
primarily due to the increased NO3 concentration in the narrow band  when  the
same quantity of fertilizer is applied in one  third the water.

     The computed values in Table 8 suggest, however, that the timing  of
fertilizer application may be more important for the infrequent  irrigation
system.  If the fertilizer were applied during  the first one-third  of the
first irrigation for an infrequent irrigation  program, the NO3 will  be pushed
deeper into the soil profile during successive irrigations and less  denitri-
fication occurs than that calculated for a uniform application during  the
irrigation.  If the fertilizer were applied during the last one-third of the
first irrigation, the NO3 remains in the upper part of the soil  profile and
is susceptible to denitrification.  The calculated denitrification for this
case was only slightly greater than that for the case where the  fertilizer
was applied uniformly during the irrigation process.

     Other management simulations demonstrate  that increasing the  soil
organic C level by three or four times would result in only a 10 to  20%
increase in denitrification.  This is due to the fact that only  a  small part
of the soil organic C is water soluble or available for denitrification.
                                      54

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                                 REFERENCES
Allison, L.E.  1965.  Organic carbon.  In:  Methods of Soil Analysis, Part 2,
     C.A. Black (ed.).  Agronomy, 9:1367-1378.

Bremner, J.M.  1965.  Inorganic forms of nitrogen.  In:  Methods of Soil
     Analysis, Part 2, C.A. Black (ed.).  Agronomy, 9:1179-1237.

Burford, J.R., and J.M. Bremner.  1975.  Relationships between the denitrifi-
     cation capacities of soils and total, water-soluble and readily
     decomposable soil organic matter.  Soil Biol. Biochem., 9:389-394.

Davidson, J.M., D.A. Graetz, P.S.C. Rao, and H.M. Selim.  1978.  Simulation
     of nitrogen movement, transformation, and uptake in plant root zone.
     Ecological Research Series.  EPA 600/3-78-029.  U.S. Environmental
     Protection Agency, Athens, Georgia.  106 pp.

Donigian, Jr., A.S., and N.H. Crawford.  1976.  Modeling pesticides and
     nutrients in agricultural lands.  EPA-600/2-76-043.  U.S. Environmental
     Protection Agency, Athens, Georgia.  318 pp.

Fried, M., K.K. Tanji, and R.M. Van De Pol.  1976.  Simplified long term
     concept for evaluating leaching of nitrogen from agricultural land.
     J. Environ. Quality,. 5:197-200.

Hahn, J.  1972.  Improved gas chromatographic method for field measurement of
     nitrous oxide in air and water using a 5 A molecular sieve trap.  Anal.
     Chem., 44:1889-1892.

LaRue, M.E., D.R. Nielsen, and R.M. Hagan.  1968.  Soil water flux below a
     ryegrass root zone.  Agron. J., 60:625-629.

Mehran, M., and K.K. Tanji.  1974.  Computer modeling of nitrogen transforma-
     tions in soils.  J. Environ. Quality, 3:391-396.

Rao, P.S.C., J.M. Davidson, R.E. Jessup, and K.R. Reddy.  1980.  Simulation
     of nitrogen and phosphorous behavior in cropped land areas receiving
     organic wastes.  EPA-600/    -80.  U.S. Environmental Protection Agency,
     Athens, Georgia,  (in review)

Rasmussen, R. A., J. Krasnec, and D. Pierott.  1976.  Nitrous oxide analysis
     in the atmosphere via electron capture-gas chromatography.  Geophys.
     Res. Lett.  3:615-618.
                                     55

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Reddy, K.R., R. Khaleel, and M.R. Overcash.   1979.  A nonpoint  source model
     for land areas receiving animal wastes:  V.   Carbon  transformations.
     Water Research,   (in press)

Rittenberg, D.  1948.   The preparation  of gas samples for mass  spectrographic
     isotope analysis,  p. 31-42.  E.W. Wilson, A.O.C. Nier,  and
     S.F. Reinmann  (eds.).  Preparation and Measurement of  Isotopic  Tracers.
     J.W. Edwards,  Ann Arbor, Mich.

Rolston, D.E., M. Fried, and D.A. Goldhamer.  1976.   Denltrification measured
     directly from  nitrogen and nitrous oxide gas  fluxes.  Soil Sci. Soc.
     Am. J., 40:259-266.

Rolston, D.E., and  M.A. Marino.   1976.  Simultaneous  transport  of nitrate and
     gaseous denitrification products in soil.  Soil  Sci. Soc.  Am. J.,
     40:860-865.

Rolston, D.E., and  F.E. Broadbent.   1977.  Field measurement  of denitrifica-
     tion.  EPA-600/2-77-233.  U.S.  Environmental  Protection  Agency, Ada,
     Oklahoma.  75  pp.

Rolston, D.E., D.L. Hoffman, and  D.W. Toy.  1978.   Field  measurement of
     denitrification:   I.  Flux of N2 and N20.  Soil  Sci. Soc.  Am. J.,
     42:863-869.

Rolston, D.E., F.E. Broadbent, and D.A. Goldhamer.   1979.  Field measurement
     of denitrification:  II.  Mass  balance and sampling  uncertainty.  Soil
     Sci. Soc. Am.  J.,  43:703-708.

Ryden, J.C., L.J. Lund, J. Letey, and D.D. Focht.   1979.  Direct measurement
     of denitrification loss from soils.  II. Development  and  application
     of field methods.  Soil Sci. Soc.  Am. J., 43:110-117.

Shaffer, M. J., R.  W.  Ribbens, and C. W. Huntley.   1977.  Prediction of
     Mineral Quality  of Irrigation Return Flow.  Volume V.  Detailed Return
     Flow Salinity  and Nutrient Simulation Model.   EPA 600/2-77-179e.  U.S.
     Environmental  Protection Agency, Ada, OK.  229 pp.

Simmons, C.S., D.R. Nielsen, and  J.W. Biggar. 1980.  Scaling of field
     measured soil-water properties.  Hilgardia.   (in press)

Tanji, K.K., and S.K.  Gupta.  1978.  Computer simulation  modeling for
     nitrogen in irrigated croplands,   p. 79-130.   In:  D.R.  Nielsen and
     J.G. MacDonald,  (eds.).  Nitrogen  in the Environment,  Vol. I.   Nitrogen
     behavior in field soil.  Academic  Press, New  York, N.Y.
           \
van Veen, H.  .1977.  Behavior of nitrogen in  soil.  A computer  simulation
     model.  Ph.D.  Thesis, Wageningen,  The Netherlands.

Yeomans, J.C., and  E.G. Beauchamp. 1978.   Limited inhibition of nitrous
     oxide reduction  in soil in the  presence  of acetylene.  Soil Biol.
     Biochem., 10:517-519.


                                      56

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                                PUBLICATIONS
     The following manuscripts have to date resulted from  this  research:

Rolston, D.E., and S. Cervelli.  1978.  Denitrification as affected by
     irrigation frequency and applied herbicides.  Combined FAD/IAEA Advisory
     Group and Research Coordination Meeting on Isotopic Tracer-Aided Studies
     of Agrochemical Residue-Biota Interactions in Soil and Water, Vienna,
     Austria.

Sharpley, A.N., and D.E. Rolston.  1980.  Comparison of the acetylene
     inhibition and *5N methods for the direct field measurement of
     denitriflcation loss from soils.  Soil Sci. Soc. Am. J.  (submitted)
                                     57

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                                   TECHNICAL REPORT DATA
                            (Please read Instructions on the reverse before completing)
  REPORT NO.
  EPA-600/2-80-066
             3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE

DENITRIFICATION AS AFFECTED BY  IRRIGATION FREQUENCY
OF A  FIELD SOIL
             5. REPORT DATE
              April  1980 issuing date
             6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
D. E.  Rolston, A. N. Sharpley,  D.  W.  Toy, D. L. Hoffman,
and F.  E.  Broadbent
             8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Land,  Air and Water Resources
University of California
Davis, California  95616
             10. PROGRAM ELEMENT NO.
                1HB617
             11. CONTRACT/GRANT NO.

                R-805550
12. SPONSORING AGENCY NAME AND ADDRESS
Robert S.  Kerr Environmental Research Laboratory
Office of Research and  Development
U.S.  Environmental Protection Agency
Ada,  Oklahoma  74820
             13. TYPE OF REPORT AND PERIOD COVERED
                Final
             14. SPONSORING AGENCY CODE
                EPA/600/15
15. SUPPLEMENTARY NOTES
16. ABSTRACT
The influence of irrigation frequency on dentrification was studied on a Yolo loam
field profile at Davis,  California.  Two carbon treatments were also established by
using plots with and without incorporated crop residues.  Irrigation frequencies of
three irrigations per  week, one irrigation per week,  and one irrigation every two
weeks were established on areas cropped with  grass.   Fertilizer was applied as KNOs
enriched with 15N to 1-m2 plots.  The flux of volatile gases at the soil surface was
measured from the accumulation of N20 and 15N£ beneath airtight covers placed over the
soil surface for 1  to  4 hours at several times after  irrigation.  For plots with and
without addition of crop residue, the largest denitrification was only 6.5 and 1.5^
of the applied fertilizer (300 kg N ha"1), respectively.  Denitrification from the
least frequently irrigated treatments was less than that in the most frequently irri-
gated treatments.   The N20 flux at the soil surface varied between 5 and_27% of the
total denitrification  over a 40 to 50 day period.   Denitrification of NOs fertilizer
was simulated using a  mathematical model that included transport and plant uptake  of
water and nitrogen  in  soil.  Reasonable agreement  was found between measured rates
and total amounts of denitrification with those calculated from the model.
17.
                                KEY WORDS AND DOCUMENT ANALYSIS
                  DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS  C. COSATI Field/Group
 Nitrogen cycle
 Nitrogen isotopes
 Nitrous oxide (N20)
 Soil water
 Fertilizer
 Irrigation
  Denitrification
  Irrigation return flow
  Nitrate leaching
  Gas fluxes
  Simulation modeling
02/A,c
18. DISTRIBUTION STATEMENT
 RELEASE TO PUBLIC
19. SECURITY CLASS (ThisReport)
  Unclassified	
                                                                         21. NO. OF PAGES
    74
                                              20. SECURITY CLASS (Thispage)
                                                Unclassified
                                                                         22. PRICE
EPA Form 2220-1 (9-73)
                                            58
                                                             (, U.S. GOVERHUEHT PRINTING OFFICE: 1980-657-146/5652

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