&EFA
          United States     Office of Air Quality
          Environmental Protection  Planning and Standards
          Agency       Research Triangle Park NC 27711
                      EMB Report 79-NHF-13
                      June 1979
          Air
Development of
Analytical Procedures for
the Determination of
Urea from Urea
Manufacturing Facilities

Evaluation Test Report
Agrico Chemical Company
Blytheville, Arkansas

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                                          DEVELOPMENT OF ANALYTICAL PROCEDURES
                                                 FOR THE DETERMINATION OF UREA
                                            FROM UREA MANUFACTURING FACILITIES

                                                         PROJECT NO.  79-NHF-13
Thomas M. Bibb
EPA Project Manager

Clyde E. Riley
EPA Technical Manager

EPA Contract No. 68-02-2820
Work Assignment 11

TRC Project 0988-E80-01
WILLARD A. WADE III, P.E.
   SENIOR PROJECT MANAGER
                \
          ERIC A. PEARSON
        PROJECT SCIENTIST

          MARGARET M. FOX
          PROJECT CHEMIST

            July 31, 1980

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                                     PREFACE









    The work reported herein was performed by  personnel  from TRC Environmental




Consultants, Inc.  (TRC)  and the  U.S. Environmental  Protection Agency  (EPA).




The scope of work,  issued under EPA Contract  No. 68-02-2820,  Work  Assignment




Number 11 (and as part of Work Assignments 9,  19, and  20)  was under  the  super-




vision  of  the TRC  Project Manager,  Mr. Willard  A.   Wade III.   Mr.  Eric  A.




Pearson of  TRC was responsible for  summarizing the  test and  analytical  data




presented in this report.  Chemical  analyses were performed  at the TRC labora-




tory  in Wethersfield,   Connecticut   under  the  direction  of  Ms.  Joanne  M.




Marechese and Ms. Margaret M.  Fox.




    Mr.  Gary   D.  McAlister, Office   of  Air Quality   Planning  and  Standards,




Emission Measurement  Branch,  EPA,  served as  Lead Chemical  Engineer and  was




responsible for  developing and evaluating  the analytical  procedures used  in




this report.




    Mr. Clyde E.  Riley, Office of Air Quality  Planning and Standards,  Emission




Measurement Branch, EPA,  served as  Technical  Manager  and was  responsible  for




coordinating this method evaluation program.
                                      -ii-

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                                            TRC-Environmental Consultants,  Inc.
                                                Willard A.  Wade III,  P.E.
                                                     Project Manager

                                                      July  31,  1980
NOTE:  Mention of trade  names  or  commercial products in this publication  does
       not constitute endorsement or recommendation for use by  the  Environmen-
       tal Protection Agency
                                     -111-

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                                TABLE OF CONTENTS

SECTION                                                                   PAGE

  1.0             INTRODUCTION  	       1
      1.1           Background	       1
      1.2           Introduction to Urea and Ammonia Analysis Methods .       1
          1.2.1       Urea Analysis Methods 	       2
          1.2.2       Ammonia Analysis  Methods  	       3
      1.3           Analytical Method  Investigations  	       3
      1.4           Description of Report Sections  	       5

  2.0             SUMMARY OF RESULTS AND CONCLUSIONS.'	       6
      2.1           Comparison of TRC arid  Agrico Scrubber Outlet
                      Gas Stream Analyses  	       6
      2.2           .Urea Audit Samples  -  Comparison of  TRC and Agrico
                      Analyses	      11
      2.3           Preservation of Urea Samples	      13
          2.3.1       Granulator C Scrubber Outlet Gas  Stream Sample
                        Preservation  	      13
          2.3.2       Preservation of Laboratory Urea Samples 	      22
      2.4           Ammonia Interference  on Urea Analysis 	      30
      2.5           Evaluation of Standard Procedures for the Proposed
                      EPA Urea Analytical  Method	      33
          2.5.1.       Effects of Preliminary Distillation 	      33
          2.5.2       Sulfuric Acid Interference	      37
      2.6           Threshold Minimum Detectable Limit  for the Proposed
                      EPA Urea Analytical  Method	      38
          2.6.1       Laboratory Evaluation of  the Absolute Urea
                        Detection Threshold 	      39
          2.6.2       Low Level Urea Analysis in the  Field	      46
      2.7           Collection Efficiency  Determination of the EPA Urea
                      Sampling Train 	      48
      2.8           Conclusions	      49

  3.0             DISCUSSION OF ANALYSIS PROCEDURES 	      52
      3.1           Preservation Analyses  	      52
          3.1.1       Field Sample Preservation Analyses	      52
          3.1.2       Laboratory Sample Preservation  Analyses 	      55
      3.2           Ammonia Interference on Urea Analysis 	      56
      3.3           Evaluation of Standard Procedures for the Proposed
                      EPA Urea Analytical  Method	      56
          3.3.1       Effects of Preliminary Distillation 	      57
          3.3.2       Sulfuric Acid Interference	      58
      3.4           Threshold Minimum Detectable Limit  for the Proposed
                      EPA Urea Analytical  Method	      61
          3.4.1       Laboratory Evaluation of  the Urea Detection
                        Threshold	      61
          3.4.2       Low Level Urea Analysis in the  Field	      62
      3.5           Collection Efficiency  Determination of EPA Urea
                      Sampling Train 	      64
          3.5.1       Sampling Methods   	      64
          3.5.2       Sample Recovery and  Preparation 	      64
          3.5.3       Sample Analysis	      66
                                      -iv-

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                                LIST OF FIGURES

Figure                                                                    Page

2-1             Interference Effects of Ammonia on Urea Analysis.  .  .        32

2-2             Urea Threshold of  Detection Determination -  Set  1,
                  1 cm Cell	        41

2-3             Urea Threshold of  Detection Determination -  Set  2,
                  1 cm Cell	        42

2-4             Urea Threshold of  Detection Determination -  Set  1,
                  5 cm Cell	        43

2-5             Urea Threshold of  Detection Determination -  Set  2,
                  5 cm Cell	        44

2-6             Urea Threshold of  Detection Determination -  Data.  .  .        47

3-1             Modified EPA Particulate Sampling  Train,  August  18,
                  1977,  Federal Register.  	        65
                                      -v-

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                                 LIST OF TABLES

Table                                                                     Page
2-1             TRC and Agrico Urea Analysis Results from "C"
                  Granulator Scrubber Outlet Gas-Stream at Agrico
                  Chemical Company  	
2-2             TRC and Agrico Ammonia Analysis Results from "C"
                  Granulator Outlet Gas-Stream at Agrico Chemical
                  Company 	
2-3             Results of Urea Audit Sample Analyses Performed by
                  TRC and Agrico at Agrico Chemical Company,
                  Blytheville, Arkansas 	        12

2-4             Agrico Granulator C Scrubber Outlet Gaseous Sample
                  Preservation - Test Run Number 1	        15

2-5             Agrico Granulator C Scrubber Outlet Gaseous Sample
                  Preservation - Test Run Number 2	        16

2-6             Agrico Granulator C Scrubber Outlet Gaseous Sample
                  Preservation - Test Run Number 3	        17

2-7             Agrico Granulator C Scrubber Outlet Gaseous Sample
                  Preservation - Test Run Number 4	        18

2-8             Agrico Granulator C Scrubber Outlet Gaseous Sample
                  Preservation - Test Run Number 5	        19

2-9             Agrico Granulator C Scrubber Outlet.Gaseous Sample
                  Preservation - Test Run Number 6	        20

2-10            Least-Squares Linear Regression Results  Agrico
                  Granulator C Scrubber Outlet Gaseous Sample
                  Preservation	        21

2-11            Laboratory Urea Sample Preservation Analysis Results
                  for Solution A:  40 ppm,  No Preservative	        24

2-12            Laboratory Urea Sample Preservation Analysis Results
                  for Solution B:  100 ppm,  No Preservative	        25

2-13            Laboratory Urea Sample Preservation Analysis Results
                  for Solution C:  40 ppm,  HgCl_ Preservative  ....        26

2-14            Laboratory Urea Sample Preservation Analysis Results
                  for Solution D:  100 ppm,  HgCl_ Preservative  ...        27

2-15            Laboratory Urea Sample Preservation Analysis Results
                  for Solution E:  40 ppm,  H so  Preservafcive  ....        28

2-16            Laboratory Urea Sample Preservation Analysis Results
                  for Solution F:  40 ppm,  H SO  Preservative  ....        29
                                            £  ^x
                                      -vi-

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                           LIST OF TABLES (Continued)

Table

2-17            Results of Interference Effects of Ammonia on Urea
                  Analysis	       31

2-18            Comparison of EPA Audit Samples and TRC Urea
                  Standards	       35

2-19            Distilled and Undistilled Urea Calibration Curves
                  for the P-Dimethylaminobenzaldehyde Analysis
                  Method	       37

2-20            Data from Urea Threshold of Detection Determination .       40

2-21            Urea Sampling Train Collection Efficiency Results
                  at Union Oil Company, Brea, California	       50
                                   APPENDICES
APPENDICES

   A            Urea Sampling and Analysis Procedures
     A.I          Original Method - August 1979
     A.2          Modified Method - August 1979
     A.3          Modified Method - January 1980
     A.4          Proposed EPA Reference Method 28
     A. 5          Kjeldahl Analysis Method

   B            Ammonia Analysis Procedures

   C            Preservation Analyses
     C.I          Field Sample Preservations
     C.2          Laboratory Sample Preservations

   D            Ammonia Interference on Urea Analysis

   E            Evaluation of Standard Procedures for Proposed EPA Urea
                  Analytical Method
     E.I          Effect of Preliminary Distillation
     E.2          Sulfuric Acid Interference

   F            Threshold Minimum Detectable Limit for the Proposed
                  EPA Urea Analytical Method

   G            Urea Sampling Train Collection Efficiency

   H            Scope of Work
                  .  Work Assignment
                  .  Technical Directives
                                     -vii-

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 1.0 INTRODUCTION




 1.1 Background




    Section  111 of  the  Clean Air Act of 1970 charges  the  Administrator  of the




 United States Environmental  Protection  Agency  (EPA)  with the responsibility of




 establishing Federal  standards of  performance  for  stationary sources which may




 significantly contribute  to  air  pollution.   When  promulgated,  these standards




 of performance for new  stationary  sources  (SPNSS)  are  to reflect the degree of




 emission  limitation achievable  through application of  the  best  demonstrated




 emission control  technology.  Emission  data, collected from controlled sources




 in the particular industry of concern,  provide a portion of the data base used




 by EPA to develop SPNSS.




    In  the  development  of  SPNSS,  EPA  follows  a  policy  of  establishing




 reference sampling and  analysis  methods  for each  regulated source  category and




 pollutant.  Current emphasis  on  the control of urea particulate emissions has




created a need for a urea analysis reference method.




    This report .presents  the results of urea analytical method investigations




conducted under EPA Contract #68-02-2820 as Work  Assignment Number 11  and  as




part of Work Assignment Numbers  9,  19,  and  20.   These  results  will  be used  as




 a data base for the development of a urea analysis reference method.









 1.2 Introduction to Urea and Ammonia Analysis Methods




    Two  urea analysis  methods  and  three  ammonia analysis methods have  been




used by EPA and its contractors  during  the  emission  testing programs conducted




 for the  development of  SPNSS for  the  urea manufacturing  industry.  Each  of




 these  analysis  methods  and   their  variations  are briefly  described  in  this




 section.   The methods themselves are presented in  their  entirety in Appendices




A and B.
                                  -1-

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     1.2.1  Urea Analysis  Method

           P-dimethylaminobenzaldehyde  (PDAS) Method

           o   Direct  Method;  The  PDAB color  reagent  is added  to the  sample,
              and  after color development  has  occurred the  absorbance of this
              solution  is measured with a  blank-zeroed spectrophotometer.  The
              measured  absorbance  is  related  to  urea concentration  through a
              calibration curve  prepared from the absorbances  of standard urea
              solutions.

           o   Preliminary Distillation  Method;  A  buffering compound  is added
              to the sample  and  this  solution is  then distilled  (boiled)  to
              remove  ammonia  and  other   potential  interferences.    The  PDAB
              reagent  is  then added and the  solution  absorbance is measured as
              in the direct method.

           Kjeldahl Method

           o   Direct Method  with Preliminary  Distillation to Remove Ammonia;  A
              buffering compound is added  to the  sample and  this  solution is
              then  distilled  (boiled)  to  remove  ammonia.   Digestion reagents
              are then  added  to  convert all organic nitrogen (urea) to ammonia,
              the  solution  is distilled,   and  the distillate  is  analyzed  for
              ammonia  either  by direct  nesslerization or  by  titration.   The
              urea concentration is then calculated  stoichiometrically from the
              measured ammonia concentration.

           o   Indirect  Method;   Two  equal  aliquots  of  sample  are  drawn.   A
              buffering compound is added  to the  first aliquot  and this solu-
              tion is  then distilled.   The distillate  is  analyzed  for ammonia.
              The  digestion  reagents  are  added  to  the  second aliquot,  con-
              verting organic  nitrogen  (urea) to ammonia.   The solution is then
              distilled and  this distillate  is  analyzed  for  ammonia.   Urea
              concentration  is   calculated   by  subtracting  ammonia  nitrogen
              (first aliquot)  from  total nitrogen  (second  aliquot)  and applying
              a  stoichiometric conversion factor.
Both of the Kjeldahl  urea analysis methods require  that  correction factors be

applied to  the urea  and  ammonia  concentrations  in order  to account  for  the

conversion  of  some urea  to  ammonia  during distillation.   The  standard  cor-

rection factor  is:   7 percent of  the urea  content  of the  sample  is converted

to ammonia  during distillation.     Thus,  the urea concentrations  should  be

increased by 7 percent, and  the ammonia concentrations should  be decreased by

a stoichiometrically equivalent amount.
       Standard Methods  of Water  and  Wastewater Analysis,  APHA, AWWA,  WPCF,
       14th edition, 1975, p. 408.
                                  — 2 —

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    1.2.2 Ammonia Analysis Methods

          Direct Nessler (or Direct Nesslerization) Method

          The  nessler  reagent  is  added to  the  sample,  and  after  full  color
          development  the   absorbance   of  this  solution  is  measured  with  a
          spectrophotometer.   Absorbance  is  related  to  ammonia  concentration
          through  a  calibration  curve  prepared  from  the   absorbances  of
          standard ammonia solutions.

          Distillation Method

          o   Distillation  and  Nesslerization;    A  buffer  is  added  to  the
              sample and  this  solution is  then  distilled into  a  boric  acid
              solution, leaving  impurities  and interferences behind.   Nessler
              reagent  is then added to the  distillate which is  then analyzed
              spectrophotometrically as in direct nesslerization.

          o   Distillation  and  Titration;    The   sample   is  distilled  as  in
              distillation and  nesslerization, but into a boric  acid solution
              containing a  color indicator  reagent.   This distillate  is  then
              titrated  with  dilute  sulfuric acid until  the  proper indicator
              color  is obtained.   Ammonia  concentration is  related  to  the
              volume of titrant used.

          Specific Ion Electrode Method

          The  sample  is pH  adjusted with  base,   and  the ammonia  content  is
          measured  with an   electrode  calibrated  specifically  for  ammonia.
          Electrode calibration  is  performed by  immersing the  electrode  in  a
          standard ammonia  solution and noting the electrode meter reading.


1.3 Analytical Method Investigations

    The  urea  analytical  method   investigations  consisted  of  immediate  and

delayed analyses  of  field  samples and  prepared  laboratory samples, utilizing

several urea  analysis  procedures  and  preservative agents.   The   analysis  in-

vestigations consisted specifically of the following:


    1.   Urea  granulator  scrubber  outlet  gas stream  samples  were  analyzed
         within 24 hours of sample collection for  urea and ammonia  by  TRC and
         by  Agrico*!' .   The  TRC  urea  analyses  were  performed  using  the
         Kjeldahl direct  method  (with  preliminary  distillation);  the  Agrico
         urea analyses were performed using the Kjeldahl indirect  method.
     EPA Report 79-NHF-13a, "Process Emission Tests Performed at the Agrico
       Chemical Company Urea Manufacturing Facility, Blytheville, Arkansas."
       Prepared by TRC under EPA contract 68-02-2820,  Work Assignment 11.
                                     -3-

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    2.   Two  identical  sets  of  twelve  urea  audit  samples  were  prepared
         according to specific EPA  instructions.  One  set was analyzed by TRC,
         the  other  by  Agrico;  both  analyses  took  place within  12  hours  of
         sample  preparation.   While  both analyses  were  performed  using  the
         Kjeldahl  total nitrogen  method  (without  preliminary  distillation),
         the final ammonia content  (subsequently converted  to urea)  was deter-
         mined by nesslerization by TRC, and by titration by Agrico.


    The results and detailed descriptions of these  two investigations  are con-

tained  in   the  EPA  report  79-NHF-13a,  referenced above.   The  results  are

briefly summarized in Section 2.0 herein.
    3.   The  Agrico  scrubber  outlet  gas  stream   samples,   preserved  with
         mercuric chloride and sulfuric acid (each sample was  divided  into two
         portions),  were  returned to  the TRC  laboratory,   and then  analyzed
         periodically over  20  days  for  urea and  ammonia.   The urea  analyses
         were  performed  using  the  direct  Kjeldahl  method  with  preliminary
         distillation.

    4.   Three pairs of identical  urea  samples  were prepared  by TRC  according
         to specific EPA  instructions.   All of  these laboratory samples  were
         analyzed periodically for  urea and ammonia, over  20 days,  with  the
         following  qualifications:   the  first   pair  remained  untreated;   the
         second pair was preserved with  mercuric chloride;  the third pair  was
         preserved  with sulfuric  acid.   The direct Kjeldahl  method with  pre-
         liminary distillation  was used  for  all  urea  analyses.

    5.   Five  urea  laboratory  samples,  prepared  according   to  specific   EPA
         instructions and each containing  different  amounts  of ammonia,  were
         analyzed by  TRC  for  urea  to  evaluate  the interfering  effects  of
         ammonia on  the p-dimethylaminobenzaldehyde urea analysis method.   All
         samples were analyzed  within 24  hours of preparation.

    6.   The  urea   detection  threshold  of  the  p-dimethylaminobenzaldehyde
         method was  evaluated  by TRC using  urea  laboratory   samples prepared
         according to specific  EPA instructions.

    7.   Urea  analyses  performed  during  an  emissions  testing  program  were
         evaluated to investigate the interfering effects of sulfuric acid  and
         the  benefits  of  preliminary  distillation  on   the   p-dimethylamino-
         benzaldehyde method.

    8.   Prill  tower  scrubber  outlet  samples  obtained  during  an emissions
         testing program were analyzed for  urea and  ammonia  at TRC within  20
         days of sample collection.  Impinger contents  and  probe catches  were
         analyzed individually  in order  to  assess the  sampling efficiency  of
         the modified EPA  particulate  sampling train.   The  p-dimethylamino-
         benzaldehyde method with preliminary  distillation  was used  for  the
         urea analyses.
                                -4-

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1.4 Description of Report Sections




    The following sections  of  this report contain  the Summary of  Results  and




Conclusions  (Section  2.0)   and  Discussion  of  Analysis  Procedures  (Section




3.0).  Detailed  information  on  methods and procedures and  all  laboratory data




are  contained  in their  associated  appendices/   as  shown in  the  Table  of




Contents.
                                   -5-

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 2.0  SUMMARY  OF  RESULTS  AND  CONCLUSIONS




     This  sections provides the results of  the  urea analytical method  investi-




 gations performed over  the period December 1978  through  May 1980.  The perti-




 nent analysis  results of  the  December 1978 emissions testing program at Agrico




 Chemical  Company,  Blytheville,  Arkansas  are briefly summarized in Sections  2.1




 and  2.2.   The results  of all  other  investigations are presented  in detail  in




 Sections  2.3 through 2.7,  and  conclusions  are  presented  in Section 2.8.    The




 order of  presentation in  this  section is generally chronological.









 2.1  Comparison of TRC and Agrico Scrubber Outlet Gas Stream  Analysis




     The TRC  and  Agrico  granulator  C  scrubber  outlet analysis results are shown




 together  in  Tables  2-1  (urea  results) and  2-2 (ammonia results).  The TRC urea




 data were obtained directly using  the  Kjeldahl with  preliminary distillation




 method.   The  Agrico urea data   were  obtained   indirectly through  separate




 Kjeldahl   (total  nitrogen)  and  distillation/titrimetric   (ammonia  nitrogen)




 analyses;  urea  was  then calculated by subtracting  ammonia nitrogen from total




 nitrogen.  Both corrected and  uncorrected data  are  shown  in Tables 2-1 and  2-2




 (corrected for conversion of urea to ammonia during distillation).




     The urea data in Table  2-1  show that on the average the Agrico results  are_




 30%  higher than the TRC results.  Run by run, however,  there is no consistency




 between the  TRC  and Agrico data;  the Agrico  results vary from much  higher  to




much  lower than  the TRC  results.   The indirect  method  of analysis  used  by




Agrico is susceptible  to  inaccuracy,  since  errors  in the  component  analyses




 (for total nitrogen and ammonia nitrogen) may be  compounded when urea nitrogen




 is calculated  by subtraction.   Relatively  small  titrant  volumes  were  used  in




 the Agrico titration analyses:  the total  nitrogen titrant volumes ranged  from




 5.8 ml to 13.5 ml; the  ammonia  nitrogen titrant volumes ranged  from 5.4 ml  to
                                    -6-

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                                                                          TABLE 2-1

                                                            TRC AND AGRICO UREA ANALYSIS RESULTS
                                                       PROM "C" GRANULATOR SOUlBBRR OUTLET GAS-STREAM
                                                      AT ACRICX) CHEMICAL COMPANY, BLYTIIEVILI.E, ARKANSAS
Run Number
Date
          Run 1
         12-18-78
                                                        Run 2
                                                       12-19-78
Volume of Gas Sampled (DSCF).
Volumetric Flowrate (DSCFM)
Production Rate (Tons/hour)

Urea Analysis By:
TRC
          34.93
          55180
          15.46
                                        Uncorrected
           Agrico
     Corrected   Uncorrected
                 Corrected
                                                        34.44
                                                        54720
                                                        15.08
                                                               TRC
                  Uncorrected   Corrected
                                                                                         Agrico
                                                                                                                                     Uncorrected  Corrected
Total Sample Weight (Milligrams)            58.9
 Grains/DSCF                             0.02597
 Pounds/Hour                               12.28
 Pounds/Ton                                0.794
        63.0
      0.02779
       13.14
       0.850
  175.5
0.07754
 36.67
 2.372
  188.7
0.08338
 39.43
 2.551
  90.0
0.04024
 18.87
 1.251
  96.3
0.04306
 20.19
 1.339
  11.8
0.00529
 2.480
 0.164
  12.7
0.00569'
 2.667
 0.176
Run Number
Date
          Run 3
         12-19-78
                                                        Run 4
                                                       12-19-78
Volume of Gas Sampled (DSCF).
Volumetric Flowrate (DSCFM) D
Production Rate (Tons/hour)

Urea Analysis By:
          32.62
          51130
          15.08
TRC
                                        Uncorrected
           Agrico
     Corrected   Uncorrected
                 Corrected
                                                        33.14
                                                        52910
                                                        15.08
                             TRC

                  Uncorrected   Corrected
                                                                                         Agrico
                                                                                                                                    Uncorrected  Corrected
Total Sample Weight (Milligrams)           33.6
 Grains/DSCF                             0.01586
 Pounds/I bur                              6.951
 Pounds/Ton                               0.461
        36.0
      0.01697
       7.438
       0.493
   26.4
 0.01249
  5.474
  0.363
   28.3
 0.01343
  5.886
  0.390
  48.1
0.02235
 10.14
 0.672
  51.5
0.02391
 10.85
 0.719
  104.8
 0.04880
  22.13
 1.468
  112.7
 0.05247
  23.80
  1.578
al)ry standard cubic feet § 68°F, 29.92 inches llg.
b,,
 Dry standard cubic feet per minute.
CTRC urea analysis by Kjeldahl with preliminary distillation.  Corrected = Uncorrected * 1.07.

 Agrico urea analysis by total Kjeldahl nitrogen minus ammonia nitrogen = urea nitrogen.

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                                                                       TABLE 2-1  (cont'd)

                                                               TRC AND AGRIOO UREA  ANALYSIS RESULTS
                                                          FROM "C" GRANULATOR SCRUBBER OUTLET GAS-STREAM
                                                         AT ACRICO CEIIMICAL COMPANY, Bl.YTHEVILLE, ARKANSAS
    Run Number
    Date
                                                              Run  5
                                                             12-19-78
                                                                    Run 6
                                                                   12-19-78
    Volume of Gas Sampled (DSCF).
    Volumetric Flowrate (DSCFM)
    Production Rate (Tons/hour)

    Urea Analysis By:
                                                    TRC
                                                               32.41
                                                               51730
                                                               15.08
                                                                    33.62
                                                                    53750
                                                                    15.08
                                             Uncorrected
                      Agrico
                                                                                                                     TRC
                                                                       Agrico
                                                         Corrected    Uncorrected
                             Corrected
                                  Uncorrected   Corrected
                                               Uncorrected  Corrected
    Total Sample Weight (Milligrams)
     Grains/DSCF
     Pounds/Hour
     Pounds/Ton
                                            28.8
                                          0.01368
                                           6.067
                                           0.402
  30.8
0.01464
 6.492
 0.430
  19.7
0.00938
 4.159
 0.276
  21.2
0.01009
 4.472
 0.297
  47.0
0.02153
 9.917
 0.658
  50.3
0.02304
 10.61
 0.7.04
  60.3
0.02768
 12.75
 0.846
  64.8
0.02976
 13.71
 0.910
I
CO
    Run Number
                                                              Average
    Volume of Gas Sampled (DSCF)  a
    Volumetric Flowrate (DSCFM)
    Production Rate (Tons/hour)

    Urea Analysis By:
    Total Sample Weight (Milligrams)
     Grains/DSCF
     Pounds/Hour
     Pounds/Ton

TRC
Uncorrected
51.1
0.02347
10.71
0.707
33.53
53237
15.14

Corrected
54.7
0.02511
11.46
0.757



Agrico
Uncorrected Corrected
66.4
0.03056
13.95
0.921
71.4
0.03286
15.00
0.990
aDry standard cubic feet e 68°F,  29.92 inches  llg.

 Dry standard cubic feet per minute.
     urea analysis by Kjeldahl with preliminary  distillation.
                                                                   Corrected =  Uncorrected * 1.07.
     Agrico urea analysis by total Kjeldahl nitrogen minus ammonia nitrogen = urea nitrogen.

-------
                                                                                 TABLE 2-2

                                                                TRC AND AGRICX) ANM3NTA ANALYSIS RESUI.TS
                                                             PROM  "C"  GRANULA10R  SCRUBBER OUTLET GAS-STREAM
                                                           AT AGRICO  CHEMICAL COMPANY, BI.YTHEVILLB, ARKANSAS
      Run Number
      Date
 I
VD
 I
      Volume of Gas Sampled (DSCF)
      Volumetric Flowrate (DSCFM) D
      Production Rate (Tons/hour)

      Airanonia Analysis By:
      Total Sample Weight (Milligrams)
       Grains/DSCF
       Pounds/Ilour
       Pounds/Ton
      Run Number
      Date
      Volume of Gas Sampled (DSCF).a
      Volumetric Flowrate (DSCFM)
      Production Rate (Tons/hour)

      Ammonia Analysis By:
      Total  Sample Weight (Milligrams)
       Grains/DSCF
       Pounds/Hour
       Pounds/Ton



DN
403.7
0.1780
84.17
5.444



DN
369.6
0.1745
76.46
5.070


TRC C
Dist.-N
Uncorrccted
423.2
0.1866
88.24
5.708


TRC
Dist.-N
Unco rrec ted
592.9
0.2799
122.65
8.133
Run 1
12-18-78
34.93
55180
15.46

Dist.-N
Corrected
420.7
0.1855
87. 72
5.674
Run 3
12-19-78
32.62
51130
15.08

Dist.-N
Corrected
591.5
0.2792
122.36
8.114


Agrico


d
Dist.-T Dist.-T
Uncorrected Corrected
464.1
0.2050
96.98
6.273


Agrico
456.6
0.2017
95.41
6.172



Dist.-T Dist.-T
Uncorrected Corrected
381 . 5
0.1805
79.10
5.245
380.4
0.1800
78.9
5.230
  DN

 332.6
0.1487
 69.74
 4.625
    TIC
 Dist.-N
Uncorrected

   328.2
  0.1468
   68.82
   4.564
                       Run 2
                      12-19-78
                       34.44
                       54720
                       15.08
                                       Agrico
                                                                                                                                  Dist.-N   Dist.-T     Dist.-T
                                                                                                                                 Corrected Uncorrected Corrected
  362.8
 0.1686
  76.45
  5.070
 324.4
0.1451
 68.02
 4.511
                       Run 4
                      12-19-78
                       33.14
                       52910
                       15.08
 484.7
0.2172
 101.9
 6.755
 484.2
0.2170
 101.8
 6.748
              TRC
                              Afirico
                                                                                                                      Dist.-N      Dist.-N   Dist.-T    Dist.-T
                                                                                                              DN     Uncorrected   Corrected Uncorrected Corrected
   348.2
  0.1618
   73.37
   4.865
   346.2
 0.1609
   72.95.
   4.837
   369.4
 0.1720
   78.01
   5.173
   364.9
  0.1699
   77.06
   5.110
      aDry standard cubic  feet @ 68°F,  29.92 inches llg.

       Dry standard cubic  feet per minute.
      CTRC ammonia analysis done by direct  nesslerization (DN)  and distillation/nesslerization (Dist.-N).   Correction is  Tor  urea  to ammonia  conversion.
       Corrected = Uncorrected - 0.07 * corrected urea/1.765.

       Agrico ammonia analysis done by distillation/titration  (Dist.-T).   Correction is for urea to ammonia ^conversion.

-------
                                                                           TABLE  2-2  (cont'd)

                                                            TRC AND AGRIOO AMMONIA ANALYSIS RESULTS
                                                         FROM "C" GRANU1ATOR SCRUBBER OUTLET GAS-STREAM
                                                       AT AGRICO CHIMICAL COMPANY, BLYTI1EVILLE,  ARKANSAS
      Run Number
      Date
      Volume of Gas Sampled (DSCF)
      Volumetric Flowrate (DSCFM) '
      Production Rate (Tons/hour)

      Aninonia Analysis by:
      Total Sample Weight (Milligrams)
       Grains/DSCF
       Pounds/Hour
       Pounds/Ton



DN
341.6
0.1623
71.96
4.772


TRC C
Dist.-N
Uncorrected
-321.9
0.1530
67.81
4.497
Run 5
12-19-78
32.41
51730
15.08

Dist.-N
Corrected
320.7
0.1524
67.56
4.480


Agrico


d
Dist.-T Dist.-T
Uncorrected Corrected
353.7
0.1684
74.68
4.952
352.9
0.1680
74.51
4.941
                                                                                       Run 6
                                                                                      12-19-78
                                                                                       33.62
                                                                                       53750
                                                                                       15.08
                                                                              TRC
                                                                                                        Agrico
                                                                                                                      Dist.-N      Dist.-N   Dist.-T     Dist.-T
                                                                                                              DN     Uncorrected  Corrected Uncorrected Corrected
                                                                 301.5
                                                                0.1381
                                                                 63.62
                                                                 4.219
                                                               305.5
                                                              0.1399
                                                               64.46
                                                               4.275
                                                               303.5
                                                              0.1390
                                                               64.04
                                                               4.247
                                                             300.7
                                                            0.1380
                                                             63.59
                                                             4.217
                                                             298.1
                                                            0.1368
                                                             63.04
                                                             4.181
 I
M
O
      Run Number
                                                                   Average
      Volume of Gas Sampled (DSCF) J*
      Volumetric Flowrate (DSCFM)
      Production Rate (Tons/hour)

      Ammonia Analysis By:
      Total Sample Weight (Milligrams)
       Grains/DSCF
       Pounds/I lour
       Pounds/Ton
  DN

 352.0
0.1617
 73.76
 4.872
               TRC
                        33.53
                        53237
                        15.14
                                Agrico
                                                        Dist.-NDist.-N     Dist.-T     Dist.-T
                                                       Uncorrected  Corrected   Uncorrected Corrected
 386.7
0.1776
 81.03
 5,352
 384.5
0.1766
 80.57
 5.322
 392.4
0.1806
 82.41
 5.465
 389.6
0.1793
 81.82
 5.426
      aDry standard cubic feet § 68°F, 29.92 inches Hg.

       Dry standard cubic feet per minute.
      CTRC ammonia analysis done by direct nesslerization (UN) and distillation/nesslerization (Dist.-N).  Correction is for urea to ammonia conversion.
       Corrected = uncorrected - 0.07 * corrected urea/1.765.
      ^Agrico aiiiirania analysis done by distillation/titration (nist.-T).  Correction is for urea to amnonia converstion.

-------
11.5  ml.   In order  to  minimize titration errors, TRC  has found  that titrant




volumes of at least  20 ml should be used.




    The ammonia data in  Table  2-2  show that  on the average the  TRC and Agrico




results  are  in close  agreement.   TRC  utilized  two analysis  methods:   direct




nesslerization  and  nesslerization  with  preliminary   distillation.    Agrico




utilized the titration with preliminary distillation method.









2.2 Urea Audit Samples - Comparison of TRC and Agrico Analyses




    TRC and Agrico each  analyzed a different set of 12  urea  samples,  each set




prepared according to specific  EPA instructions.   Both  analyses  were performed




at the Agrico laboratory within 12  hours of  sample preparation.   The TRC audit




sample  set was  analyzed using  the total  Kjeldahl  nitrogen method  with  no




preliminary distillation, ending with  nesslerization.  The  Agrico audit sample




set was  analyzed  using  the  same  total  Kjeldahl  nitrogen  method,  but  ending




with  titration.   The results of the urea  audit sample  analyses are  shown  in




Table 2-3.




    The TRC  analysis results average  6.0  percent lower  than the  actual  urea




sample weights,  and each  sample  analysis  is less  than the  actual.   It  was




initially  thought that  the  consistently low  results were due  to the  blank




correction.  Discounting  the  blank correction  in the  analysis  calculation,




however, yields  an  overall  +5.0  percent error.   This  indicates  that  factors




other than the blank correction may also be  involved in the  consistently low




(blank corrected)  results.




    The Agrico  analysis results average  92.9 percent  higher than  the  actual




urea  sample weights.  These  analyses  were concluded  with  titration,  and  very




low titration volumes  were  often  used  (7  of the  12  titrations  required  less




than 6 ml of titrant).  Larger titrant volumes  (at least  20 ml)  are necessary
                                  -11-

-------
                                                                                  TABLE 2-3
                                                                     RESULTS OF UREA AUDIT SAMPLE ANALYSES
                                                                          PERFORMED BY TRC AND AGRICO
                                                               AT AGIUCO CHEMICAL COMPANY, BLYTIIbVILLE, ARKANSAS
K>
 I
           Audit
          Sample
 1
 2
 3
 4
 5
 6
 7
 8
 9
10
11
12
TRC Analysis*
Actual Urea
Sample Weight
(mg)
A
100.71
311.98
598.36
5.64
11.60
40.40
2.60
6.84
9.42
5.40
4.30
30.16
As
Measured
(mg)
B
94.04
288.90
568.75
5.44
11.15
38.69
2.43
6.49
8.96
4.90
3.93
27.93
Error a
(»)

6.6
-7.4
-4.9
-3.5
-3.9
-4.2
-6.5
-5.1
-4.9
-9.3
-8.6
-7.4
AGRICO Analysis**
Actual Urea
Sample Weight
Ong)
C
100.54
292.78
598.08
5.26
9.64
42.48
2.04
6.16
9.54
5.96
4.18
31.32
Measured As
Nitrogen
(mg)
D
96.3
281.1
582.4
3.6
11.8
38.6
1.1
5.0
9.5
5.3
3.9
27.4
Equivalent
Urea b
(mg)
E
206.4
602.4
1248.0
7.7
25.3
82.7
2.4
10.7
20.4
11.4
8.4
58.7
Error c
(*)

105
106
109
46.4
162
94.7
17.6
73.7
114
91.3
101
87.4
          Average
                                                                  -6.0
                                                                                                                                               92.9
             Percent error = (100 * B/A)  -  100
          J  E = D * 60/28
          :  Percent error = (100 * E/C)  -  100

          *  TRC Analysis by total Kjeldahl nitrogen method,  ending with Nesslerization.  No preliminary distillation.
          ** Agrico analysis by total Kjeldahl nitrogen method,  ending with Titration.  No preliminary distillation.

-------
 in  order to  help minimize  errors during  titration.   A  disadvantage  of  the




 titration method  is  that the entire sample  is used for one  titration;  conse-




 quently,  if  an error  is  made or  if a  result is  suspect,  there  is  no  possi-




 bility of re-analysis.








 2.3 Preservation of Urea Samples




    Two  different  groups of urea  sample  solutions were analyzed  over  time in



 order  to assess   the  stabilizing  effects  of  mercuric chloride  (HgCl_)  and




 sulfuric  acid  (H_SO.)  on  the urea and  ammonia content of the  samples.   The




 granulator  C  scrubber  outlet  gaseous  samples   (obtained  from  the  Agrico




 December  1978  emission testing  program)  and six specially  prepared laboratory




 urea samples were  analyzed at TRC  in this manner.   The  urea analyses were per-




 formed with  the  direct  Kjeldahl  method  with  preliminary distillation.   The




 results of these preservation analyses are as follows.








    2.3.1 Granulator C Scrubber Outlet Gas Stream Sample Preservation




    After the  initial  urea and  ammonia  analyses  were  performed at Agrico on




 the granulator C  scrubber  outlet gas steam  samples,  the samples  were divided




 into  two  portions.    To  one  portion  was  added  saturated  HgCl_  solution




 (approximately 2 ml per  liter of  sample) ;  to the other portion  was added con-




centrated sulfuric acid  (approximately  2  ml  per  liter   of  sample) .   These




portions were returned to TRC and  then analyzed  for urea and  ammonia,  starting




 6-7 days  after the initial field  analysis  and  then every  2-3 days through  a




 2-week period  (for a  total of six  analyses  of each sample portion,  including




 the initial field  sample).  The  urea  analyses were performed  using the  direct




Kjeldahl  with  preliminary  distillation  method   (finishing   with  nessleri-




 zation).   The  ammonia  analyses  were  performed   with  two  methods:  direct
                                  -13-

-------
 nesslerization and nesslerization with preliminary distillation.

    The  results  of these  analyses  are shown  in  Tables 2-4  through  2-9.  The

 urea  and • distilled  ammonia data  include as-measured  values and  values cor-

 rected  for  urea-to-ammonia conversion during  distillation,  using the standard

 7  percent correction  factor.      Nearly  all  the  samples  exhibit occasional

 large  fluctuations in measured  urea or  ammonia  content.   These  fluctuations

 often interrupt or reverse  what,  in  some  instances,  initially may appear to be

 progressive  changes  in  urea  or  ammonia content.   Reasons  for  these large

 positive  and  negative fluctuations are not  evident,  and overall  there  are no

 discernable trends in  the data.  Graphs of  the corrected urea and ammonia data

 in Tables 2-4 through  2-9 are contained in Appendix C.

    Least-squares  linear  regressions were performed on  the  corrected  urea and

 ammonia data  in  order to quantify the degree of  correlation  between  the urea

 or ammonia content  of a sample and  time  of analysis.   The  calculated coeffi-

 cients  for  each  set  of  data are shown  in  Table  2-10.   In general,  the urea

 correlation coefficients indicate  there  is  little  relationship  between time

 and urea content of the samples, for either preservative agent.

    The HgCl.-preserved  ammonia analysis results  indicate  a  general  trend of

 ammonia   content   decreasing   with  time.   • The   H2SO.-preserved   ammonia

analysis results show no general change or trend.

    Further corroboration of the  stability  of urea field  samples was  obtained

during a  sampling  program conducted by TRC  in April  1980.     Two series of
       Standard Methods  of Water  and -Wastewater Analysis,  APHA, AWWA,  WPCF,
       14th edition, 1975, p. 408

       EPA  Report   80-NFH-14,   "Process   Emission   Tests  at   the   Reichhold
       Chemicals  Inc.  Urea  Manufacturing  Facility,   St.   Helens,   Oregon".
       Prepared by TRC under EPA contract 68-02-2820, Work Assignment 19.

                                        -14-

-------
                                          TABLE  2-4

             AGRICO GRANULATOR C SCRUBBER OUTLET GASEOUS SAMPLE PRESERVATION

                                     TEST RUN NUMBER 1
                       Direct        Distilled Ammonia^ (mg)    	Urea^ (mg)
Preservative
HgCl2





H2S04





Day
0
7
10
15
17
21
0
7
10
15
17
21
Ammoniaa(mg)
404
NA
NA
419
478
444
404
NA
NA
497
488
470
As Measured
423
507
422
389
424
429
423
453
*
462
529
507
Corrected0
421
503
419
385
420
425
421
450
*
4_59
526
504
As Measured
58.9
97.2
70.9
93.8
91.2
86.0
58.9
72.2
A
77.4
81.7
75.7
Corrected'
63.0
104.0
75.9
100.4
97.6
92.0
63.0
77.3
*
82.8
87.4
81.0
 a  Direct Nessler Analysis method.
 b  Nessler with preliminary distillation analysis method.
 c  Corrected for urea to ammonia conversion.  Corrected = uncorrected - 0.07*
    corrected urea/1.765.
 d  Kjeldahl with preliminary distillation analysis method.
 e  Corrected for urea to ammonia conversion.  Corrected = uncorrected * 1.07.
NA  Not Analyzed.
 *  Suspect and not used.
                                              -15-

-------
                                         TABLE 2-5
             AGRICO GRANULATOR C SCRUBBER OUTLET GASEOUS SAMPLE PRESERVATION
                                     TEST RUN NUMBER 2
 Preservative   Day
  HgCl2
 0
 6
 9
14
16
20

 0
 6
 9
14
16
20
      Direct         Distilled Ammonia13 (mg)     	Uread (mg)	
     Ammonia5(mg)    As  MeasuredCorrected0  As Measured   Corrected6
333
NA
NA
307
361
332

333
NA
NA
327
500
361
Distilled Ammonia^ (mg)
As Measured Corrected'
328
312
270
313
285
173
328
351
*
335
314
332
324
309
266
310
282
169
324
348
*
330
311
329
90.0
77.7
84.5
82.1
79.5
85.6

90.0
77.7
 *
110
76.9
73.4
96.3
83.1
90.4
87.8
85.1
91.6

96.3
83.1
 *
118
82.3
78.5
 a  Direct Nessler Analysis method.
 b  Nessler with preliminary distillation analysis method.
 c  Corrected for urea to ammonia conversion.  Corrected = uncorrected  -  0.07*
    corrected urea/1.765.
 d  Kjeldahl with preliminary distillation analysis method.
 e  Corrected for urea to ammonia conversion.  Corrected = uncorrected  *  1.07.
NA  Not Analyzed.
 *  Suspect and not used.
                                             -16-

-------
                                        TABLE 2-6
            AGRICO GRANULATOR C SCRUBBER OUTLET GASEOUS SAMPLE PRESERVATION
                                    'TEST RUN NUMBER  3
Preservative   Day
 HgCl,
 H2S04
                 0
                 6
                 9
                14
                16
                20
                 0
                 6
                 9
                14
                16
                20
                       Direct
                      Ammoniaa(mg)
370
NA
NA
358
476
369
370
NA
NA
338
429
374
Distilled
Ammonia" (mg)
As Measured Corrected
593
341
350
342
303
215
593
369
350
378
349
363
592
341
349
341
302
214
592
368
349
378
347
362
                                                                    Uread  (mg)
33.6
 *
26.2
25.0
33.8
27.4
33.6
26.1
19.4
 6.6
38.1
25.8
Corrected"6

   36.0
    *
   28.0
   26.8
   36.2
   29.3
   36.0
   27.9'
   20.6
    7.1
   40.8
   27.6
a  Direct Nessler Analysis method.
b  Nessler with preliminary distillation analysis method.
c  Corrected for urea to ammonia conversion.  Corrected = uncorrected  - 0.07*
   corrected urea/1.765.
d  Kjeldahl with preliminary distillation analysis method.
   Corrected for urea to ammonia conversion.  Corrected = uncorrected  * 1.07.
   Not Analyzed.
   Suspect and not used.
 e
NA
 *
                                            -17-

-------
                                         TABLE 2-7
             AGRICO GRANULATOR C SCRUBBER OUTLET GASEOUS SAMPLE PRESERVATION
                                     TEST RUN NUMBER 4

                       Direct        Distilled Ammonia0(mg)          Urea^  (mg)	
 Preservative   Day   Ammoniaa(mg)   As MeasuredCorrected0  As Measured   Corrected6
  HgCl-
  H2S04
 0
 6
 9
14
16
20

 0
 6
 9
14
16
20
363
NA
NA
308
403
354

363
NA
NA
349
398
420
Distilled
Ammonia^ (mg)
As Measured Corrected1
348
330
325
333
310
206
348
359
333
401
395
342
346
328
324
332
309
204
346
357
331
400
394
340
48.1
45.4
32.5
21.2
19.7
40.1

48.1
49.8
43.1
32.5
23.3
39.0
51.5
48.6
34.8
22.7
21.1
42.9

51.5
53.4
46.1
34,8
24.9
41.7
 a  Direct Nessler Analysis method.
 b  Nessler with preliminary distillation analysis method.
 c  Corrected for urea to ammonia conversion.  Corrected = uncorrected - 0.07*
    corrected urea/1.765.
 d  Kjeldahl with preliminary distillation analysis method.
 e  Corrected for urea to ammonia conversion.  Corrected - uncorrected * 1.07.
NA  Not Analyzed.
         	— 4
 *  Suspect and not used.
                                             -18-

-------
                                          TABLE  2-3
 Preservative   Day
  HgCl2
  H2S04
 0
 6
 9
14
16
20

 0
 6
 9
14
16
20
       Direct
      Ammonia5 (mg)
342
NA
NA
301
334
329

342
NA
NA
318
372
367
IBBER OUTLET
GASEOUS SAMPLE
PRESERVATION
TEST RUN NUMBER 5
Distilled Ammonia*3 (mg)
As Measured
322
307
326
299
276
198
322
*
367
294
312
329
Uread
Corrected0 As Measured
321
306
326
298
274
197
321
*
367
293 '
311
328
28.8
28.3
9.9
13.5
38.1
16.4
28.8
*
5.8
21.3
15.1
15.1
(mg)
Corrected6
30.8
30.3
10.6
14.4
40.8
17.5
30.8
*
6.2
22.8
16.2
16.2
 a  Direct Nessler Analysis method..
 b  Nessler with preliminary distillation analysis method.
 c  Corrected for urea to ammonia conversion.  Corrected = uncorrected  - 0.07*
    corrected urea/1.765.
 d  Kjeldahl with preliminary distillation analysis method.
 e  Corrected for urea to ammonia conversion.  Corrected = uncorrected  * 1.07.
NA  Not Analyzed.
 *  Suspect and not used.
                                               -19-

-------
                                         TABLE  2-9
            AGRICO GRANULATOR C SCRUBBER OUTLET GASEOUS SAMPLE PRESERVATION
                                    TEST RUN NUMBER' 6

                      Direct        Distilled Ammonia0(mg)          Urea"1  (mg)	
Preservative   Day   Ammoniaa(mg)   As Measured   Corrected'^  As Measured   Corrected6
 HgCl.
.H2S04
                 0
                 7
                 9
                14
                16
                20

                 0
                 7
                 9
                14
                16
                20
302
NA
NA
271
296
284

302
NA
NA
281
317
312
Distilled
Ammonia'3 (mg)
As Measured Corrected*
306
276
286
240
251
183 .
306
296
289
275
NA
317
304
274
285
240
249
181
304
295
288
275
NA
316
47.0
44.3
27.8
 4.6
37.3
38.7

47.0
33.9
12o8
 *
 NA
31.0
50.3
47.4
29.7
 4.9
39.9
41.4

50.3
36.3
13.7
 *
 NA
33.2
a  Direct Nessler Analysis method.
b  Nessler with preliminary distillation analysis method.
c  Corrected for urea to ammonia conversion.  Corrected = uncorrected  -  0.07*
   corrected urea/1.765.
d  Kjeldahl with preliminary distillation analysis method.
e  Corrected for urea to ammonia conversion.  Corrected = uncorrected  *  1.07.
   Not Analyzed.
   Suspect and not used.
NA
 *
                                             -20-

-------
                                                                                  TABLE 2-10

                                                                    LEAST-SQUARES LINEAR REGRESSION RESULTS

                                                        AGRICO GRANULATOR C SCRUBBER OWLET GASEOUS SAMPLE PRESERVATION


                                                                  Concentration (ppm) = M * time (days) + b
                                                                UREA**
AM>tONIA**
I
NJ
Test
sservative Run
HgCl2 1
2
3
4
5
6
H2S04 1
2
3
4
5
6
Slope
m
1.277
• -0.201
-0.219
-1.067
-0.312
-0.842
0.957
-0.362
-0.288
-0.003
-0.548
-0.777
Intercept
b
73.9
91.2
33.8
48.5
27.4
44.9
66.8
95.7
29.8
42.3
24.9
40.4
Correlation
Coefficient
r
0.6040
-0.3071
-0.374S
-0.5983
-0.1947
-0.3619
0.8681
-0.1805
-0.1762
-0.0471
-0.4630
-0.4271
Slope
m
-1.626
-5.667
-15.480
-S.323
-5.245
-5.531
4.370
-0.485
-9.529
1.278.
-0.739
0.208
Intercept
b
448
338
524
365
344
316
420
334
503
347
333
294
Correlation
Coefficient
r
-0.3147
-0.7273
-0.8947
-0.7459
-0.7984
-0.9129
0.8682
-0.2939
-0.7292
0.3211
-0.2075
0.1044
         **Corrected for urea to amnonia conversion during distillation.

-------
 emissions  test runs were  performed on  the  outlet of  a  prill tower  scrubber.

 The  urea content of these  samples  was analyzed in the  field  (within 24  hours

 of  sample collection)  and at TRC  up  to  16 days later.   Urea  analyses  were

 performed   with  the  p-dimethylaminobenzaldehyde method  (with   preliminary

 distillation).   The  average  impinger  catches   for  each  test series  were  as

 follows:
                                        Average  Impinger Catch  (mg)
                                       TRC Analysis   Field Analysis
    Series A  (2  runs)
    Series B  (3  runs)
        Average
                       19.1
                       12.0
                       14.8
               18.8
               13.1
               15.4
These data  show  an insignificant average difference  between  the field and .TRC

analyses.   Complete details  of  this emissions testing program are contained  in

EPA Report  80-NHF-14.



    2.3.2   Preservation of Laboratory Urea Samples

    Six urea  sample  solutions were prepared  and  analyzed  periodically over  19

days  in  order to  determine  the effect of mercuric  chloride  (HgCl_)  and sul-

furic  acid   (H SO  )  as preservative  agents.   The six  sample  solutions were

as follows:
    Sample

      A
      B
      C
      D
      E
      F
Urea (ppm)

     40
    100
     40
    100
     40
    100
       Preservative Added

              None
              None
2 ml saturated HgCl2/liter
5 ml saturated HgCl2/liter
2 ml concentrated H2S04/liter
5 ml concentrated H2SC>4/liter
These solutions were  analyzed for urea  and ammonia every  2 to 3  days over a

period of  19  days  (a  total  of 9  analyses).   Separate blanks  containing the
                                         -22-

-------
appropriate  preservative  agent  but  no  urea  were  prepared  and  analyzed  as

well.   The  urea analyses  were  performed using  the  direct Kjeldahl  with pre-

liminary distillation  method.   The ammonia analyses were  performed using both

the  direct  nessler  method  and   the   nessler  with  preliminary  distillation
                         N
method.  The  correction  for conversion of urea  to  ammonia during distillation

was  applied  to the urea and  distilled nessler ammonia  results.   The analysis

data  for  all  six  solutions  (A through F)  are  shown  in  Tables  2-11  through

2-16, respectively.

    None of  these  solutions,  including the "unpreserved"  solutions A  and  B,

showed  any detectable change in urea  or ammonia with  time.   Because  of this

clear consistency,  no  linear  regressions were performed.  Each  solution exhi-

bited small  fluctuations  in  urea  and  ammonia  concentration  from  analysis  to

analysis;  but  these fluctuations  can  be considered  within the  resolution  of

the  analysis  methods.   Some  of  the fluctuations  (positive and  negative)  may

also be due  to small  changes  in reagent characteristics or  analyst technique.

Evidence of this may be the consistently  "low" urea  and ammonia concentrations

measured on Day 8.

    The direct nessler ammonia concentrations  are always  less than the dis-

tilled   nessler   ammonia   concentrations.     The   differences   are    small

(approximately  1-2 ppm)  and  may   be  due  to  slight,  normally  insignificant

interferences  introduced   by  the  distillation  procedure.   In  addition,  the

distilled   ammonia  data  may  reflect  some  urea  converted to  ammonia  during

distillation.

    The standard 7  percent correction  applied  to the urea  and  ammonia  results

(in  order  to  account  for  urea  converted  to  ammonia  during  distillation)

appears reasonable  for the urea  data, but  is  clearly  inappropriate  for  the

ammonia data.   Negative ammonia  concentrations result  from this  correction
                                     -23-

-------
                                        TABLE 2-11

                  LABORATORY UREA SAMPLE PRESERVATION ANALYSIS RESULTS
                      SOLUTION A: . 40  PPM UREA,  NO PRESERVATIVES
             Direct   _     Distilled Ammonia  (ppm)  _                Urea  (ppm)
                                                                                        36
)ay
0
1
4
6
8
11
13
15
18
Ammonia (ppm)
0
NA
NA
0.1
0
0.1
0.1
0.3
0
As Measured Corrected
2.2 0.7
0 *
0.6 *
0 *
0.4 *
0.7 *
0.8 *
1.2 *
1.1 *
As. Measured
35.3
34.9
38.2
37.9
34.0
36.8
37.6
37.0
37.6
Corrected
37.8
37.3
40.9
40.6
36.4
39.4
40.2
39.6
40.2
 a  Direct Nessler Analysis Method.
 b  Nessler with preliminary distillation analysis method.
 c  Corrected for urea to ammonia conversion.  Corrected = uncorrected - 0.07 *
    corrected urea/1.765.
 d  Kjeldahl with preliminary distillation analysis method.
 e  Corrected for urea to ammonia conversion.  Corrected = uncorrected * 1.07.
NA  Not analyzed.
 *  Less than zero.
                                         -24-

-------
                                       TABLE 2-12

                  LABORATORY UREA SAMPLE PRESERVATION ANALYSIS RESULTS
                      SOLUTION B:  100 PPM UREA, NO  PRESERVATIVES
             Direct
Distilled Ammonia (ppm)
Urea (ppm)
Day_
0
1
4
6
8
11
13
15
18
Ammonia (ppm)
0
NA
NA
0.2
0.2
0.4
0.3
0.1
0.2
As Measured
2.4
0
1.4
1.2
1.4
. 1.6
2.0
2.5
2.6
Corrected.
*
*
*
*
*
*
*
*
*
As . Measured
90.6
92.7
94.3
93.1
81.6
91.5
90.3
92.6
91.4
Corrected
96.9
99.2
100.9
99.6
87.3
97.9
96.6
99.1
97.8
 a  Direct Nessler Analysis Method.
 b  Nessler with preliminary distillation analysis method.
 c  Corrected for urea to ammonia conversion.  Corrected = uncorrected - 0.07 *
    corrected urea/1.765.
 d  Kjeldahl with preliminary distillation analysis method.
 e  Corrected for urea to ammonia conversion.  Corrected = uncorrected * 1.07.
NA  Not analyzed.
 *  Less than zero.
                                            -25-

-------
                                       TABLE  2-13

                  LABORATORY UREA SAMPLE PRESERVATION ANALYSIS RESULTS
                      SOLUTION C:   40 PPM UREA,  Hga2 PRESERVATIVE
Direct
Distilled Ammonia CppnQ
                                                                     Urea (ppm)
Jay
0
1
4
6
8
11
13
15
18
Ammonia (ppm)
0
NA
NA
0.1
0
0.2
0
0.2
0
As Measured Corrected.
2.1 0.6
0.7 *
0.8 *
2.8 1.2
0.9 *
1.3 *
1.3 *
0.9 *
0.9 *
As .Measured
35.9
35.6
37.9
37.5
35.9
38.0
38.9
39.8
38.1
Corrected
38.4
38.1
40.6
40.1
38.4
40.7
41.6
42.6
40.8
 a  Direct Nessler Analysis Method.
 b  Nessler with preliminary distillation analysis method.
 c  Corrected for urea to ammonia conversion.  Corrected = uncorrected - 0.07 *
    corrected urea/1.765.
 d  Kjeldahl with preliminary distillation analysis method.
 e  Corrected for urea to ammonia conversion.  Corrected = uncorrected * 1.07.
NA  Not analyzed.
 *  Less than zero.
                                           -26-

-------
                                       TABLE  2-14

                  LABORATORY UREA SAMPLE PRESERVATION ANALYSIS RESULTS
                      SOLUTION D:  100 PPM UREA,  HgCi2  PRESERVATIVE
             Direct
Distilled Ammonia (ppm)
 Day     Ammonia  (ppm)     As Measured     Corrected.
                                As.Measurea
Urea (ppm)(
         "Corrected
0
1
4
6
8
11
13
15
18
0
NA
NA
0.1
0
0
0
0.2
0
2.2
1.2
1.6
1.6
1.6
1.0
2.4
2.1
2.4
*
*
*
*
*
*
*
*
*
97.2
91.0 •
94.8
93.3
86.4
91.8
93.1
92.8
95.0
104.0
97.4
101.4
99.8
92.4
98.2
99.6
99.3
101.7
 a  Direct Nessler Analysis Method.
 b  Nessler with preliminary distillation analysis method.
 c  Corrected for urea to ammonia conversion.  Corrected = uncorrected - 0.07 *
    corrected urea/1.765.
 d  Kjeldahl with preliminary distillation analysis method.
 e  Corrected for urea to ammonia conversion.  Corrected = uncorrected * 1.07.
NA  Not analyzed.
 *  Less than zero.
                                        -27-

-------
                                       TABLE  2-15

                  LABORATORY UREA SAMPLE PRESERVATION ANALYSIS RESULTS
                      SOLUTION E:   40 PPM UREA, H2S04  PRESERVATIVE
Direct
Distilled Ammonia Cppm)
                                                                     Urea
Jay
0
1
4
6
8
11
13
15
18
Ammonia (ppm)
0
NA
NA
0.2
0.1
0
0
0
0
As Measured
0.2
0.3
0.6
0.5
0.6
0.6
0.6
0.8
0.5
Corrected
*
*
it
*
*
*
*
is
*
As. Measured
35.3
35.8
38.1
37.7
34.3
36.1
37.4
37.8
38.8
Corrected
37.8
38.3
40.8
40.3
36.7
38.6
40.0
40.4
41.5
 a  Direct Nessler Analysis Method.
 b  Nessler with preliminary distillation analysis method.
 c  -Corrected for urea to ammonia conversion.  Corrected = uncorrected - 0.07 *
    corrected urea/1.765.
 d  Kjeldahl with preliminary distillation analysis method.
 e  Corrected for urea to ammonia conversion.  Corrected = uncorrected * 1.07.
NA  Not analyzed.
 *  Less than zero.
                                           -28-

-------
                                       TABLE  2-16

                  LABORATORY UREA SAMPLE PRESERVATION ANALYSIS RESULTS
                      SOLUTION F:  100 PPM UREA, H2S04  PRESERVATIVE
             Direct
Urea (ppm)'
Jay
o-
1
4
6
8
11
13
15
18
Ammonia (ppm)
0
NA
NA
0
0
0
0
0.1
0
As Measured
2.1
1.3
1.9
2.1
2.8
2.7
2.9
1.8
1.6
Corrected
*
*
*
*
*
*
*
*
*
As . Measured
90.6
95.6
93.7
94.9
92.3
91.7
91,9
81.9
96.2
Corrected
96.9
102.3
100.3
101.5
98.9
98.1
98.3
87.6
102.9
 a  Direct Nessler Analysis Method.
 b  Nessler with preliminary distillation analysis method.
 c  Corrected for urea to ammonia conversion.  Corrected = uncorrected - 0.07 *
    corrected urea/1.765.
 d  Kjeldahl with preliminary distillation analysis method.
 e  Corrected for urea to ammonia conversion.  Corrected = uncorrected * 1.07.
NA  Not analyzed.
 *  Less than zero.

                                           -29-

-------
 because  the urea  concentrations  are relatively  much higher  than  the ammonia

 concentrations  and  because  the  ammonia concentrations  are  themselves  abso-

 lutely low.



 2.4 Ammonia Interference on Urea Analysis

    TRC  prepared standard urea solutions  containing known  amounts  of ammonia

 in order  to assess the interfering effects of  ammonia  on the p-dimethylamino-

 benzaldehyde urea  analysis method (with no preliminary distillation).   A urea

 calibration curve  was  first  prepared with urea solutions  ranging  from zero to

 200  ppm.   Five  additional solutions were  then prepared,  each  containing  100

 ppm urea  and  100 to 1000  ppm  ammonia (as ammonium  chloride) .   The absorbance

 of each  of these  sample  solutions was  then  read  and  then converted  to urea

 concentration using  the prepared calibration curve.   The indicated  urea con-

 centrations and  related data are  shown  in Table  2-17.  A  plot of  ammonia/urea

molar ratio vs. urea analysis error is shown in Figure 2-1.

    These  data  indicate that  an  ammonia/urea  molar  ratio  of  about  3.5 will

yield a 1% positive  error  in the  urea analysis, and a molar ratio  of about 20

will  yield a  3%  positive error.   These  ammonia  effects  are  only  slightly

greater   than   the  effects   stated  in  the  article  that   introduced  the

p-dimethylaminobenzaldehyde urea analysis method:   "Ammonium chloride does  not

interfere  when  present in a  10  to  1   mole  ratio  and  introduces  only  a  1%

 relative  error  when the  mole  ratio is  15".      The  first  two  ammonia/urea

solutions  (100 ppm and  500 ppm  ammonia)  gave  absorbances  only  slightly greater

than the  standard  100  ppm  urea solution (see Appendix D).   These  differences
       Watt,   G.W.   and   J.D.   Chrisp,   "Spectrophotometric   Method   for
       Determination  of  Urea",  Analytical  Chemistry,   Volume  26,  1954,  pp.
       452-453.
                                     -30-

-------
                                     TABLE 2-17

                     RESULTS OF INTERFERENCE EFFECTS OF AMMONIA
                                  ON UREA ANALYSIS*
  Actual Ammonia          Actual Urea       Mole Ratio**     Indicated Urea      Percent
Concentration(ppm)     Concentration(ppm)   Urea/Ammonia   Concentration(ppm)   Error***

100
500
1000
5000
10000
B
100
100
100
100
100

3.52
17.60
35.21
176.0
352.1
C
101
102
106
130
151

+ 1
+ 2
+ 6
+ 30
+ 51
      * p-dimethylaminobenzaldehyde  analysis method (no preliminary distillation)

     ** 100 ppm urea = 100 mg/liter = 0.00167 M
        100 ppm ammonia = 100 mg/liter = 0.00588 M

    *** percent error = 100 * (C-B)/B-
                                         -31-

-------
 1000
  100
<=C
LU
OH
           z
   10
                 10
  20          30          40          50

POSITIVE PERCENT ERROR IN UREA ANALYSIS
60
              FIGURE 2-1:  INTERFERENCE  EFFECTS OF AMMONIA ON UREA ANALYSIS
                                                                                   0988-001
                                            -32-

-------
can  be  considered within the precision limits  of  the analysis  method  and,  on

this  basis,  the  TRC  data  generally  corroborate   the  ammonia  interference

effects stated by Watt and Chrisp.
2.5 Evaluation  of Standard  Procedures  for  the Proposed  EPA Urea  Analytical
    Method
    Emissions testing was  performed  by  TRC on prill tower  scrubbers  at a urea

manufacturing plant  during August 1979.      Additional urea  analysis invest-

igations  were  performed by TRC  during  the  analysis  of the  samples  collected

during  this  test program.   These investigations were  performed  in  order  to

evaluate  two  aspects of  the  p-dimethylaminobenzaldehyde  (PDAS)  urea analysis

method:   preliminary  distillation  (to  remove   ammonia)   and   the  effect  of

sulfuric  acid as  an  interference.  The  results of  these  investigations are  as

follows.



    2.5.1 Effects of Preliminary Distillation

    Urea-in-mannitol audit samples were prepared by EPA  and  given to  TRC for

analysis  in  order to  assess  the  accuracy of the  'p-dimethylaminobenzaldehyde

urea analysis method for this test program.  The  samples were  dissolved in 100

mis of water, and a  portion  of  each  of  these audit sample  solutions  was first

distilled and then analyzed for  urea; another portion was  analyzed without any

preliminary  distillation   (direct  analysis).    Distilled   and   undistilled

standard urea solutions were prepared and  the audit sample solutions  were read

against the standard solution calibration  curves.   The  purpose of the investi-

gation  was to  evaluate  the  effect  of  the preliminary   (ammonia-removing)
      EPA Report 78-NHF-3,  "Process  Emissions  Tests at the W.R.  Grace and Co.
      Urea  Manufacturing  Facility  in Memphis,  Tennessee".   Prepared by  TRC
      under EPA Contract No. 68-02-2820,  Work Assignment No. 9.
                                    -33-

-------
 distillation  on the  indicated  urea content  of samples.   The  results  of the




 analyses and comparisons are shown  in Table 2-18.




    Audit  sample number  4  aside, these data  show  that comparison of distilled




 samples to distilled  standards  (column A) and  comparison  of  direct samples to




 direct  standards  (column  C)   both  yield  small   errors   (within   5%  on  the




 average).   However/  comparison  of  distilled  samples  to  direct  standards




 (column B) yields relatively large errors (about 14%).




    The  column A  and column  C  data  indicate that  it  makes  no  difference




 whether you distill or not,  as  long as both  samples and  standards  are handled




 in  the  same way.  However,  the  column B data  indicate that  the distillation




 process results in the loss  of  urea.  This result  is  qualitatively consistent




 with  the  effect of the  preliminary distillation step used with the  Kjeldahl




 urea analysis method.




    The reason for the anomalous results with the audit  sample number  4 is not




evident.   The  fact that the  audit  sample  4  results  are  consistently  higher




 than the actual concentration  (even in column B) indicated the possibility of




an  initially  erroneous  sample  weight  or an   error  in  the   initial  sample




 solution preparation.




    These  results above  should be  viewed  as applicable only  to urea solutions




of high concentrations (on the order of 100,000  ppm).  The  extent of urea loss




 at  lower  concentrations  is  indicated  by  a  comparison  of  the  distilled  and




undistilled  urea  calibration curves  used  to  analyze the August   1979  field




 samples.   Two  sets of standard  urea solutions  were  prepared:   the  absorbances




of  one  set  were  measured  directly;  the  absorbances of  the  other set  were




measured after  the  standards were  distilled.   These  data  are  shown in  Table




2-19 and indicate an  average decrease  in  absorbance of about  12 percent  (dis-




tilled standards read  12% lower  than undistilled).
                                    -34-

-------
                                                                        TABLE 2-18

                                                 COMPARISON OF EPA AUDIT SAMPLES AND TUC UREA STANDARDS
                                              Distilled snnples against
                                              distilled standards curve
Distilled samples against
  Direct standards curve
Direct samples against
Direct standards curve



1
U)
Ul
1
Audit Sample
Number
1
2
3
4
5
Actual Urea
Concentration
(ppm)
265600
480000
419600
99200
199900
Indicated
Concentration
(ppm)
263000
459000
428000
117000
193000
Percent
Error*
-1.0
-4.4
2.0
17.9
-3.5
Indicated
Concentration
(ppm)
230000
402000
371000
103000
172000
Percent
Error*
-13.4
-16.3
-11.6
3.8
-14.0
Indicated
Concentration
(ppm)
263000
455000
408000
. 126000
200000
Percent
Error*
-1.0
-S..2
-2.8
27.0
0.1
*Percent error =  (indicated  - actual) *  100/actual.

Note:   1  ppm   =  I  )ig/ml

-------
                                 TABLE 2-19

              DISTILLED AND UNDISTILLED UREA CALIBRATION CURVES
             FOR THE P-DIMETHYLAMINOBENZALDEHYDE ANALYSIS METHOD
Urea Concentration
      (ppm)
        0

       125

       250

       375

       500
               Slope

               Intercept

               Corr.
               Coefficient
Absorbance
Undistilled
0.000
0.186
0.362
0.526
0.680
0.00136
0.011
0.9993
Distilled
0.000
0.162
0.312
0.461
0.614
0.00122
0.004
0.9999
Decrease (%)*
__
-12.9
-13.8
-12.4
- 9.7



*Decrease = (distilled - undistilled) * 100/undistilled.
                                     -36-

-------
    2.5.2 Sulfuric Acid Interference

    The  sampling train  used  for  these  August  1979  emissions  tests  included

impingers  with  IN  sulfuric acid  (H_SO  ) .   During  the urea  analyses  of  the

first  series of water  and acid  impinger  samples  (using  the  p-dimethylamino-
                                   i
benzaldehyde  method with  preliminary ammonia  distillation),  the  TRC chemist

noted that all the acid impinger  samples  read  below the standard blank used to

zero  the spectrophotometer.  Since  the  most   obvious  difference  between  the

acid impinger  samples, the  water  impinger  samples,  and  the urea standards used

to prepare the calibration  curves was  their  acid content,  the  chemist reasoned

that H2S04 mav be a ne9afcive interference:

       acid  impinger samples  -   IN H_SO

       water impinger samples -   2 ml H_SO ./liter (preservative)

       Calibration standards  -  No acid

    To test  this hypothesis,  the chemist prepared  four  different water  blanks

and measured their  absorbances   (after  zeroing the  spectrophotometer  on  the

first blank).

                           Blank                           Absorbance

       Water with preliminary NH3 distillation                0.000

       Dilute H2S04 solution (2 ml/liter water)

         with preliminary NH3 distillation                   +_0.004

       IN H2S04 with preliminary NH3  distillation            -0.048

       Water without preliminary NH3  distillation             0.000


    The  absorbance  of  the dilute  acid  blank was slight  (several measurements

yielded  absorbances in  the  range of  +0.004).   The  IN  H SO.  blank  result

was significant:  an absorbance of 0.05 was  equivalent  to about  36  mg urea in

a  1  liter   sample.   In  order  to compensate  for  this  interference,   urea
                                -37-

-------
standards were  subsequently  prepared  to contain the same acid concentration as

the sample being analyzed.

    In  addition to emissions tests on  prill tower scrubbers,  tests were also

performed on  the  urea solution synthesis tower vent  during  this program.  The

high  ammonia  content  of  the vent  emissions required  the  use  of   5N  and  ION

H_SO    in   the   sample  train  impingers.   Negative   absorbances   were  also

obtained with these  samples,  and  the same procedure  of urea standard solution

acidification was  followed to compensate.

    The  synthesis tower  acid  impinger  samples exhibited  turbidity when  the

PDAB color  reagent was added.   The turbidity was  removed with  the  addition of

2 ml concentrated  HC1 to each sample.  This turbidity  problem  was  encountered

during  two  other  field programs conducted by TRC  in April  1980.      On these

programs, the  turbidity was removed  by adding  1  ml  concentrated HC1  to each

sample.


2.6 Threshold Minimum Detectable  Limit  for  the Proposed  EPA  Urea  Analytical
    Method


    The absolute  threshold  of  detection  (lowest urea  concentration  detectable

in a spectrophotometer  sample cell) for the  p-dimethylaminobenzaldehyde  (PDAB)

analysis  method was  evaluated by  TRC  using  laboratory  urea   solutions.   In

addition, during an emission testing  program at  a  urea manufacturing facility,

TRC investigated ways to improve  the sensitivity  of  the PDAB  analysis method

so that  samples with urea concentrations too  low  to  normally  measure  can  be

readily analyzed.
       Reichhold Chemicals, Inc.,  St.  Helens Oregon; Union Oil  Company,  Brea,
       California.   EPA Contract 68-02-2820, Work Assignments 19 and 20.
                                     -38-

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     2.6.1 Laboratory Evaluation of the Absolute Urea Detection Threshold

    EPA requested TRC  to perform  analyses  of  standard  urea solution samples in

order  to estimate  the minimum urea concentration  detectable  by  the  p-dime-

thylaminobenzaldehyde  urea  analysis method   (with  no  preliminary  distilla-

tion) .  Two  sets of urea  solutions  were prepared:  set  1 included  five urea

samples  ranging  from  50 ppm to  250 ppm;   set 2  included seven  urea  samples

ranging from  1 ppm to 30  ppm.   Both sets  were analyzed  with  a  spectrophoto-

meter  using  both a 1  cm  sample cell and  a 5  cm  sample  cell.   The  resulting

four data sets were plotted  on  rectilinear graph paper as absorbance vs. urea

concentration, and  least-squares  linear  regression analyses were  performed to

determine best-fit  line equations.   These  data are  shown in  Table 2-20  and

Figures 2-2 through 2-5.

    These data reflect the  linear  relationship  between  absorbance  and  con-

centration described by Beer's Law:

                     A = kdC

         where:      A = absorbance
                     k = absorptivity coefficient
                     d = path length (cell  size)
                     C = concentration

The  two  1-cm  cell  data sets yielded  similar slopes.   By  applying the  low
concentration  (set  2)  absorbances to the  high concentration  (set  1)  equation
(rearranged to solve for concentration),  the following  concentrations were
       Strobel,  H.A.,  Chemical  Instrumentation  -  A  Systematic  Approach  to
       Instrument Analysis,  Addison - Wesley,  1960,  pp.  150 ff.
                                    -39-

-------
                              TABLE 2-20
                      DATA FROM UREA THRESHOLD OF
                        DETECTION DETERMINATION
     Concentration
         Group

         Set 1
         Set 2
Concentration
    (ppm)

     250
     200
    ' 150
     100
      50
       0
      30.
      20
      10
       7
       5
       2
       1
       0
Absorbance
1-cra Cell
0.415
0.332
0.250
0.157
0.087
0
0.051
0.033
0.015
0.010
0.003
0.000
-0.007
0
5-cm Cell
1.044
0.984
0.860
0.618
0.368
0
0.223
0.132
0.067
0.048
0.013
0.003
	 *
0
* Indefinite, but less than zero.
  Not used as a data point.

        Least-Squares Linear Regression Analyses of Above Data
                  Absorbance = M * Concentration + Y
                       1-cm Cell
                     5-cm Cell

Set 1
Set 2

0
0
M
.00166
.00185

-0
-0
Y
.0005
.0042

0
0
R**
.9996
.9914

0.
0.
M
00418
00757

0.
-0.
Y_
1235
0106
R**
0.9685
0.9941
** Correlation Coefficient
                               -40-

-------
   0.50
   0.40
o
CO
CO
   0.30
   0.20
   0.10
                   50
                                            I
                         I
                                  A = MC + Y
                                  R = 0.9996
                                  M = 0.0016589
                                  Y = -0.0005238
100         150         200
     C  UREA CONCENTRATION  ( ppm)
250
300
                           FIGURE 2-2: UREA THRESHOLD OF DETECTION DETERMINATION
                                              SET 1   1 cm CELL
350
                                                              0988-003

-------
M
I
       0.05
       0.04
       0.03
CO
a:
o
CO
03
   0.02
       0.01
             ®
       -0.01
                                               l
                                                            A
                                                            R

                                                            M

                                                            Y
MC + Y
0.9914

0.0018478

-0.0041977
                                               15          20
                                             UREA CONCENTRATION   (Ppm)
                                                                   25
                   30
                                                                                               35
                                FIGURE  2-3:  UREA THRESHOLD OF DETECTION DETERMINATION
                                                    SET 2  1 cm CELL
                                                                                               0988-004

-------
U>
I
                1.0
                0.8
             o
                0.6
CO
ce.
o
CO
CO
                0.4
                0.2
                          A =  MC + Y

                          R =  0.9685

                          M =  0.0041771

                          Y =  0.123500
                  0
                   0
                                                                   j_
                 50
100         150         200

    C  UREA CONCENTRATION  (ppm)
250
300
350
                                       FIGURE  2-4:  UREA TRESHOLD OF DETECTION DETERMINATION
                                                         SET 1  5 cm CELL
                                                                                                             0988-005

-------
£>.
           0.25
           0.20
           0.15
           0.10
        CO
        C£
        O
        to
        CO
           0.05
                                                               ®
A = MC + Y
R = 0.9941

M = 0.0075739

Y =-0.0106386
10          15          20          25

      C  UREA CONCENTRATION  (ppm)
                                                                                       30
                       35
          -0.05
                                        FIGURE 2-5:  UREA THRESHOLD OF DETECTION DETERMINATION
                                                          SET 2  5 cm CELL
                                                                                                         0988-006

-------
calculated:
              Low Concentrations Calculated        Actual Low
             By High Concentrations Equation     Concentrations
                           (ppm) •                      (ppm)

                           31.1                       30.0
                           20.2                       20.0
                            9.4                       10.0
                            6.3                        7.0
                            2.1                        5.0
                            0.3                        2.0
                           -3.9                        1.0
    One  may  infer  from  these  results  that  the  sensitivity  of  this  urea

analysis method  fails  at about 7 ppm  and  that the threshold of the  method is

at  this  point.  Further  consideration of  these  1-cm cell  data  and  the  5-cm

cell  data can,  however,  yield more  refinement  in  the  estimated  detection

threshold, as follows.

    The 5-cm cell  data show slopes more positive  than the 1-cm cell  data,  as

predicted by Beer's  Law.  The  apparent  bending over  of  the 5-cm set  1  curve

above  150  ppm  (Figure 2-4) may  be evidence  of  a  fundamental constraint  on

Beer's Law,  namely that the law  is applicable  primarily  in dilute  solutions

(less than 0.02  M) .      For urea in a  5-cm cell,  the upper limit may in  fact

be considerably  less than 0.02 M  (1200 ppm).   This deviation from  linearity

results in the considerable difference  between  the  slopes of  the  5-cm set  1

and set 2 equations.

    Both set  2 data groups (1-cm cell  and  5-cm  cell)  indicate  considerably

better resolution  at very  low  concentrations than do  the  set 1  (high concen-

tration)  data,  as would be expected.   Concentrations as low as 3-5 ppm could
      Ibid.
                                    -45-

-------
be  read  with a fair degree  of confidence from  Figures  2-3 and  2-5,  with the

5-cm cell data providing  even  slightly more accuracy than  the  1-cm cell data.

(The  integrating  effect  of the  larger  path  length  would naturally  provide

better resolution at low concentrations.)

    Extrapolating  relatively  high  concentration  calibration   curves  down  to

read low concentrations is  not advisable in most  analytical  situations.   The

best approach is to  prepare a curve  that covers  the  concentration  range  of

interest.  The advantage  of  this technique  is  evident in  Figures  2-3 through

2-5.  Also  evident  is  the utility  of  using a  5-cm cell over  a 1-cm cell  in

order to obtain  better resolution  at  low urea  concentrations.  At high  urea

concentrations a 1-cm cell would be preferred.

    The  continuity  of  both  the  1-cm cell  data  and the  5-cm  cell  data  is

clearly  shown  in  Figure 2-6, where the  absorbance vs. concentration  data are

plotted  on  log-linear graph paper.   This figure  also illustrates  the  points

discussed above:
    o  The  separation of  the  two curves  reflecting  the  slope  change  that
       occurs when the path length is changed.

    o  The  slightly  increased resolution of  the  5-cm  cell data  at low  con-
       centrations.

    o  The saturation apparent in the 5-cm cell at high concentrations.


    2.6.2  Low Level Urea Analysis in the Field

    During  an  emissions  testing  program     at  a  urea manufacturing  facility

in April 1980,  TRC modified some steps in the PDAB urea analysis method  (with
       EPA  Report  80-NHF-14,   "Process  Emissions  Testing  at  the  Reichhold
       Chemicals,  Inc.,  Urea  Manufacturing  Facility,  St.  Helens,  Oregon".
       Prepared by TRC under EPA Contract 68-02-2320,  Work Assignment 19.
                                    -46-

-------
0.700
0.100
                                10                         100
                                   UREA CONCENTRATION (ppra)
                                                                   LEGEND
                                                               XSET 1
                                                               ®SET 2
                                                               • SET 1
5 cm CELL
                1000
                                                               ®SET 2
                                                                       1 cm CELL
                 FIGURE  2-6:  UREA THRESHOLD OF DETECTION DETERMINATION
                                                                               0988-002
                                      -47-

-------
preliminary  distillation)  in order to analyze  very  low urea concentrations in

the  impinger samples.   Low urea emissions were  expected  at this facility, but

even with  extended  sampling  times  (up to 500 minutes per  test  run) ,  urea con-

centrations   in  the  sampling  train  impingers  were   near  the  threshold  of

detection  (using the PDAB analysis method as written).

    The method was  modified  by  increasing the size  of  the sample aliquot,used

for  analysis from  100 ml up  to  700  ml and boiling  this  larger  volume down to

100  ml  (to  remove  ammonia).   In  this  way/  the  amount of  urea  available for

final  analysis was increased  by  up  to a  factor  of  seven,  and  the  sample

absorbances  were brought into the working range of the calibration curve.



2.7 Collection Efficiency Determination of the EPA Urea Sampling Train

    Three  emission  test runs were performed  by TRC on April 24, 1980  on the

outlet  of  a prill  tower  scrubber.       One purpose   of  these  tests was  to

provide  information on  the  urea  collection efficiency   of  the modified EPA

particulate  sampling train.


  The impinger sequence used for these tests was as follows:

       impingers 1 and 2  -  deionized, distilled water
       impingers 3 and 4  -  IN sulfuric acid
       impinger 5         -  empty
       impinger 6         -  silica gel


The probe  wash,  the contents of  impinger 1, the  contents of impinger  2, and

the combined contents of impingers 3, 4, and 5 were analyzed individually for
(1)  EPA Report  80-NHF-15,  "Process  Emissions  Tests at  the Union Oil  Company
    Urea Manufacturing Facility, Brea, California".  Prepared  by  TRC under EPA
    Contract No. 68-02-2820,  Work Assignment No. 20.
                                  -48-

-------
urea and  ammonia  at  the TRC laboratories within  20  days  of sample collection.

Urea analysis  was performed using the  p-dimethylaminobenzaldehyde  method with

preliminary  distillation.   Ammonia analysis  was  performed using  the specific

ion electrode method.

    The  analysis  results for these  three prill  tower  scrubber test  runs are

shown in  Table  2-21.   These data indicate that 70% of the  urea in  the sampled

gas  is  retained  by  the first water  impinger  (and  probe), and  the  remaining

urea is all  retained  by the second water impinger.  The  ammonia data indicate

that half the  ammonia  is retained  by  the water impingers and  half  by the acid

impingers.   To determine whether  any  significant amount  of  ammonia gets  by

even the acid impingers would require other tests using additional impingers.

    As  mentioned  in  Section  2.5.2,  the  acid  impinger  samples  exhibited

turbidity when  the  PDAB color reagent  was  added.  This  turbidity  was  removed

when 1 ml of concentrated HC1 was added to each sample.



2.8 Conclusions and Recommendations

    The following  conclusions  are based  on  the urea  analysis  method investi-

gation results  and  supplemental  discussions presented in Sections  2.0  and 3.0

of this report.


    1.    Of  the  two  urea analysis  methods  evaluated  (the  p-dimethylaminoben-
         zaldehyde (PDAB) method  and  the Kjeldahl method), the  PDAB  method  is
         preferred because it is simpler to use and measures urea directly.

    2.    The absolute  threshold  of  detection for  the  PDAB method  is  5-7 ppm.
         Urea  concentrations  lower   than  this   in  impinger  samples  can  be
         readily  determined  by  concentrating   the  urea  sample   prior  to
         analysis.  This concentration  step  involves a slight  modification  to
         the proposed EPA Reference Method procedure.

    3.    The interfering effects of ammonia on  the PDAB method as discussed  by
         Watt  and  Chrisp in 1954 are  generally  corroborated  by  the  effects
         determined by  TRC,  described herein.  The  TRC  results show  a  slight
         (less than 2%)  interference  for a  20:1  ammonia  to urea molar  ratio.
         Higher molar ratios increase the interference.
                                      -49-

-------
                              TABLE 2-21

           •UREA SAMPLING TRAIN COLLECTION EFFICIENCY RESULTS
                  UNION OIL COMPANY, BREA, CALIFORNIA
Test
Run
Urea 1
2
3
Average
Ammonia 1
2
3
Average
milligrams
percent
milligrams
percent
milligrams
percent
milligrams
percent
milligrams
percent
milligrams
percent
milligrams
percent
milligrams
percent
Probe
Wash
4
5
4
9
5
9
4
7
5
3
2
1
3
0
3
1
.50
.8
.83
.6
.58
.0
.97
.8
.43
.1
.83
.5
.10
.8
.79
.5
Impinger
1
44.
57.
31.
63.
41.
66.
39.
61.
72.
42.
50.
25.
6
3
8
4
1
3
2
9
6
1
1
7
110
29.3
77.
31.
6
3
Impinger
2
28
36
13
27
15
24
19
30
26
15
40
20
63
16
43
17
.8
.9
.5
.0
.3
.7
.2
.3
.9
.6
.1
.6
.3
.9
.4
.5
Impingers
3,4,5
<1.64*
0
<1.58*
0
<1.49*
0
0
67.5
39.2
102
52.2
199
53.0
123
49.7
Total
77.90
100
50.13
100
61.98
100
63.34
100
172.43
100
195.03
100
375.40
100
247.62
100
* Detection Threshold (0.010 absorbance reading).   Urea standards were
  prepared with similar acid contents as these acid impinger samples.
                                   -50-

-------
4.   The extent  of urea  loss during  preliminary  distillation  to  remove
     ammonia prior to PDAB analysis appears  to  be 12 to  14  percent,  based
     on analyses  of  samples  with  urea concentrations  in  the  ranges  of
     0-500  ppm and 100,000-500,000 ppm.

5.   Sulfuric acid  is a negative  interference  in  the  PDAB urea  analysis
     method.  For  this  reason, the  sulfuric acid  content of samples  and
     standards should  be the same.

6.   The  urea  content   of  field  and   laboratory  samples  undergoes  no
     detectable  deterioration over  time,   up  to  21  days  after  sample
     collection/preparation.   Mercuric chloride and sulfuric acid  have  no
     discernable effect  as  urea stabilizing agents.

7.   Nearly 100% of all  sampled urea appears to be  caught  in the  first two
     (water) impingers of the  EPA  urea  sampling  train.
                                      -51-

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 3.0  DISCUSSION  OF  ANALYSIS  PROCEDURES

     This  section  presents  more detailed descriptions  of the  analysis proce-

 dures  used in  the investigations presented  in Section  2.0.   The  EPA report

 79-NHF-13a      fully  describes   the  December  1978  Agrico  Chemical  Company

 emissions  testing  program,  and  details  of  the Agrico data  presented  in

 Sections 2.1 and 2.2 are not included in this section.
 3.1 Preservation Analyses

    The  scrubber  outlet  gas  stream  samples  obtained  during   the  emissions

 testing program at  the Agrico Chemical Company  in  December  1978, and prepared

 laboratory  urea  samples were  treated  with two  preservative  reagents  in order

 to assess  the stabilizing effects  of  these reagents  on  the urea  and  ammonia

 content of  the samples.  Mercuric chloride and  sulfuric acid were added to the

 samples which were then  analyzed over  a 15-20 day  time period in December 1978

 and January 1979.



    3.1.1 Field Sample Preservation Analyses

    The  six scrubber  outlet gas stream   samples  were initially  analyzed  for

 urea  and  ammonia  at  the  Agrico laboratory  within  24 hours  of  sample  col-

 lection.  The samples  were then  treated with preservative and  returned  to TRC

 for the  preservation  analyses.   A white  precipitate  formed  in  the  mercuric

chloride preserved  samples.   The nature  of this  precipitate is  unknown,  but

during subsequent analyses at  TRC  these samples were  agitated  to include  this

precipitate in the analyzed aliquot.
       EPA Report  79-NHF-13a,  "Process  Emissions Tests at the  Agrico Chemical
       Company Urea  Manufacturing  Facility,  Blytheville,  Arkansas".   Prepared
       by TRC under EPA Contract No. 68-02-2820,  Work Assignment No. 11.
                                   -52-

-------
    The  preservation procedure consisted  of separating  each sample  into two




equal portions.  To  one  portion was  added  saturated mercuric chloride (approx-




imately  2 ml/liter  of  sample);  to  the  other  portion  was  added  concentrated




sulfuric  acid  (approximately  2 ml/liter  of sample).  The samples then remained




at  room  temperature  and  were  analyzed for  urea and  ammonia,  starting 6-8 days




after the initial  analyses  and then  every  2-4 days for about  a  2  week period.




The  urea analyses were  performed  with  the  Kjeldahl method,  with preliminary




distillation  and  finishing  with   nesslerization.   The  ammonia  analyses  were




performed  by direct  nesslerization and by  nesslerization with preliminary dis-




tillation.




    The  preliminary  distillation  was a  step common  to  the Kjeldahl  urea and




distillation/nesslerization   ammonia   analyses.    Sodium  borate   and  sodium




hydroxide  were  added to  a  portion of  the  sample  to act as  a  buffer  and  to




bring the  pH  to 9.5  or greater.   The  sample was  then distilled,  and  the dis-




tillate  (containing  the  ammonia)  was collected in  a boric acid solution.  To




this solution was  added  the nessler  reagent, and after  full  color development




the absorbance of  this solution was measured with  a spectrophotometer.  To the




distillation residue  was added the Kjeldahl digestion  reagent which converts




organic nitrogen (urea)  to  ammonia.  This  converted ammonia  was  then distilled




into an acid solution and analyzed by nesslerization as above.




    Sample  absorbance measurements  were  converted  to  ammonia  concentration




through  a  calibration  curve prepared  with a  series  of  standard  ammonia




solutions.  Urea  concentrations  were calculated  by multiplying  the  organic




nitrogen ammonia concentrations by the stoichiometric factor 60/34.




    Direct nesslerization ammonia measurements were made  by  adding the nessler




reagent directly to a portion of the  sample,  awaiting full color development,
                                  -53-

-------
 and  taking  the absorbance  reading  with  the  spectrophotometer.   A separate




 calibration curve was prepared  for  the direct nesslerization measurements.




    One  complication  of the preliminary distillation step to remove  ammonia  is




 the hydrolysis  of urea  to ammonia that  occurs during the distillation.  It has




 been  estimated  that about  7  percent  of the  urea  in a  sample  is converted  to




 ammonia  during  the  preliminary  distillation  step.   Therefore,  the  indicated




 urea  concentration  multiplied  by 1.07  equals  the  actual  urea concentration.




 At  the same  time,  the  indicated ammonia  concentration  must  be reduced  by  a




 stoichiometrically  equivalent amount.   Since  2  moles (34 grams) of ammonia are




 formed from  the hydrolysis of  1  mole  (60  grams)  of urea,  the  ammonia correc-




 tion equation is as follows:




             Aa  =  Ai  -   (Ua  *  0.07 * 34/60)




    Where    Aa  =  actual ammonia concentration




             Ai  =  indicated ammonia concentration




             Ua  =  actual urea concentration




 If the actual  urea  concentration is  small relative to  the  ammonia concentra-




 tion,  then these corrections  are insignificant.  However,  if  the urea concen-




 trations are  large  (as, for example, in  scrubber  liquor streams)  compared to




 ammonia  concentrations,   then   the  ammonia  corrections  are   -unrealistic,




 resulting in negative actual ammonia concentrations.




    The direct  nesslerization analysis  and  the preliminary distillation  step




were often performed on one day and the  subsequent nesslerization and Kjeldahl




 analyses performed  one or  several  days later.  In these  cases,  the date  of



 analysis  was  defined  as  the  day  that  the  preliminary  distillation  was




performed.




    During the  urea analyses of the scrubber  outlet gas  stream  samples,  an




 absorbance reading  was occassionally higher  than  the  color  intensity  would
                                   -54-

-------
normally  indicate.   This occurred with blanks  also.   In these cases  when the

absorbance  appeared to  be too  high,  the  samples were  visually  compared  to

standards.   Since  these  gas  stream  samples  contained relatively  low  urea

concentrations,  high blank corrections  were  significant  when they  occurred.

(See  Appendix  C  for  a  breakdown  of  each sample  analysis.)   This effect was

probably due to a reagent  since it occurred in both blanks and samples.



    3.1.2 Laboratory Sample Preservation Analyses

    When  the field  sample preservation analyses were completed,  the  following

series  of  laboratory  urea  solutions were  prepared  at TRC with  distilled,

deionized water:
       A:  40 mg urea per liter of water
       B:  100 mg urea per liter of water
       C:  40 mg urea per liter of water with 2 ml saturated mercuric chloride
       D:  100 mg urea per liter of water with 5 ml saturated mercuric chloride
       E:  40 mg urea per liter of water with 2 ml concentrated sulfuric acid
       F:  100 mg urea per liter of water with 5 ml concentrated sulfuric acid

       Blank M:  5 ml saturated mercuric chloride per liter of water
       Blank A:  5 ml concentrated sulfuric acid per liter of water
The preservation  reagents  were added  to  the urea  and  blank  solutions  before

they were diluted to volume.  These  solutions remained  at  room temperature for

19  days  and were analyzed for urea and ammonia  every 2-3  days during  that

time,  for a  total of 9 analyses.  The  initial  analysis was done the  same day

that  the samples were prepared.   The  analyses  were  performed  in  the  same

manner and with the  same methods as  the  field samples,  as  described  in Section

3.1.1. above.

    The  blanks in  some  cases yielded  absorbances  that   appeared  high  when

compared to  standards,  presumably due  to  a reagent,  as mentioned in  Section

3.1.1.  A breakdown  of each sample analysis  is  shown in Appendix C.
                                    -55-

-------
 3.2  Ammonia  Interference  on  Urea  Analysis



     The   interfering  effects  of  ammonia   on  the  p-dimethylaminobenzaldehyde



 (PDAS)  urea  analysis method  (with no preliminary  distillation)  were  investi-



 gated  by  TRC in March 1979  under  technical directive  No. 2 of EPA Work Assign-



 ment 11.  -Four urea  standard  solutions  (50,  100,  150, and 200 ppm) and a  blank



 were analyzed by  adding the PDAS  reagent,  waiting  for full color development,



 and  measuring  the  absorbance  of  each solution  in  a  spectrophotometer.   A



 calibration  curve of absorbance  vs.  urea  concentration was  then drawn.   Five



 additional solutions were then  prepared, each containing 100 ppm urea and 100,



 500, 1000,  5000,  and 10000  ppm ammonia,  respectively.  The  ammonia  was  added



 from a standard  solution of ammonium chloride  (NH.C1).  To each  of  these five
                                                   4


 solutions was  added  the PDAB reagent,  and the  absorbance  of  each was measured



 and  converted to urea concentration with the prepared  calibration curve.



     The  results,   as  discussed  in Section  2.4,  indicate  that  ammonia   is  a



 noticeable positive  interference  (indicating  higher   urea  concentrations than



 actually  exist)  when  the  mole  ratio  of  urea/ammonia  exceeds  approximately



 three.  At a mole  ratio of  3.5, a 1% error was measured.   These  analyses were



 performed with  100 ppm urea  solutions,  and may  not  necessarily  apply  to all



 urea concentrations.  The relationship  between  the  urea/ammonia mole  ratio and



 the  indicated error may change  with the absolute  urea  concentration.





 3.3  Evaluation of Standard  Procedures  for  the  Proposed  EPA  Urea  Analytical

    Method





    Two  procedural  aspects  of  the  p-dimethylaminobenzaldehyde  (PDAB)   urea



analysis method were investigated  by TRC during an  emissions  test program at a



urea manufacturing facility  in  August  1979.  These aspects  were:  preliminary



distillation  (to remove ammonia) and sulfuric acid as an interference.
                                    -56-

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    3.3.1 Effects of Preliminary Distillation




    As  is  shown in Sections  2.4,  ammonia can interfere  with the  analysis  of




urea by the PDAB method.  Ammonia can  be  removed  by first distilling (boiling)




a sample;  the  effects  of this distillation on the  urea content of  the  sample




were  investigated   and  the  results of  this  investigation  are  discussed  in




Section 2.5.




    The  method of  investigation  centered on  the  analysis  by  TRC  of  five




urea-in-mannitol audit  samples  that were prepared  by EPA.   These  samples were




each dissolved  in 100 ml of distilled, deionized  water,  and these  audit sample




solutions  were then divided  into  two portions.   A  sodium borate  buffer  and




sodium  hydroxide were  added  to the  first  portions to  bring  the  pH to  9.5  or




greater; these portions were  then  distilled  (boiled)  to  remove  ammonia.   To




the residues were  added the  PDAB  reagent and the  absorbances of  these solu-




tions  were measured  in a  spectrophotometer.   The  second portions  remained




undistilled and their absorbances were measured after the addition of  the PDAB




reagent.




    The absorbances of  distilled  and undistilled standard  urea solutions were




also measured,  and  a distilled calibration  curve and  an undistilled  calibra-




tion curve  were prepared by  plotting absorbances vs. urea  concentration.   The




audit  sample  absorbances (distilled and  undistilled)  were then   read  against




both distilled and undistilled standard calibration curves.




    The results, as  discussed in Section  2.5,  show that  the  preliminary dis-




tillation  step,  while  removing  ammonia,  also  apparently  removes  some urea.




Hydrolysis  of   some  urea to  ammonia  may be  occurring  (as  in   the  Kjeldahl




preliminary distillation  step) and this  converted urea  is  boiled off along




with any original ammonia.   The degree of  urea removal appears to  be  about  14




percent.
                                          -57-

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     An  effect  of the  ammonia-removing  preliminary  distillation  step  is  an




apparent  decrease in  the sensitivity  of  the PDAB  method.   This  decrease  in




sensitivity  is,  however, only  apparent.   As  discussed above,  distillation




results  in a loss of urea.   This  loss is  reflected  in a decrease  in the in-




tensity  of color development and,  therefore, a decrease in  absorbance.   The




data  for  the distilled  and   undistilled  standard  calibration curves  used for




the  August 1979 field sample  analyses,  shown in Table  2-19,  illustrate this.




The  average  decrease  in  absorbance  (averaged over  the four urea concentrations




used)  is  about 12.2  percent.   This  implies that  the  distilled  absorbances




reflect not  the indicated urea concentrations but urea concentrations 12 per-




cent  lower,  and  that the distilled  calibration curves should  be  a  plot  of



distilled  absorbance  vs.  decreased urea  concentrations.  Further  investiga-




tions are needed to better define the extent of urea loss during distillation.








    3.3.2 Sulfuric Acid Interference




    The water  impinger samples  from  this  August  1979  emissions  test program




were  preserved  with  2  ml  sulfuric acid   (H_SO )  per   liter  of sample.   The




acid  impingers  used  at  the  prill tower  scrubber   contained   IN  H.SO ,  and




the  acid  impingers. used  at  the synthesis tower vent contained  5N  and  ION




H2S04-   The  water  and  acid  impinger  samples  were   analyzed   for  urea  with




the PDAB method with preliminary distillation.   Immediately prior to distilla-




tion, the pH of the samples  was  brought to greater  than  9.5 with the addition




of sodium  hydroxide  (IN  NaOH added  to  the  water samples and  ION added  to the




acid samples).




    In the analysis of the first test run  samples, the  absorbances of  the  acid




impinger samples were less than  the absorbance  of the  blank  used to  zero the



spectrophotometer; one of these  samples read about -0.040 absorbance  units.
                                   -58-

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To  test  whether  H2S^4  was  interfering,  four  different  water   blanks  were




prepared  and  their  absorbances were  measured,  as  described in  Section  2.5.




The two straight  water blanks  (one distilled,  the other undistilled) both read




zero.   The  absorbance of  the  dilute acid  blank  (2  ml H_SO./  liter)  ranged




between ±0.004,  and  the  absorbance of  the  strong  acid  blank (IN  H SO )  was




-0.048.   This result appeared  to confirm the  fact that  the H_SO.  did nega-




tively  interfere  with the  urea analysis, and subsequently  urea  standards were




prepared  containing  the  same amount  of  acid as  the  samples.  Water impinger




samples and  acid  impinger samples were, therefore, analyzed separately.




    The synthesis  tower sample  analyses were more  complex than the prill tower




scrubber  analyses.   The  acid  impingers used in synthesis tower  tests 1 and 2




contained  ION  H SO  ,  and  the  impingers  in  test  3  contained  5N  H SO .




For  all  three  tests the  impingers  were washed  with  IN  H.SO  .   Thus,  two




different  H2S^4   concentrations  resulted  when  impinger  contents  and  washes




were combined.  Since the volumes  of  each acid used were  known,  the normality




of  each  combined  samples  was  calculated:  samples  1  and  2 averaged  6.ON;




sample 3 was 3.7N.




    The synthesis  tower acid  impinger samples  and standards  required  40 to  60




ml of  ION NaOH per  100 ml  aliquot in order  to adjust  the pH to  9.5  for  the




preliminary  ammonia  removal.   It was  impossible  to boil  down the  samples  to




less  than 100 ml  without  severe  "bumping"  due to  the high  concentration  of




dissolved  solids.  Therefore,  these samples  and standards  were diluted  to  200




ml.   This decreased  the sensitivity of this  method by  a factor of  2 for these




three samples.
                                    -59-

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    A  10 ml aliquot  of  the 200 ml  dilution was added  to a  25  ml volumetric

flask  and  10  ml  of  the  PDAB color  reagent  was  added.    All  samples  and

standards  then formed a  precipitate  which caused turbidity.   With the addition

of 2.0 ml  concentrated HC1  to  each the  precipitate completely dissolved in the

3.7N   H-SO   solutions  and   almost  completely  in  the   6. ON   HnS04  s°lu~

tions.   However, the  absorbances of the three test samples remained below zero:


             Synthesis Tower Test No.            Absorbance

                         1                        <-0.010
                         2                         -0.004
                         3                         -0.009


When  the test  1  sample  was read  against a  blank  containing the  exact H-SO.

normality  (5.8N) of  test sample 1  (after the spectrophotometer  was  zeroed on

this blank), the sample still read -0.007.

    These  synthesis  tower  data were interpreted  to mean  that  the  synthesis

tower  urea  concentrations  were  less  than  the  detection   threshold  of  the

analysis  method.   Further  investigations  on  the  effects   of   H -SO   on  the

PDAB method are warranted.

    The  turbidity  (mentioned  above)  that occurred  with  the addition  of  the

PDAB color reagent to the acid  and NaOH treated  samples  was  encountered during

two  urea  prill  tower  emissions  test  programs  conducted   by  TRC  in  April

1980.       During  these  programs,  when  the  color  reagent  was  added   to  the

treated  samples and  standards  (after preliminary distillation),  the  solutions

turned  cloudy.   This  turbidity was removed  with  the   addition of  1.0  ml
       Reichhold Chemicals, Inc., St. Helens, Oregon; Union  Oil Company,  Brea,
       California.  EPA contract 68-02-2820, Work Assignments 19 and 20.
                                 -60-

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concentrated  hydrochloric  acid.   The  turbidity  was  probably  caused  by  an

excess  amount of NaOH  added for  ammonia  removal.  The  subsequent absorbance

readings were consistent with the visual color development.
 3'. 4 Threshold  Minimum Detectable Limit  for the  Proposed  EPA  Urea Analytical
    Method
    3.4.1 Laboratory Evaluation of the Urea Detection Threshold

    The  absolute urea detection  threshold of  the  p-dimethylaminobenzaldehyde

 (PDAB) analysis  method was  evaluated  by  TRC in March 1980.   Two sets of stan-

dard  urea  solutions were  used:   set  1  included five  solutions  ranging  from

 50 ppm  to  250  ppm  (high  concentrations);  set 2  included seven  solutions

 ranging  from 1  ppm to 30  ppm  (low concentrations) .   PDAB color  reagent  was

added directly  to these solutions  (without preliminary distillation)  and  the

solution absorbances  were  measured in a spectrophotometer using  both a 1  cm

sample cell  and  a  5 cm  sample cell.   Four  calibration  curves were prepared  by

plotting absorbance vs. urea concentration for  both  solution  sets  and  both

sample cells.

    As discussed in Section 2.6.1, the slopes  of  the set 1 and  set 2 calibra-

tion curves were similar for the 1 cm cell  data.  This  allows for accurate  low

concentration  analyses,  down to  about  7  ppm;  the threshold  of  the  method,

using a high concentration calibration curve, is then about 7 ppm.

    The 5 cm cell slopes of  the  set 1  and set 2  calibration  curve  differed,

primarily due to the non-linearity of  the  high concentration  curve.  This non-

linearity is  apparently  the result of saturation within the  5 cm  cell  at  the

highest concentrations.   It  does  appear,   however,  that  the 5  cm  cell  will

allow for  slightly lower absolute concentration  measurement  (lower  than  what

could be obtained  from  a 1 cm cell)  because of the integrating effect  of  the

larger path length.
                                 -61-

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     3.4.2 Low Level Urea Analysis  in the Field


     The proposed urea  analysis  EPA Reference  Method 28 (PDAS)  was used for the


analysis of prill  tower  scrubber  outlet samples during an April 1980 emissions


testing  program.      Both   samples   and   urea  standards  were  treated  for


ammonia  removal  by  adding   sodium borate  buffer  and  sodium hydroxide  and


boiling.  Urea  analysis was  then  performed by  adding PDAB color  reagent  and


measuring absorbance in a spectrophotometer.


     The  lowest  practical  absorbance  reading  with  the   spectrophotometer  is


about 0.010 absorbance units;  this was equivalent  to  about  10.4  ppm,  based on


an average from the eight urea  calibration  curves used for the analysis of  the


field samples.   The calibration  curves were prepared in accordance  with  the


proposed EPA PDAB reference method  (contained in Appendix A).


     It was known beforehand that  the controlled urea emissions from this prill


tower scrubber  would  be extremely low.  Consequently,  the  sampling  time  for


each test  run  at the  outlet  was  planned to  be unusually long  (320 minutes) .


Even with this long  sampling  time,  the analysis of  the  first  samples  resulted


in urea concentrations near  the threshold  of  detection.   It  was  decided that


the  sampling time  should be  lengthened to  500  minutes,  and that  the  analysis


procedure should  be modified  to  be able  to accurately  measure  the  low urea
            *

sample contents.


    The  PDAB  method presently  calls  for  a  100  ml  aliquot  of  sample  to  be


boiled to  remove ammonia and then be  diluted  back  up  to  100  ml; the  color


reagent  is  then added to  a  10  ml portion  of  this  solution.   In order  to


increase the  amount  of  .urea  in   the  spectrophotometer  sample cell,  larger
    Reichhold Chemicals, Inc., St. Helens, Oregon.
                                  -62-

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 sample  aliquots  were  taken (up to 700 ml)  and boiled down  to  100  ml.   A 10 ml

 portion of  this  solution now contained up  to  7  times  as  much urea as the 10 ml

 portion prepared  under  the  originally followed  procedure.   And  the sample

 absorbances were brought into  the working  range of the calibration curve.

    The total  water impinger  sample  volumes  for  the six  scrubber outlet test

 runs performed on  this program were as fol ows:


         Run No.                 Water Impinger Sample Volume  (ml)

            1                                   1073
            2                                   1175
            3                                   1220
            4                                   1180
            5                                   1140
            6                                   1060
         Average                                1141



Sufficient sample  volume remained  after  the initial aliquot was  drawn  so that

a repeat analysis could be performed if necessary.

    By  using  this  urea  concentrating procedure,  the  effective,  threshold  of

detection of the method  (the  minimum urea concentration in  the sampling train

impingers that  is  detectible)  was  lowered by  up  to a  factor of  seven (from

10.4 ppm to 1.5  ppm).  The minimum detectable urea concentration in a spectro-

photometer  sample  cell  (absolute threshold  of  detection)   remained unchanged,

of course.

    Whatever can be done  to increase  the  urea  concentration  in  the impingers

will help increase  the sensitivity  of the analysis method  without the  need to

concentrate sample  aliquots.   Factors involved  here are the  sampling  time and

wash  volumes.    When  urea concentrating  is  needed,  the  best  sensitivity  is

obtained by concentrating  the  largest possible sample aliquot.   Enough sample

may need  to be retained,  however, in  order  to  do  repeat  analyses or  analyses

for different parameters.
                                   -63-

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3.5 Collection Efficiency Determination of EPA Urea Sampling Train

    Three  144-minute  emissions tests were  performed  by TRC  on the  outlet  of

the  northeast scrubber  atop the  prill  tower  at  the  Union  Oil  Company  urea

manufacturing plant in Brea, California, on April  24,  1980.   This sampling was

performed with a modified EPA  sampling  train and  the contents  of  the sampling

train  impingers  were  analyzed  in  a manner  to evaluate  the  urea  collection

efficiency  of the train.   A brief  description of the sampling  and analysis

methods  used  for  these tests  is presented  in  this section.   Complete details

of this  sampling program are contained in EPA report 80-NHF-15.



    3.5.1 Sampling Methods

    The  sampling  train used is shown in Figure 3-1,  and is  a  modification  of

the standard  EPA  Reference  Method  5  sampling  train.   The sampling  train  con-

sists  of a nozzle," probe,  teflon  line,  six impingers, vacumm pump, dry gas

meter, and  an orifice flow meter.  The nozzle  is  stainless  steel and is  of a

buttonhook  shape.   It  was  connected to  a  5/8"   stainless  steel glass  lined

probe.   Following the  probe, the  gas stream passed through a 3/8" I.D.  Teflon

line into an  ice bath/impinger system.

    The  first two  impingers  each  contained   100  ml  of  deionized  distilled

water.   The  next  two  impingers  were  filled  with  IN  H-SO.  (100   ml  each) .

The fifth impinger remained empty while the sixth  was filled  with  200 grams  of

indicating silica gel to remove any remaining moisture.



    3.5.2 Sample Recovery and Preparation

    At the completion of each test  run, the train  was leak checked.   Then  the
       EPA Report 80-NHF-15, "Process Emissions Tests at  the  Union Oil Company
       Urea Manufacturing Facility, Brea,  California".   Prepared  by  TRC  under
       EPA Contract No.  68-02-2820, Work Assignment No.  20.


                                   -64-

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             STACK  WALL 	
            THERMOMETER
en
ui
                                                                                      LEGEND
                                                                 1 - NOZZLE          7
                                                                 2 - PROBE           8
                                                                 3 - TEFLON LINE     9
                                                                 4 - ICE BATH        10
                                                                 5 - FLEXIBLE LINE   11
                                                                 6 - VACUUM GAGE     12
NEEDLE VALVE
PUMP
DRY GAS METER
ORIFICE
PITOT TUBE & INCLINED MANOMETER
POTENTIOMETER
                                   FIGURE 3-1:   MODIFIED EPA PARTICULATE  SAMPLING TRAIN
                                                    AUGUST 18,1977,  FEDERAL  REGISTER

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 nozzle,  probe,  flexible teflon line,  first two impingers, and.  their connecting

 glassware  were rinsed  with  deionized,  distilled water.  The  samples  were put

 in glass containers with  teflon-lined caps as follows:


    Container  II - nozzle, probe and teflon line washes.

    Container  #2 - contents  of  the  first impinger  and the distilled water wash
                   of  the impinger and  its glassware connector.

    Container  #3 - contents  of the  second  impinger  and  the  distilled  water
                   wash of the  impinger  and its glassware connector.

    Container  f4 - contents  of the third, fourth  and fifth  impingers  and the
                   IN   H2SC>4  wash  of   these   impingers   and  their  connecting
                   glassware.


 These  samples  containers were  then  returned   to  TRC  for  urea and  ammonia

 analysis.



    3.5.3  Sample Analysis

    At  TRC the  volumes  of  each  sample were  measured   and  the  samples  were

 analyzed for ammonia with the  specific  ion electrode method  and  for  urea with

 the p-dimethylaminobenzaldehyde (PDAB)   method  with  preliminary  distillation.

 Analyses were  performed  within  20  days  of  sample collection.   For  the  urea

 analysis,  a sodium borate buffer  and NaOH were added to  each  sample  to adjust

 the pH to  9.5 or greater.  The  samples  were then boiled  to remove ammonia, and

 the PDAB color  reagent was added  to the  residue.  The  solution absorbance was

 then measured  in a spectrophotometer.

    An  additional  1  ml concentrated  hydrochloric acid  per liter of  solution

was added  to acid  impinger sample solutions prior to  the absorbance  readings.

This was done  in order to remove  the  turbidity that  resulted upon addition of

the PDAB  color  reagent.   Urea  standards were  prepared  with  the  same  acid

content  as   the  samples.    Sample   absorbances   were   converted   to   urea

concentration  with  the  calibration curve  drawn  from  the  analysis  of  these

standards.   No problems were encountered in the analysis of these samples.


                                 r-66-

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              APPENDIX A

 UREA SAMPLING AND ANALYSIS PROCEDURES

               Includes:

A.I  Original Procedure - August 1978*
A.2  Modified Procedure - August 1979*
A.3  Modified Procedure - January 1980*
A. 4  Proposed Reference Method 28*
A.5  Kjeldahl Analysis Procedure


* p-dimethylaminobenzaldehyde analysis method

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          APPENDIX A.I




ORIGINAL PROCEDURE - AUGUST 1978

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                                                                    AUG29197
               DETERMINATION OF PARTICULATE, UREA, AND
                 AMMONIA EMISSIONS FROM UREA PLANTS
                                                                        - ».
 1.   Principle  and Applicability
      1.1   Principle.  A gas sample is extracted isokinetically from
 the stack.   The  urea  and the ammonia are separated and both are
 measured  by  colorimetric procedures.
      1.2   Applicability.  This method is applicable for the determination
  2"  / ; •     "/: .•     c) en  AI » /\ j o     -£' ^ o /»"..
^pf^urea manufacturing facilities.
      Interferences Tor :the.urea determination are hydroxylamine in a
 mole ratio of  8:1 and ammonium ion in a ratio of 15:1.  Hydrazine and
 semicarbazide  interfere at a 1:1 mole ratio.
      Possible  interferences with the ammonia procedure are calcium,
 magnesium, iron  and sulfide.
 2.   Apparatus
      2.1   Sampling Train.  A schematic of the sampling train used in
 this method  is shown  in Figure 1.  Complete construction details are
 given in  APTD-0581 (Citation 2 in Section 7); commercial models of this
 train are also available.  For changes from APTD-0581 and for allowable
 modifications  of the  train shown in Figure 1, see the following subsection?
      The  operating and maintenance procedures for the sampling train are
 described in APTD-0576 (Citation 3 in Section 7).  Since correct usage is
 important in obtaining valid results, all users should read APTD-0576 and
 adopt the operating and maintenance procedures outlined in it, unless
 otherwise specified herein.  The sampling train consists of the following
 components:

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     2.1.1  Probe Nozzle.  Stainless steel (316) or glass with sharp,
                                '/:                            r
leading edge.  The angle of tapeys shall be <_ 30° and the tape/ shall  be
on the outside to preserve a constant internal diameter.  The probe
nozzle shall be of the button-hook or elbow design, unless otherwise
specified by the Administrator.  If made of stainless steel, the nozzle
shall be constructed from seamless tubing; other materials of construction
may be used subject to the approval of the Administrator.
     A range of nozzle sizes suitable for isokinetic sampling should  be
available, e.g. 0.32 to 1.27 cm (1/8 to 1/2 in.) - or larger if higher
volume sampling trains are used  inside diameter (ID) nozzles in increments
of 0.16 cm (1/16 in.).  Each nozzle shall be calibrated according to  the
procedures outlined in Section 5.
     2.1.2  Probe Liner.  Borosilicate or quartz glass tubing with a
heating system capable of maintaining a gas temperature at the exit end
during sampling of 120 +_ 14°C (248 +_ 25°F), or such other temperature as
specified by an applicable subpart of the standards or approved by the
Administrator for a particular application.  (The tester may opt to
operate the equipment at a temperature lower than that specified.)
Since the actual temperature at the outlet of the probe is not usually
monitored during sampling, probes constructed according to APTD-0581  and
utilizing the calibration curves of APTD-0576 (or calibrated according
to the procedure outlined in APTD-0576) will be considered acceptable.
     Either borosilicate or quartz glass probe liners may be used for
stack temperatures up to about 480°C (900°F); quartz liners shall be
used for temperatures between 480 and 900°C (900 and 1650°F).  Both

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                                                               0
     TEMPERATURE SENSOR.
           ^ PROBE

            TEMPERATURE
               SENSOR
PITOTTUBE
                                        IMPINGER TRAIN OPTIONAL. MAY BE REPLACED
                                             BY AN EQUIVALFNT CONDENSER
                          HEATED AREA   THERMOMETER   /.
                                                               THERMOMETER
                    oy
                     ft
PROBE  / I  I   STACK ~.
       /    k-VVALL
     —"™'^^\__   ' -
REVERSE-TYPE
 PITOTTUBE
                                 .IMPINGERS    .                ICE BATH
                                          BY-PASS VALVE  VALVE
            PITOT MANOMETER
                                                                 VACUUM
                                                                  GAUGE
          THERMOMETERS
                                                          MAIN VALVE
                      DRY GAS METER
                                        AIR-TIGHT
                                          PUMP '
                                                                              CHECK
                                                                              VALVE ..
                                                                               VACUUM
                                                                                LINE '
                '.     Fjgure5-1. Paniculate-sampling train.
                                     t»

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  types of liners may be used at higher temperatures than specified for
short periods of time, subject to the approval of the Administrator.
The softening temperature for borosilicate is 820°C (1508°F), and for   .
quartz it is 1500°C (2732°F).
     Whenever practical, every effort should be made to use borosilicate
or quartz glass probe liners.  Alternatively, metal liners (e.g., 316
stainless steel, Incoloy 825,  or other corrosion resistant metals) made
of seamless tubing may be used, subject to the approval of the
Administrator.
     2.1.3  Pitot Tube.  Type S, as described in Section 2.1 of Method 2,
or other device approved by the Administrator.  The pi tot tube shall be
attached to the probe (as shown in Figure 5-1) to allow constant monitoring
of the stack gas velocity.  The impact (high pressure) opening plane of the
pitot tube shall be even with or above the nozzle entry plane (see
Method 2, Figure 2-6b) during sampling.  The Type S pi tot tube assembly
shall have a known coefficient, determined as outlined in Section 4 of
Method 2.
     2.1.4  Differential Pressure Gauge.   Inclined manometer or equivalent
device (two), as described in Section 2.2 of Method 2.  One manometer
shall be used for velocity head (Ap) readings, and the other, for orifice
differential pressure readings.
     2.1.5  Filter Holder.  Borosilicate glass, with a glass frit filter
support and a silicone rubber gasket.  Other materials of construction
(e.g., stainless steel, Teflon, Viton) may be used, subject to. the
approval  of the Administrator.  The holder design shall provide a positive
 Mention of trade names or specific products does not constitute
 endorsement by the Environmental Protection Agency.

-------
seal  against leakage from the outside  or around  the  filter.  The  holder
shall be attached immediately at the outlet of the probe  (or  cyclone,  if
used).
     2.1.6  Filter Heating System.   Any heating  system  capable  of main-
taining a temperature around the filter holder during sampling  of
120 £ 14°C (248 + 25°F), or such other temperature as specified by  an
applicable subpart of the standards or approved  by the  Administrator for
a particular application.  Alternatively, the tester may  opt  to operate the
equipment at a temperature lower than  that specified.   A  temperature gauge
capable of measuring temperature to within 3°C (5.4°F)  shall  be installed
so that the temperature around the filter holder can be regulated and
monitored during sampling.  Heating systems other than  the one  shown in
APTD-0581 may be used.
     2.1.7  Impingers—Five as Shown in Figure 1. The  first  and  third
shall be of the Greenburg-Smith design with standard tips; The second,
fourth, and fifth shall be of the Greenburg-Smith design, modified  by
replacing theMnsert with an approximately 13 millimeter  (0.5 in) I.D.
glass tube, having an unconstricted tip located  13 mm  (0.5 in.) from the
bottom of the flask.  Similar collection systems, which have  been approved
by the Administrator, may be used.
     2.1.8  Metering System.  Vacuum gauge, leak-free  pump, thermometers
capable of measuring temperature to within 3°C (5.4°F), dry gas meter
capable of measuring volume to within  2 percent, and related  equipment,
as shown in Figure 5-1.  Other metering systems  capable of maintaining
sampling rates within 10 percent of isokinetic and of  determining sample
volumes to within 2 percent may be used, subject to  the approval  of

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the Administrator.  When the metering system is used in conjunction
with a pitot tube, the system shall enable checks of isokinetic rates.
     Sampling trains utilizing metering systems designed for higher
flow rates than that described in APTD-0581 or APTD-0576 may  be used
provided that the specifications of this method are met.
     2.1.9  Barometer.  Mercury, aneroid, or other barometer capable
of measuring atmospheric pressure to within 2.5 mm Hg (0.1 in.  Hg).  In
many cases, the barometric-reading may be obtained from a nearby national
weather service station, in which case the station value (which is the
absolute barometric pressure) shall be requested and an adjustment for
elevation differences between the weather station and sampling point shall
be applied at a rate of minus 2.5 mm Hg (0.1 in. Hg) per 30 m (100 ft)
elevation increase or vice versa for elevation decrease.
     2.1.10  Gas Density Determination Equipment.  Temperature sensor and
pressure gauge, as described in Sections 2.3 and 2.4 of Method 2, and gas
analyzer, if necessary, as described in Method 3.  The temperature sensor
shall, preferably, be permanently attached to the pitot tube or sampling
probe in a fixed configuration, such that the tip of the sensor extends
beyond the leading edge of the probe sheath and does not touch any metal.
Alternatively,.the sensor may be attached just prior to use in the field.
Note, however, that if the temperature  sensor is attached in the field, the
sensor must be placed in an interference-free arrangement with respect to
the Type S pitot tube openings-(see Method 2, Figure 2-7).  As a second
alternative, if a difference of not more than 1 percent in the. average
velocity measurement is to be introduced, the temperature gauge need
not be attached to the probe or pitot tube.  (This alternative is

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subject to the approval of the Administrator.)
     2.2  Sample Recovery.  The following items are needed:
     2.2.1  Probe-Liner and Probe-Nozzle Brushes.   Nylon bristle brushes
with stainless steel wire handles.   The probe brush shall have extensions
(at least as long as the probe) of stainless steel, Nylon, Teflon, or
similarly inert material.  The brushes shall be properly sized and
shaped to brush out the probe liner and nozzle.
     212.2  Wash Bottles—Tv/o.  Glass wash bottles are recommended;
polyethylene wash bottles may be used at the option of the tester.  It
is recommended that acetone not be stored in polyethylene bottles for
longer than a month.
     2.2.3  Glass Sample Storage Containers.  Chemically resistant,
borosilicate glass bottles, for acetone v/ashes, 500 ml or 1000 ml.
Screw cap liners shall either be rubber-backed Tefloji or shall be
                                      ~                          '^ .
constructed so as to be leak_free and resistant to chemical  attach'by
acetone.  (Narrow mouth glass bottles have been found to be less prone
to leakage.)  Alternatively, polyethylene bottles  may be used.
     2.2.4  Petri Dishes.  For filter samples, glass or polyethylene, unless
otherwise specified by the Administrator.
     2.2.5  Graduated Cylinder and/or Balance.  To measure condensed water
to within 1 ml or l.g.  Graduated cylinders shall  have subdivisions no
greater than 2 ml.  Most laboratory balances are capable of weighing to
the nearest 0.5 g or less.  Any of these balances  is suitable for use
here and in Section 2.3.4.
     2.2.6  Plastic Storage Containers.  Air_tight containers to store
silica gel.

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     2.2.7  Funnel and Rubber Policeman.  To aid in transfer of silica
gel to container; not necessary if silica gel is weighed in the field.
     2.2.8  Funnel.  Glass or polyethylene, to aid in sample recovery.  •
     2.3  Analysis.
     2.3.1  Pipettes.  Volumetric type 0.5-ml, ,1-ml, 2-ml , 5-ml , 8-ml ,
10-ml, 20-ml, and 25-ml sizes.
     2.3.2  Volumetric Flasks.  25-ml size, 100-ml size, 250-ml size,
500-ml size and 1000-ml size.
     2.3.3  Graduated Cylinder.  100-ml size.
     2.3.4  Spectrophotometer.  To measure absorbance at 405 manometers
and 420 manometers..
     2.3.5  Sample Cells.  Two matched absorbance cells to 'fit the
Spectrophotometer.
3.  Reagents
     Unless otherwise indicated, all reagents must conform to the speci-
fications established by the Committee on Analytical Reagents of the
Arrerican Chemical Society.  Where such specifications are not available,
use the best available grade.
     3.1  Sampling.
     3.1.1  Water.  Deionized, distilled to conform to ASTM
D 1193-74, type 3.  At the option of the Analyst, the KMNO, test for
 ^ ___  ~                                                   ^
oxidizable organic matter may be omitted when high concentration of
organic matter are not expected to be present.
     3.1.2  Sulfuric Acid, 1.0. N.  Dilute 28 ml of concentrated, ACS
grade sulfuric acid to 1 liter with deionized, distilled water.
     3.2  Sample Recovery.

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     S.'Z.'l  Water.  Deionized, distilled, as in 3.1.1.
     3.2.2  Sulfuric Acid, 1.0 N.  As in 3.1.2.
     3.2.3  Acetone—Reagent Grade, <_ 0.001  percent residue,  in glass
bottles, is required.  Acetone from metal containers generally has a
high residue blank and should not be used.   Sometimes,  suppliers
transfer acetone to glass' bottles from metal containers;  thus, acetone
blanks shall be run prior to field use and only acetone with  low blank
values (<_ 0.001 percent) shall be used.  In no case shall  a blank value
of greater than 0.001 percent of the weight of acetone used be subtracted
from the sample weight.
     3.3  Analysis.
   '"3.3.1  Water. Deionized, distilled, as in 3.1.1.
   >x/3.3.2  Annhydrous Mercuric Iodide (Hg I2).  ACS grade.
   ••/ 3.3.3  Potassium Iodide (KI).  ACS grade.
   •''3.3.4  Sodium Hydroxide (NaOH).  ACS grade.
     3.3.5  Stock standard Ammonium Chloride Solution.   Dissolve 3.141 g
of ammonium chloride (NHAC1) in l.ON FUSO, in a 1-liter volumetric flask
and dilute to exactly 1 liter with l.ON H2S04.  One milliliter of this
solution contains 1.0 mg of ammonia (NH3).
     3.3.6  Working Standard Ammonium Chloride Solution.   Dilute 10 ml
of the stock standard solution to 1 liter with 1.0 N H^SO, in a 1-liter
volumetric flask.  One milliliter of this solution contains 10 yg of
ammonia (NH,).
     3.3.7  Sodium Hydroxide, 10 N.  Dissolve 40 grams of NaOH in a
100-ml volumetric flask and dilute exactly to 100-ml with deionized
distilled v/ater.

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                3.3.8  Nessler Reagent.   Dissolve  160  g  of  NaOH  in  50      of
           deionized distilled water in  a 1-liter  volumetric  flask.  Allow to  cool.
           Dissolve 100 g  of mercuric iodide  and 70  g  of potassium  iodide  in a small
           volume of deionized distilled water  and while stirring add  to the sodium
           hydroxide solution.   Dilute to exactly  1  liter with deionized,  distilled
           water.   This reagent is  stable up  to 1  year.
                3.3.9  Ethyl  Alcohol, 95 Percent.  ACS grade.
             \            ~r~~-   '          3
             ^  3.3.10  P-dimethyl ami nobenzg*! dehyde.   ACS grade.
              v/ 3.3.11   Hydrochloric, Concentrated (36.5 -  38 percent  by weight).
           ACS grade.
 1-/-U--      \3.3.12  Stock Standard Urea Solution.  Dissolve  5.00 g of  urea in
C           ^~~
           500 ml  of distilled, deionized water in a 1-liter  flask  and dilute  to
           exactly 1  liter with deionized, distilled water.
                3.3.13  Working Standard Urea Solution.   Pipette 25 ml  of  stock
           standard urea solution into a 100-ml volumetric  flask and dilute to
           exactly 100 ml  with deionized distilled water.   One milliliter  of
           this solution contains 1.250  mg of urea.
                3.3.14  Urea Color  Reagent.   Prepare the color reagent by  dissolving
           2.000 g of P-dimethylaminobenzaldehyde  in a mixture of 100  ml of 95 percent
           ethyl  alcohol and 10 ml  of hydrochloric acid.
           4.   Procedure
                4.1   Sampling.   The  complexity  of  this method is such  that, in order
           to obtain reliable results, testers  should  be trained and experienced with
           the test procedures.
                4.1.1  Pretest Preparation.   All the components  shall  be maintained
           and calibrated  according  to the procedure described in APTD-0576, unless'
           otherwise specified herein.

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      Weigh several 200 to 300 g portions of silica  gel  in ai
 containers to the nearest 0.5 g.  Record the total  weight of  tta silica
 gel  plus  container, one each container.  As an alternative, the silica"
 gel  need  not be preweighed, but may be weighed directly in  its impinger
 or sampling holder just prior to train assembly.
      Check filters visually against light for irregularities  and flaws
 or pinhole leaks.  Label filters of the proper diameter on  the back  side
 near the  edge using numbering machine ink.  As an alternative,
 label the shipping  containers  (glass or plastic  petri  dishes)  and
 keep, the  filters  in these  containers at all times  except  during
 sampling  and weighing.   ..--..-                         .
                       ^
      Desiccate  the'filters at  20 +. 5.6°C (63 +_ 10°F) and  ambient   '
•pressure  for at least 24 hours and weigh at intervals  of at  least
 6 hours to a constant weight,  i.e., <0.5 mg change from previous
 weighing; record  results to the nearest 0.1 mg.   During each
 weighing  the filter must not be exposed to the laboratory atmosphere
 for a period greater than  2 minutes and a relative humidity  above
 50 percent.  Alternatively (unless otherwise specified i>y the
 Administrator), the filters may be oven dried at 105°C (220°F)  for   . •
 2 to 3 hours,  desiccated for 2 hours, and weighed.  Procedures  other
 than those described, which account for relative humidity effects,  .   .
•may be used,  subject to the approval of the Administrator.   .          .
      4.1.2  Preliminary Determinations.  Select.the sampling site and
 the minimum number of sampling points according to-Method 1  or as '  •
 specified by the  Administrator.  Determine the stack pressure,
 temperature, and  the range of velocity heads using Method 2; it is

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 recommended that a leak-check of the pi tot  Tines  (see Method 2,
 Section 3.1) be performed.   Determine the moisture content using .
 Approximation Method 4 or its alternatives  for the purpose of making  "
 isqkinetic sampling rate settings.   Determine the stack gas dry
 molecular weight, as described in Method 2, Section 3.6; if integrated
 Method 3 sampling is used for molecular weight determination, the
 integrated bag sample shall  .be taken simultaneously with, and for
 the same total length of time as, the particulate sample run.-         :
     Select a nozzle size based on the range of velocity Heads, such
that it is not necessary to change the nozzle size in order to maintain
isokinetic sampling rates^  During the run, do not change the nozzle
size.  Ensure that 'the proper differential  pressure gauge is chosen for
the range of velocity heads encountered (see Section 2.2 of Method 2).
     Select a suitable probe liner and probe length such that all
                                                                      •
traverse points can be sampled.  For large stacks, consider sampling
fron) opposite sides of the stack to reduce the length of probes.
                 •
     Select a total sampling-time greater than or equal  to the minimum
total sampling time specified in the test procedures for the"specific  .
industry such that (1) the sampling timejger point is not Jess than 2  •
rain, (or some greater time interval as specified by the Administrator),
and (2) the sample volume taken (corrected to standard conditions) will
exceed the required minimum total gas sample volume.  The latter is  '-. -,•
based on an approximate average sampling rate.
     The sampling time at each point shall  be the same..  It is recom-
mended that the number of minutes sampled at each point be an integer or
an integer plus onchnlf minute, in order to avoid timekeeping errors.'

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      In.some circumstances, e.g., batch cycles,  it may be rveccesary to
sample  for shorter times at .the traverse points  and'to obtain sina-ller
gas sample volumes.  In these" cases, the Administrator's  approval  must
first be  obtained.            •   .  •       •.      •       .•               '
      4.1.3  Preparation of Collection Train.  During preparation and
        •                                           •
assembly  of the  sampling train,  keep all opc-ninrja where contamination
can occur covered  until just prior to assembly or until  sampling is  about
to begin.
      Place 75 ml of water in the first impinger, 100 ml  of 1.0 N sulfuric
acid  into each, of  the next  two impingers, leave the fourth impinger empty
  and transfer 200 - 300 g  of preweighed silica gel from its container to
  the fourth impinger.  More silica gel may be used, but care should be taken
to ensure that it  is not entrained and carried out from the impinger during
sampling.   Place the container in a clean place for later use in the sample
recovery.   Alternatively, the weight of the silica gel plus impinger may be
determined to the  nearest 0.5 g and recorded.
      Using a tweezer or- clean disposable surgical gloves, place a labeled
  (identified) and weighed  filter in the filter holder.   Be sure that the
  filter  is properly centered and the gasket properly placed so as to prevent
  the sample gas stream from circumventing the filter.  Check the filter for
               N
  tears after assembly  is completed.
        When glass  Tiners are used, install the selected nozzle using a Viton
  A 0-ring when  stack temperatures are less than 260°C  (500°F) and an
  asbestos string  gasket when temperatures are higher.  See APTD-0576 for
  details.  Other  connecting systems using either 316 stainless steel or
  Teflon  ferrules  may be used.  When metal liners are used, install the
  nozzle  as above  or by a leak-free direct mechanical connection.  Mark

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proper distance  Info.the stack or duct for each sampling  po
     Set. up the train as in Figure -..I, using  (if necessary^ 
-------
  the rest of the sampling  train,  in  one  step,  at  380 mm  Hg  (15 in. Hg)
  vacuum.   Leakage rates in excess of 4 percent of the  average sampling
  rate or  0.00057 m/min (0.02 cfm),  whichever  is  less, are  unacceptable.-
                    •                                        • *
                    *      •                        •                .      '
       The following leak-check instructions  for the sampling train
  described in APTD-0576 and APTD-0581 may be helpful.  Start the  pump
  with bypass valve fully open and coarse adjust valve  completely  closed.
  Partially open'the coarse adjust valve  and  slowly close the bypass
.  valve until the desired vacuum is reached.   Do. not reverse direction
  of bypass valve; this will cause water  to back up into  the filter      • •
  holder.   If the desired vacuum is exceeded, either leak-check at
  this higher, vacuum or end the leak check as shown below and start over.
       When the leak-check is completed,  first slowly  remove the  plug
  from the inlet to the probe, filter holder, or cyclone  (if applicable)
  and immediately turn off the vacuum pump.  This  prevents the v/ater  in   .-.
 • the impingers from being forced backward into the filter holder and
  silica gel from being entrained backward into the. third impinger.
                       '                         *                  •   •
       4.1.4.2  Leak-Checks During Sample Run.  If, during the  sampling
  run, a component  (e.g.,  filter assembly or impinger)  change  becomes-
        —          .          _                                 • "••   ""
  necessary, a leak-check  shall be conducted immediately before the
  change is mada— The  leak-check shall  be done according to the  procedure
  outlined in Section 4.1.4.1 above,  except that it shall be done at a
  vacuum equal to or greater  than the maximum value recorded up to that
  point in the test.  .If the  leakage  rate is found to be no  greater than
  0.00057 m/min  (0.02  cfm) or 4  percent of the average sampling  rate

-------
  (whichever is less), the results are acceptable, and no correction
  will need to be applied.to the total volume of dry gas metered; •
  if, however, a higher leakage rate is obtained, the tester shall
  either record the leakage rate and plan to correct the sample volume
  as shov/n in Section 6.3 of this method, or shall void the sampling run.
       Immediately after, component changes, leak-checks are optional;.
  if such leak-checks are done, the procedure outlined in Section 4.1.4.1
  above shall be used.   '                         '
       4.1.4.3  Post-test Leak-Check.  A leak-check is mandatory at the
                  • %                                *
  conclusion of each sampling run.  The leak-check shall be done in
  accordance with the procedures outlined in Section 4.1.4.1, except
                                             f                      .
  that it shall be conducted at a vacuum equal to or greater than the
  maximum value reached during the sampling run.   If the leakage rate
  is.found to be no greater than 0.00057 m /min  (0.02 cfm) or 4 percent  •
.  of the average sampling rate (whichever is less)» the results are
  acceptable, and no correction need  be applied  to the total.volume of
  dry gas metered.  If, however, a higher leakage  rate is obtained, the  .
 *                                              •                      •,
  tester shall either record the'leakage rate and  correct the sample
  volume as shown in Section 6.3 of this method, or shall void the
  sampling run. '           '           .                 •    ' •       '    •
       4.1.5  Particulate Train Operation.  During the sampling' run,
.  maintain an isokinetic sampling rate (within 10  percent of true'
  isokinetic unless otherwise specified by the Administrator) .and a
  temperature around the filter of 120 £ 14°C (248 £25°F}, or such other

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temperature as specified .by an applicable subpart of the standards

or approved by the Administrator.     •

     For each run, record.the data required on a data sheet such as

the one shown in Figure V?.  Be sure to record the initial dry gas
                     • •

meter reading.  Record the dry gas meter readings at the beginning

and end of each sampling time increment, when changes in flow rates

are made, before and after each leak  check, and when sampling is halted.

Take other readings required by Figure £-2 at least once at each sample

point during each time increment and  additional readings when significant

changes (20 percent variation in velocity head readings) necessitate   .  •
                 • »                                                     ,
additional adjustments in flow rate.  Level and zero the manometer.

Because the manometer level and zero  may drift due to vibrations and

.temperature changes-, make periodic checks during the traverse.

     Clean the portholes  prior to the test run to minimize the chance
                                                                        W
of sampling deposited material.  To begin sampling, remove the nozzle

cap', verify that the  filter and probe heating systems are up to

temperature,  and that the pilot tube  and probe are properly positioned.

Position  the  nozzle at the first traverse point with the tip pointing

directly  into the  gas stream.   Immediately start the pump and adjust

the flow  to isokinetic conditions.  Nomographs are available, which

aid in  the rapid adjustment of  the  isokinetic sampling  rate without

excessive computations.   These  nomographs are designed  for use when the

Type S  pitot  tube  coefficient is 0.85 +_ 0.02, and the stack gas  •  .
                                 *
equivalent density (dry molecular weight) is equal to 29 +.4.  APTD-C375

details the procedure for using the nomographs.  If  C   and M.  are

outside the above  stated  ranges, do not use  the  nomographs  unless     .      -
           '        -''  '«  r-i *•/">  7  /'/,  •:,<*•< ,w, |7) G,'<\*  ''<*>/<'*••«- (0

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PLANT
LOCATION.
OPERATOR.
DATE	
RUN NO	
SAMPLE BOX NO..
METER BOX NO._
METER AHip	
CFACTOR	
                 AMBIENT TEMPERATURE
                 BAROMETRIC PRESSURE.
                 ASSUMED MOISTURE.'/._
                 PROBE LENGTH.m (fi)	
                 NOZZLE IDENTIFICATION NO..
                 AVERAGE CALIBRATED NOZZLE DIAMETER, cinfin.).
                 PROBE HEATER SETTING	.	
                 IEAK RATE. m3/inin.{cfm)	
                 PROBE LINER MATERIAL	_
PlTOTTUBECOEFFICIENT.Cp.
                                          SCHEMATIC OF STACK CROSS SECTION
                 STATIC PRESSURE, nim Hg (In.Hg).
                  FILTER H0:_	
TRAVERSE POINT
NUMBER












TOTAL
SAMPLING
TIME
(0). min.











•
•
AVERAGE
VACUUM
nwn Hg
(in Hg)














STACK
TEMPERATURE
<'s>
°C(°F)














VELOCITY
HEAD
«APS).
mm(in.;HjO












•

PRESSURE
DIFFERENTIAL
ACROSS
ORIFICE
METER
mm H20
(in. H20I














GAS SAMPLE
VOLUME
n,3 (It3|














*
GAS SAMPLE TEMPERATURE
AT DRV GAS METER
INLET
°C ('F|












Awg.
OUTLET
°C (°F(












Avi|.
Avg.
B .»
FILTER HOLDER
TEMPERATURE.
°C |°F|




'









TEMPERATURE
' OF GAS
LEAVING
CONDENSER OR
LAST IMPINGER.
°C I°F|







\


•



                                                   Figure
Paniculate field data.

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     When the stack is under significant negative pressure (height


of impinger stem), take care to close the coarse adjust valve before


inserting the probe into the stack to prevent water from backing .into  '
                  0
                   . *• *
the filter holder.  'If necessary, the pump.may be turned .on with the

coarse adjust valve closed.  f.

     When the probe is in position, block off the openings around  .

the.- probe and porthole to prevent unrepresentative dilution of the

gas stream.
                                                                     •

     Traverse the stack cross-section, as required by Method 1 or;as
    x
specified by the "Administrator, being careful not to bump the probe
                ,               •
nozzle into the stack walls when sampling near the walls or when

removing or inserting the probe through the portholes; this minimizes

the chance of extracting deposited material.

     During the test run, make periodic adjustments to keep the       ~

temperature around the filter holder at the proper level; add more

ice and, if necessary, salt  to maintain a temperature of less than

20"C (68°F) at the condenser/silica gel outlet.  Also, periodically

check the  level and zero of  the manometer.
                             •

     If  the pressure drop across the filter becomes too high, making

isokinatic sampling difficult to maintain, the filter may be replaced

in the midst of a sample run.  It  is recommended that another complete

filter assembly be used rather than attempting to change the filter

itself.  Before a new filter assembly is installed, conduct a leak-check


(see Section 4.1.4.2).  The  total  particulate weight shall include the

summation  of all  filter assembly catches. •'..'-.'/.

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     A single train shall be used for the entire sainple run, except .
in cases where simultaneous sampling is required in .two or more
separate ducts or at two or more different locations within the same
duct, or, in cases- where equipment failure necessitates a change of
trains.  In all other situations, the use of tv/o or more trains will
                                                ;
be subject to the approval of the Administrator.      .   .
     Note that when tv/o or more trains are used, separate analyses of
the front-half and (if applicable) irnpinger catches from each train
                          o
shall be performed, unless identical nozzle sizes were used on all
trains, in which case, the front-half catches from the individual trains
                • *
may be combined  (as may the impinger catches) and one analysis of front-
half catch and one analysis of impinger catch may be performed.  Consult
with the Administrator for details concerning the calculation of
results when tv/o or more trains are used.      .                   .
     At the end of the sample run, turn "off the coarse adjust valve,
remove the probe and nozzle from the stack, turn off the pump, record
the final dry gas meter reading, and conduct a post-test leak-check, as
outlined in Section 4.1.4.3.  Also, leak-check the^pitot lines as .
described in Method 2, Section 3.1; the lines must pass this leak-check,
in order to validate the velocity head data.
     4.1.6  Calculation of Percent Isokinetic.  Calculate percent
isokinetic (see  Calculations, Section 6) to determine whether the run
v/as valid or another test  run should be made.   If there was difficulty
in maintaining isokinetic  rates due to source conditions, consult with
                                                                  •
the Administrator for possible variance on the isokinetic rates.

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     4.2  Sample Recovery.  Proper cleanup procedure begins  as  soon
as the probe is removed from the stack at the end of the sampling
period.  Allow the probe to cool.
     When the probe can be safely handled, wipe off .all  external  .
particulate matter near the tip of the probe nozzle and place a cap
over it to prevent losing or gaining particulatejpatter.  Do not cap
off the probe tip tightly while the sampling train is cooling down
as this would create a vacuum in the filter holder, thus drawing water
from the impingers into the filter holder.
     Before moving the sample train to the cleanup site, remove the
probe  from the sample train, wipe off the silicone grease, and cap
the open outlet of the probe.  Be careful not to lose any condensate
that might.be present.  Wipe off the silicone grease from the filter-
inlet  where the probe was fastened and cap it.  Remove the umbilical
                              *
cord from the last impinger and cap the  impinger.   If a flexible line
is used between the  first impinger or condenser and the filter holder,
disconnect the  line  at the filter holder and  let any condensed water
or liquid drain into the  impingers or condenser.  After wiping off the
silicone grease,  cap off  the filter holder outlet and impinger inlet.
Either ground-glass  stoppers, plastic caps, or serum caps may be used
to close these  openings.
     Transfer the probe and filter-impinger assembly to'the  cleanup
area.  This area  should be clean and protected from the wind so that
the  chances of  contaminating or  losing the sample will  be minimized.

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     Save a portion of  the  acetone used for cleanup as a blank-  Take
200 ml of this  acetone jJirectly from
place  it  in a  glass  samp.le  container  labeled ."acetone blank."
   .  Inspect the  train  prior to  and during disassembly and note any
abnormal  conditions.  Treat the  samples as follows:
   s Container No. 1.   Carefully remove the filter from the filter holder
and place it in its  identified petri  dish container.  Use a pair of
                                                i
tweezers  and/or clean disposable surgical gloves to handle the filter.
If it  is  necessary to fold  the filter, do so such that the particulste
                      • *
cake is inside the fold.   Carefully transfer to the petri dish any
parti cul ate matter and/or filter fibers which  adhere to the filter
.holder gasket, by using a dry Nylon bristle brush and/or a sharp-edged
blade.. Seal the  container.
     Container No. 2.   Taking care to see that dust on the outside
of the probe or other exterior  surfaces does not get into the sample,
quantitatively recover  parti cul ate matter or any condensate from the  •
probe  nozzle,  probe  fitting, probe liner, and  front half of the
                                            /          •
filter holder  by  washing these  components with acetone and placing.
the wash  in a  glass  container.   Distilled water may be used instead
                                                             *
                            •                                          , •  •
of acetone when approved by the Administrator  and shall be used when  •
specified by the  Administrator;  in these cases, save a water blank
and follow the Administrator's. directions on analysis.  Perform the   •• .»  '•
.acetone rinses as follows:           "      '•.',••••.    '.. - : •

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     Carefully remove  the  probe nozzle and clean.the inside surface
                                                         • .
by rinsing with  acetone  from a wash  bottle and  brushing with a Nylon
bristle  brush.   Brush  unti->  the acetone  rinse shows no visible particles,
after  which  make a -final rinse of the inside surface with acetone...  '
    • Brush and rinse the inside parts of the Swage!ok fitting with  •
acetone  in a similar way until no visible particles remain.   ••        •  .
     Rinse the probe liner with acetone  by tilting and rotating  the
probe  while  squirting  acetone into its upper end so that all  inside
surfaces will be wetted, with acetone. Let the  acetone drain  from the
lower  end into the sample container. A  funnel  (glass or polyethylene)
may.be used  to aid in  transferring liquid washes to the  container..  Follow
                                                                   •
the acetone  rinse with a probe brush. Hold  the probe in an inclined    '  -.
                                           •
 position, squirt acetone into the upper  end  as  the probe brush is being
 pushed with  a >wisting action through the probe; hold a  sample container
 underneath the lower end of the probe,  and  catch any acetone and 'parti cu-
 late matter which is brushed from the probe.   Run the  brush through  the
. probe three times or more until  no visible participate matter is.carried
                                          *                              •
 out with the acetone or until none remains in the probe  liner on visual
              *                                   '                *
 inspection.   With stainless steel or other metal probes, run the brush •
 through in the above prescribed manner at least six times since metal
 probes have small crevices  in which particulate matter can be entrapped.
 Rinse the brush with acetone, and quantitatively collect these washings  '
 in the sample container.  After the brushing, make a final acetone- rinse-  .
                                                     • , •     -•.'._  i.
 of the probe as described above.      •          . •   .      • '  .   • r'
                                                           r

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     It is recommended that two people be used to clean the probe

to minimize sample losses.  Between sampling runs, keep brushes clean
                                         *             •           *    • .'
and protected from contamination.             .

     After ensuring that all joints have been wiped clean of silicons

grease, clean the inside of the front half of the filter holder by

rubbing the surfaces with a i\'ylon bristle brush and rinsing v/ith^

acetone.  Rinse each surface three times or more if needed to remove

visible particulate.  Make a final rinse .of the brush and filter

holder.  Carefully rinse out the glass cyclone, also  (if applicable).

After all acetone washings and particulate matter have been collected

in the sample container, tighten the lid on the sample container so

that acetone will not leak out when it is shipped to  the laboratory..
                                    •     •                   %
Nark the height of the fluid level to determine whether_^£-ftot    .'   :

leakage occurred during.transport.  Label the container;to clearly

identify its contents.          "           '           .    .

     Container No. 3.  Note the color of the indicating silica gel.-.

to determine if it has been completely spent and make a notation of

its condition.  Transfer the silica gel from the fourth impinger to •'.'"'

its original container and seal.  A furine 1 m'ay,'ma-ke-it easier-to.pour
                                                                     *
the silica  gel without spilling.  A rubber policeman  may be. used as   :
                                • ":      •    •   *•'    ' .*• '     .-.  : ' **
an aid in removing the silica gel from the impfhger.  It is not '
                          s                     • •                     •  •

necessary to remove  the small amount of dust particles that may  adhere

to the impinger wall and are.difficult to. remove.  .Since .the gain in

weight is to be used for. moisture calculations, do.not use any water

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 Plant.
 Date	


 Run Wo	
                  *
.Filter No	—1	

Amount liquid lost during transport

 Acetone blank volume, ml	

 Acetone wash volume, ml	
Acetone blank concentration, mg/mg (equation 5-4).

Acetone wash blank, mg (equation 5-5)	
CONTAINER
NUMBER
1
2
TOTAL
WEIGHT OF PARTICULATE COLLECTED.
mg
«
FINAL WEIGHT


H^x^L
TARE WEIGHT


I^xiT
Less acetone blank
Weight of particulate matter
WEIGHT GAIN






FINAL
INITIAL
LIQUID COLLECTED
TOTAL VOLUME COLLECTED
VOLUME OF LIQUID
WATER. COLLECTED
IMPINGES
VOLUME. '
ml.
-



SILICA GEL
WEIGHT.
9



g* ml
      'CONVERT WEIGHT OF WATER TO VOLUME BY DIVIDING TOTAL WEIGHT
       INCREASE BY DENSITY OF WATER (Iff/ml).
                                   INCREASE, g

                                      'I g/ml
« VOLUME WATER, ml
                         Figure 5-3. Analytical data.

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    or other liquids to transfer the silica gel.  If a balance is available
    in the field, follow the procedure for container No. 3 in Section 4.3.
         Container No. 4.  Measure and record the volume of the first impinger.
    Then transfer the contents to a storage container.  Rinse the first
 \ _•
V  impinger and the connecting glassware with water and add the rinse water
    to the container.  Mark the level of the liquid on the container and
    identify the sample container.
         Container No. 5  Measure and record the volume of the second and third
    impingers.   Then transfer the contents to a storage container.   Rinse the
    impinger and connecting glassware with 1.0 N sulfuric acid and add the
    rinsings to the sample container.  Mark the level  of liquid on the container
    and identify the sample container.
         4.3  Analysis.  Record the data required on a sheet such as the one
    shown in Figure 5-3.  Handle each sample container as follows:
         4.3.1   Container No 1.  Leave the contents in the shipping container
    or transfer the filter and any loose particulate from the sample container
    to a tared glass weighing dish.  Desiccate for 24 hours in a desiccator
    containing anhydrous calcium sulfate.  Weigh to a constant weight and
    report the results to the nearest 0.1 mg.  For purposes of this section,
    4.3, the term "constant weight" means a djfference .of no more than O.j  mg
    or 1 percent of total weight less tarejveight, whichever is greater, between
    two consecutive weighings, with no less than 6 hours of desiccation time
    between weighings.
         Place  the filter in a beaker with 50 ml of deionized, distilled water
    and place the beaker in an ultrasonic bath for 15 minutes.  Combine this
    solution with the solution from Container No. 4 as discussed under
    Section 4.3.4.

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      4.3.2  Container No.  2.   Note  the  level  of liquid  in  u.d  container
 and confirm on the analysis  sheet whether or  not leakage occurred  during
 transport.  If a noticeable  amount  of leakage has occurred,  either void
 the sample or use methods, subject  to the approval  of the
 Administrator, to correct  the final  results.   Measure the  liquid  in
 this container either volumetrically to +_ 1 ml  or gravimetrically  to
 +_ 0.5 g.   Transfer the contents  to  a tared 250-ml  beaker and evaporate
 to dryness at ambient temperature and pressure.   Desiccate for 24  hours
"and weigh to a constant weight.  Report  the results  to the  nearest  0.1  mg.
      Add  50 ml of deionized  distilled water to the  residue in  the  beaker
 and place the beaker in an ultrasonic bath for 15 minutes.  Combine this
 solution  with the solution from  Container No. 4 as  discussed under
 Section 4.3.4.
     .4.3.3. Container No.  3.   Weigh- the spent silica  gel (or silica gel
 plus impinger) to the nearest 0.5 g  using a balance.  This step may be
 conducted in the field.                    '            '•
      4.3.4  Container No.  4.   Quantitatively  transfer the  contents of
 Container No.4 to a 250-ml volumetric flakj.   Add to  this  flask the
 extracts  from Containers 1 and 2.  Dilute to  exactly  250 ml  with
 deionized, distilled water.   Pipette 10 ml of this  solution  into  a
 25-ml volumetric flask and add 10 ml of the urea color  reagent.  Dilute
 to exactly JJ3xml with deionized, distilled water.  Mix  well  and allow to
 stand for at least 10 minutes for full  color  development.   Measure the
 absorbance of the solution at 420 NM using the blank  solution  (Section 5.5)
 as a zero reference.  Dilute the sample and the blank with equal  amounts
 of deionized distilled water if  the absorbance exceeds  that of the
 5.00 mg urea standard.

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              4.3.5  Container No. 5.  Quantitatively transfer the coorWfcs of
         Container No. 5 to a 1-liter volumetric flask.  Rinse the container
         and cap with several portions  of 1.0 N sulfuric acid and transfer to
         the flask.  Dilute to exactly 1 liter with l.ON sulfuric acid.   Pipette
         10 ml of the sample from the 1-liter flask into a 500 mi-volumetric flask
         and dilute to exactly 500 ml with 1.0 N'H2S04.  Pipette 20 ml  of this
         solution into a 25-ml volumetric flask.  Add 10 N sodium hydroxide drop-
\A      wise to the flask until the pH is between eight and ten.  Then  add 0.5 ml
v.
v.              •   .
         of Nessler reagent and dilute to exactly 25 ml with deionized  distilled
         water.  Mix well and allow to stand for the same amount of time as the
         standards used for calibration.  Measure the absorbance at 405  nm using
         the blank solution (Paragraph 5.5) as a zero reference.  Dilute the sample
         and the blank with equal amounts of deionized distilled water  if the
         absorbance exceeds that of the 100 yg NH~ solution.
              4.3.6  "Acetone Blank" Container.  Measure acetone in this container
         either volumetrically or gravimetrically.  Transfer the acetone to a
         tared 250-ml beaker and evaporate to dryness at ambient temperature and
         pressure.  Desiccate for 24 hours and weigh to a constant weight.  Report
         the results to the nearest 0.1 mg.
         5.  Calibration
              Maintain a laboratory log of all calibrations.
              5.1  Probe Nozzle.  Probe nozzles shall be calibrated before their
         initial use in the field.  Using a micrometer, measure the inside
         diameter of the nozzle to the nearest 0.025 mm (0.001 in.). Make three
         separate measurements using^different diameters each time, and  obtain
         the average of the measurements.  The difference'between the high and

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    low numbers  shall not exceed 0.1 mm (0.004 in.).  When nozzle?
    nicked,  dented, or corroded, they shall be reshaped, sharpened-  and
    recalibrated before use.  Each nozzle shall be permanently and uniquely
    identified.
         5.2  Pitot Tube.  The Type S pitot tube assembly shall be calibrated
    according  to the  procedure outlined in Section 4 of Method 2.
         5.3  Metering System.  Before its initial use in the field, the
    metering system shall be calibrated according to the procedure outlined
    in APTD-0576.  Instead of physically adjusting the dry gas meter dial
    readings to  correspond to the wet test meter readings, calibration
    factors  may  be used to mathematically correct the gas meter dial readings
    to the proper values.  Before calibrating  the metering system, it is
    suggested  that a  leak-check be conducted.  For metering systems having
    diaphragm  pumps,  the  normal leak-check procedure will not detect leakages
    within the pump.   For these cases, the following leak-check procedure is
  -= pumps,-the-normal-leak-check -procedure will not detect leakages within—
  -the pump.—For--these-cases-the-following  leak-check procedure-is    - -
               i '          •                    •       '                     •   •
,   suggested i^ake  a 10-minute calibration'run at 0.00057 m3/min (0.02 cfia);
                      *                      '               •               .  -
    at the end of the run",  take the difference of the measured v/et test meter
    and dry  gas  meter volumes;  divide the difference by 10, to get the leak
    rate.  The leak  rate  should not exceed C.00057 ra3/nrin (0.02 cfrn).    '
         After each  field use,  the calibration of the metering system
    shall  be checked  bv  performing three calihratinn runs at a single.      •  .
    intermediate orifice  setting  (based  on the previous field test), with
   the vacuum set at the maximum  value  reached during the test series.
   To  adjust  the  vacuum,  insert a  valve  between the v/et test mater and

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 the inlet of the metering system.  Calculate the  average  value- Q£ the
 calibration factor.  If the calibration has changed  by more  than 5 per-.
 cent,  recalibrate the meter over the full range of orifice settings,  as  '
 outlined in APTD-0575.               '
     Alternative procedures, e.g., using the orifice meter coeffi-
 cients,  may be used, subject to the approval of the Administrator.
     Note:   L£-±hP dry gas meter coefficient valuesjib.tained  before
 and afi£r_atest series differ by more than 5 percent, the test.
series  shall  either be voided, or calculations for the test' series '
shall be  performed using whichever meter coefficient value  (i.e.,'
before  or after)  gives the lower^jolug. of total sample volume.
                  ^^^^^^^""^^"••^^^^^^^•^•^•^^^^^      •^^•^•^^^""•^^•^^^™™*™»     ^^^^^^^^^^
      5.4   Probe Heater Calibration.  The probe heating system shall  be
calibrated before its initial  use in the field according to. the pro-'
cedure  outlined in APTD-0576.   Probes constructed according to APTD-0581
need  not be calibrated if the  calibration curves in APTD-0576 are used.
      5.5   Temperature Gauges.   Use the procedure in Section 4.3 of
Method 2 to  calibrate in-stack temperature gauc-ec.
 such as are used for the dry gas  meter and  condenser outlet,  siiaVl  be
                                     thermometers.
      5.6  Leak Check of Metering System Shown in  Figure  5-1.   That portion
 of the sampling train from the pump to the orifice  meter should be leak
 checked prior to initial use and after each shipment.  Leakage after the
 pump will  result in less volume being recorded than is actually sampled.
 The following procedure is suggested (see Figure  5-4):   Close the main
 valve on the meter box.  Insert a one-hole rubber stopper with rubber

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 tubing attached  into  the  orifice exhaust pipe.  Disconnect and vent
 the  low side  of  the orifice manometer.  Close off the low side orifice
 tap.   Pressurize the  system to  13  to 18 cm  (5 to 7 in.) water column
 by blowing  into  the rubber tubing.  Pinch off the tubing and observe
 the  manometer for one minute.   A loss of pressure on the manometer
 indicates a leak in the meter box;  leaks, if present, must be corrected.
      5.7 Barometer.  Calibrate against a mercury barometer.
      5.8 Determination of Spectrophotometer Calibration Factor K.
      5.8.1  Urea Analysis.  Add 0.0, 1.0, 2.0, 3.0, and 4.0 ml of
 working standard urea solution  to  a series  of five 25-ml volumetric
 flasks.  Pipette 10 ml of the urea  color reagent into the flask and
 dilute to exactly 25  ml with deionized distilled water.  Mix well and
.allow each  to stand for at least 10 minutes for color development.
 Measure the absorbance of each  standard at  420 nm.  The calibration
 procedure must be 'repeated each day that samples are analyzed.  Calculate
 the  spectrophotometer calibration  factor as follows:

 '     K     -   1250   -4	f-	\	\	2
       CU             A^  + A+A+A+A
                      An   ~ AO      *2     A     C
 Where:      '   '
      K  =  Calibration factor for  urea analysis.
      A-,  =  Absorbance of  the 1250  yg standard
      A2 =  Absorbance of  the 2500  yg standard.
      A3 =  Absorbance of  the 3750  yg standard.
      A4 =  Absorbance of  the 5000  yg standard.
      5.8.2  Ammonia Analysis:   Add 0.0, 1.0, 2.0, 5.0, 8.0, and 10.0
 ml of working standard ammonium chloride solution to a series of  six
 25-ml volumetric flasks.  Adjust the total  volume of solution in  each

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     6.5  Moisture Content.
                  w(std)
                      ~
ws
ws
                                                  .   _   _
             \T~, - +~u -                     ,  Equation 5-3
             Vni{std) * vw(std)                            .
     Note: . In saturated or water droplet-laden gas streams, two
              -- . - , - , —             / - •    — •
calculations of the moisture content of the stack gas shall be made,
one^from the iir.pinger analysis (Equation 5-3), and a second from the
assumption of saturated conditions.   The lower of the two values of
BWS shall be considered correct.  The procedure for determining the
moisture content based upon assumption of saturated conditions is
                                             »
given in the Note of Section 1.2 of Method 4. .ipor the purposes of this
method, the average stack gas temperature from'Figure 5-2 may be used  to
make this determination, provided that the accuracy of the in-staek
temperature sensor is +. 1°C (2°F).- .   '          '          '  .  '
     6.6  Acetone Blank' Concentration.
                            • •                                .  .    t
          c    -   -A-  '",,
           a   "   V.
     6.7  Acetone Wash Blank.
                          .                    •
          wa   =   Vv»».
     6.8  Total .Particulate  Weight.   Determine the total participate
catch from the sum of the weights  obtained from containers 1 and 2
less the acetone .blank (see  Figure 5-3).  Note:  Refer to Section 4.1.5
                        -*
to assist in calculation of results involving two or more filter    •
                                         •*••     «
assemblies or two or more sampling trains.   '

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     6.9  Participate Concentration.



          Cs = (0.001 g/mg) (Ma/Vm(std))      .    Equation 6





     6.10  Total Mass of Urea Per Sample.

              .   .           i . •  •


                          VaV       •'     •

          Mu  =  Kcu AF  V—~~                    Equation 7
     6.11  Urea Concentration.                      ;

                                                    I



          Cu  =  K2  	                          Equation 8


                      sc



Where:

                    3


     K   = 1C)3         for metric Un1ts'
           6.243 x 10"5          for; English units".
     6.12  Total Mass of NK, Per Sample.
                           «3





     MNH3 -=  KC NH3  AF                          Equation 9
     6/13  Ammonia Concentration.
                K2    -                         .  Equation 10

                     sc
                      3

Where:  K2' = 103    /    for Metric units.
                   x 1Q-5  lb/SCF
                   x IU    pg/ml  for English units.

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          APPENDIX A.2




MODIFIED PROCEDURE - AUGUST 1979

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                                                                     --/,
                 DETERMINATION OF PARTICULATE,  UREA,  AND
                    AMMONIA EMISSIONS FROM UREA PLANTS   '

1.  Princ-iale and Applicability
     1.1  Principle.  A gas sample is extracted isokinetically from the
stack.  The urea and the ammonia are separated  by distillation, the urea
is converted to ammonia, and both are measured  by a colorimetric procedure.
     1.2  Applicability.  This method is applicable for the determination
of urea and ammonia from.urea manufacturing facilities.
     Possible interferences with the ammonia procedure  are calcium, mag-
nesium, iron and sulfide.                                                .
2.  Apparatus
     2.1  Sampling Train.  A schematic of the sampling  train used in this
method is shown in Figure 1.  Complete construction details are given in
                                       i
APTD-0581 (Citation 2 in Section 7); commercial models  of this train are
also available.  For changes from APTD-0581 and for allowable modifications
Of the train shown in Figure 1, see the following subsections.
     The operating and maintenance procedures for the sampling train are
described in APTD-0576  (Citation 3 in Section'7).  Since correct usage is
important in obtaining valid results, all users should  read APTD-0576 and
adopt the operating and maintenance procedures outlined in it, unless other-
wise specified herein.  The sampling train consists of the following components:
     2.1.1  Probe Nozzle.  Stainless steel (316) or glass with sharp, lead-
ing edge.  The angle of taper shall be <_ 30  and the taper shall be on the
outside to preserve a constant  internal diameter.  The  probe nozzle shall
be of the button-hook or elbow  design, unless otherwise specified by the
Administrator.   If made of stainless steel, the nozzle  shall be constructed
from seamless tubing; other materials of .construction may be used subject

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                                    2
to the approval of the Administrator.
     A range of nozzle sizes suitable for isokinetic  sampling  should  be  .
available, e.g. 0.32 to 1.27 cm (1/8 to 1/2 in.)  - or larger if higher     •  .
volume sampling trains are usedMnside diameter (ID)  nozzles in incre-        '
ments of 0.16 cm (1/16 in.). Each nozzle shall  be calibrated according to
the procedures outlined in Section 5.                •
     2.1.2 Probe Liner.  Borosilicate or quartz glass tubing with  a heat-
ing system capable of maintaining a gas temperature at the exit end during
                                                          •
sampling of no greater than 80°C (176°F) 120 + 14°C (248 + 25°F),  or  such
other temperature as.specified by an applicable subpart of the standards or
approved by the Administrator for a particular application.  (The  tester
may opt to operate the equipment at a temperature lower than that  specified).
     Whenever practical, every/effort should be made  to use borosilicate
or quartz glass probe liners.  Alternatively, metal liners (e.g.,  316
stainless steel, Incoloy 825,  or other corrosion resistant metals) made of
seamless tubing may be used, subject to the approval  of the Administrator.
     2.1.3  Pitot Tube.  Type S, as described in Section 2.1 of Method 2,
or other device approved by the Administrator.   The pitot tube shall  be
attached to the probe (as shown in Figure 5-1)  to allow constant monitoring   .
of the stack gas velocity.  The impact (high pressure) opening plane  of
the pitot tube shall be even with or above the nozzle entry plane  (see
Method 2, Figure 2-6b) during sampling.  The Type S pitot tube assembly
shall have a known coefficient, determined as outlined in Section  4 of
Method 2.                     ,     •      •        .               V   :  •  '  •  '
.Mention of trade names or specific products does not constitute endorse-'.
 ment by the Environmental Protection Agency.    .            :

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                                 3
     2.1.4  Differential Pressure Gauge.  Inclined manometer .or equivalent        :
device (two), as described in Section 2.2 of Method 2.   One manometer
shall be used for velocity head (Ap) readings, and the  other,  for orifice   . '
differential pressure readings.
              - •                                                                   «
     2.1.5  Impingers—Six as shown in Figure 1.  The first and third shall       :
be of the Greenburg-Smith design with standard tips.  The second, fourth,          ,
and fifth shall be of the Greenburg-Smith design, modified by replacing            ;
the insert with an approximately 13 millimeter (0.5 in) I.D. glass tube,
                                                                                   t
having an unconstricted tip located 13 mm (0.5 in) from the bottom of the          ;
flask.  Similar collectiln systems, which have been approved by the Admini-
                                                               '•                   i
strator, may be used.                                          •                    '
     2.1.6  Metering System.  Vacuum gauge, leak-free pump, thermometers           j
capable of measuring temperature to-'within 3°C  (5.4°F), dry gas meter              !
                                                                                   i
capable of measuring volume to within 2  percent, and related equipment,            j
                                                                                   I
as shown in  Figure 5-1.   Other metering  systems capable of maintaining    '         I
                                  '                                            .1
sampling rates within  10  percent of isokinetic and of determining sample           '
.volumes to within 2 percent may be  used, subject to the approval of the            '•
                                                                                   i
Administrator.  When the  metering system is used in conjunction with a             ;
                                                                     >       •       i
pitot  tube,  the system shall  enable checks of isokinetic rates.               '     j
                                                                                   t
     Sampling trains utilizing metering  systems designed for hfgher flow           \
rates  than that described in  APTD-0581  or APTD-0576 may be used"provided
                                                                                   i
that the specifications of this method  are met.                -.                   i
                                                                                   i
     2.1.9   Barometer.    Mercury, aneroid, or other barometer capable of           I
measuring atmospheric  pressure to within 2.5  mm Hg- (0.1 in. Hg).  In many          •
cases, the barometric  reading may be obtained from a nearby national weather
service station, in which case the  station value  (which is the absolute '
barometric pressure) shall be requested and an  adjustment for elevation

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differences between the weather station and sampling  point shall be  applied
at a rate of minus 2.5 mm Hg (0.1 in.  Kg)  per 30 m (100 ft)  elevation  inr
crease or vice versa for elevation decrease.
     2.1.10  Gas Density Determination Equipment.   Temperature sensor  and
pressure gauge, as described in Sections 2.3 and 2;4  of Method 2,  and  gas
analyzer, if necessary, as described in Method 3.   The temperature sensor
shall, preferably, be permanently attached to the  pitot tube or sampling
probe in a fixed configuration, such that the tip  of  the  senor extends be-  .
yond the leading edge of the probe sheath and does not touch any metal.
Alternatively, the sensor may be attached just prior  to use  in the field.
Note, however, that if the temperature sensor is attached in the field, the
seaspr must be placed in an interference-free arrangement with respect to
the Type S pitot tube openings (see Method 2, Figure  2-7).  As a second
alternative, if a difference of not more than 1 percent in the average
velocity measurement is to be introduced, the temperature gauge need not
be attached to the probe or pitot tube.  (This alternative is subject to   ;
the approval of the Admini strati or).            .  '•'.           "             •.
     2.2  Sample Recovery.  The following items are needed:              •  .
     2.2.1  Probe-Liner and Probe-Nozzle Brushes.   Nylon  bristle brushes  :
with stainless steel wire handles.  The probe brush shall have extensions
(at least as long as the probe) of stainless steel, Nylon, Teflon, or
similarly inert material.  The brushes shall be properly  sized and shaped
  to
       2.2.2  Wash'Bottles—Two.  'Glass wash  bottles are recommended;
  polyethylene wash.bottles may be  used at the  option of the tester.
       2.2.3  Glass Sample Storage  Containers.   Chemically resistant,

-------
      ' .    •'              •  •    • 5  •       .    •                .
borosilicate glass 'bottles 500 ml or 1000 ml.  Screw cap liners  shall
either be rubber-backed Teflon or shall be constructed so as to  be  leak-
free.  (Narrow mouth glass bottles have been found to be less  prone to .
leakage).  Alternatively, polyethylene bottles may be used.        '   v
     2.2.4  Petri Dishes.  For filter samples, glass or polyethylene,
unless otherwise specified by the Administrator.
     2.2.5  Graduated Cylinder and/or Balance.  To measure condensed water
to within 1 ml or 1 g.  Graduated cylinders shall have subdivisions no
greater than 2 ml.  Most laboratory balances are capable of weighing to  .
the  nearest 0.5  g or less.   Any  of these  balances is suitable for use
here and  in Section 2.3.4.         .     .         .    !            .      .-•-.'•
     2.2.6  Plastic7Storage  Containers.   Air-tight  containers to store'.,;-.
silica gel.'                   .     '"''•'':''             .   '   ~ •' •     .'.'•'.•
     2."2.7  Funnel  and  Rubber Policeman.   To  aid in transfer of silica  .
gel  to container;  not  necessary if silica gel  is weighed in the field.
     2.2.8  Funnel,  Glass  or po-yethylene, to aid  in  sample recovery..
     2.3 Analysis.               :
     2.3.1  Pipettes.   Volumetric type 0.5-ml, 2-ml, 5-ml, 8-ml, 10-ml,'•  •'.
20-ml, and  25-ml sizes.       •                   •;     :••       • -
     2.3.2  Volumetric Flasks.   25-ml  size, 100-ml  size,.250-ml size,
500-ml size and 1000-ml size.                   •      .-  " . . ',.  •;.•;.._...
     2.3.3    Graduated .Cylinder.  100-ml  size.     •        ••••'-./•'.''.•<...-._'••'
     2.3.4   Distillation Apparatus.
           2.3.4.1  Kjeldahl  Flasks.   At least two  800 ml  size.        .
           2.3.4.2  Connecting bulb.   To connect the kjeldan! flask  to the
condenser and prevent  liquid carry over.                          •   "  .
                                      W s      '
          2.3.4.3 ' Condenser.  Glass-wert type or equivalent.. '  .

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VT(J> .
      ., '  TEMPERATURE SENSOR
                                       '.  "••*" IMPINGER TRAIN OPTIONAL,MAY BE REPLACED
                                       •-.-•'•;• -   . BY AN EQUIVALENT CONDENSER  ^ -...
 PITQTTUBE


    .  PROBE
               PROBE .


             TEMPERATURE  HEATED AREA   .THERMOMETER   /

                SENSOR         %        X
                                                                     THERMOMETER
REVERSE-TYPE
 P1TOTTUBE
               PITOT MANOMETER


                 ;•"••"": ORIFICE
           •  THERMOMETERS P
                                                        I  MAIN VALVE
                                           AIR-TIGHT '
                                            •PUMP  '
               •  ' -    DRY GAS METER  '
                  . " ' • .       «
                 *   •    "    f« . •
                  • •  .  •    • '"  - *
                 • . " •   *  - • ••   .* •
               .  -  ..' ':   ... -  •  -  -  <
                 **    *•   *     *     •     ...»

              • •  ^   FJgure 5-1. Partrcufatc-sampling train.
                                                                                    CHECK •
                                                                                    VALVE ..
                                                                                    VACUUM
                                                                                     LINE '
                                                                                             > • .

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                                  . o
           2.3.4.4   Receiving Adapter... To  connect the condenser to the .  '.  •
 receiving flask.         '   •    '       .-.''•••'•'•'  -;    • ..•  •
 .   .  2.3.5  Erlenmeyer Flasks..  500 ml size.           :   .        •
      2.3.6  Spectrophotometer.  To measure absorbanca at 405  nanometers..
      2.3.7  Sample Cells.  : Two matched absorbance cells/to  fit the spectro-
 photometer.     ••.:''•   ••.•••.•'.•.•  •'    "'•.•'  ;   ,•:•.  "•': •. •.•':;'..-.'  '
.3.  Reagents                        '   . '  '   .              •             '•:..•"". '.'  •'
      Unless otherwise indicated,  all  reagents must conform  to the speci-.  .
 fications established by the Committee on  Analytical Reagents of the .   •.•'.;•  -,.
.American Chemical  Society. • Where-such'specifications are not .available,.-•••;'.
 use the best  available'grade. '        •  .'      :•   •'.-'.•" ".''•  •./.'•' ' . ••  '. ' "'
      3.1  'Sampling..          •            '                .    •        '   •.   • •.
      3.1.1- Water.  Deionized, distilled to conform to  ASTM specification '•  ••
 D 1193-74,  type 3. . At the option of the Analyst, the .KKNO. test.for•...•';:'•';..
 oxidizable  organic matter may be  omitted when high concentration of .V
                                                      >.              •     ''  .-
 organic matter are not expected to be present.                 '  •  .   •
      3.1.2   Sulfuric Acid, 1.0.N.  Dilute 28 ml'of concentrated,'ACS grade  ..
 sulfuric  acid to 1 liter with deionized, distilled water.::-r .-•''•'• ".•:-•;'.' ';.;'•;•.;
      3.2   Sample Recovery.   ' '.        .   •        • •'•..;-i/-'..?,'-/?.-',-:--.-^.''.'-;
      3.2.1   Water.  Deionized, distilled, as  in  3.1.1.,•'••; .'• 'KV"^ 'A\ ?\  '
      3.2.2   Sulfuric Acid, 1.0 N.-  As in 3.1.2.   '/".  '•;/  '•-.  •"••;':;.;.'-':., -:'.-..
      3.3  Analysis.-   ;     '                   •      •      .-'  ••'/,: •••'''; v •;!.•.. i .'•'.'...'•'•
      3.3.1  Water.  Deionized, distilled, as  in  3.1.1.   '   •;-.-  '•.•;';.. |:.";:''•;".'••/' '.-•
    :  3.3.2   Annhydrous;Mercuric  Iodide (Kg I2).  ACS grade. '.'• ..._•.;;;:''--. :-.;•-•'•   .
      3.3.3   Potassium  Iodide  (KI).   ACS grade.      .' •   /  '.'•';  ';''.-'..    .
      3.3.4   Sodium Hydroxide  (NaOH).  ACS grade. •     '         ...
    •  3.3.5  -Stock standard AfKnorriurn Chloride  Solution.  Dissolve  3.141  g of

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ammonium  chloride  (NH^Cl) in deionized distilled water in a 1-liter
volumetric  flask and dilute to exactly 1 liter with deionized distilled   '  •
-water.  'One milliliter  of this solution contains l.G mg of aiuv.onia (NH,).
      3.3.6   Working Standard Ammonium Chloride Solution.  Dilute 10 nil of
the stock standard solution to 1  liter with deionized distilled water in
                           . •! '                                        .    -
a 1-liter volumetric flask.  One  milliliter of this solution contains
10 pg of  ammonia  (NH,).                      '               . .
                    3         /O                                           ;
      3.3.7   Sodium Hydroxide, &  N.  Dissolve 40 grams of NaOH in a 100-ml
 volumetric  flask  and dilute exactly  to 100-ml with deionized distilled
water.
      3.3.8   Nessler Reagent.  Dissolve 160 g of NaOH in 500 ml of deionized.
 distilled water in a  1-liter  volumetric flask.  Allow to cool.  Dissolve   '
 100 g of mercuric iodide and  70 g of potassium iodide in a small, volume
 of deionized distilled water  and  while stirring add to the sodium hydro-
 xide solution.  Dilute to exactly 1  liter with deionized, .distilled water.
 This reagent is stable up to  1 year.
      3.3.9   Borate Buffer.   Dissolve 2.5 g of sodium tetraborate, Ka2B.07,
 or 4.8 gof the decahydrate Na2B407 ' 10 H20, in 500 ml of distilled      • ; .
 deionized water in a  1  liter  volumetric flask.  Add 88 ml of 0.1 N NaOH   :
 solution and dilute to exactly  1  liter with distilled deionized water.   ;•'.".
      3.3.10  Sodium Hydroxide 6 N.  Dissolve 240 g of NaOH in 800 ml of
 distilled deionized water in  a  1  liter flask.  Dilute to exactly 1 liter    .
 with distilled deionized water.                                    ';':..
      3.3.11 Sodium  Thiosulfute Dachlorinating Agent.  Dissolve 3.5 g of  •'.
 Ma2S2°3 ' 5iy^ 1
-------
                                 8'            .••;••        .:.--.-•:
distilled deion.ized water in  a  1  liter flask and dilute to exactly 1
liter with distilled deionize water.                                       ..
     3.3.13  Sulfuric Acid 1  N.   Slowly add 56 ml of concentrated sulfuric
to 800 ml of distilled deionized  water in a 1 liter flask and dilute to     -
exactly 1 liter with distilled  deionized water.             .            .
            74
         3.3.9"  Ethyl  Alcohol,  95  percent.  ACS grade.
              /jT                  '          '                  • • '
         3.3.W P-dimethylaminobenzaldehyde.  ACS grade,
              (t>
         3.3.W Hydrochloric,  Concentrated (36.5 - 38 percent by weight).
    ACS grade.      .                   '           .  •    .
              t7             •   '     '   •      '   .
         S.S.l^T Stock Standard Urea Solution.  Dissolve 5.00 g of  urea  in
    500 ml of distilled, deionized water  in a 1-liter flask and dilute to
    exactly 1 .liter with deionized, distilled water.                .       .
         3.3.18  Working Standard  Urea Solution.  Pipette 25 ml of  stock  •
    standard urea solution into a  100-ml  volumetric flask and dilute  to
                                      i
    exactly 100 ml with, deionized  distilled water.  One milliliter  of
    this solution contains 1.250 mg of urea.
         3.3.1*]  Urea Color Reagent.  Prepare the color reagent by  dissolving
    2.000 g of P-dimethylaminobenzaldehyde in a mixture of 100 ml of  95  percent
    ethyl alcohol and 10 ml of  hydrochloric acid,
    4.  Procedure        ,
         4.1  Sampling.  The complexity of this method is such that,  in  order
    to obtain reliable results, testers should be trained and experienced  with
                                                 .**
    the test procedures.
         4.1.1  Pretest Preparation.  All the components shall be maintained
    and calibrated according to the procedure described in APTD-0576, unless1  '
    otherwise specified herein.

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                                 9      '.         .'   :••   '    • '   •."'-.
otherwise specified herein.
     Weigh several 200 to 300 g portions of silica gel  in air-tight
containers to the nearest 0.5 g.  Record the total weight of  the silica
gel plus container, on-  each container.  As an alternative, the silica
gel need not be preweighed, but may be weighed directly in its impinger or'.
sampling holder just prior to train assembly.
     4.1.2  Preliminary Determinations.  Select the sampling  site and the
minimum number of sampling points according to Method 1 or as specified by
the Administrator.  Determine the stack pressure, temperature, and the
range of velocity heads using Method 2; it recommended that a leak-check
of the pi tot lines  (see Method 2, Section 3.1) be performed.   Determine the
moisture content using Approximation Method 4 or its alternatives for the
purpose of making isokinetic sampling rate settings.  Determine the stack
                                   *"•
gas dry molecular weight,  as described in Method 2, Section 3.6-, if inte-
grated Method 3 sampling is used for molecular weight determination, the
integrated bag sample.shall be  taken simultaneously with, and for the same
total length of time.as, the particulate sample run.
     Select a nozzle size  based on  the range of velocity heads, such that
it is not necessary to change the nozzle size in order to maintain isokine-
tic sampling rates.  During the run, do not change the nozzle size.  Ensure
that the proper differential pressure gauge is chosen for the range of
velocity heads encountered (see Section 2.2 of Method 2).
     Select a suitable probe liner  and probe length such that all traverse
points can be sampled..  For large stacks, consider sampling from opposite
sides of the stack  to reduce the length of probes.               •
     Select a total sampling time greater than or equal to the minimum
total sampling time specified in the test procedures for the  specific

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                                io      •   :       •  ••                .
industry such that (1)' the sampling time per point is not less  than 2 min.    ••
(or some greater time interval  as specified by the Administrator),  and (2)
the sample volume taken (corrected to standard, conditions)'wi11  exceed the
required minimum total gas sample volume. . The lattery's based  on an apprpx- ...
imate average sampling rate.               ••'.''•     .            •  .   .
     The sampling time at each point shall be the same.   It is  recommended
that the number of minutes sampled at each point be an integer  or an integer
plus one-half minute, in order to avoid timekeeping errors. •    .  •    .      .
     In some circumstances, e.g., batch cycles, it may be necessary to       .  :  '
sample for shorter times at the traverse points and to obtain smaller gas
sample volumes.  In these cases, the Administrator's approval must  first
be obtained.     '.•'"'                 ••                    ':.''•'
     4.1.3  Preparation .of Collection Train.  During preparation and assem-
bly of the sampling train, keep allropenings where contamination can occur
covered until just prior, to assembly or until.sampling is about to  begin,..  '.;'•
     Place 75 ml of water in the first two impingers, 100 ml -of 1.0 N sul-
furic acid into  each  of the next two.impingers, leave the fifth impinger   .       . ;
                                                       .                           . i
empty and transfer 200 - 300 g of preweighed silica gel from its container      .  !
                               o                   •                           ''     «'
to the sixth impinger.  More silica gel may be used, but care should be
                   • •                            ...               ••..,.
taken to ensure  that  it--is not entrained and carried out from the impinger  .       ;
during sampling.  Place the container in a clean place for later used in .
the sample recovery.  Alternatively, the weight of the silica gel. plus       .  '    '
impinger may be  determined to the nearest 0.5 g and recorded.                      :
     When glass  liners are used, install the selected nozzle using a Viton        .. •
A 0-ring when  stack temperatures are less than 260°C (500°F) and an asbestos
string gasket  when temperatures are higher.  See APTD-0576 for details.
Other connecting systems using either 316 stainless steel, or Teflon ferrules

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                                 11
 may be used.   When metal  liners  are used,  install  the  nozzle  as  above or by
 a leak-free direct mechanical  connection.   Mark the probe with heat resistant
:tape or by some other method to  denote the proper  distance  into  the.stack .
 or duct for each sampling point.       .  .                .  .                    ;'
      Set up the train as  in Figure 1, using (if necessary)  a  very light  . '    .
 coat of silicone grease on all ground glass joints, greasing  only the      •
 outer portion (see APTD-0576)  to avoid possibility of-contamination by the
 silicone grease.  ."•.;•     .   .  •    .     ./. ;'  •'>...'.">'•':"..::';  \.  •:••  '••"...'.••';
      Place crushed ice'around  the impingers.
      4.1.4  Leak-Check Procedures.        '      •     .._•':.
      4.1.4.1  Pretest Leak-Check. A pretest leak-check is  recommended, but
 not required.  If the tester opts to conduct the pretest leak-check, the
 following procedure shall be used.  ,  .    .            '..•'. ..     '  ;.
      After the sampling train has been assembled,  turn on  and set the fil-
 ter and probe heating systems at the desired-operating temperatures.  Allow    •
 time for the temperatures to stabilize.   If a Viton A  0-ring  or  other leak-
 free connection is used in assembling the probe nozzle to  the probe liner,  .
 leak-check the train at the sampling site by plugging'the  nozzle and pull-.   :
 ing a 380 mm Kg (15 in. Hg) vacuum.'
      Note:  A lower, vacuum may be used,  provided that  it is not  exceeded
 during the test.    • .  "••                          •                            :
      If an asbestos string is used,- do not connect the probe  to  the train
 during the leak-check.  Instead, leak-check the train  by first plugging the •
 inlet to the first impinger and pulling a 380 mm Hg (15 in. Hg)  vacuum (see
 Note immediately above)..   Then connect the probe to the train and leak-check
 at about 25 mm Hg (1 in.  Hg) vacuum; alternatively, the probe may be leak-
                       i
 checked with the rest of the sampling train, in one step,  at  380. mm Kg    :

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                                 12                 : ,       •'••'•..!
(15 in. Kg)  vacuum.  Leakage rates in excess  of 4  percent of the average     •     :
                          3                                               •
sampling rate or 0.00057 m /min (0.02 cfm),  whichever  is  less,  are un-  •       .    •
acceptable.    .                      .                                            •  i
     The following leak-check instructions for the  sampling train described     '•  ;
in APTD-0576 and APTD-0581 may be helpful.  Start the  pump with bypass
valve fully open and coarse adjust valve completely closed.  Partially  .     .     .;
open the coarse adjust valve and slowly close  the bypass  valve  until  the .  '. '      ;
desired vacuum is reached.  Do not reverse direction of bypass  valve;
this will cause water to back up into.the probe. • If the  desired vacuum is         -;
                                   *                        '            .
exceeded, either leak-check at this higher vacuum or end  the leak check           .'••
                              ,.            ' .      • .          .                     • j
as 'shown below and start over.
                                                                                   :
     When the leak-check is completed, first slowly remove the  plug from        .   '
the inlet to the probe,.filter holder, or cyclone (if  applicable) and imme-        ;
diately turn off the vacuum pump.  This prevents the water in "the impingers
                                                                             ' '     '
from being forced backward into the filter holder and  silica gel from being  .      :
                                                            • •'            •  •  ..     i
entrained backward into the third impinger.     .                                    |
     4.1.4.2  Leak-Checks During. Sample Run.  If, during  the sampling run,          !
a component (e.g., filter assembly or impinger) change becomes  necessary,          :
                                                                    .            .-  i
a leak-check shall be'conducted immediately before  the change is made.             .1
                                                                                   t
The leak-check shall be done according to the procedure outlined In Section        |
                                                                                   i
4.1.4.1 above, except that it shall be done at a vacuum equal to or greater   .     j
than the maximum value recorded up to that point in the test.-  If the leak-
                                                 3
age rate is found to be no greater than 0.00057 m /m^ttt (0.02 cfm) or 4 per-
cent of the average sampling rate (whichever is less), the results are
acceptable, and no correction will .need to. be applied to the total volume.
of dry gas metered; if, however, a higher leakage rate is obtained, the
tester shall either record the leakage rate and plan to correct the sample
volume as shown in Section 6.3 of this method, or shall void the sampling run.

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      •                           ..13              •               '"•'•".
      Immediately  after  component changes,' leak-checks are optional; if
such  leak-checks  are  done,  the  procedure outlined in Section  4.1.4.1
above shall  be used.             '                                   .   •
      4.1.4.3  Post-test Leak-Check.  A  leak-check is mandatory  at the  •  :: -.
conclusion  of each sampling run.   The leak-check shall  be done  in ac-     . :.
cordance with the procedures outlined in Section 4.1.4.1, except that
it shall be conducted at a  vacuum  equal to  or  greater than  the  maximum
                                                                          •
value-reached during  the sampling  run.  If  the leakage  rate is  found to
                             3                                     '          '*
be no greater than 0.00057  m /min.  (0.02 cfm)  or 4 percent  of the average"
sampling rate (whichever is less),  the  results are acceptable,  and no   • -..-'•
correction  need be applied  to the  total volume of dry gas metered.   If,
however, a  higher leakage rate is  obtained, the tester  shall  either  re-,.;
cord the leakage rate and correct  sample volume as shown in Section  6.3
of this method, or shall void the  sampling  run.     .   .   .
      4.1.5   Particulate-Train Operation.   During the sampling run, main-
 tain an isokinetic sampling rate (within  10 percent of  true isokinetic
 unless  otherwise specified by the  Administrator) and a  probe temperature  ..-.
 of no greater than 80°C (176°F) temperature as specified by an.applicable   .
 subpart of the standards or approved by the Administrator.                   ;
      For each run, record the data required on a data sheet such as  the
one shown in Figure 2.   Be sure to record  the  initial dry gas meter  read- .  .
 ing.   Record the dry gas meter readings at the beginning and end of
 each sampling time increment, when changes  in  flow rates are made, before
 and after each leak check,  and when sampling is halted.  Take other  read-- '.'
 ings required by Figure 2 at least once at each sample:.point during  each "
 time .increment and additional readings  when significant changes (20  per-  '
• cent variation in velocity head readings)  necessitate additional  adjustments.

-------
                                   H      ...    .    -
                                                                             j
 in  flow  rate.   Level  and  zero  the manometer.  Because the manometer level
 ancl zero may drift due  to vibrations and  temperature changes, make, periodic
 checks during the traverse.        .             .           .                .' .
      Clean the portholes  prior to the  test  run  to minimize the  chance  of   •  .,
 sampling deposited material.   To begin sampling, remove the  nozzle cap,
 verify that the filter  and probe heating  systems are up to temperature,
 and that the pi tot tube and probe are  properly  positioned. '  Position the'/
 nozzle at the first traverse point .with the tip pointing directly  into
 the gas  stream.  Immediately start the pump and adjust the flow to iso-
• kinetic  conditions.  Nomographs are  available,  which aid in  the rapid
 adjustment of the isokinetic sampling  rate  without  excessive computations.
 These nomographs are designed for use  when  the  Type S pitot  tube coefficient
 is 0.85  +_ 0.02, and the stack gas 'equivalent density  (dry molecular weight)
 is equal to 29 £ 4.  APTD-0576 details the  procedure  for using  the nomo-
 graphs.   If C  and M^ are outside the  above stated  ranges, do not  use  the  .  :
 nomographs unless appropriate steps  (see  citation 7 in Section  7)'are
 taken to compensate for the deviations.
      When the stack is  under significant  negative pressure  (height of  im-   •"
 pinger stem), take care to close the coarse adjust  valve before inserting
 the probe into the stack to prevent water from backing inot  the probe.
 If necessary, the pump may be turned on with the coarse adjust  valve  closed.
      When the probe is in position,  block off the openings around  probe  .
 and porthole to prevent unrepresentative  dilution of  the gas stream.
      Traverse the stack cross-section, as required  by Method'l  or  as
 specified by the Administrator, being careful  not to  bump .the probe  nozzle  •
 into the stack walls when sampling  near the walls or  when  removing or in-
 serting the probe through the portholes;  this minimizes  the  chance of
                                                             »
 extracting deoisited material.             .    "''.•'   '..'.'

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'NNO.,
MPLE BOX NO..
 TERAH@
 ACTOR.
                                                                                 BAROMETRIC PRESSURE.
                                                                                 ASSUMED MOISTURE.'/,.
                                                                                 PROOE LENGTH.m (It) ___
 OT TUBE COEFFICIENT. Cp
                                         SCHEMATIC OF STACK CHOSS SECTION
  NOZZLE IDENTIFICATION NO	'
  AVERAGE CALIBRATED NOZZLE DIAMETER. cm(in.J.
  PROBE HEATER SETTING	'
 . LEAK RATE. ni3/ii)in.(cfni]	:____-______
  PROBE LINER MATERIAL.	'
.  STATIC PRESSURE. nvn Hfl (in.Hg).
fiAVERSE POINT
NUMBER
•









-
*
fAL
SAMPLING
TIME
(01. min.




'






•'

flAGE
1 • ••
VACUUM
nvu Kg
(in H3)


•

' ' •


. . •
*



'
. .
STACK
TEMPERATURE
 <•
GAS SAMPLE
VOLUME
n>3 (ft3)

• '|;








.. - .-
i •

• •
4
•
GAS SAMPLE TEMPERATURE
AT DRY GAS METER
INLET
°C ("F)







\




Avg.
OUTLET
°C l°F)


•




*
FILTERXHOLOER
TEf.J?EBAIURE.
°C{°F)\
	 -
. • ^ . * • .
• • .'
.
•
'.








•• .. ' -.-•.•
•TEMPERATURE
;' OF GAS
' : LEAVING
CONDENSER' OR
LAST IMPINGER.
. °ClaF|



f



t
* "•_

•_ -


' '
                                                  Figure  '  2. 'Paniculate field data.

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                                  15          '    -
     During the test run, add more ice and,  if necessary,  salt  to  main-
tain a temperature of less than 20 C (68°F)  at the condenser/silica  gel   .
outlet.  Also, periodically check the level  and  zero  of  the manometer.
     A single train shall be used for the entire sample  run,  except
in cases where simultaneous sampling is required in two  or more separate.
ducts or at two or more different locations, within the same duct,  or,    .
in cases where equipment failure necessitates a  change of trains.   In
all. other situations, the use of two or more trains will  be subject  to
the approval of the Administrator,               •          .     .
     Note that when two or more trains are used, separate analyses of
the impinger catches from each train shall be performed, unless identical   .
nozzle sizes were used on all trains, in which case,'the impinger catches
from the individual trains may be .combined (as may the  impinger catches)
and one analysis of impinger catch may be performed.   Consult with the
Administrator for details concerning the calculation of results when two
or more trains are used.       '                                . .          .
     At the end of the sample run, turn off the coarse adjust valve,
remove the probe and nozzle from  the stack, turn off the lamp, record
the final dry gas. meter  reading,  and conduct a post-test leak-check, as
outlined in Section 4.1.4.3.  Also, leak-check the pitot lines as described
in Method 2, Section 3.1;' the lines must pass this leak-check, in order to
validate the velocity head data.
     4.1.6  Calculation  of Percent  Isokinetic.  Calculate percent iso-
kinetic  (see Calculations, Section 6) to determine whether the run was  .    :
                      »•                   "                 '*'       •
valid  or another test run should  be made.  If there was difficulty in.  '  .
                      T .           '               "           ^  • •   -
maintaining isokinetic rates due  to source conditions, consult with the
Administrator for possible variance on'the isokinetic rates.

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                                   16            .  .   '
     4.2  Sample Recovery.   Proper cleanup procedure  begins  as  soon as
the probe is removed from the stack at the end of the sampling  period. :..
Allow the probe to cool-.           '             .      .     '     •        .
     When the probe can be safely handled, wipe off all  external  p.art-
iculate matter near the tip of the probe nozzle and place  a  cap over it
to prevent losing or gaining particulate matter.  Do  not cap off the
probe tip tightly while the sampling train is cooling down as this would
create a vacuum in-the filter holder, thus drawing  water-from the impingers
into'the filter holder.  .      •  .  •     .                  .      .  .    ;...
     Before moving the sampling train to the cleanup  site, remove the  .  ;
probe from the sample-train, wipe off the silicone  grease, and  cap the
open outlet of the .probe..  Be careful not to lose any condensate that
might be present.  Wipe off the silicone grease from  the impinger inlet •   .
where the probe was fastened and cap it.  Remove the  umbilical  cord
from the last impinger and cap the impinger.  If a  flexible  line is used
between the first impinger or condenser and the probe disconnect the line
at the probe and let any condensed water or liquid  drain into the impingers
or condenser.  Either ground-glass stoppers, plastic  caps, or serum caps
may be used to close these .openings.                         •            .  '
     Transfer the probe, impinger assembly to the cleanup area.   This area
should be clean and protected from the wind so that the  chances of con-
taminating or losing the sample will be minimized.     '          '-.-••
     Save a portion of. the water used for cleanup as  a blank.  Take 200 ml •
of this water directly from the wash bottle being, used and place'it in a
glass sample container labeled "acetone blank."                    ": .
     Inspect the train prior to and during disassembly and note any ab- '
                                                      •
normal conditions.  Treat the samples as follows:    "' •      "    •

-------
          '            •       '      17     .'•••..•              ''   .
     Container No.  1.   Taking care to  see that  dust on the outside of
the probe or other exterior surfaces does not get  into the sample, '.'
quantitatively recover particulate matter or any condensate  from the      :
probe nozzle, probe fitting, and probe liner, by washing  these  components
with water and placing the wash in a*glass container.  Perform  the water
rinses as follows:
     Carefully remove the probe nozzle and clean the  inside  surface  by    '
rinsing with water.from a wash bottle  and brushing with a Nylon bristle
brush.  Brush until the water rinse shows no visible  particles, after
which make a final  rinse of the inside surface  with acetone.  .    ;   .    .•
     Brush and rinse the inside parts  of the Swagelok fitting with water
in a similar v/ay until no visible particles remain.               .      :   .
    . Rinse the probe liner with water  by tilting and  rotating the probe  .
while squirting acetone into its upper'end so that all inside surfaces
will be wetted with water.  Let the water drain from  the  lower  end  into  ..
the sample container.  A funnel (glass or polyethylene) may  be  used  to
aid in transferring liquid washes to the container.   Follow  the water
            •'••('                        '            •        •
rinse with a probe brush.  Hold the probe in an inclined  position,  squirt
water into the upper end as the probe brush is  being  pushed  with  a  twist-
ing action through the-probe; hold a sample container underneath  the lower.
end of the probe, and.catch any water and-particulate matter which  is  .
brushed from the probe*  Run the brush through  the probe  three  times or
more until no visible,particulate matter is carried  out with the  water  or
until none remains in.the probe liner on visual inspection.; With stain-
less steel or other metal probes, run the brush through  in  the  above pre-
scribed manner at least six times since metal probes  have, small crevices
                      ')•.••                 •    .
in which particulate matter can be entrapped.'  Rinse the brush with water,

-------
 •  .and  quantitatively collect these  washings  in  the  sample  container.
    the  brushing,  make a  final  water  rinse  of  the probe as described    '•••,:
 ..   above.  .                     '             .        ..     .   •
         It is  recommended that two people  be  used to clean  the  probe to ':•_'.
• '.  minimize  sample losses.  Between  sampling  runs, keep  brushes clean    [•:
 .   and  protected  from contamination.                             .
. . .       Container No. 2.  Measure and record  the volume  of  the  first two
. .   impingers.   Then transfer the  contents  to  a storage container.  Rinse
    the  first.two  impingers and the connecting glassware  with water and  :.
    add  the rinse  water to the container.   Mark the level of the liquid ;•
.   on the container and identify  the sample container.
         Container No. 3.  Measure and record  the volume  of  the  third and  :
  .  fourth impingers.  Then transfer  the contents to  a shortage  container.'
    Rinse the impinger and connecting glassware with  1.0  N sulfuric acid   '•
    and add the rinsings to the sample container.  Mark the  level of.      •
    liquid on the  container and identify the sample container..
         Container No. 4. Note the color of the  indicating silica gel to
                       •*                                    •
    determine if it has been completely spent  and make a  notation of  its :
    condition.   Transfer the silica gel from the  fourth impinger to its  '-."
    original  container and seal..  A funnel  may make it easier to pour
    'the silica gel without spilling.   A rubber policeman  may be  used  as
    an aid in removing the silica  gel from the impinger.   It is  not
    necessary to remove the small  amount of dust  particles that  may adhere
    to the impinger wall.and are difficult to  remove. Since the gain in
    weight is to be used for moisture calculations, do not use any water
 .   or other  liquids to transfer the  silica gel.   If  a balance is ayail-
 :  able in the field, follow the  procedure for container No. 3  in Section

-------
 '•   4.3.       .                                    •           '.'  "   .'•'
          4.3  Analysis.  Record the data required cm a sheet such as the ,'   .  '
 .'   one shown in  Figure  5-3.  Handle  each  sample container as follows:    '.   .'
.-•••'•>         •                    •            .                     ' '"'•'
          4.3.1  Container  No. 1 and 2.  Note  the level of Liquid in  each    '
     container and.confirm  on the  analysis  sheet whether or not leakage"   .
v   ' occurred during transport.  If a  noticeable amount of leakage has
     occurred, either  void  the sample  or use methods, subject to the    .    '.'.'
     approval of the Administrator, to correct the final results.  Measure-
     the liquid in each-container  either volumetrically to £ 1 ml or  '• '
   .  gravimetrically to +.1.0 g and record  on  the data sheet;  Combine the     .
  . .  contents of both  containers in a  1 liter  volumetric flask and  dilute    •  '
' •  '           '                        '                 '             •
   .  to exactly 1  liter with distilled deionized water.  Distill .the  sample   ..
     following the procedure in 4.3.5.       .     .           ":     '          •'.'•
           4.3.2.   Container No. 3.. Quantitatively transfer the  contents  of    •
                                                            ;-         .
     Container No. 3 to a 1-liter volumetric flask.   Rinse  the container   '   .
     and  cap with several portions of 1.0  N sulfuric  acid and transfer to   .  '.
     the  flask.   Dilute to exactly 1  liter with distilled deionized water.  .
           4.3.3  .Container No.  4.   Weigh the spent silica gel  (or silica   ' .
     gel  plus  impinger) to the nearest 0.5 g using a  balance.  This step  .   . . •
     may  be conducted in the field.                                          •  •
           4.3.4   "V.'ater Blank"  Container.   Measure water in.this container
      either volumetrically or gravimetrically and record on the data sheet.
      ^£iVl\th.e,;:sample..foil owing the rpocedure in 4.3.5,   •' v   '   .         :.
            4.3.5  Sample Distillation.        . •         -..   •      '.          •';'.•
            4.3.5.1 ;Pi'e!Udi"dLioii of CtjtiiuHiHril.—Add 53 iul uf distil leu u<=-    .
        •ionized v/ater^atrd 20 ml of  borat
-------
                                    20
                             )r. to 9.5 '.'/"!• th 5 M MaOH
              .                                               .  •
 measure the pH. — Add a few glass beads OP boiling chips and -heat this  •  •
-mlxttaye until— the distillate 'Shows 'no-traces of-an'«rnor.1a"QS'-'d&te>a.T.ir'.ed' '...".
 with Nessrer reagent:;.                                      '       •••'
••        •/-'.'     '        '        ' •• •                        ••""•
      4.3.5.^ Preparation of Sample,  Pipette a  100-ml aliquot of -sample
                            Of raunA ba-*To<^ di^-t-'i /U-fUX)  ?/«$<£'          -
 into a 500 ml Kjedahl^flask/\and adci 400 ml  of distilled deionized water.  '
 Add 1 ml of sodium thiosul fate.  Then add 25 ml  of borate  buffer and   ' '  :'. '
 adjust the pH to 9.5 with 6N NaOH using short-range pH paper  to measure
 the pH.  ^4.*  VXe.  -f/&sZ    to
              "            ,/      t*
             , d'ist'iVlud iVdLer.  Pipette 10 ml of this solution into a
    25-ml volumetric flask and add 10 ml of the urea color reagent.  Dilute
    to exactly 10 ml with deionized, distilled water.  Mix well and. allow to
    stand for at least 10 minutes for full color development.  Measure the
    absorbance of the solution at 420 nm' using the blank solution  (Section 5.5)
    as a zero reference.  Dilute the sample and the blank with equal amounts
    ef-doiom'aod distilled water Cff the absorbance exceeds that of the
    5.00 mg urea standard.
               c.  lo-^I
  5.  Calibration      .         •         •
                       *              •                        -
       Maintain a laboratory log of  all  calibrations.
       5.1  Probe Nozzle,  Probe nozzles shall be calibrated before their
                                                                                   r

-------
 'initial  use in the field.   Us'irig  a micrometer^measure the inside   • .     _     •   !
  diameter of 'the nozzle 'to  the 'nearest  0.025 .ran (0.001 -in.}.: Make' three'     > •   ',

 'separata measurements using different  diameters each time, and obtain..  ••'•_.  .  j
                    •.   •      •              •   ••• ,            .          ••.';.' '•' •'  , .  i.'
  the average of the measurements..' The-difference  between the high and  .  '   .   ' : ^.j
                   1          • •          •          v       . .   •

  low numbers shall not exceed 0.1 Kim (Q.QG4 in.). ' When, nozzles-, become •
  •'  '              '•        .  ' ..     '     '   .     .    '    .      •    .      v.t>
 • nicked, dented, or corroded, they shall be reshaped, sharpened,"and.  -.  "
                       —v—^	  .        .' '    .    '       .-   .''.''-    •.
  recalibrated before'-use.   Each nozzle shall be permanently and*uniquely
  identified.
          •             .      •         .            •                  •
       5*2  Pitot Tube.  The Type S pi tot tube assembly shall be .calibrated '•'
                    •::     .' •         .          1            •   ' *'••       •     •
  according to the procedure outlined in'Section 4 of Method 2.    •   • •   .'   •••
•               .                  '           '                       ••••.••

       5.3  Metering System.   Before  its initial use 'in the field, the   ••''•••
                     •...'•            i   .      •                            •
  metering system shairbe.'-palibrated according' to the'procedure outlined  '
  •             •'*«•*•'            .          •                     *
  in APTO-0575.  Instead of physically.'adjustir,g the dry  gas me>er dial'.
                                               *                 •            ' •
  readings to  correspond to the wet test meter readings,'calibration  ' .

  factors may  be used  to mathematically correct the gas meter dial readings .
».                ••'?                .1           .**        ».•
                                  *        i'*   ....       •      ' •  •       . .  •
  to  the proper values.. Before c&%!ibrating\'the metering  system, it is   •   .
                                    *        •'
 ''"suggested  that a. leak-checktbe conducted.^  For metering systems having

  diaphragm  pumps,  the normal  leak.-check  procedure will,not  detect leakages  •
             .*'•'••'.      ' •   '    .             •     '     •
  within the pump/-» For these cases,  the  following'leak-check  procedure is '
             . (    •  -    •••..-..      .  '       •      .        •  -  -    .   ,       .
 . r;;c;sestec:-joako  a lO-rninuta calib'ration'rur, at 0.00057 nA^in '(0.02 cfr.O-  •
            /•«•*              ••                              . *       .••
                   -  v  • •-.•.   •      •  -.    •         • .    '    .     .       ..   •
  at the end of the run',  take the difference of the measured v/et tost meter:
                                           «                 •  •
                     •                    .                 • .      *
•^and cry gas  meter'volumes; divide  the difference'by 10, to get tha'leak, V
       •i          .        *                 •    •              *...-'•..
       ,                      t'                     *^ "                •.'•*••»
  rate.   The leak  rate should not exceed 0.00057 r.vV»vir.  (0.02  cfm}.-';-.0 •'. .   ''
                     '".            '     •." '    .'...-.' "' "•;   •;.   ..  ./:<•
       After a«ch  field us.e,.the calibration of the metering  system  :":,:- '•'•• '
                                               •'*,.'•'-.•    ' ..' •  ••"'•'
  shajl  ba checked by performing three calibration runs  at'&  single,
                             *                                 .     .          • '
                  »                                           *
  intormoci^to  orifice sorting  (based on the'previous p field tost), with

  the. vacuum sot at the maximum valua roachcid during  the tost  series.

-------
                         v.V--..J    • 23 J
the inlet of the metering system.   Calculate the average value of the

                                    "*•".••                 •                 *


calibration factor.   If the calibration-has changed by more than 5 par-  .




cant, recalibrate  the meter, over the.full 'range of orifice settings, as ~ •'




outlined in APTD-0575.  ,- ::>;'  '     '       . '=;  '•  ./  >  •'  V  •• '•-.':••''.• f!t'
                         • ... •' ..-'       .-  .       ''       '     '           •  '. •


     Alternative ..procedures, e.g., using the orifice meter coeffir  ' •'•   "•

         •  .  '   -   v '    ".  " "          -               •          '        ' • •  ; »

cients, .may.be-..used,  -subject to the approval of the Administrator.. ,
                                                                    V * • • '   *"
           • '••       •                      •"                  '."•

     Note:-.1 If the .dry-gas meter coefficient values'obtained before  • '
            ' '              *             .             -       .        . •   »
   *                •                   •.                    '•.'•**.»


and after a .test series differ by more  than 5 percent, the test    .  ;   •  '••
                                   •                                 *  '. •  •



series shal 1- either ~be voided,  or calculations for the tesfseries '•'..''•'.




shall be.performed using whichever meter coefficient value (i.e.,'" '   •*'    ;

                           *         •                  "      .       ..'*'"*


before'or after)-gives the lower value  of total sample volume.  ,  .. .   •...',;:'

                                              •     *        '    -'***•
                        '•.-•'                  :       •             ••

  • •  5.4- Probe Heater Calibration.  The probe heating system.shall be •' '.



calibrated  before^its"initial.use in  the field according'to the pro-'



cedure outlined inr APfD-0576.'  Probes constructed according to APTD-0581  •-.




need not be calibrated if the. calibration curves in. APTD-0576 are used. =•..":




     •5.5  'Temperature'Gauges.   Use the  procedure in Section 4.3 of




Method 2 to calibrate in-stack  temperature gauges,-  Dial thermometers, ••-



 such as  are used''for't'he dry gas meter  and  condenser outlet, shall  be     : .




 calibrated against mercury-in-glass thermometers.        .       ' /



   .   5.5  Leak Check  of Metering System Shown  in  Figure  5-1.  That  portion   .




 of the sampling train-from-the  pump to  the  orifice meter should be  leak



 checked prior "to  initial use and after  each shipment.  Leakage after the



 pump will  result .in  less volume being recorded than  is actually sampled..



 The following..procedure.is. suggested  (see Figure 5-4):   Close the main      .



 valve on the  .meter b.ox.. .Insert a one-hole rubber stopper with 'rubber

-------
                                        24           .  •              •     .-.,,.
                               V	'    •      '                    '        :  v:    ;
     tubing attached into the orifice exhaust p.ipe. -Disconnect and vent
        »                   .                        '                   .
!•  '  the low side of.the orifice manometer.  £3ose off the low side orifice   •
                     *••'                  *              *                     •
•   '^tap.  ^ Pressurize the system to'13'to 18.era (5'to 7 in.), water column  '• '
     by blowing into the rubber tubing. -Pinch off the tubing and observe'i
• •   '  •         .. •'.•-   -.-'.             i1',-''     .'           • •            •  •      '    -••
     the manometer for one minute.  A'loss of .pressure on the manometer.      .    •
                                                                         • .
  • •.  •          >.- ,. \. ••-, -...,.   ._,•-.           •••..       .        •   .
     indicates a leak in the meter box; leaks, if present, must be corrected.'
     - '•••  :.  '•'..,••                                       .      ..''"•'••
          5.7  Barometer.-  Calibrate against a mercury barometer.  :...     '.  '  '.
            . i        :     .                              •      /      ••.-'/'.•
          5.8'. Determination of Spectrophotometer Calibration.Factor K.     .
•                   .      •          *                  * "                    ."
  -  -    5.8.1  Urea Analysis.   Add 0.0,  1.0,  2.0,  3.0,  and  4.0 ml  of      .
     working standard urea solution to  a series of five 25-ml  volumetric
     flasks.  Pipette 10 ml of the urea color reagent into the flask and
     dilute to exactly  25 ml  with deionized distilled water.   Mix well and
                                                          •*'
     allow each to stand for at least 1.0 minutes for color development.     •  .- -
     Measure the absorbance of each standard at 420 nm.   The  calibration
     procedure must be'repeated each day that samples are  analyzed.   Calculate
     the spectrophotometer calibration  factor as follows:
             :  •            A, + 2A9 + 3A, + 4AA.   .   .    . : .-.'.
          K  .   =   1250 . '   '     *     *     *
                          A,2 + A22 + A/ + A/ •+ A52
    .Where:
          K   = Calibration factor for urea analysis.
          A,  = Absorbance of the 1250 ng standard
          A2  =. Absorbance of the 2500 yg standard. '                  .   •
          A3  = Absorbance of the 3750 ug standard.    i
          A4  = Absorbance of the 5000 yg standard.
          5.8.2  Ammonia Analysis:  Add 0.0, 1.0, 2.0, 5.0, 8.0, and 10.0  .
     ml of working standard ammonium chloride solution to a series of six
     25-ml volumetric flasks.  Adjust the total volume of solution in each

-------
                                 32
to 20 ml using 1.0 N H2S04.  Adding 10 N NaOH dropwise,  adjust the  pK
to between -8 and 10.  Pipette exactly 0.5 ml  of Nessler  reagent into
each flask arid dilute to exactly 25 ml with deionized distilled water.
Mix well and allow .each to stand for 10 to 30 minutes for color develop-
ment.  Note the time allowed for color development of the standards and
use the same time for the samples.   Measure the absorbance of each
standard at 405 nm.  The calibration procedure must be repeated each  day
that samples are analyzed.  Calculate the spectrophotometer calibration
factor as follows:                       .     ,
                   .     A, * 2A, + 5A, + 8A+ 10AC
     K      =   10    -J -  *    93 - 1  '. .,5  -
        3   ,-  •    •  A-  +'A   +A    + A  -.+ A
Where:    •                                                             •
     K . = Calibration factor. _,                           _.
     A^  = Absorbance of the 10 yg standard.
     Ag  = Absorbance of the 20 yg standard.
     A^  - Absorbance of the 50 pg standard.
     A>  = Absorbance of the 80 pg standard. .
     Ac  = Absorbance of the 100 yg standard.
6.  Calculation    •             •
     Carry out calculations, retaining at least one  extra  decimal  figure
beyond that of the acquired data.  Round off figures after final
calculation.
     6.1  Nomenclature.        .
     A    = Absorbance of sample.
                                            2    2         •
     A    = Cross-sectional area of nozzle,  m   (ft ).

-------
                             33
B    = Water vapor in the gas stream,  proportion by volume.
 ws
C    = Acetone blank residue concentration,  mg/g.'
 a
C NH, = Concentration of ammonia,  dry basis  corrected to standard
        condition, mg/dscm (Ib/dscf).
c    = Concentration of particulate matter in stack gas, dry
       basis, corrected to standard conditions,  g/dscm (g/dscf).
C    = Concentration of urea, dry  basis  corrected to standard
       condition, mg/dscm (Ib/dscf).
F    = Dilution factor (i.e., 25/5, 25/10* etc.) required only
       if sample dilution was needed to  reduce the absorbance
       into the range of calibration.
I    = Percent of isokinetic sampling.
K  WH  = Spectrophotometer calibration factor, ammonia analysis.
KU   = Spectrophotometer calibration factor, urea analysis.
L,   = Maximum acceptable leakage  rate for either a pretest  leak
 a
       check or for a leak check following a component change; equal
                   o
       to 0.00057 m /min (0.02 cfm) or 4 percent of the average
       sampling rate, whichever is less.
L.   = Individual leakage rate observed  during the leak check  conducted
       prior to the "i**"" component change (i = 1, 2, 3...n),
       m /min (cfm).
L    = Leakage rate observed during the  post-test leak check,
       m /min (cfm).
M    = Mass of residue of acetone after  evaporation.
 a
M    = Total amount of particulate matter collected, mg.
Mwu  = Mass of ammonia in gas sample yg.

-------
    .:                         34           '             •
M    '- Mass of urea in gas sample, ug.   '•
M    = Molecular weight of water, 18.0 g/g-mole (18.0 Ib/lb-mole).
P.   .'= Barometric pressure' at the sampling site, mm Hg (in. Hg).
 oar.     •
P    = Absolute stack gas pressure, mm Hg (in. Hg).
P., = Standard absolute pressure, 760 mm Hg (.29.92 in. Hg).
R    = Ideal gas constant, 0.06236 mm Hg-m /°K-g-mole (21.85 in.
       Hg-ft3/°R-lb-mole).
T    = Absolute average dry gas meter temperature (see Figure 5-2),
T    = Absolute average stack' gas temperature (see Figure. 5-2),
 v                                                        •  .
Tstd = standard absolute temperature, 293°K (528°R).      ...
V3   = Volume of acetone blank, ml.                          •
 a                                              ...
Val  = Volume' of sample aliquot, analyzed, ml.        -
Va,   = Volume of acetone used in wash, ml.
 oW                   . .                        .          .
V-,.  = Total volume of liquid collected in impingers and silica
 ICi
       gel  (see Figure 5-3), ml.
V    = Volume of gas sample as measured by dry gas meter, dcm (dcf).
V /  .j\ = Volume of gas sample measured by the dry gas meter,
       corrected to standard conditions, dscm (dscf).
V i  = Total volume of solution in which the sample is contained, ml.
V / td\= Volume of water vapor in the gas. sample, corrected to
        standard conditions, scm (scf).
v    =' Stack gas velocity, calculated by Method 2, Equation' 2-9,
       using data obtained from Method 5, m/sec (ft/sec).

-------
                                 35                  .
     W,    = Weight of residue in  acetone wash, mg.
      a
     Y    =• Dry gas meter calibration factor.                 ...
     AH    = Average pressure differential across  the orifice meter.             :.,
      .. '.   (see Figure 5-2), mai  H20 (in. K20)..             '                .
     p    = Density of acetone, mg/ml (see label  on bottle).   "       }        '••'•'
     PW   = Density of water, 0.9982 g/ml (0.002201 Ib/ml).
     9.    = Total sampling time,  min.      .                          .  .
     9,    = Sampling time interval,  from the  beginning of a  run.until            ..
            the -first component change,  min.
     9.   .= Sampling time interval,  between two  successive component
            changes, beginning with  the  interval  between the first         -.   :
                  N         _ ,                  '                                  .
            arid second changes, min.         .  .                            .
     9    = Sampling.time interval,  from the  final  (n  ) component       .  .   •  •.
            change until the end  of  the  sampling run, min.     ..               •',''•
     13.6 = Specific gravity of mercury.
     60   = Sec/mi n..                 .      '                                  •'•
     100  = Conversion to percent.           .     .
     6.2  Average dry gas meter temperature and  average orifice pressure
drop.  See data sheet (Figure 5-2).           •                 .                .
     6.3  Dry Gas Volume.  Correct the sample volume measured by the           :
dry gas meter to standard conditions (20°C, 760  mm Hg or 68°F, 29.92 in..
Hg) by usfng Equation  -1.                 •'*.'••                    •          ;

     „   .     •  '   '.  Tstd   PK,^T^             Ph,. + (4H/13.6)
                                            Equation  --1.

-------
                                    36
 Where:
      K, = 0.3858  °K/mm  Hg  for metric units        .   .
         = 17.64 °R/in.  Hg  for English units
      Mote:   Equation  -1 can  be used as written unless the leakage rate
 observed during any of  the mandatory leak checks (i.e., the post-test
 leak check or  leak checks  conducted prior to component changes) exceeds
 L .  If L  or  L.  exceeds L ,  Equation  -1 must be modified as follows:
  a       p     i           a'   n
      (a) Case  I.  No  component changes made during sampling run.  In
 this case, replace .Vm in Equation  -1 with the expression:
      (b)  -Case. II.  One  or  more component changes made  during the ''-'.
 sampling run.  .In this case, replace V^.lri Equation 5-1 by the'.'.   ,
 expression:   ..-.•''•'.:   . :' ''':.'• •••.-'  •:..•.".'•"•'••'••'•'•'•' ;:-.-'-;i.V'-:i-'''"'^'-
'                 '*        '           '     ''                   '    " '
and  substitute only for those  leakage rates (L^ or L } whic.h  exceed •'•'

  •••'  6.4  Volume of water vapor./' . •  j.  • . '•/;'.'.  -•/• ^, : '•  " ' ''••• -.'• •'•'•  :;..•! \v;
'w(std) " vlc  N
where:
  .   K2 = 0.001333 m3/ml for metric units
        « 0.04707  f£3/iiil for English units.   •
                                                       Equation 5-2.
                                                                                -.1.

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                               '  •37      '    '              .
    •  6.5  Moisture Content.       ....'.     .  '        ••-.-.   ":".~~:"' '

":  ••  Bws''"'• V—. Wfodj	   '          -'•••    . Equation-5-3 x :.'•'.".
= •...-   WS  ;:. Vm(std) T Vw(std).       .;-      '   -.  -••    •   /.     ••;..';.:•;
  *                          .                                "            '
      Note:  In saturated or water droplet-laden gas streams, two     ..••  '
                      •        '     *        .               •''"*''"..
 calculations of the moisture content of the stack  gas shall be made, .
.one from the impinger analysis (Equation 5-3), and a second 'from .the.'. -.
 assumption of saturated conditions.  . The lov/er of  the two  values of  ;
 BWS shall be considered correct.  The procedure for determining  the".-. . ;'
 moisture content based upon assumption of saturated conditions is    •
 given in the Note of Section 1.2 of Method 4. /for the purposes  of this
 method, the average stack gas temperature from Figura 5-2 may be used to
                                ..    ".     '   ."'.'''"      •    '••••'
make this determination, provided that the accuracy of the in-stack
temperature sensor is > 1°C (£°F).   '                   '.'••   '    :  . ••  .
      6.6  Acetone Blank Concentration.
      6.7  Acetone Wash Blank.
           W    =   C  V   p                          '          .
      6.8  Total Particulate Weight.   Determine the  total  particul.ate
 catch from the sum of .the weights obtained from containers  1  and 2
 less the acetone blank (see Figure 5-3).   Note:  Refer to Section 4.1.5
 to assist in calculation of results  involving two.or more filter
 assemblies or two or more sampling trains.

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      6.9  Particu!ate Concentration.



  .  .       'Cs =  (0.001 .g/mg)  (Ma/Vm(std))    ..':•




     .6.10  Total  Mass'of  Urea Per Sample."  ..'


                             V  , •''',:"''•"'.'.'•••'••


         '  Mu  =   Kcu AF   ^~    •"''••'       "•   •   •  Equation 7 ':
                             Soln •   •'.•'•..;: •     .- ". .:,..•.':   ; ••'.; '"




      6.11  Urea Concentration.    ....     '  •'.'_''••  ,.  .    •.....;



                  ;  --M    .     •   •'  ::;-.;-. \ •••{•.''•:.*>'. •':•'. '•  .  -.; •'-,

            u  °   ^2  	.      ''/•'•'     '•'•'•   '.••.•••••• Equation 8 -

  '.              ' ' •    sc      '    '     .   .'•'.-' .-'-.o •".":'• "•':'•;;  •• -v'-;.:/"1
               '.  '     :               '     '  ' . -     .• '- : *.'!   .  ••''•. •  :

Where:  ;   '•'   .    , •; '  .    '        ..'•     -r  "';:. ;'.. .'':.:"•"'.; ••:..'' -:--'' '•'



      K2..="1°3  .§/iT. f°r metl"1C V^tS.  -'..'.v'V'-:>5:-=';-::;
            6.243 x 10'5  —. for English unitsV.;,"'
      6.12 .Total  Mass of  NH.'Per Sample.'   :      .   •   '.
                        '  "    v •  . .  .           •  '-''.'.''..  "   "

                             V ...     '   ,      '  •.••••;,•'         '••'


      MNH ' '"  Kc  NH"'  AF   \TT           .          'Equation 9
      6/13  Ammoni a » Concentration.      .    .      •;•..-     ;.






      CNH  '•''"•'  K2  T~ '         :   •       ::-/:x; Equation' 10
       *»n7   .     . *• i  v cr            '         • '    -.-.'•
         O            ;^ O W    -                - .  : ;    ".'-,''•:..'      ;


                    ^'  / 3                     '•  .:•-••• :'..:  ' •-•••:•- -•  .•'•••••'

Where:.  K2!=10   S^f. for Me trie, units.   '..-...,'  ;;,
                 947 Vin"5               ..           .
               ..243- x 10     T^gTinT for English  units.

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                                   38
        6.H  Conversion Factors:
        From
        scf
        g/ft3
        g/ft3
        g/ft2
                   I?.
                   m3
                   gr/ft3
                   lb/ft3
                   g/m3
Multiply by
 0.02832
 15.43
 2.205 x 10
 35.31
-3 '
        6.15  Isokinetic: Variation.
        6.15.1  Calculation From Raw Data.
100 Ts [K3 V,c * (Vm Y/Tm)
              60 '
                                   vsPsAn
wnere:
                                                  4H/13.6)]
                                                        Equation 11
                                                       .
   :: K, ='0.003454 mm Hg-m /ml-°K for metric units  ":.:'-;-'-''-
      "3                                   '          ''.••'.
      ... = .0:002669 in. Hg-ft3/ml-°R  for English units.  .'"'.:
   •'   '    r  •       •       .     •'            /•    .••••.-••:' •
     6;J_5_.2  CalculatTon From  Intermediate Values. ;v.:.:  •? •
                 . Ts Vmfstd) pstd
                            60
                                      .
                  Ts Vmtstd)
where:
                  vs An
           4.320 for metric units
           0.09450 for Knjjl 1ftl» unit:;.

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                                     41

      6.16  Acceptable Results.  If 90 percent  <. I  <. 110 percent, the_ ;   .     .
 results are acceptable.  If the results are  low in comparison to the  '; '.„ -.v
                                                 •            ..-..'.
 standard  and I is beyond the. acceptable range, or, if I is less than-  (  ..    '•
.90 percent, the Administrator nay opt to accept the results.; Use '   .    .   '  ;
 Citation 4 to make. judgments. ' Otherwise,  reject the. results 'and repeat  '.
 the test.     ••    '• ."     '••''•;  •'.'••   ";••'•..  .:'• '. 'x'r-"-'-  ;• = '•  .•'..   > '  ..  ', • .  '•
 7.  Bibliography  '           .        '".-''..'.. •*.•-.":._'.''...•".'  '•'•/•'  :'  .  •-.. .  : •
                                         * '      ••'-'     »     m      . • '
      1.  Addendum to Specifications  for Incinerator Testing at Federal .-.
 Facilities.  PHS, NCAPC.  Dec. 6, 1967.  •'''••   -'..:/•;     '. ".'.'• ' "• "\''>' :•.'•''
      2. .Martin, Robert M.  Construction Details of Isokinetic Source-;  .' •  -Y-
 Sampling Equipment.  Environmental  Protection  Agency.  Research ;;;V • ••' .-..''.:
 Triangle Park, N. C.  APTD-058i.  April, 1971.  .   ;    v  .   '  >' v:.:;.'; -•".;
      3.  Rom, Jerome- J.  Maintenance,  Calibration, and. Operation ..;.•  '.': .-'   :  ;
 of Isokinetic Source Sampling  Equipment.   Environmental Protection.
                                                 • i .
                                                                              •
 Aycncy.  KosoarcJi TrUnuU fork. N.  C. . APTD-05/6.  March,  1972.
  Ot
  63d Annua'
 '•St. Louis,      MUIie '{4-19, 1970.           •  -."''      .-'..••'   :. ;'':••?':'
       5.  .Smith, W. S., et al.  Stack Gas Sampling  Improved and : ;    •;
  Simplified With New Equipment.  APCA Paper No. 67-119;   1967.      .
       6.  Specifications for Incinerator Testing at Federal .Facilities.'
  PHS.  NCAPC.   19C7,   .         ..                  '            :'    '":'.'..-=.

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                                   42
     7.  Shigehara, R.T.  Adjustments in the EPA Nomograph  for •    •.  . ;  ';•
                 1 •                       ..''''.••••      '.••'"
Different Pitot Tube Coefficients and Dry Molecular"Weights.   Stack ,    .

Sampling News 2.:4-11.  October,  1974.          •''•"''•.

     8.  Vollaro, R. F.  A Survey of Commercially  Available Instrumentation

For the Measurement of Low-Range Gas Velocities. -U.  S.  Environmental   ' '•'
                                                 ;      .     .   •     ' '   •*«.  ' '
                                                                     . •  * «•*•.
Protection Agency, Emission Measurement  Branch.  Research Triangle '.   ..:

Park, N. C.  November, 1976  (unpublished paper).       •        .    ... :

   .  9.. Annual'Book of  ASTM'Standards.   Part  26.  .Gaseous  Fuels;  :-.•••  •"• .

Coal and Coke; Atmospheric Analysis.  American Society for  Testing  , ;  .. •'.'•

and Materials.  Philfuiolphia. Pa.   1974.  pp.  617-622.  .              ;.  ;

     10.  Standard Methods for the  Examination  of Water and  Wastewater,

13th Edition.  American Public Health Association,  Washington,  D.C.,  1974.

pp. 226-232.            '...*'•''                    "                .

     11.  Watt, George W. and Joseph D.  Chrisp. Spectrophotometric
                   '•                                     * •
Method for Determination of Urea.  Analytical Chemistry.   26:452-453,

1954.              '• '  '      '             . '                                 .

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          APPENDIX A.3




MODIFIED PROCEDURE - JANUARY 1980

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                                                     DRAFT
                                           DO NOT QUOTE OR CITI
             DETERMINATION OF PARTICULATE,  AND  UREA      J —//-
                  EMISSIONS FROM UREA PLANTS
1.   Principle and Applicability
     1.1   Principle.  A gas sample is extracted  isokinetically from
the stack.   The ammonia is removed from the sample  by  boiling,
and the urea is measured by a colorimetric procedure.
                                                     t
     1.2  Applicability.  This method is applicable for the
determination of urea from urea manufacturing facilities.
2.   Apparatus
     2.1   Sampling Train.  A schematic of the sampling train used
in this method  is shown in Figure 1; it is similar  to  construction
to Method 5. The sampling train consists of the following
components.
     2.1.1   Probe Nozzle, Probe Liner, Pi tot Tube,  Differential
Pressure Gauge, Metering System, and Barometer.   Same  as
Method 5, sections 2.1.1, 2.1.2, 2.1.3, 2.1.4, 2.1.8,  and 2.1.9
respectively.   Stainless steel probe liners may also be used.
     2.1.2  Impingers—Five as shown in Figure 1.  The second
and third shall be of the Greenburg-Smith design with  standard
tips.  The first, fourth, and fifth shall be of the Greenburg-
Smith design, modified by replacing the insert with an
approximately 13 millimeter (0.5 in) I.D. glass tube,  having an
unconstricted tip located 13 mm (0.5 in) from the bottom of the
flask.  Similar collection systems, which have been approved
by the Administrator, may be used.

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     2.2  Sample Recovery.  The following equipment is needed:
     2.2.1  Probe-Liner and Probe-Nozzle Brushes,  Graduated
Cylinder and/or Balance, Plastic Storage Container, and Rubber
Policeman.  Same as Method 5, sections 2.2.1,  2.2.5, 2.2.6,
2.2.7, respectively.
     2.2.2  Wash Bottles--Two.  Glass wash bottles are recommended;
polyethylene wash bottles may be used at the option of the tester.
     2.2.3  Glass or Plastic Sample Storage Containers.  Chemically
resistant, borosilicate glass bottles 500 ml or 1000 ml.  Screw cap
liners shall either be rubber-backed Teflon or shall be constructed
so as to be leak-free.  (Narrow mouth glass bottles have been found
to be less prone to leakage).  Alternatively,  polyethylene bottles
may be used.
     2.2.4  Funnel, Glass or Polypropylene.
     2.3  Analysis.
     2.3.1  Pipettes.  Volumetric type 0.5-ml, 2-ml, 5-ml, 8-ml,
10-ml, 20-ml, and 25-ml sizes.
     2.3.2  Volumetric Flasks.  25-ml size, 100-ml size, 250-ml
size, 500-ml size and 1000-ml size.
     2.3.3  Graduated Cylinder.  100-ml size.
     2.3.4  Distillation Apparatus.
     2.3.4.1  Flasks or Beakers.  At least two, 800-ml size.
     2.3.4.2  Hot Plate.  Capable of heating the distillation
flasks to 120°C (248°F).
     2.3.5  Spectrophotometer.  To measure absorbance at 420
nanometers.

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     2.3.6  Sample Cells.   Two matched  absorbance  cells  to  fit
the spectrophotometer.
3.  Reagents
     Use ACS reagent-grade chemicals or equivalent,  unless  otherwise
specified.  The reagents used in sampling  and  sample recovery are
as follows:
     3.1  Sampling and  Sample Recovery.
     3.1.1  Silica Gel, Crushed Ice, and Stopcock  Grease.   Same  as
Method 5, sections 3.1.2,  3.1.4, 3.1.5, respectively.
     3.1.2  Water.  Deionized distilled to conform to ASTM
specification D 1193-74, type 3.  At the option of the analyst,  the
KMNCL test for oxidizable organic matter may be omitted  when high
concentrations of organic matter are not expected  to be  present.
     3.1.3  Sulfuric Acid, 1  N.  Dilute 28 ml  of concentrated
sulfuric acid to 1 liter with deionized distilled  water.
     3.2  Analysis.  The reagents need  for analysis are  listed  below.
     3.2.1  Water.  Same as 3.1.2.
     3.2.2  Sodium Hydroxide (NaOH), 10 N.  Dissolve 40  g of NaOH
in a 100-ml volumetric  flask and dilute to exactly 100 ml with
deionized distilled water.
     3.2.3  Sodium Hydroxide 6 N.  Dissolve 240 g  of NaOH in 800 ml
of deionized distilled  water in a 1-liter  flask.  Dilute to exactly
1 liter with deionized  distilled water.
     3.2.4  Sodium Hydroxide 1 N.  Dissolve 40 g of NaOH in 800 ml
of deionized distilled  water in a 1-liter  flask and dilute  to  exactly
1 liter with deionized  distilled water.

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     3.2.5  Sodium Hydroxide 0.1  N.   Dilute 100 ml  of 1  N  NaOH  to
exactly 1 liter with deionized distilled  water.
     3.2.6  Borate Buffer.   Dissolve 2.5  g  of sodium tetraborate,
Na2B407, or 4.8 g of the decahydrate Na2B.07 '  10 H20,  in  500 ml of
deionized distilled water in a 1-liter volumetric flask.   Add 88 ml
of 0.1 N NaOH solution and  dilute to exactly 1  liter with  deionized
distilled water.
     3.3.7  Sulfuric Acid 1  N.  Slowly add  28 ml  of concentrated
sulfuric acid to 800 ml of deionized distilled water in a  1-liter
flask and dilute to exactly 1 liter  with  deionized distilled water.
     3.3.8  Ethyl Alcohol,  95 percent.
     3.3.9  P-dimethylaminobenzaldehyde.
     3.3.10  Hydrochloric Acid, Concentrated (36.5 - 38 percent by
weight).
     3.3.11 Stock Standard Urea Solution.  Dissolve 5.000  g of
urea -in 500 ml of deionized distilled water in a 1-liter flask  and
dilute to exactly 1 liter with deionized  distilled water.
     3.3.12  Urea Color Reagent.   Prepare the color reagent by
dissolving 2.000 g of P-dimethylaminobenzaldehyde in a mixture  of
100 ml of 95 percent ethyl  alcohol and 10 ml of hydrochloric acid.
4.  Procedure
     4.1  Sampling.  Because of the  complexity of this method,  testers
should be trained and experienced with the test procedure  to insure
reliable results.
     4.1.1  Pretest Preparation.   Follow  the general procedure  given
in Method 5, section 4.1.1, except omit the directions for the  filter.

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     4.1.2  Preliminary Determinations.   Follow  the  general
procedure given in Method 5,  section  4.1.2.
     4.1.3  Preparation of Sampling Train.   Follow the  general
procedure given in Method 5,  section  4.1.3,  except place  100 ml
of deionized distilled water  in each  of  the  first two impingers,
place 100 ml of 1  N H2S04 in  the third impinger, leave  the  fourth
impinger empty, and place the preweighed silica  gel  in  the  fifth
impinger.  Assemble the train as shown in Figure 1.
     4.1.4  Leak Check Procedures.  Follow the leak-check procedures
given in Method 5, sections 4.1.4.1  (Pretest Leak Check), 4.1.4.2
(Leak-Check During Sampling Run) and  4.1.4.3 (Post-Test Leak-Check).
     4.1.5  Sampling Training Operation.  Follow the general procedure
given in Method 5, section 4.1.5.  For each  run, record the data
required on a data sheet such as the  one shown in Method  5, Figure  5-2.
     4.1.6  Calculation of Percent Isokinetic.   Same as Method  5,
section 4.1.6.
     4.2  Sample Recovery. Proper cleanup procedure begins as  soon
as the probe is removed from  the stack at the end of the  sampling
period.  Allow the probe to cool.
     When the probe can be safely handled, wipe  off  all external
particulate matter near the tip of the probe nozzle  and place a
cap over it to prevent losing or gaining particulate matter.  Do  not
cap off the probe tip tightly while  the  sampling train  is cooling
down as this would create a vacuum  in'the filter holder,  thus drawing
water from the impingers into the filter holder.

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     Before moving the sampling  train  to  the cleanup site, remove the
probe from the sample train,  wipe  off  the silicone grease, and cap
the open outlet of the probe. Be  careful not  to  lose any condensate
that might be present.  Wipe  off the silicone  grease from the
impinger inlet where the probe was fastened and cap  it.  Remove  the
umbilical cord from the last  impinger  and cap  the impinger.  If  a
flexible line is used between the  first impinger  or condenser and
the probe, disconnect the line at  the  probe and let any  condensed
water or liquid drain into the impingers  or condenser.   Either
ground-glass stoppers, plastic caps, or serum  caps may be used to
close these openings.
     Transfer the probe-impinger assembly to the  cleanup area.   This
area should be clean and protected from the wind  so that the chances
of contaminating or losing the sample  will be  minimized.
     Save a portion of the deionized distilled water used for cleanup
as a blank.  Take 200 ml of this water directly from the wash bottle
being used and place it in a  glass sample container labeled  "water
blank."
     Inspect the train prior  to  and during disassembly and note  any
abnormal conditions.  Treat the  samples as follows:
     Container No. 1.  Taking care to  see that dust on the outside
of the probe or other exterior surfaces does not  get into the sample,
quantitatively recover particulate matter or any  condensate  from the
probe nozzle, probe fitting,  and probe liner,  by  washing these
components with water and placing  the  wash in  a glass container.
Perform the water rinses as follows:

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     Carefully remove the probe nozzle and  clean  the  inside  surface
by rinsing with water from a wash bottle and  brushing with a Nylon
bristle brush.  Brush until the water rinse shows no  visible
particles, after which make a final  rinse of  the  inside surface with
water.
    .Brush and rinse the inside parts of the  Swagelok fitting with
water in a similar way until no visible particles remain.
     Rinse the probe liner with water by tilting  and  rotating the
probe while squirting water into its upper  end so that all  inside
surfaces will be wetted with water.   Let the  water-'-drain from the
lower end into the sample container.  A funnel (glas-s or polyethylene)
may be used to aid in transferring liquid washes  to  the container.
Follow the water rinse with a probe brush.   Hold  the  probe  in an
inclined position, squirt water into the upper end as the probe
brush is being pushed with a twisting action  through  the probe;
hold a sample container underneath the lower  end  of  the probe, and
catch any water and particulate matter which  is brushed from the
probe.  Run the brush through the probe three times  or more  until
no visible particulate matter is carried out  with the water  or
until none remains in the probe liner on visual inspection.   With
stainless steel or other metal probes, run  the brush  through in
the above prescribed manner at least six times since  metal  probes
have small crevices in which particulate matter can  be entrapped.
Rinse the brush with water, and quantitatively collect these
washings in the sample container.  After brushing, make a final
water rinse of the probe as described above.

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     It is recommended that two people be used to clean the probe
to minimize sample losses.  Between sampling runs, keep brushes
clean and protected from contamination.
     Container No. 2.  Measure and record the volume of the first
two impingers.  Then transfer the contents to the container.   Rinse
the first two impingers and the connecting glassware with water
and add the rinse water to the container.  Mark the level of the
liquid on the container and identify the sample container.
     Impingers Nos. 3 and 4.  Measure and record the volume of
the third and fourth impingers.  Discard the liquid.
     Container No. 3.  Note the color of the indicating silica
gel to determine if it has been completely spent and make a
notation of its condition.  Transfer the silica gel from the
fifth impinger to its original container and seal.  A funnel  may
make it easier to pour the silica gel without spilling.  A rubber
policeman may be used as an aid in removing the sifica gel from
the impinger.  It is not necessary to remove the small amount of
dust particles that may adhere to the impinger wall and are
difficult to remove.  Since the gain in weight is to be used
for moisture calculations, do not use any water or other liquids
to transfer the silica gel.  If a balance is available in the
field, follow the procedure for container No.' 3 in section 4.3.
     4.3  Analysis.  Record the data required on a sheet such
as the one shown in Figure 5-3.  Handle each sample container as
fol1ows:  -
                                 8

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     4.3.1   Container Nos.  1  and  2.   Note the  level  of  liquid
and confirm on the analysis sheet whether or not leakage
occurred during transport.   If a  noticeable amount of leakage  has
occurred, either void the sample  or use methods, subject  to the
approval of the Administrator, to correct the  final  results.
Measure the liquid either volumetrically to +_ 1  ml or gravimetrically
to +_ 1.0 g and record on the data sheet.  Combine the contents of
both containers in a 500-ml volumetric flask and dilute to
exactly 500 ml with deionized distilled water.  Distill the sample
following the procedure in 4.3.4.
     4.3.2  Container No. 3.  Weigh the spent  silica gel  (or
silica gel plus impinger) to the nearest 0.5 g using a balance.  This
step may be conducted in the field.
     4.3.3  "Water Blank" Container.  Measure  water in this
container either volumetrically Or gravimetrically and record on
the data sheet.  Distill the sample following  the procedure in 4.3.4.
     4.3.4  Sample Distillation.   Treat the combined sample 1  and 2
and the water blank as follows:
     4.3.4.1  Preparation of Sample.  Pipette a 100-ml aliquot
of sample into a 1-liter flask or beaker and add 400 ml of
deionized distilled water.  Then add 25 ml of borate buffer
and adjust the pH to 9.5 with 6N NaOH using short-range pH
paper to measure the pH.  Heat the flask to boiling and boil until
the volume is reduced to about 75 ml.   (Caution:  This step should
be conducted  under a hood.)  Transfer the  remaining sample to a

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100-ml volumetric flask and dilute to exactly 100 ml  with  deionized
distilled water.
     4.3.4.2  Analysis.  Pipette 10 ml  of this solution  into  a
25-ml volumetric flask and add 10 ml of the urea  color reagent.
Dilute to exactly 25 ml with deionized distilled  water.  Mix  well
and allow to stand for at least 10 minutes for full  color  development.
Measure the absorbance of the solution at 420 nm  using the blank
solution (section 5.5) as a zero reference.  If the  absorbance
exceeds that of the 5.00 mg urea standard, prepare another sample
using less than a 10-ml aliquot.
5.  Calibrations
     5.1  Sampling Train.  Calibrate the sampling train  components
according to the indicated section of Method 5.  Probe Nozzle (5.1);
Pitot Tube (5.2); Metering System (5.3); Temperature Gauge (5.5);
Leak-Check of the Metering System (5.6); and Barometer (5.7).
     5.2  Determination of Spectrophotometer Calibration Factor K.
Add 0.0, 5.0, 10.0, 15.0, 20.0 and 25.0 ml of the stock  standard urea
solution to a series of six 250-ml volumetric flasks.  Then follow
the distillation and analysis procedures described for the samples
in section 4.3.4 of this method.  Each standard at the time of
analysis will contain 0, 1.00, 2.00, 3.00, 4.00,  and 5.00  mg
respectively.  The calibration procedure must be  repeated  each day
that samples are analyzed.  Calculate the spectrophotometer
calibration factor as follows:
                                  10

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                         A,  +  2A9  +  3A~  + 4A. +  5A,
               K  - 1.00 -4	-S	-2	\	~
                c                     ^    *
Where:
     K  = Calibration factor,
      c
     A, = Absorbance of the 1.00 mg standard.
     A« = Absorbance of the 2.00 mg standard.
   t
     A- = Absorbance of the 3.00 mg standard.
     A. = Absorbance of the 4.00 mg standard.
     Ag = Absorbance of the 5.00 mg standard.

6.  Calculations
     6.1  Average Dry Gas Meter Temperature and Average Orifice
Pressure Drop, Dry Gas Volume, Volume of Water Vapor,  Moisture
Content, Isokinetic Variation, and Acceptable Results.  Using
   I '
data from this test, same as Method 5, sections 6.2,  6.3,  6.4,
6.5, 6.11, and 6.12 respectively.
     6.2  Mass of Urea.  Calculate the total weight of urea
collected in the sample by Equation 1.
                                                   Eq.

-------
Where:
     M     = Mass of urea collected,  mg.
     K     = Spectrophotometer calibration factor.
     A     = Absorbance of sample.
     A     = Absorbance of the water  blank
     V i   = Volume of sample aliquot analyzed,  ml.
     V.     = Volume of water-blank  aliquot analyzed,  ml.
     V  -I  = Total volume of solution in  which the  sample
             is contained, ml.
     V     = Volume of sample returned for analysis,  ml.

     6.3  Particulate Concentration:   Calculate the particulate
(urea) concentration as follows:
                   c = 1C  rr-^ - 10'6               Eq.  2
                        2  Vm(std)
Where:
     c       = Particulate (urea) concentration at dry
               standard conditions, g/dscm (gr/dscf).
     M       = Mass of urea collected, g.
     V / .  ,x = Volume of gas sample measured by;;dry gas meter,
               corrected to standard conditions, dscm  (dscf).
     K       =1.0 for metric units.
             = 0.4370 for English units.
                                 12

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7.  Bibliography
     1.  Standard Methods  for  the  Examination of Water and
Wastewater, 13th Edition.   American  Public  Health Association,
Washington, D.C., pp.  226-232, 1974.
     2.  Watt, George  W.  and Joseph  D.  Chrisp.  Spectrophotometric
Method for Determination  of Urea.  Analytical Chemistry.
26:452-453, 1954.
     3.  Same as Method 5, Citation/through 9 of section 7.
                                 13

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    TEMPERATURE SENSOR
                                      IMPINGER TRAIN OPTIONAL, MAY 8E REPLACED
                                        * . BY AN EQUIVALENT CONDENSER
P1TOTTU8E
TEMPERATURE  .
   SENSOR
                         HEATED AREA   THERMOMETER
                                                             THERMOMETER
        :'   c	
._..   •-••  I
KEVERSE-TYPE
  PITOTTUBE
           PITOT MANOMETER
                                .IMPINGERS  •     .  ---  _      ICE BATH
                                          BY-PASS VALVE VALVE
        .THERMOMETERS  ?
                                                              VACUUM
                                                               GAUGE'
                                                       MAIN VALVE,
                   • DRY GAS METER
                                         rr  i
                                       AIR-TIGHT- !
                                        • PUMP    \
                / r
                '     Figure 1.  Particuiate samplinq train
                                                                            CHECK
                                                                            VALVE
                                                                            VACUUM
                                                                             LINE  '

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        APPENDIX A.4




PROPOSED REFERENCE METHOD 28

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                  APPENDIX A - REFERENCE TEST METHOD
             METHOD 28 - DETERMINATION OF PARTICIPATE (UREA)
                        EMISSIONS FROM UREA PLANTS
1.''Applicability and Principle
     1.1  Applicability.  This method applies to the determination of
particulate emissions as urea from urea manufacturing facilities.
     1.2  Principle.  A gas sample is extracted isokinetically from
the stack.  The ammonia is removed from the sample by boiling, and
the particulate emissions are determined as urea by a colorimetric
procedure.
                                  „
2.  Apparatus             _
     2.1  Sampling Train.  A schematic of the sampling train used  in
                        /•
this method is shown in Figure 28-1; it is similar in construction to
Method 5.  The sampling train consists of the following components.
     2.1.1  Probe Nozzle, Probe Liner, Pitot Tube, Differential
Pressure Gauge, Metering System, and Barometer.  Same as Method 5,
sections 2.1.1, 2.1.2, 2.1.3, 2.1.4, 2.1.8, and 2.1.9 respectively.
Stainless steel probe liners may also be used.
     2.1.2  Impingers.  Five impingers connected in series as shown
in Figure 28-1.  For the second and third impinger, the tester shall
use the Greenburg-Smith design with standard tips.  For the first,
fourth, and fifth impingers, the tester may use the Greenburg-Smith
design, modified by replacing the tips with a 1.25 cm (0.5 in.)  ID

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glass tube extending to 1.25 cm (0.5 in.)  from the  bottom  of the
flask.  Similar collection systems,  which  have been approved by
the Administrator, may be used.
     2.2  Sample Recovery.  The following  equipment is  needed:
     2.2.1  Probe-Liner and Probe-Nozzle Brushes, Graduated  Cylinder
and/or Balance, Plastic Storage Containers,  and Rubber  Policeman.
Same as Method 5, sections 2.2.1, 2.2.5, 2.2.6, 2.2.7,  respectively.
     2.2.2  Wash Bottles.  Glass wash bottles  are recommended;
polyethylene wash bottles may be used at the option of  the tester.
     2.2.3  Sample Storage Containers.  Chemically  resistant,
borosilicate glass bottles, 500-ml or 1000-ml.  Screw cap  liners
shall either be rubber-backed Teflon or shall  be constructed so as
to be leak-free.  (Narrow mouth glass bottles  have  been found to  be
less prone to leakage).  Alternatively, polyethylene bottles may
be used.
     2.2.4  Funnel.  Glass or Polyethylene.
     2.3  Analysis.  For analysis, the following equipment is needed.
     2.3.1  Pipettes.  Volumetric type, 0.5-ml, 2-ml, 5-ml,  8-ml,
10-ml, 20-ml, and 25-ml.
     2.3.2  Volumetric Flasks.  25-ml, 100-ml, 250-ml,  500-ml, and
1000-ml.
     2.3.3  Graduated Cylinder.  100-ml.
    . 2.3.4  Distillation Apparatus.
     2.3.4.1  Flasks or Beakers.  At least two, 800-ml.
     2.3.4.2  Hot Plate.  Capable of heating the distillation flasks
to 120°C  (248°F).

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     2.3.5  Spectrophotometer.   To measure absorbance at 420
nanometers.
     2.3.6  Sample Cells.  Two  matched absorbance  cells  to  fit
the spectrophotometer.
3.  Reagents
     Use ACS reagent-grade chemicals or equivalent,  unless
otherwise specified.
     3.1  Sampling and Sample Recovery.  The reagents used  in
sampling and sample recovery are as follows:
    . 3.1.1  Silica Gel, Crushed Ice, and Stopcock  Grease.  Same
as Method 5, sections 3.1.2, 3.1.4, 3.1.5, respectively.
     3.1.2  Water.  Deionized distilled to conform to ASTM
specification D 1193-74, type 3.  At the option  of the analyst,'
the KMNO^ test for oxidizable organic matter may be  omitted when
high concentrations of organic  matter are not expected to be
present.
     3.1.3  Sulfuric Acid, 1 N.  Slowly add 28 ml  of concentrated
sulfuric acid to 800 ml of deionized distilled water in  a 1-liter
flask and dilute to exactly 1 liter with deionized distilled  water.
     3.2  Analysis.  The reagents need for analysis  are  listed
below:
    . 3.2.1  Water.  Same as 3.1.2.
     3.2.2  Sodium Hydroxide (NaOH), 10 N.  Dissolve 40  g of  NaOH
in a 100-ml volumetric flask and dilute to exactly 100 ml with
deionized distilled water.

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     3.2.3  Sodium Hydroxide 6 N.   Dissolve 240 g of NaOH  in 800 ml
of deionized distilled water in a  1-liter flask.   Dilute to exactly
1 liter with deionized distilled water.
     3.2.4  Sodium Hydroxide, 1 N.  Dissolve 40 g of NaOH  in 800 ml
of detonized distilled water in a  1-liter flask and dilute to  exactly
                                                •
1 liter with deionized distilled water.
     3.2.5  Sodium Hydroxide, 0.1  N.  Dilute 100 ml  of 1 N NaOH to
exactly 1 liter with deionized distilled water.
     3.2.6  Borate Buffer.  Dissolve 2.5 g of sodium tetraborate
CNa2B407) or 4.8 g of the decahydrate (Ka^Oy .  10 H20) in 500 ml
of deionized distilled water, in a  1-liter volumetric flask.  Add 88 ml
of 0.1 N NaOH solution, and dilute to exactly 1 liter with deionized
distilled water.    ,                      .            "        .   .
                    "              ;«
     3.3.7  Sulfuric Acid,.! N. Same as 3.1.3.
     3.3.8  Ethyl Alcohol, 95 percent. '
     3.3.9  p-dimethylaminobenzaldehyde.
     3.3.10  Hydrochloric Acid, Concentrated.
     3.3.11  Urea Solution, 2.5 mg/ml.  Dissolve 2.500 g of urea in
500 ml of deionized distilled water in a 1-liter flask and dilute to
exactly 1 liter with deionized distilled water.
     3.3.12  Urea Color Reagent.  Dissolve 2.000 g of
p-dimethylaminobenzaldehyde in a mixture of 100 ml of 95 percent
ethyl alcohol and 10 ml of concentrated hydrochloric acid.

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4.  Procedure
     4.1  Sampling.  Because of the complexity of this method,
testers should be trained and experienced with the test procedure
to insure reliable results.
     4.1.1  Pretest Preparation.  Follow the general  procedure  given
in Method 5, section 4.1.1, except omit the directions for the  filter.
     4.1.2  Preliminary Determinations.  Follow the general  procedure
given in Method 5, section 4.1.2.
     4.1.3  Preparation of Sampling Train.  Follow the general
procedure given in Method 5, section 4.1.3, except place 100 ml  of
deionized distilled water in each  of the first three  impingers,  place
100 ml of 1 N HpSO. in the fourth  impinger, and place the preweighed
silica gel in the fifth impinger.   Assemble the train as shown  in
Figure 28-1.
     4.1.4  Leak Check Procedures.  Follow the leak-check procedures
given in Method 5, sections 4.1.4.1 (Pretest Leak Check), 4.1.4.2
(Leak-Check During Sampling Run) and 4.1.4.3 (Post-Test Leak-Check).
     4.1.5  Sampling Training Operation.  Follow the  general  procedure
given in Method 5, section 4.1.5.   For each run, record the data
required on a data sheet such as the one shown in Method 5,  Figure 5-2,
     4.1.6  Calculation of Percent Isokinetic.  Same  as Method  5,
section 4.1.6,
     4.2  Sample Recovery.  Begin  proper cleanup procedure as soon
as the probe is removed from the stack at the end of  the sampling
period.  Allow the probe to cool.

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   .  When the probe can be safely handled,  wipe off all  external
participate matter near the tip of the probe nozzle, and place a
cap over it to prevent losing or gaining participate matter.  Do
not cap off the probe tip tightly while the sampling train  is
cooling down as this would create a vacuum, thus drawing water from
the impingers into the probe.
     Before moving the sampling train to the cleanup site,  remove
the probe from the sample train, wipe off the silicone grease, and
cap the open outlet of the probe.  Be careful not to lose any
condensate that might be present.  Wipe off the silicone grease from
the impinger inlet where the probe was fastened and cap it. Remove
the umbilical cord from the last impinger and cap the.impinger.  If
a flexible line is used between the first impinger or condenser and
the probe, disconnect the line at the probe and let any condensed
water or liquid drain into the impingers or condenser.  Either
ground-glass stoppers, plastic caps, or serum caps may be used to
close these openings.
     Transfer the probe-impinger assembly to the cleanup area.  This
area should be clean and protected from the wind so that the chances
of contaminating or losing the sample will  be minimized.
     Inspect the train prior to and during disassembly and  note any
abnormal conditions.  Treat the samples as follows:
     4.2.1  Container No. 1.  Taking care to see that dust  on  the
outside of the probe or other exterior surfaces does not get into
the sample, quantitatively recover particulate matter or any condensate
from the probe nozzle, probe fitting, and probe liner, by washing

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these components with water and placing the wash in a glass
container.  Perform the water rinses as follows:
     Carefully remove the probe nozzle and clean the inside surface
by rinsing with water from a wash bottle and brushing with a Nylon
bristle brush.  Brush until the water rinse shows no visible
particles, after which make a final rinse of the inside surface
with water.
     Brush and rinse the inside parts of the Swagelok fitting with
water in a similar way until no visible particles remain.
     Rinse the probe liner with water by tilting and rotating the
probe while squirting water into its upper end so that all  inside
surfaces will be wetted with water.  Let the water drain from the
lower end into the "sample container.  A funnel (glass or polyethylene)
may be used to aid in transferring liquid washes to the container.
Follow the water rinse with a probe brush.  Hold the probe in an
inclined position, squirt water into the upper end as the probe
brush is being pushed with a twisting action through the probe;
hold a sample container underneath the lower end of the probe, and
catch any water and particulate matter which is brushed, from the
probe. 'Run the brush through the probe three times or more until
no visible particulate matter is carried out with the water or
until none remains in the probe liner on visual inspection.  With
stainless steel or other metal probes, run the brush through in
the above prescribed manner at least six times since metal  probes
have small creyices in which particulate matter can be entrapped.

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Rinse the brush with water, and quantitatively collect these
washings in the sample container.  After brushing, make a final
water rinse of the probe as described above.
     It is recommended that two people clean the probe to minimize
sample losses.  Between sampling runs, keep brushes clean and
protected from contamination.
     4.2.2  Container No. 2.  Mark the liquid level of the container
to determine later if leakage occurred during shipment.  Cap and
seal the containers and identify.  Measure to the nearest +_ 1 ml and
record the volume of the first three impingers.  Then transfer the
contents to the container.  Rinse the first three impingers and the
connecting glassware with water, and add the rinse water to the
container.  Mark the level of the liquid on the container and identify
the sample container.
     4.2.3  Impinger No. 4.  Measure to the nearest +_ 1 ml and record
the volume of the fourth impinger.  Discard the liquid.
     4.2.4' Container No. 3.  Note the color of the indicating silica
gel to determine if it has been completely spent and make a notation
of its condition.  Transfer the silica gel from the fifth impinger
to its original container and seal.  The tester may use a funnel
and rubber policeman as aids in transferring the silica gel.  It is
not necessary to remove the small amount of dust particles that may
adhere to the impinger wall and are difficult to remove.  Since the
gain in weight is to be used for moisture calculations, do not use
any water or other liquids to transfer the silica gel.  If a balance

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is available in the field,  the tester may follow  the procedure  for
container No. 3 in section  4.3.2.
     4.2.5  Water Blank.  Save a portion of the deionized  distilled
water used for cleanup as a blank.   Take 200 ml of this water directly
from the wash bottle being  used and place it in a glass sample
container labeled "water  blank."
     4.3  Analysis.  Record the data required on  a sheet such as  the
one shown in Figure 5-3 of  Method 5.  Handle each sample container
as follows:
     4.3.1'"Containers No.  1  and 2.  Note the level  of liquid and
confirm on the analysis sheet whether or not leakage occurred during
transport.  If a noticeable amount of leakage has occurred,  either
void the sample or use methods, subject to the approval of the
Administrator, to correct the final results.  Measure the  liquid
either yolumetrically to  t_ 1  ml or gravimetrically to +_0.5  g,  and
record on the data sheet.  Combine the contents of both containers
in a 500-ml volumetric flask, and dilute to exactly 500 ml with
deionized distilled water.   Distill the sample following the
procedure in 4.3.4.
     4.3.2" Container No. 3.   Weigh the spent silica gel  (or silica
gel plus impinger) to the nearest 0.5 g using a balance.   This  step
may be conducted in the field.

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     4.3.3  "Water Blank" Container.   Measure water in  this
container either volumetrically or gravimetrically and  record  on
the data sheet.  Distill the sample following the procedure  in
4.3.4.
     4.3.4.V  Preparation of Sample.   Pipette a 100-ml  aliquot
of sample Into a 1-liter flask or beaker, and add 400 ml  of
deionized distilled water.  Then add 25 ml of borate buffer* and
adjust the pH to 9.5 with. 6N NaOH using short-range pH  paper to
measure the pH.  Heat the flask to boiling and boil until  the
volume is reduced to about 75 ml.  (Caution:   Conduct this step
under a hood.)  Transfer the remaining sample to a 100-ml
volumetric flask and dilute to exactly 100 ml with deionized
distilled water.
     4.3.4.2  Analysis.  Treat the sample and blank as  follows:
Pipette 10 ml into a 25-ml volumetric flask and add 10  ml  of the
urea color reagent.  Dilute to exactly 25 ml  with deionized
distilled water.  Mix well and allow to stand for at least
10 minutes for full color development.  Measure the absorbance of
the solution of 420 nm using the blank solution as a zero reference.
If the absorbance exceeds that of the 5.00-pg/ml urea standard,
prepare another sample using less than a  10-ml aliquot.
5,''Calibrations
     5.1  Sampling Train.  Calibrate the sampling train components
according to the indicated section of Method 5.  Probe  Nozzle  (5.1);

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Pitot Tube (5.2); Metering System (5.3);  Temperature Gauge (5.5);
Leak-Check of the Metering System (5.6);  and Barometer (5.7).
     5.2  Determination of Spectrophotometer Calibration Factor K.
Add 0.0, 1.0, 5.0, 10.0, 15.0, 20.0 and 25.0 ml  of the standard urea
solution to a series of six 250-ml  volumetric flasks.   Then follow
the distillation and analysis procedures  described for the samples
in section 4.3.4 of this method.  Each standard  at the time of
analysis will contain 0, 0.100, 0.500, 1.00, 1.50, 2.00, and 2.50 mg
respectively.  The calibration procedure  must be repeated each day
that samples are analyzed.  Calculate the Spectrophotometer calibration
factor as follows:
                       A, +.5A« + 10A, + 15A,  + 20AC + 25AC
                   inn _J	t	2	2	2	2.
                  . 1UU                                    ^
Where:
     K   = Calibration factor.
      c
     A,  - Absorbance of the 0.100 mg standard.
     A2  = Absorbance of the 0.500 mg standard.
     A3  a Absorbance of the 1.00 mg standard.
     A*  " Absorbance of the 1.50 mg standard.
     Ac  = Absorbance of the 2.0 mg standard.
     A6  = Absorbance of the 2,50 mg standard.

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6.  Calculations
    " 6.1  Average Dry Gas Meter Temperature and  Average Orifice
Pressure Drop, Dry Gas Volume, Volume of Water Vapor,  Moisture
Content, Isokinetic Variation, and Acceptable Results. Using
data from this test, same as Method 5, sections  6.2,  6.3,  6.4,
6.5, 6.11, and 6.12 respectively.
     6.2  Mass of Urea.  Calculate the total weight of urea
collected in the sample by Equation 28-1.
Where:
     m     = Mass of urea collected, ing.
     K     = Spectrophotometer calibration factor.
     A     = Absorbance of sample.
     AW    a Absorbance of the water blank.
     Yai   s- Volume of sample aliquot analyzed, ml.
     ^soln = T°ta>i volume of solution in which the  sample is
             contained, ml.
     6,3  particulate Concentration:  Calculate the particulate
(ureal concentration as follows:
                                      10"3                Eq.  28-2
                              Vm(std)

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Where:
     c       =  Participate (urea) concentration  at dry
                standard conditions, g/dscm (gr/dscf).
     m       »  Mass of urea collected,  g.
     V / .j% =  Volume of gas sample measured  by  dry gas meter,
                corrected to standard conditions, dscm  (dscf).
     K«      3  1.0 for metric units.
             =  0.4370 for English units.
7.' Bibliography
     1.  American Public Health Association.   Standards Methods for
the Examination of Water and Wastewater, 13th  Edition.
Washington, D.C.  1974..  pp. 226-232.
     2.  Watt, George  W. and Joseph D.  Chrisp.   Spectrophotometric
       ..            ^-•              ^            .
Method for Determination of Urea.   Analytical  Chemistry.   2£:452-453.
1954.
     3.  Same as Method 5, Citation 1 through  9 of section 7.

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      APPENDIX A.5




KJELDAHL ANALYSIS METHOD

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                       NITROGEN,  KJELDAHL, TOTAL

             Method 351.3  (Colorimetric; Titrimetric;  Potentiometric)

                                                                STORET  NO.  00625

 1.   Scope and Application
     M  This method covers the determination of total Kjeldahl nitrogen in drinking, surface and
          saline  waters,  domestic  and industrial wastes.  The  procedure converts nitrogen
          components of biological origin such as amino acids, proteins and peptides to ammonia,
          but may not  convert the nitrogenous  compounds of some industrial wastes such as
          amines, nitro compounds, hydrazones, oximes, semicarbazones and some refractory
          tertiary amines.
     1.2  Three  alternatives are listed for the determination of ammonia after distillation: the
          titrimetric  method which is applicable to concentrations above  1  mg N/liter; the
          Nesslerization method which is applicable to concentrations below 1  mg N/liter; and the
          potentiometric method applicable to the range 0.05 to 1400 mg/1.
     1.3  This method is described for macro and micro glassware systems.
 2.   Definitions
     2.1  Total Kjeldahl  nitrogen is defined as the sum of free-ammonia and  organic nitrogen
          compounds which are converted to ammonium sulfate (NH4)2SO4, under the conditions
          of digestion described below.
     2.2  Organic Kjeldahl nitrogen is defined as the difference  obtained by subtracting the free-
          ammonia value (Method 350.2,  Nitrogen, Ammonia, this  manual) from the  total
          Kjeldahl nitrogen value. This may be determined directly by removal of ammonia before
          digestion.
 3.   Summary of Method
     3.1  The sample is heated  in the presence  of cone, sulfuric acid, K2SO4 and HgSO4  and
          evaporated  until SO3 fumes are  obtained and the solution becomes  colorless or pale
          yellow. The residue is cooled, diluted, and is treated and made alkaline with a hydroxide-
          thiosulfate  solution. The  ammonia  is  distilled and  determined after  distillation by
          Nesslerization, titration or potentiometry.
 4.   Sample Handling and  Preservation
     4.1  Samples may be preserved by addition of 2 ml of cone. H2SO4 per liter and stored at 4"C.
          Even when  preserved in this manner, conversion of organic nitrogen to ammonia may
          occur. Preserved samples should be analyzed as soon as  possible.
 5.   Interference
     5.1  High nitrate concentrations (10X or more than the  TKN level) result in low TKN
          values. The reaction between nitrate and ammonia can be prevented by the use of an
          anion exchange resin (chloride form) to remove the nitrate prior to the TKN analysis.

Approved  for NPDES
Issued 1971
Editorial revision  1974 and 1978

                                         351.3-1

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6.    Apparatus
   .  6.1   Digestion apparatus: A Kjeldahl digestion apparatus  with  800 or 100 ml flasks  and
           suction takeoff to remove SO3 fumes and water.
     6.2   Distillation apparatus: The macro Kjeldahl flask is connected to a condenser and an
           adaptor  so that the distillate can  be collected. Micro Kjeldahl steam distillation
           apparatus is commercially available.
     6.3   Spectrophotometer for use at 400 to 425 nm with a light path of 1 cm or longer.
7.    Reagents       "
     7.1   Distilled water should be free of ammonia. Such water is best prepared by the passage of
           distilled  water through an  ion exchange column containing a strongly acidic cation
          .exchange resin mixed with a strongly basic anion exchange  resin. Regeneration of the
           column should be carried out according to the manufacturer's instructions.
           NOTE 1: All solutions must be made with ammonia-free water.
     7.2   Mercuric sulfate solution: Dissolve 8 g red mercuric oxide (HgO) in 50 ml of 1:4 sulfuric
           acid (10.0 ml cone. H2SO4 : 40 ml  distilled water) and dilute to  100 ml with distilled
           water.
     7.3   Sulfuric acid-mercuric sulfate-potassium sulfate solution: Dissolve 267 g K2SO4 in  1300
           ml distilled water and 400 ml cone. H2SO4. Add 50 ml mercuric sulfate solution (7.2) and
           dilute to 2 liters with distilled water.
     7.4   Sodium  hydroxide-sodium  thiosulfate  solution: Dissolve  500 g  NaOH and  25  g
           Na2S2O3»5H2O in distilled water and dilute to 1 liter.
     7.5   Mixed indicator: Mix 2 volumes of 0.2% methyl red in 95% ethanol with 1 volume of
           0.2% methylene blue in ethanol. Prepare fresh every 30 days.
     7.6   Boric acid solution: Dissolve 20 g boric  acid, H3BO3, in water and dilute to 1 liter with
           distilled water.
     7.7   Sulfuric acid, standard solution:  (0.02 N) 1 ml =  0.28 mg NH3-N. Prepare a stock
           solution of approximately 0.1 N acid by diluting 3 ml of cone. H2SO4 (sp. gr. 1.84)  to 1
           liter with CO2-free distilled water. Dilute 200 ml of this solution to 1 liter with CO2-free
           distilled water. Standardize the approximately 0.02 N acid so prepared against 0.0200 N
           Na2CO3 solution. This last solution is prepared by dissolving 1.060 g anhydrous Na2CO3,
           oven-dried at 140°C, and diluting to 1 liter with CO2-free distilled water.
           NOTE 2: -An  alternate  and  perhaps  preferable  method  is  to standardize  the
           approximately 0.1 N H2SO4 solution against a 0.100 N Na2CO3 solution. By proper
           dilution the 0.02 N acid can the be prepared.
     7.8   Ammonium chloride, stock solution: 1.0 ml =  1.0 mg NH3-N. Dissolve 3.819 g NH4C1
           in water and make up to 1 liter in a volumetric flask with  distilled water.
     7.9   Ammonium chloride, standard solution: 1.0 ml = 0.01 mg NH3-N. Dilute 10.0 ml of the
           stock solution (7.8) with distilled water to 1 liter in a volumetric flask.
     7.10  Nessler reagent: Dissolve 100 g of mercuric iodide and 70 g potassium iodide in a small
           volume-of distilled water. Add this mixture slowly, with stirring, to a cooled solution of
           160 g of NaOH in 500 ml of distilled water. Dilute the mixture to 1 liter. The solution is
           stable for at least one year if stored in a pyrex bottle out of direct sunlight.
                                        351.3-2

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           NOTE 3: Reagents 7.7, 7.8, 7.9, and 7.10 are identical to reagents 6.8, 6.2, 6.3, and 6.6
           described  under  Nitrogen,  Ammonia  (Colorimetric;  Titrimetric;  Potentiometric-
           Distillation Procedure, Method 350.2).
8.    Procedure
     8.1   The distillation apparatus should be pre-steamed before use by distilling a 1:1 mixture of
           distilled water and sodium hydroxide-sodium thiosulfate solution (7.4) until the distillate
           is ammonia-free. This operation should be repeated each time the apparatus is out of
           service long enough to accumulate ammonia (usually 4 hours or more).
     8.2   Macro Kjeldahl system
           8.2.1 Place a measured  sample or the residue  from the distillation  in the ammonia
                determination (for Organic Kjeldahl  only) into an 800 ml Kjeldahl flask. The
                sample size can be determined from the following table:

                   Kjeldahl Nitrogen                                 Sample Size
                    in  Sample, mg/1                                      ml
          »
                        0-5                          -                   500
                       5-10                              s               250
                      10-20                                             100
                      20-50                                            50.0
                     50-500      .                                      25.0

                Dilute the sample, if required,  to 500 ml with distilled water, and add 100 ml
                sulfuric acid-mercuric  sulfate-potassium sulfate solution (7.3). Evaporate  the
                mixture in the Kjeldahl apparatus until SO3 fumes are given off and the solution
                turns colorless or pale yellow. Continue heating for 30 additional minutes. Cool the
                residue and add 300 ml distilled water.
           8.2.2 Make the digestate alkaline by careful addition  of 100 ml of sodium hydroxide -
                thiosulfate solution (7.4) without mixing.
                NOTE 5: Slow addition of the heavy caustic solution down  the tilted neck of the
                digestion flask will cause heavier solution to underlay the aqueous sulfuric acid
                solution without loss of free-ammonia. Do not  mix until the digestion flask  has ,
                been connected to the distillation apparatus.
           8.2.3 Connect the Kjeldahl flask to  the  condenser with the tip of condenser or an
                extension of the condenser tip below  the level of the boric acid solution. (7.6) in the
                receiving flask.
           8.2.4 Distill 300 ml at the rate of 6-10 ml/min., into 50 ml of 2% boric acid (7.6)
                contained in a 500 ml Erlenmeyer flask.
           8.2.5 Dilute the distillate to 500 ml in the flask.  These flasks should be marked at the 350
                and the 500 ml volumes. With such marking, it is not necessary to transfer  the
                distillate to volumetric flasks. For concentrations above 1 mg/1, the ammonia can
                be determined titrimetrically. For concentrations below this value, it is determined
                colorimetrically. The potentiometric  method is applicable to the range 0.05 to 1400
       .  '     mg/1.
                                         351.3-3

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8.3   Micro Kjeldahl system
      8.3.1  Place 50.0 ml of sample or an aliquot diluted to 50 ml in a 100 ml Kjeldahl flask
           and add  10  ml sulfuric acid-mercuric  sulfate-potassium  sulfate solution (7.3).
           Evaporate the mixture in the Kjeldahl apparatus until SO3 fumes are given off and
           the solution  turns colorless or pale yellow. Then digest for an  additional  30
           minutes. Cool the residue and add 30 ml distilled water.
      8.3.2  Make  the digestate alkaline by careful addition  of 10 ml of sodium hydroxide-
           thiosulfate solution (7.4) without mixing. Do not mix until the digestion flask has
           been connected to the distillation apparatus.
      8.3.3  Connect the Kjeldahl flask to the condenser with the tip  of condenser or  an
           extension of the condenser tip below the level of the boric acid solution (7.6) in the
           receiving flask or 50 ml short-form Nessler tube.
      8.3.4  Steam distill 30 ml at the rate of 6-10 ml/mm., into 5 ml of 2% boric acid (7.6).
      8.3.5  Dilute the distillate to 50 ml. For concentrations above 1 mg/1 the ammonia can be
           determined titrimetrically.  For concentrations below this value, it  is determined
           colorimetrically. The potentiometric method is applicable to the range 0.05 to 1400
           mg/1.
8.4   Determination of ammonia in distillate: Determine the ammonia content of the distillate
      titrimetrically, colorimetrically, or potentiometrically, as described below.
      8.4.1  Titrimetric determination: Add 3 drops of the mixed indicator (7.5) to the distillate
           and titrate the ammonia with the 0.02 N H2SO4 (7.7), matching the endpoint
           against a blank containing the same volume of distilled water and H3BO3 (7.6)
           solution.
      8.4.2  Colorimetric determination: Prepare a series of Nessler tube standards as follows:

               ml of Standard
         1.0  ml = 0.01 mg NH3-N                         mg NH3-N/50.0 ml

                  0.0                                         0.0
                  0.5                                         0.005
                   1.0                                         0.010
                  2.0                                         0.020
                  4.0                                         0.040
                  5.0                                         0.050
                  8.0                                         0.080
                  10.0                                         0.10

           Dilute each tube to 50  ml with ammonia free water, add 1 ml of Nessler Reagent
           (7.10) and mix. After 20 minutes read the absorbance at 425 nm against the blank.
           From the values obtained for the standards plot absorbance vs. mg NH3-N for the
           standard curve. Develop color in the 50 ml diluted distillate in exactly the same
           manner and read mg NH3-N from the standard curve.
      8.4.3  Potentiometric determination: Consult the method entitled Nitrogen, Ammonia:
           Potentiometric, Ion Selective Electrode Method, (Method 350.3) in this manual.
      8.4.4  It  is not imperative that all standards be treated in the same manner as the samples.
           It  is recommended that at least 2 standards (a high and low) be digested, distilled,
                                    351.3-4

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                and compared to similar values on the curve to insure that the digestion-distillation
                technique is reliable. If treated standards do not agree with untreated standards the
                operator should find the cause of the apparent error before proceeding.
9.    Calculation
     9.1   If the titrimetric procedure is used, calculate Total Kjeldahl Nitrogen, in  mg/1, in the
           original sample as follows:
                              TKN, mg/1 =  (A ~  B)N x F  x 1.000
                                                      S
          where:
          A = milliliters of standard 0.020 N H2SO4 solution used in titrating sample.
          B = milliliters of standard 0.020 N H2SO4 solution used in titrating blank.
          N = normality of sulfuric acid solution.
          F = milliequivaJent weight of nitrogen (14 mg).
          S = milliliters of sample digested.

          If the sulfuric acid is exactly 0.02 N the formula is shortened to:


                              TKN, mg/1 „ (A -  B> X 28°
     9.2   If the Nessler procedure is used, calculate. the Total Kjeldahl Nitrogen, in mg/1, in the
          original sample as follows:
                              wx.     .,   Ax 1,000     B
                              TKN , mg/1 = -  -1 - x  --
          where:
          A = mg NH3-:N read from curve.
          B = ml total distillate collected including the H3BO3.
          C = ml distillate taken for Nesslerization.
          D = ml of original sample taken.

     9.3   Calculate Organic Kjeldahl Nitrogen in mg/1, as follows:
          Organic Kjeldahl Nitrogen = TKN -(NH3-N.)
                                          351.3-5

-------
      9.4   Potentiometric  determination: Calculate  Total  Kjeldahl  Nitrogen,  in  mg/1, in the
           original sample as follows:
                                    TKN, mg/1 = -   x  A
           where:
        *•
           A = mg NH3-N/1 from electrode method standard curve.
           B = volume of diluted distillate in ml.
           D = ml of original sample taken.


 10.   Precision
      10.1  Thirty-one analysts in twenty laboratories analyzed natural water samples containing
           exact increments of organic nitrogen, with the following results:
      Increment as
    Nitrogen, Kjeldahl
       mg N/liter

          0.20
          0.31
         * 4.10
          4.61
   Precision as
Standard  Deviation
   mg N/liter

      0.197
      0.247
      1.056
      1.191
           Accuracy as
  Bias,
+ 15.54
+  5.45
+  1.03
 - 1.67
   Bias,
mg N/liter

   -fO.03
   +0.02
   +0.04
   -0.08
(FWPCA Method Study 2, Nutrient Analyses)
                                       Bibliography

1.    Standard Methods for the Examination of Water and Wastewater, 14th Edition, p 437,
     Method 421(1975).
2.    Schlueter, Albert, "Nitrate Interference In Total Kjeldahl Nitrogen Determinations and Its
     Removal by Anion Exchange Resins", EPA Report 600/7-77-017.
                                          351.3-6

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        APPENDIX B




AMMONIA ANALYSIS PROCEDURES

-------
                                                                   ~ loot'  -I--? 9 -0-2.0
                              NITROGEN,  AMMONIA     ^<^Jk  ^79

            Method  350.2  (Colorimetric;  Titrimetric;  Potentiometric  - .
                                Distillation Procedure)

                                                          STORET  NO.  Total 00610
                                                                       Dissolved 00608
  »*•

 1.   Scope and Application                '
     •1.1  This distillation method covers the determination .of ammonia-nitrogen exclusive of total
          Kjeldahl nitrogen, in drinking, surface and saline waters, domestic and industrial wastes.
          It is the method of choice where economics and sample load do not warrant the use of
          automated equipment.
      1.2  _The method covers  the range from about 0.05 to !.0 mg NH3-N/1 for the colorimetric
          procedure, from 1.0 to 25 mg/1 for the titrimetric procedure, and from 0.05 to 1400
          mg/1 for the electrode method.           "  x  ^
     1.3  This method is described for macro glassware; however, micro distillation equipment
          may also be used.
 2.   Summary of Method
     2.1  The sample is buffered at  a pH of 9.5 with a borate buffer in order to decrease hydrolysis
          of cyanates and organic nitrogen compounds, and is then distilled into a solution of boric
          acid. The ammonia in the distillate can be determined colorimetrically by nesslerization,
          titrimetrically with  standard  sulfuric acid with  the use of a  nibced  indicator,  or
          potentiometrically by  the ammonia  electrode. The choice  between  the first  two
          procedures depends on the concentration of the ammonia.
 3.   Sample Handling and Preservation
     3. 1  Samples may be preserved with 2 ml of cone. H2SO4 per liter and stored at 4°C
 4.   Interferences
     4.1  A number of aromatic and aliphatic amines, as  well as other compounds, both organic
          and inorganic,  will cause turbidity upon  the  addition  of Nessler reagent, so direct
          nesslerization (i.e., without distillation), has been discarded as an official method,
     4.2  Cyanate, which  may be encountered in certain industrial effluents, will hydrolyze  to
          some extent even at the pH of 9.5 at which distillation is carried  out Volatile alkaline
          compounds, such as certain ketones, aldehydes, and alcohols, may cause an off-color
          upon nesslerization in the distillation method. Some of these, such as formaldehyde, may
          be eliminated by boiling off at a low pH (approximately 2 to 3) priop to distillation and
          nesslerization.
     4.3  Residual chlorine must also be removed by pretreatment of the sample with sodium
          thiosulfate before distillation.
Approved for  NPDES
Issued  1971
Editorial revision 1974

                                         350.2-1

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5.    Apparatus
     5.1   An all-glass distilling apparatus with an 800-1000 ml flask.
     5.2   Spectrophotometer or filter photometer for use at 425 nm and providing a light path of 1
           cm or more.
     5.3   Nessler tubes: Matched Nessler tubes (APHA Standard) about 300 mm long, 17 mm
           inside diameter, and marked at 225 mm ±1.5 mm inside measurement from bottom.
     5.4   Erlenmeyer flasks: The distillate is collected in 500 ml glass-stoppered  flasks. These
           flasks should be marked at the 350 and the 500 ml volumes. With such marking, it is not
           necessary to transfer the distillate to volumetric flasks.
6.    Reagents
     6.1   Distilled water should be free of ammonia. Such water is best prepared by  passage
           through  an ion exchange column containing a strongly acidic cation exchange resin
           mixed with a strongly basic anion exchange resin. Regeneration of the column should be
           carried out according to the manufacturer's instructions.
           NOTE 1: All solutions must be made with ammonia-free water.
     6.2   Ammonium chloride, stock solution: 1.0  ml = 1.0 mg NH3-N. Dissolve 3.819 g NH4C1
           in distilled water and bring to volume in a 1 liter volumetric flask.
     6.3   Ammonium chloride, standard solution: 1.0 ml =  0.01 mg. Dilute 10.0 ml of stock
           solution (6.2) to 1 liter in a volumetric flask.
     6.4   Boric acid solution (20 g/1): Dissolve 20  g H3BO3 in distilled water and dilute to 1 liter.
     6.5   Mixed indicator: Mix 2 volumes of 0.2% methyl red in 95% ethyl alcohol with 1 volume
           of 0.2%  methylene blue in 95% ethyl alcohol. This  solution should be prepared fresh
           every 30 days.
           NOTE 2: Specially denatured ethyl alcohol conforming to Formula 3A or 30 of the U.S.
           Bureau of Internal Revenue may be substituted for 95% ethanol.
     6.6   Nessler reagent: Dissolve 100 g of mercuric iodide and 70 g of potassium iodide in a small
           amount of water. Add this mixture slowly, with stirring, to a cooled solution of  160 g of
           NaOH in 500 ml of water. Dilute the mixture to 1 liter. If this reagent is stored in a Pyrex
           bottle out of direct sunlight, it will remain stable for a period of up to 1 year.
           NOTE 3: This reagent should give the  characteristic color with ammonia within 10
   " x      minutes  after addition, and  should  not  produce a precipitate with small amounts of
           ammonia (0.04 mg in a 50 ml volume).
     6.7   Borate buffer: Add 88 ml of 0.1 N NaOH solution to 500 ml of 0.025  M  sodium
           tetraborate solution (5.0 g anhydrous Na2B4O7 or 9.5 g Na2B4O7»10H2O per liter) and
           dilute to  1 liter.
     6.8   Sulfuric acid, standard solution: (0.02 N, 1 ml  = 0.28 mg NH3-N). Prepare a stock
           solution of approximately 0.1 N acid by diluting 3 ml of cone. H2SO4 (sp. gr. 1.84) to  1
           liter with CO2-free distilled water. Dilute 200 ml of this solution to 1 liter with CO2-free
           distilled water.
           NOTE  4:  An alternate and  perhaps preferable  method  is  to standardize the
           approximately 0.1  N  H2SO4 solution against a  0.100 N Na2CO3 solution. By proper
           dilution the 0.02 N acid can then be prepared.
                                         350.2-2

-------
          6.8.1  Standardize the approximately 0.02 N acid against 0.0200 N Na2CO3 solution.
                This last solution is prepared by dissolving 1.060 g anhydrous Na2CO3, oven-dried
                at 140°C, and diluting to 1000 ml with CO2-free distilled water.
     6.9  Sodium hydroxide, 1 N: Dissolve 40 g NaOH in ammonia-free water and dilute to 1 liter.
     6.10 Dechlorinating reagents: A number of dechlorinating reagents may be used to remove
          residual chlorine prior to distillation. These include:
          a.    Sodium thiosulfate (1/70 N): Dissolve 3.5 g Na2S2O3»5H2O in distilled water and
                dilute to 1 liter. One ml of this solution will remove 1 mg/1 of residual chlorine in
                500 ml of sample.
          b.    Sodium arsenite (1/70 N): Dissolve 1.0 g NaAsO2 in distilled water and dilute to 1
                liter.
7.    Procedure
     7.1  Preparation of equipment: Add 500 ml of distilled water to an 800 ml Kjeldahl flask. The
          addition of boiling  chips  which  have been previously treated with dilute NaOH will
          prevent bumping. Steam out the distillation apparatus until the distillate shows no trace
          of ammonia with Nessler reagent.
     7.2  Sample  preparation:  Remove  the  residual  chlorine in  the sample by adding
          dechlorinating agent equivalent to the chlorineVesidual. To 400  ml of sample add 1 N
          NaOH (6.9), until the pH is 9.5, checking the pH during addition with a pH meter or by
          use of a short range pH paper.
     7.3  Distillation: Transfer the sample, the pH of which has been adjusted to 9.5, to an 800 ml
          Kjeldahl flask and add 25 ml of the borate buffer (6.7). Distill  300 ml at the rate of 6-10
          ml/min. into 50 ml of 2% boric acid (6.4) contained in a 500 ml Erlenmeyer flask.
          NOTE 5: The condenser tip or an extension of the condenser tip mus( extend below the
          level of the boric acid solution-
          Dilute the distillate  to 500 ml with distilled water and nesslerize an aliquot to obtain an
          approximate value of the ammonia-nitrogen concentration. For concentrations above 1
          mg/1 the ammonia  should be determined titrimetrically. For  concentrations below this
          value it is determined colorimetrically. The electrode method may also be used.
     7.4  Determination of ammonia in distillate: Determine the ammonia content of the distillate
          titrimetrically, colorimetrically or potentiometrically as described below.
          7.4.1  Titrimetric determination: Add 3 drops of the mixed indicator to the distillate and
                titrate the ammonia with the 0.02 N H2SO4, matching the end point against a blank
                containing the same volume of distilled water and H3BO3 solution.
                                         350.2-3

-------
           7.4.2 Colorimetric determination: Prepare a series of Nessler tube standards as follows:

                    ml of Standard
               1.0 ml = 0.01  mg NH3-N                        mg NH3-N/50.0 ml

                       0.0                                            0.0
                       0.5                                          0.005
                        1.0                                           0.01
                       2.0                                           0.02
                       3.0                                           0.03
                       4.0                                           0.04
                       5.0                                           0.05
                       8.0                                        .   0.08
                       10.0                                        •  0.10

                Dilute each tube to 50 ml with distilled water, add 2.0 ml of Nessler reagent (6.6)
                and mix. After 20 minutes read the absorbance at 425 nm against the blank. From
                the  values obtained  plot absorbance vs. mg NH3-N for the standard curve.
                Determine the ammonia in the distillate by nesslerizing 50 ml or an aliquot diluted
                to  50 ml and reading the  absorbance at 425 nm as described above  for the
                standards. Ammonia-nitrogen content is read from the standard curve.
           7.4.3 Potentiometric determination: Consult the method entitled Nitrogen, Ammonia:
                Selective Ion Electrode Method (Method 350.3) in this manual.
     7.5   It is not imperative that all standards be distilled in the same manner as the samples. It is
           recommended that at least two standards (a high and low) be distilled and compared to
           similar values on the curve to insure that the distillation technique is reliable. If distilled
           standards do not agree with undistilled standards the operator should find the cause of
           the apparent error before proceeding.
8.    Calculations
     8.1   Titrimetric

                                  .. VIU    „.   A x  0.28  x  1,000
                              mg/1 NH, - N = 	5	'	
          where:
          A = ml 0.02 N H2SO4 used.
          S = ml sample.
     8.2  Spectrophotometric

                              mg/1 NH, - N = Ax^OOO  x  B.

          where:
          A = mg NH3-N read from standard curve.
          B = ml total distillate collected, including boric acid and dilution..
          C = ml distillate taken for nesslerization.
          D = ml of original sample taken.
                                          350.2-4

-------
      8.3   Potentiometric
                                   mg/1 NH, - N =
                        500
                         D
xA
           where:
           A = mg NHj-N/1 from electrode method standard curve.
           D = ml of original sample taken.
9.   Precision and Accuracy
     9.1   Twenty-four analysts in sixteen laboratories analyzed natural water samples containing
           exact increments of an ammonium salt, with the following results:
      Increment as
   Nitrogen, Ammonia
       mg N/liter

           0.21
           0.26
           1.71
           1.92
   Precision as
Standard  Deviation
    mgN/liter

      0.122
      0.070
      0.244
      0.279
           Accuracy as
  Bias,
  -5.54
 -18.12
 +0.46
  -2.01
   Bias,
mg N/liter

   -0.01 N
   -0.05
   +0.01
   -0.04
(FWPCA Method Study 2, Nutrient Analyses)
                                       Bibliography

1.   Standard  Methods for  the Examination of Water and Wastewater,  14th  Edition,  p 410,
     Method 418A and 418B (1975).
2.   Annual Book of ASTM Standards, Part 31, "Water", Standard D1426-74, Method A, p .237
     (1976).                                 ....
                                          350.2-5

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           PART III

SPECIFIC .ION.ELECTRODE METHOD
        Wade Shepherd
           Ed Tew
   Northrop Services, Inc.
    Research Triangle Park
       North Carolina

-------
                            SPECIFIC ION ELECTRODE
INTRODUCTION
     Aqueous ammonia concentrations may be determined using a specific ion
electrode attached to a standard pK meter.  This procedure may be used to
measure dissolved ammonia or ammonium ion in aqueous solutions.  After proper
pH adjustment, the ammonia electrode responds logarithmically to the level of
ammonia in the solution.  The response of the electrode to ammonia concentration^  |
is recorded in millivolt readings directly from the pH meter.  A standard
calibration curve is prepared by ploting the log of the ammonia concentration
vs. the millivolt response. ...The.samples are then analyzed accordingly.and ....
their concentration are calculated from the calibration curve.  The method is
simple and quick, requiring littTe sample preparation.

THEORY
     The electrode consists of an internal reference solution separated from
the sample solution by a hydrophobic gas-permeable membrane.  The principle
of operation involves the passage of dissolved ammonia in the solution through
the membrane until the "partial pressures of ammonia on both sides of the mem-
brane are equal.  As the ammonia passes through the membrane, it dessolves
in the filling solution and to a small extent'reacts reversibly with the water.
in the filling solution:

                       NH3 + H20  ^   NHJ  + OH"

The relationship between ammonia, ammonium and hydroxide ion  is given by  the
following equation:

-------
                                         constant.(K)   •
Since the internal fining solution contains ammonium chloride  at a  sufficiently
high level so that the ammonium ion concentration is  fixed,  then  this  relation-
ship may be rewritten:

                        C OH" ] = C NH3 ]  .   constant

This shows the relationship betv/een the free ammonia  in the  sample and the
hydroxide ion concentration in the filling solution.   As the NH-  migrates
through the membrane, the concentration of hydroxide  ion changes  in  the
internal reference solution, thus changing the potential of  the electrode
sensing element in a Nerstean manner:

                          E = EQ  -  S log COH~]

Therefore,
                          E = E1  -  S log CNH3]

From the above two equations, one can see that the sensing element changes
with the change in concentration of NH3 in the sample.  In order to convert
ammonium ion to ammonia, the pH of the sample must be adjusted with standard
base to a pH of 11 or greater according to the following equation:

                         NH3 + H20  •£  NH4* + OH"
                 •
APPRATUS
     Ammonia Electrode, Model  95-10, Orion Research  Incorporated
     Model 701 Digital pH Meter
     Electrode Holder, Cat. No. 92-00-01, Orion  Research  Incorporated
     Magnetic Stirrer with stirring bar

-------
REAGENTS
     Sodium Hydroxide, 5 Normal, NaOH
         Prepare by dissolving 200 grams of reagent grade sodium
         hydroxide in a 1-liter volumetric flask and dilute to mark
         with ammonia-free distilled-deionized water.   This will
         give you a 0.1 Molar solution.

INTERFERENCES
                                             •
     Ionic species cannot cross the gas-permeable membrane, so they cannot
affect electrode operation.  The level of ions in solution.can, however, chance
the solubility of ammonia to some degree",' a~f fee ting" the electrode'calibration.
Best results are obtained if standards and samples have about the sarr.e level
of ions (and other dissolved species) present."  Therefore, the samples analyzed
must be dilutedtto a dissolved species concentration of 0.2 Molar or less.
     The only other interference recorded is water vapor, which can diffuse
across the membrane.  The addition of NaOH will help equalize the osmotic
pressure on both sides of the membrane so that the water vapor will not diffuse
across the membrane.

STANDARD CURVE
     Prepare a standard calibration curve by making serial dilutions from the
10"1« ammonium sulfate solution to prepare 10"-M, 10"-PI, 10"%, 10"%, and
10"-M_ standards.  Starting with the least concentrated standard, 10"-M, and
                                              2
working to the most concentrated standard, 10 -M_, take a 10-ml aliquot of each,
add 0.2 ml of 5-N. NaOH and place the electrode in the standard solution until
a constant millivolt reading is obtained.  Use a stirring bar to agitate the
sample.  Repeat this procedure until all standards have been analyzed.  Between
each standard, rinse the electrode with several portions of distilled-deionized
water.  Once all standards have been analyzed, a calibration curve as in

-------
                  Specific Ion Electrode

                    'Calibration Graph
-I 232
-sa
  a        ST23

M IL-L 1 VDLT5

      Figure 6
                                                               2 £10
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-------
                                        -5        -2
Figure 6 should be produced.  Between 10  M_ and 10  M.  the curve is linear, but
a correction factor must be added to produce a linear curve betv/een 10" M_  and
10~ M ammonia concentration.
SAMPLE ANALYSIS
     Because the probe wash, probe plug and impinger catches are very acidic, it
is necessary to dilute them so'the total concentration of dissolved species is
~0.2 M.  To reach this level, 1 ml "aliquots are diluted by a factor .of 20 with
     ~~                        "    . ~ t*.
distilled-deionized water then treated as normal samples.  Record the mv reading
after a constant value is observed.  For best results, start with the least con-
centrated samples (probe plug and probe wash), then analyze the impinger catches.
Also, the samples and standards should be at the same temperature and should be
agitated by the stirring bar at the-same rate.
     From the standard curve, record the millivolt readings from the samples and
note concentrations.

CALCULATIONS                     '                                •
          ing NH.  =  (moles/1000 ml)  (D^) (D2) (17 grams/mole) (1000 mg/g)

          ug/M3   =  (mg NK3) (103 ug/mg)/M3
          ppm     .  (ug/M3,  (0,02445)

               where:  0-,  =  dilution volume of original sample, ml
                       Dp  =  dilution factor of sample analyzed
                       M3  =  volume of flue gas sampled corrected to standard
                              conditions, M3

-------
             APPENDIX C

 SAMPLE PRESERVATION ANALYSIS DATA


             Includes:

C.I  Field Sample Preservation
Co2  Laboratory Sample Preservation

-------
       APPENDIX C.I




FIELD SAMPLE PRESERVATION

-------
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             APPENDIX D




AMMONIA INTERFERENCE ON UREA ANALYSIS

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                                                     Report of Chemical Analysis of Non-Routine Samples
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                           Date Reported: __3_r.
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                                                                                          ANALYTICAL  C H I MIS 7
 wrre I'rcji.ircil mid  will be di.-,;-u.-.s<-d <-.!.-'•»),'. re.  The fir;t  four
 of thrso iIrrivutivi-5 give blue or bhjc-gnfii colv.'a in >-!.*g  hcid
 solution.  Appan-nUy 1.1 ie ."j-ecificity of the an.i'ylir.tl j.roci-i!ure
 dujx-nda on  Ihp  fiirmr.linn of  tlic pyiazinojihriKizine under (lie
 given conditions.   If the dc-rivalives arc ivilM/"] first (£), inauy
 of them form highly colored products in slroiig f>ciJ fjlulion.

                     A CK NO W LEI iG.M t>T

   This work was supported by research grants from the'N'Htional
 Heart Institute and National Microbiological Institute.   It is a
 pleasure to thank-Otto Schnlts  for samples of 2,3-bulancdione,
 4,5-octadione, and  the cthanodisil bisulfite compound ind for criti-
 cism of the manuscript.   Thanks are due to Thomas B.  Cruin-
 pier f'ir his n)g£Citii/i>j concerning the J>:<-p.sration of 'Jit ir.swJ
 H ripL  A  simple of hyjiophoi'jihoro'js  arid  r«v./;!i-yj  fjoin t}>
 Ol'll.ury Kle<.lrO"C)ir:nica) Co. i.« acVii'jwlodji'J' with
                                        I
                      UTKItO VIIE Cl CKD

 (1) ri»-:lier, O.. »nd Hej/p, E., Srr., Q, 2iO (li-SO). •
 (2) /Ud., 23, S41 (IS'JO).                 ...••.•-'
 (3) Kuhn, R.,  and  Uccksher, R., Z. j,l-jiwi. Cl^m., l&O, 118
 (4) Kun, E., /. fJCn/. Cl.em., 1H7, CS9 (1S5O;.  T'-   ;v  /.•,,-.
 (5) /(-Crf., 194.  003 (1952).    :        • •;-:.'• .. .' \ - ^':- "
 (C) N'eulx-ig,  C., Failfcr, E., &nd  LcviU, 'A., Bi^J^rm, Z., f3,'ji
       (1017).                .    ..   -./'.-• :•-.•;- .;• ;,  :.«.
 (7) Stcignmn,  A.. Bnt. J. Pl,ol.. 93. 25fl (1W6).:: S,. •. • .:.-.-,  -.

 Hr.CLirto for review July 22. 1953.  Accfpled  D«-eeai'b«>j- 7  !Pi3.    • -
             Specirophoiomelric  F/ielhod  for  Oeferminsiion  of  bfrea:'-
             GEORGE W. V/AH «nd JOSEPH D. CHRISP
             TAe University of Tex&t, Austin, Tex.
    'Die work described in  this j>apcr M'as Hone to provide a
    dependable rnclJiod  for the determination of urea in
    samples containing urra,  liydraiine,  ^•elnicarbaziJe,
    and arniiioniufn ion.   This method io\'ol\'cs u spt'.ctro-
    photometric determination of iirca and is based ii|»on
    the yellow-greea  color produced  when /i-dimethyl-
    aminohcnzaldchyde is added to urea  in dilute hydro--
    chloric acid solution.   This  system exhibits  a trans-
    mittancy minimum at 420 mp and shows yood agree-
    ment with Recr's law at urea cniirvntralions up to 320
    p.p.m.   \Vith  tlic  inslrument  and procedure  used, a
    relative error of only 19£ is re-uli*ed o^er the optimum
    urea concentration range of 50 to  2)0 p.p.m.  Inlcrrcr-
    enc^s investigated,  include  ammonium ion, hydroxyl-
    amine, hydraiine,  and scmicurb;i^i(Ie;  the  latter  two
    interfere, but  a procedure  for thitir rrrnuval  is yi\e.n.
    Although developed for the analysis of a particular type
    of sample, this method should he readily arlaplablc to
    the determination of urea in a wide variety of samples.
   IN A recent communication, (.he present authors de-scribed a
    spectropholometric method for the determination of hydra-
zine (4) that is based upon the use of p-dimclhylaniinobonzalde-
hyde to develop yellow-colored solutions having a tmnsniittancy
minimum at 458 mp.  In the course, of certain studies in which
this method w.is employed for the determination of hydnizinc, it
became necessary to analyze numerous samples not only for hy-
drazine, but alao for semicarbazide and urea,  all in the presence
of appreciable concentrations of ammonium ion.   Spectrophoto-
melric determination of hydrazine followed by determination of
hydraiine and semicarba^ide by the iodflte litration method "of
Jarnieson  (S) permitted the determination of scmiesrbazide by
difference.  However, the easting methods for the determination
of urea were either cle-arly'inapplic-iblc or f.tili-d  to give salis-
factorj'results when used in the analysis of samples of known urea
content.
  From an inspection of Figure 2 in the previous paper (4),  it is
evident that the broad traosmittanry minimum region exhibited
by solutions containing urea and p-dinii-thylaminobemalilehyde
might serve  as  a  b"-sis for the.development of a. satisfactory
method for the determination of uri-a.   Further experiments have
shown that this system exhibits  a rcjiro.lut-ililp trar.fmittancy
minimum  at 420 m^i, which h:ts ln-en utilizi-d  in  t!.e manner de-
scribed bfclow for (he dc-tti-rruii.ition of urt-a iti E-jir.^lrf of the- type
already indicated.
                        EXTER I.MENTAL
   Apparatus.   A Bcckman Nfodel DU  sjx-ctropholometcr so>-
 m.-itthed Corex cells of  1.001-cm. light  p.-xth «cre  ux-d for »1
 transmittjncy mp.osureinenta.  The instrument  «'as ojxrratod a
 constant .^ensitivitj- using a slit width of 0.1 mm., correspondia
 to .1 nominal band width of 2.4 mp at 420'mn-
   Materials.  Urea  (B.iker's C.P. analyzed) was recrystulliw
_twire_froni  mclh:inq]J_«'.'ishcd \vith dii-Ui^-l eOier, and itrird t
 vac.no  for  48  hours over  anhydrous magnesium  jn-rchloral.
 molting i>oint,  132°  C.,  rorrecUd.  Hydrazine dihydrochlorii
 (Enstman No. 1117) and scmicarbazide hyd/oi:hluride (Eas'.ra;
 No. 220) were  titrated by the J.imieson ^mtthod  (3), and tin
 purity  w.-vs found to be 9'J.S and 99.4%, resportivoly.  Pol.i.->iu
 lodate  (Merck  ACS reagent grade) and  p-dirni:thylaminol>ei
 aldehyde (Eastman N'o. 95) were used as received.  All otlic-r n.
 tcrials  employed in this work were rerigent grade chemicals th
 were used witJiout further purification.
   Standard Urea Solulion.  This solution w.is prepnred by d
 solving 0.4 gram of urea in  distilled wa!«r and diluting to IOC-
 mi.  Aliquots of this solulion were u>od to make up the vario
 uic.1 Filutions from which 
-------
         :
           ««
                                 tii
i    iii
                            U*t>.
        Figure 2.  Calibration Curve for Urea with
        p-DimelbyTamiiiobenxuMchj'de  at 420  m/i
           that 95% ethyl alcohol was employed instead of abso-
  jle ethyl alcohol.  [Although absolute alcohol was specified for
 tj; in the determination of hyd.-azine (4), it has since peen found
 i>^t Co/c ethyl alcohol is equally satisfactory.]  This color rc-
 t^at consists of:  p-diraethylaminobenzaldehyde (2.000 grams),
 5% ethyl alcohol (100.0 ml.),  and concentrated  Ji3P   .,'i (i..v • :  '!,.: .!..• -y. .-.::.:;
   rVocvduie.  )"i.i  tJ.c  d' '••nf.inVii'.n of ],} i'.::-.7i:n:, - :i.ii i"h»-
 ji'lr, :»ii>i  urr.a in t-olu'.i'in« C'iiil:'.ining  «ll ll.r't of tllnrci> were rin|iloyfij;  ,\n h;,j.ioj>ri-
 .stf  ali'i'jiil wiu uii-'ily^i-rl for hylr.'iiinc liy tl.c  mcUiod ol \\ntt
 tii') CIiri.«|i (^).  .Ano(ln-r uliijU'it w:ia f iikun fur the <}rt< rniimiion
 of I'jt.tl liyilr.izini: iiii'l K-inic:irli:izitlc liy  the ridliod of J^inicron
 (.1)  and the .'•vmii ;irli:i/.i.lc content w:is  olit.iinod by d:jrd  sodium Uiif.sulf»te !>olu-
 tion usine the  disappearance of the chnractcristic color of  iudins
 in the chloroform layer RS the end  point.  The resulting wlution
 (ca. 4;U To hydrochloric ftcid)  was  neutralized  with sodium
 hydroxide to the  plierioljiblhalcin  end j>oint, after whith 2 or 3
 drops of 1,V hydrorliloric acid were udded to dissipate the indi-
 cator color.  The aqueous phase WHS separated, the chloroform
 layer was washed once with 10 ml.  of water, the  aqueous solution
 and washings  were made  up to a known  volume, and aliquot*
 were taken Tor subsequent color development and sptctrophoto-
 melric determination of  urea.

  Six standard samples containing urea,  eeraicarbazide  hydro-
 chloride, and hydrazine  dihydrocHoride were thus analyzed for
 urea over  the  working range of concentration  at  420  m^;  the
 relative error in (he urea determination did not exceed 4% in  any
 case.  In a typical instance  involving determination of all three •
 components by the  procedures  outlined above,  a sample  wag
 known to contain 0.187  gram of hydrazine, 0.603 gram of urea,
 and  O.CSS  gram of semicarbazide; the values found by analysis
 were O.IS5, O.C1C, .ind O.f»!>2, rcspi-rlively.


                         DISCUSSION

  The calibration curve employed in this work is shown  in Figure
 2, in which per  cent absorliance (100 —  per cent transmittancy) ia
 plotted agninst the  logarithm of the concentration of urea ex-
 pressed in pnrts per million.  The inflection point in the curve oc-
 curs at 03% absorbance  (urea at a concentration of 110 p.p.m.),
 and  the slope of the curve at this point corresponds to a maximum
 relative error  of 2.7% per  1%  absolute photometric  error, in,
 agreement with JV-cr's law (7).  The working range of concentra-
 tion of urea is 50 to 240 p.p.m. fora 4% relative  error per ^ab-
 solute  photometric error;  these limits were determined  as  de-
 scribed  by  Ay res :\ Young (2).  The  absolute  photometric
 error can !>c kept down to 0.25% with good temperature control;
 henri: the relative analysis error should not be greater than 1.0%
 for this concentration range.           -
  Partir.ular care should b<: exercised in making up and adding the
 color re.'igcnl,  as yignifir.-int errors are introduced  by small  dif-
 ferences in the  quantity  of color reagent in blank and unknown.
 The true optimum quantity of color reagent for use in this method
 was not eslalilishi-d in the present studies owing to the fact that
 the color nvigcnt has a mnximum absorption wave length at  415
 m;i.   As stated alx>ve, however, use of  more than the specified
 quantity of color  n-agcnt results in a decrease iu trar.smittsncy
 pn-sunuilily owing to  absorption attributable to the color reagent;
 the use of lower concentrations of this reagent  was not investi-
 gated.
  Although this method was developed for use in the analysis of a
 particular type of sample, the nature of the method is such that it
 should he readily adaptable to the determination of urea in a wide
 variety of samples.

                     ACKNOWLEDGMENT

  The authors  wisli to express their gratitude to G. H. Ayres for
his interest and assistauce.

                     LITKHATURE CITED

 (1) Ayrcs. G. H., A>-AL. CHEM., 21, 652 (1949).
 (2) Ayrea. G. H., and  Young. K . Ibid.. 22. 12SO (1950).
 (3) Jamieson. G. S.. Am. J. SCT.. 33, 352 (1912).
 (4)  Watt. G. W.. and  Cliri;p. J. D-,  A.VAL. CHEM.. 24, 200G (1952).

 RECEIVED for review November 2.  1933.  Arrejil«J December 28. 1953.
 This  »ork wsa supported by the U. S. Navy Bureau ol Onios&ce. Contract
 N123i-673&3. Ta-k Order 2.

-------
                  APPENDIX E

EVALUATION OF STANDARD PROCEDURES FOR PROPOSED
          EPA UREA ANALYTICAL METHOD
                   Includes:

        E.I  Effect of Preliminary Distillation
        E.2  Sulfuric Acid Interference

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           APPENDIX E.I




EFFECT OF PRELIMINARY DISTILLATION

-------
                                                     S~J^

             £j£S<->~ ~£
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AUDIT SAMPLES - W.R. GRACE - AUGUST 1979





     Five urea-in-mannitol audit samples were analyzed as a quality assurance




check.  Samples were weighed, then dissolved in 100 mis of water and analyzed




for urea according to the preliminary ammonia distillation, p-dimethylaraino-




benzaldehyde colorimetric procedure.  Samples were also analyzed by the direct




colorimetric procedure.  The distilled samples were also read against the




direct standards to determine whether it was necessary to distill the standards.




     Excluding sample //4, the errors for the distilled samples and standards




and the direct samples and standards were within the 5% tolerance allowed.




The distilled samples analyzed against direct standards were approximately 14%




lower than the actual value.  It was decided to do a preliminary ammonia distil-




lation on both samples and standards followed by the colorimetric procedure




for this project.

-------
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-------
       APPENDIX E.2




SULFURIC ACID INTERFERENCE

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-------
              APPENDIX F

THRESHOLD MINIMUM DETECTABLE LIMIT FOR
THE PROPOSED EPA UREA ANALYTICAL METHOD

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-------
               APPENDIX G




UREA SAMPLING TRAIN COLLECTION EFFICIENCY

-------
                                                                            h
            UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
                    Office of Air Quality Planning and Standards
                   . Research Triangle Park, North Carolina 2771 1
                              April  10,  1980
Mr. Will Wade
TRC Environmental Consultants, Inc.
125 Silas Deane Highway
Wethersfield, Connecticut 06109

Reference:  EPA Contract No.  68-02-2820, Assignment No.  20, Union Oil
            Company, Brea, California,  EMB Report No.  80-NHF-15

Dear Will:

     This letter is to document and  clarify the scope  of work proposed
under the above referenced work assignment.

Test Program Sampling and Analytical  Procedures
              •s
     Three individual urea-ammonia particulate runs shall be performed
at the prill tower Northeast  stack.   The test runs shall be conducted
at the outlet location while  the tower  is producing fertilizer grade
prills.   The three runs shall  each cover approximately 144 minutes
over 48 traverse points.

     The train configuration  shall consist of a glass-lined probe
connected by a flexible Teflon line  to  six(6) impingers.  The first
two impingers are to be prefilled with  deionized, distilled water
(100 mis each).   The next two are to be prefilled with IN rLSO^
(100 mis each).   The fifth impinger  shall remain empty while trie sixth
shall be prefilled with 200 grams of indicating silica gel.

     The first,  third, fifth,  and sixth impingers shall  be of the
Greenburg-Smith design, modified by  replacing the tip  with an 1/2
inch glass tube extended to within 1/2  inch of the impinger's bottom.

     The second and fourth impingers are of the regular design for the
Greenburg-Smith units including tips with orifice plates located within
1/2 inch of the bottom.  No filter is required.

     The probe shall be heated 'to the temperature range of the stack
plus 10°F.  The probe temperature shall  be measured and recorded for
each point.   However, if you  do not  have this capability you may record
the variable transformer setting and submit calibration curves utilizing
the procedures outlined in APTD-0576.   Data  measurements shall be required
for each, traverse point.   In  addition the train operator shall maintain a
daily log detailing problems,  delays, elapsed sampling times, and
associated comments.

-------
      Sample cleanup  and recovery procedures include the following:

      (1)   The  probe,  flexible Teflon line, and their connecting glassware
 shall  be  rinsed with  deionized, distilled water into one container.  The
 probe shall  be brushed and rinsed.

      (2)   The  first  impinger's contents shall  be placed in a second
 container.  The impinger and its U-tube shall  be rinsed with deionized,
 distilled water into  the same container.

      (3)   The  second  impinger's contents shall be placed in a third
 container.  The impinger and its U-tube shall  be .rinsed with deionized,
 distilled water into  the same container.

      (4)   The  third,  fourth and fifth impingers and their connecting
 glassware shall be rinsed with a IN H-jSO^ solution and placed in a fourth
 container.

      Brush and rinse  the parts in the above prescribed manner at least
 three times  or until  no visible particles remain.

      The  prill tower  emission samples shall be analyzed as follows:

      1.   Analyze each individual water portion for.urea content by the
 colorimetric (p-dimethylaminoberizaldehyde)  procedure - add buffer compound,
 boil  off  ammonia and  analyze for urea.

      2.   Analyze the  combined water portion (probe, first and second
 impinger  water) for ammonia content by the Specific Ion Electrode method.

      3.   Analyze the  IN H^SO. portion for urea content by the above
 colorimetric procecdure - caution should be used as an interference
 problem (turbidity) is expected.  These values are not to be combined
jyith  the  urea values  from the water portions., whfin Cfllfi^lfltinQ the^emission
 rates.                                                    '^

     4.   Analyze the  IN H-SO. portion for ammonia content by specific
 ion electrode.

     Contractor shall analyze the three outlet samples for urea by the
 colorimetric procedure within 20 days after collection.

     Contractor shall analyze all emission samples for ammonia by Specific
 Ion Electrode within  20 days after collection.

     Scrubbing liquor aliquots shall  be collected approximately every
 30 minutes during the test periods.  Aliquots  shall be collected at an
 existing  valve located in the low pressure scrubber solution recirculating
 system (see  Figure 1).

     For  each aliquot sample, the temperature  shall be measured following
 its collection time and the pH shall  be measured as soon as  the sample
 reaches room temperature (70°F).   Afterwards,  the aliquots are to be
 combined  to  form one  composite sample per run.

-------
                                                      TRC — Environmental Consultants, Inc.


                                                    Report of Chemical Analysis of Non-Routine Samples
-   E-
                           O\\
Contract No:
Reviewed by:.
                                                                   Laboratory No:.



                                                                   Date Received:.



                                                                   Date'Repor'ted:.
                                                                                                TO
Report to:   Li) • (JU Ctf(<^
Type Sample:  Filter
                                  Fuel Oil
Sediment
Impinger
Other
    Sample Number
                       Location
                                             Analysis No. 1
                                                          Analysis No. 2
                      -
               AnalysftNo. 3
       Analysis No. 4
  Analysis No. 5
Analysis No. 6
                                                  ^
                                                                J^t V ~> me
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                                                                       m
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-------
                                                      Report
Client:.
Contract No:.
Reviewed by:
Report to:	
                                                             Analysis of Non-Routine Samples

                                                                  Laboratory No:.
                                                                  Date  Received: _
                                                                  Date  Reported: .
Type Sample:   Filter
                               Fuel Oil
                      Sediment
Impinger
                 Other
    Sample Number
                   Location
Analysis No. 1
  UsiJiA
                                                                  Analysis No. 2
                                                                           Analysis No. 3
Analysis No. 4
                          Analysis No. 5
Analysis No. 6
      3HPL
                                                         3.)
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                                                                                                                        A
                              it
7

                             a
                                                          V
                                                                                                                          Analyzed
                                                                                                                                           Form CL-0012, Rev.

-------
   TRC — Environmental Consultants, Inc.
Report of Chemical Analysis of Non-Routine Samples
riipnf r.r/X, - /Vx^y/W-C^X. 1 ahnr»tnry Nn- /K.Y~W(^ \
Contract No: (I/<7 O% ^fc^'KO — ?/ .'' Datp Received: Of~— X-— <^O
Reviewed by: DatP Rpoorted: J~ -T^^-S'O
Report to: LL/, ££/£? ($&-'


Typp Samplp; Fjlfpr ... . FlIPl ^il Spriimpnt Impinrjpr n^hpr /^^VVl^^^iv — ^

Sample Number
p~t — /is/ 1 si
'^-^ Y^*/&\
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Location
Jla*,M»J









Analysis No. 2
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pj f^a^
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iff7









Analysis No. 3
^A^>c/>s>C/--















Analysis No. 4















Analysis No. 5












\


Analysis No. 6















                                                                   Analyzed

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                    Project  No.

                     Book  No.flx/&.   TITLE
                                                                                               ^ •/
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-------
TITLE
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                                                                                  To Page No..
Witnessed & Understood by me,
Date
Invented by
                                           Recorded by
                                           Date

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                    Project No. £'?£'? -C^-?/


                     Book No. F.CrLfiS TITLE'
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                                    Recorded
                                                                 Date

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I  I  I

TITLE
'QiL
              Project
               Book No
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   APPENDIX H

  SCOPE OF WORK

   Includes:

Work Assignments
Technical Directives

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WORK ASSIGNMENT ' '• " vC.v-v.' ~'v ' •
" i •
" EHVISb.'J.MSNTAL PROTECTION AGEf/Cr
•
' " Research Triage Part. N.C. 27711 ' -•••*"•:•.
T>Tt-E. Conduct Emission -Test -Program- at an Urea- Manufacturing
Plant . ' '...''..
* • v
E^A cc^TPAcr NCX
' ""68-02-2820
coMTriAcroR
TRC of New England
ASSIGN-JEM T NO . ,
ASSIpNMSNf CMAJlCe NO. .
OATfi . ' • . • .
s o£c 1978 :• •._•'. ; .
           The Contractor-shall  perform an emission  test  program In accordance with
      the basic contract scope of work for the Emission Measurement Branch,  and  as  set
      forth .in the attached  "Source Sampling and Analysis Schedule" at the following "site:

             • . Company:. Agrico Chemical      '                                   .
                Location:  Blytheville, Ark*.  '            '.
                Industry:  ..Ammonium Fertilizer
           :  .   Project No..:   79-NHF-13   •••                         '

           The Emission Measurement Branch's Technical Manager is Clyde E. Riley.
      Mail  Drop -13, EMB, ESED,' OAQPS,  Research Triangle Park,  .North Carolina.27711.   ." _

           Upon.notification  of  approval of the proposed  source- test report,' the  Contractor'
      shall provide 25 copies  of the final .report with appendices.     •   •
                                                   U = NT TSTIMATE
                                                                             CON-TRACTOR SSTI'MAT-
                                              ' 200
                                             3 months
CO.'.:PLcT(O.V CATS
                                           March
                 • • 3 GO
   JlS'Sa S S.'GNATU^S

     Clyde  E.  Riley
?:'
•7^
      ':mf J
CSG CCOE.

ESED/EMB
T£Uc?HO.-.-c  (919

541-5243 •
OATt-
•11/30/78
                                                                                         DATE
                                          ^ S n*r"
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                                                                                                                            J_
                                                         J
nrn: SA.'.FOT/G AKOTALYrnTcHEPULE
See Figure 1
J~.il in 9
P2
Al-

San

One
Sec
the

SW-1
SW-2




Teul
•'.'o. of
Jo.-plcs
6
quots

pie an
,T roil
porti
ond po
•j
Socple
Type
Urea
Participate
;hall be col'

alysis shall
nipt "ion nf ai
on shall be 1
rtion shall
itirms chflll
y shaljl be analyze

6
i "
6





Scrubber
Scrubber
Solution Out


.

Sii:pl ing'
Modified
EPA-5
ected from e

>e conducted
.V^i. rpmai
reatsd with
e treated wi

by tf:i Kjel

Compos 'i e
Composite



i 	 	 _
	 -...AcjHco Chemical
	 Bly.thevi.llfi, Ark.
industry: process: Conirol C^uip:-.cnt:
— • Ammonium Fertilizer • --Ur-ea-Gwmulator 	 Scrubber -
Sample
Collected'
M
CTR
ch of the

within 24
iinn samn
saturated
;h concent
-n thp Tl
:e qyery t

N. A.
N. A.



i ,'
Initinl Analysis
Type Method
Urea
Mass
Urea
Mass

i on each o
ito 2 equal
approximate
(approxima
stand at r
fio days for

Percent
Solids
Percent
Solids




Kjeldahl
jeldahl

* the H20 -s
portions a
ly 2 ml
per
tely 2 ml p
)on\ tempera
urea conte

Filtration
Filtration




Oy
* *
CTR,
Agrico

amples.
id treatec
•liter of
^r liter (
ture for r
it during



CTR




Final Anolvsis
Type Method
Ammonia


-. •.
with a stt
water)
f water)
period of
this perio<

Urea
NH0
j
Urea
NHJ




(EPA)
Nessler


- -
bilizer.


20 days; hi
•

Kjeldahl
Nessler
Kjeldahl
NP<;<; pr



.

CTR






wever


CTR
CiR
CTR
T.TlV .



.
                                                                                                   REMARKS:
   .                   Required
CTfi"Con'.''JCC£"
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                       Figure T
  Agrico Co./The Williams Co., Blytheville, Arkansas
    SW-1
 TP1

-Y-
    Dilution
      Air
Scrubber
      Urea Formaldehyde

   Recycled fines
-- Solution Urea
                                           TP2
                                      " SW-?
                                                    Afr
         D runr G ra n u 1 a to r~

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                                              PrujVct f.'o. 7rJ- !,'!ir-13






 yClL-llii'l''0^ P'-'V_Gl opment I us true 1 ions



 1.   Contractor shall determine stability conditions for the following



     six urea solution concentrations.  TRC shall use the Kjeldahl  urea



     method to analyze for urea content and the Messier method to



     determine the  ammonia content.



     a.   40 mg of urea per liter of water



     b.   100 ng of urea per liter of water



     c.   40 mg of urea per liter of water with 2 ml  of saturated mercuric



         i.hloride solution added



     d.   100 mg of urea per liter of water with 5 ml of saturated mercuric



         chloride solution added



     e.   40 mg of urea per liter of water with 2 ml  of concentrated



        .sulfuric acid added



     f.   100 mg of urea per liter of water with 5 ml of concentrated



         sulfuric acid added.    •' • •



  These  solutions shall be allowed to stand at room  temperature for a



  period of 20 cays; however,  they shall  be analyzed once every 2 days



  for urea and ammonia content.  Questions regarding these instructions



  or the urea and ammonia analysis procedures shall  be directed to



  Mr. Gary HcAlister at 919-541-5276.






  2.  Contractor shall prepare two duplicate sets of "dry" urea audit



      samples.  Each set shall contain 12 individual urea samples.



      Both sets of Samples shall be forwarded to the Agrico Chemical



      plant in Blytheville,'Arkansas, by TRC personnel.  One set of



      samples shall be analyzed by Agrico personnel  and the second  set



.'     shall be'analyzed by TRC personnel.  •••_•.  "••'  _•••"'... .  --"'".'•'•  . -

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     3.  Agrico nudit sample '"jn.ilyr> i s rJioll le performed nccording to



         methods and procedures employed while analyzing th'e urea samples



         generated during the October 9, 1978, EPA test program.





     4.  TRC audit analysis shall be performed using the Kjeldahl urea



         method as directed by Mr. Gory McAlister, EPA.





     5.  Contractor shall specify procedures directing Agrico personnel



         to dilute the 12 audit samples v/ith solutions of v/ater and/or



         IN H.-SO,.  Audit sample analyses shall  be conducted within 12 hours
             *-  *                          ^ .


         after dilution.  The 12 audit -samples shall  be prepared and diluted



         as follows:
Dilute With 400 mis H0
No. 1   100 mg urea     .



No. 2   300 rng urea  •   •   •



No. 3   600 mg urea



No. 4   5 mg urea



No. 5   10 mg urea



No. 6   40 mg urea
                                          Dilute v/ith 250 mis IN




                                          No.  7"   2 rag urea



                                          Ho.  3   5 mg urea



                                          No.  9  1 0 mg urea



                                          No. 10   5 mg urea



                                          No. 11    4 nig urea



                                          No. 12   30 mg urea
8 •   Agrico Test Program                                         ..."".



    1.  Contractor shall collect six urea  particulate samples from one of



        the operating granulator outlet stacks.   Samples  shall  be collected



        using isokinetic sampling conditions  for  a  period of approximately



        1  hour.  The collection train shall  consist of a  probe  heated to



 • •-'••'  stack temperature", 'a flexible teflon  line,  and five irnpi fibers'."  "  -



        The first, three iripingers shall  each  be prefilled v/ith  100 mis

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    Dist. il^O, Hie  fourth  :;h.ill rcinoin empty, and the fifth shall


    contain approximately  200 g;ns of silica gel.  The second and


    third shall bp  of the  Greenburg-Smith design with standard tips.


    The first, fourth, and  fifth shall be modified with a 1/2" tube.



2.  Cleanup shall consist  of measuring the solution volumes and rinsing


    the probe, flex line,  and impinger several times (3) with Dist.

    H^O.  Afterwards the v/ater samples shall be filtered through a

    preweighed fiber glass  filter using a Buchner funnel and vacuum

    pump.



3.  Analysis shall consist of v;eighing the liquid samples initially.

    Afterward tv/o equal aliquots shall  be withdrawn.  One aliquot shall

    be analyzed for urea and ammonia by Agrico personnel using the Kjeldahl

    urea-method. •  The second aliquot shall be analyzed  for urea'a'hd "   '"'•'.."

    ammonia by TRC personnel using the Kjeldahl  method  as directed by


    EPA.  Sample  analysis shall  be conducted within  24  hours of collection

    of al1  samples.               .                                      .   -
                                                                   .»


    After the two analysis aliquots have been withdrawn  the  remaining
                                                                     _ fT
    sample volumes shall  be split into two equal  portions and  treated

    with a stabilizer solution.   One portion shall.be combined with a


    saturated mercuric chloride solution (approximately  2 mis  per liter

    of water).  The second portion shall  be combined with concentrated


    sulfuric acid  (approximately 2 mis  per liter  of  water).

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4.  TliC'jG r.olutions  shall  !,•'.•  re-turned  to  the  TRC  lu>jor;itory ond

    allowed to stand'at  room  temp or a ture  for  a  period  of 20 days;

    ho'.vever, they shall  be analyzed  by, the  Kjc-ldahl  urea method once

    every 2 days during  this  period  for urea  and  ammonia content.



5.'  The preweighc-d glass fiber  filters used to  filter  the v/ater

    solutions shall  be returned to the TRC  laboratory,  dried and

    weighed for undissolved solids.

                                           -*-"
                                        x^'"
6.  Contractor shall  separate and report  all  Research  and Development

    data -in a separate EPA proposed  draft report.  These method and

    evaluation data  shall  not be included in  the  Agrico NSPS report.

    Contractor shall  submit 3_ copies of the proposed R£D final  report

    directly to Mr.  J. E.  1-icCarley,  EMB,  ESED,  Mail  Drop 13,  Research

   •Triangle Park, N. C.  27711.  The separate R.SD report shall  be

    entitled "Development of  Analytical Procedures for  the Cetennination

    of Urea from Urea Manufacturing  Facilities" and  listed under

    Project No. 79-NHF-13.'

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                         EMISSION MEASUREMENT BRANCH
                           TECHNICAL DIRECTIVE NO. •   1  •
Project Number    •   79-NHF-13.  •	         Date    February 16, 1979

Contractor	TRC of New' England	
Contract Number    68-02-2820-	    Work Assignment Number     11

Technical Manager    Clyde E.  Riley

Verbal Directions  Given  To   vim  l-.'ade •	

Directive:

1.  The Contractor shall  perform formaldehyde  analysis on  each of the six urea
    participate samples.
                                                  Clyde E.  Riley
                                                Tec h >i i c aT~i-ianager"V~ETi3~:
                                                Section Chief, ii.MB

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                         F.MJSSIOil ML'ASUREK.EMT BRANCH

                           TECH.'.'ICAl DIRECTIVE MO.    2
Project Number    79-NHF-13    .   •


Contractor        TRC  of  'lew  England
                                                Date   March 21, 1979
Contract Number
                     68-02-2820
Work Assignment Number     ''
Technical Manager    Clyde  E.  Riley	^


Verbal Directions  Given  To     Mr- wil1 Wade
Directive:
                  See attached  pages.
                                                __,_._	H^L_
                                                Techiyfcal  Manager,  EMS/
                                                Soe'tion  Chief,  EHo

                                                i/

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Contractor shall perform  the  following oval nation  analyses:

1.  Prepare an urea standard  solution containing 2;;ig  urea /ml  hLO


    V.'eigh 0.2000g of urea  into  a  100 nil  volumeteric flask  and dilute
    to 100 ml with deionized, distilled  H?0.

2.  Prepare an am-.onia  standard solution  containing 20 mg  f,'H.,/ml H-0


    V.'eigh 31.4lOOg of NH.C1 into  a  500 ml  volumeteric flask and  dilute
    to 500 ml with deionized, distilled  H20.

3.  Prepare nine samples  from the above  standards  as  follows:

    Sample Nos.     ml  of  Urea  Std.    ml  of NhL Std.   Total Volume ml


        1
        2
        3
        4
        5
        6
        7
        8
        9
             i
    Note:  Samples must be analyzed within  24 hours after  being  prepared.

4.  Analyze the nine samples  using  the coloriineteric  (p-aminobenzaldehyde)
    procedures.  Use samples  1,2,3, and  4  to prepare1  a standard  curve.

5.  Calculate the measured values for the  remaining samples 5 through 9.

6.  Data shall be presented in mg urea/ml  of solution along with  the
    standard curve.
If additional information is required please contact Mr. Gary McAlister at
919/541-2237.
5
5'
15
10
10
10
5
5
5
0
0
0
0
1
5
5
25
50
100
200
200
100
200
200
100
100
100
cc:  Gary McAlister
File:  79-NHF-13

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          i       UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
o  s\i'/x  ^               Office of Air Quality Planning and Standards
\~*~-•••-:'-±~~*'g               Research Triangle Park, North Carolina 27711
 "      c^
                                   February 13, 1980
     Mr.  Hill  Wade
     TRC  of New England
     125  Silas Deane Highway
     Uethersfield, Connecticut 06109

     Reference:  EPA Contract No. 68-02-2820, Assignment No. 11, Agrico Chemical,
                 Blytheville, Arkansas, EMB Report No.  79-MHF-13 '

     Dear Will:

          This correspondence is to document the enclosed Technical  Directive
     instructions for conducting an evaluation of slope linearity for standard
     urea curves.

          It has come to our attention that the standard curve slope may change
     v/ith low-urea concentrations.   In order to verify  this  conjecture Mr.  Gary
     i'icAlister has requested that curves for t'.vo sets of standard samples, be
     compared.  The first set of standard samples will  range from 50 mg urea/liter
     to 250 mg urea/liter.  The second set will range .from 1 mg urea/liter to
     30 mg urea/liter.  Standard solutions containing the following  urea concen-.
     trations  will be used to establish the two curves.

          Set  flo. 1                                 Set No.  2

          1.  50 mg urea/liter           .           1.   1  mg urea/liter
          2. 100 mg urea/liter                      2.   2 mg urea/liter .
          3. 150 mg urea/liter                      3c   5 ing urea/liter
          4. 200 nig-urea/liter                      4.   7 mg urea/liter"
          5. 250 mg urea/liter                      5/10 mg urea/liter
                                                    6.  20 mg urea/liter
                                                    7.  30 mg urea/liter
                                                    r>—     "
          TRC  shall prepare and analyze the standard solutions as follows.

          Samples containing urea and deionized distilled water shall  be made
     up in 100 ml volumeteric flasks.

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     Samples shall be analyzed by the P-dimethylaminobenzaldehyde coloriineteric
procedure.  Do not boil off the samples as there should be no impurities
present to interfere with the c--.alyses4.

     Establish calibration curve No. 1  using urea results  obtained from
Set No. 1 samples.

     Determine urea concentrations from calibration curve  No. 1  using
measured values obtained from Set No. 2 samples.

     Establish calibration curve No. 2 using urea results  obtained from
Set No. 2 samples.

     Compare the slope of the No. 1  curve to the slope of  the No.  2 curve.

     Please report your conclusions  and recommendations-along with a summary
of the data to me by March 14, 1980.  These data will  be used to establish
guidelines for the upcoming prill'tower test in St. Helens,  Oregon.

     If you have any questions regarding these instructions  or require additional
information, please do not hesitate  to contact me.

                                        Sincerely yours,
                                        Clyde E.  Riley^
                                    Field Testing Section
                                 Emission Measurement Branch
Enclosure

cc:  Gary McAl ister
     Marge Fox, TRC

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                          EMISSION  MtASUKLKt.Tr BRANCH

                           TECHNICAL DIRECTIVE NO. -   4   '
'Project Number	79-HHF-13     .           .    Date   Feb.  12. 1980

Contractor   •   TRC of'New En91and	•

Contract Number    68-02-2820.	    l;ork Assignment Number

Technical  Manager      Clyde E. Riley	^

                                   Mr. Reed Cass        •      .
Verbal  Directions Given To
Directive:
 Contractor  shall  determine  slope linearity for standard urea curves  using the
 following  sets  of samples.       '                   .           -."'.'

      Set No.'I     '.        "            '' '  .   Set No- 2

      1.   50 mg  urea/liter                     1-  Img urea/liter
      2.  100 mg  urea/liter          .           2.  2 mg urea/ iter
      3.  150 mg  urea/liter '                    3.  5 mg urea/liter
      4.  200 mg  urea/liter                     4-  7 mg urea/liter
      5.  250 mg  urea/liter                     5. 10 mg urea/liter
                      -           -            6. 20 mg urea/liter
                       »          •              7. 30 mg urea/liter


 Contractor shall prepare and analyze  samples  per  instructions presented
 in February 12, 1980 correspondence to Mr. Will Wade.
                                                 	
                                                 Technical Manager, Ef-jH"
                                                 Section Chief, Ei-!3
                                                 I/

-------