&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.
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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
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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
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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
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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
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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
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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.
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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.
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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.
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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.
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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
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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.
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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.
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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-
-------
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-
-------
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-
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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-
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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
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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.
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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.
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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.
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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.
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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.
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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.
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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.
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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.
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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
-------
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
-------
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
-------
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.
-------
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.
-------
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.
-------
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.
-------
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
-------
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.'
-------
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
-------
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
-------
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
-------
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.
-------
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. •'..'-.'/.
-------
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.
-------
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.
-------
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: " '•.',••••. '.. - : •
-------
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
-------
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
-------
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.
-------
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.
-------
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.
-------
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
-------
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
-------
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
-------
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
-------
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. '
-------
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.
-------
APPENDIX A.2
MODIFIED PROCEDURE - AUGUST 1979
-------
--/,
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
-------
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. . :
-------
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
-------
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.. ' .
-------
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 '
> • .
-------
. 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
-------
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.
-------
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
-------
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
-------
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 :
-------
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.
-------
• ..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. . "''.•' '..'.'
-------
'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.
-------
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.
-------
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.
-------
' •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.
-------
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.
-------
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:;.
-------
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, . .. ' :' '":'.'..-=.
-------
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. '• ' ' ' . ' .
-------
APPENDIX A.3
MODIFIED PROCEDURE - JANUARY 1980
-------
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.
-------
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.
-------
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.
-------
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.
-------
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.
-------
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:
-------
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.
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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 '
-------
APPENDIX A.4
PROPOSED REFERENCE METHOD 28
-------
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
-------
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).
-------
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.
-------
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.
-------
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.
-------
. 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
-------
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.
-------
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
-------
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.
-------
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);
-------
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.
-------
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)
-------
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.
-------
APPENDIX A.5
KJELDAHL ANALYSIS METHOD
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
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IE-tit;
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1E-04
iEI-yx
1E-02
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SICMfl
0. 00
0.14
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SLOFE«
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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
Client:
Contract No:.
Reviewed by:
Report to:
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Laboratory No:
Date Received: *^~
Date Reported: __3_r.
Type Sample: Filter
Fuel Oil
Sediment
Impinger
Other
Sample Number
Location
Analysis No. 1
Analysis No. 2
Analysis No. 3
Analysis No. 4
Analysis No. 6
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REPLY .
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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
-------
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
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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
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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
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Analysis No. 6
Analyzed
-------
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Date
-------
Project No. £'?£'? -C^-?/
Book No. F.CrLfiS TITLE'
O/l.
No.
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I I I
TITLE
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-------
APPENDIX H
SCOPE OF WORK
Includes:
Work Assignments
Technical Directives
-------
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"
-------
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£"
-------
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~
-------
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/
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