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                                ill
                                                                 	1",
                                                    °OOR70008
                                                        1
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-------
•ir

-------
                 REPORT TO
          THE TECHNICAL COMMITTEE
    OF THE CALUMET AREA-LAKE MICHIGAN
           ENFORCEMENT CONFERENCE
    A STUDY OF PRECISION AMD ACCURACY OF
    LABORATORIES AND METHODS OF ANALYSIS
    OF PHOSPHATE IK LAKE MICHIGAN WATERS
                    BY
     THE LABORATORY DIRECTORS OF THE
       CALUMET AREA-LAKE MICHIGAN
         ENFORCEMENT CONFERENCE
UNITED STATES DEPARTMENT OF THE INTERIOR
  FEDERAL WA'i'T? QUALITY .'ri-aiTIS^PATIO:;
          GREAT LAKES REGION
     LAKE MICHIGAN BASIN OFFICE
           CHICAGO,  ILLINOIS
               MAY 1970

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                          TABLE OF CCi:i_~"

                                                                Page

ACKNOWLEDGEMENTS                                                i i i

LIST OF PARTICIPATING LABORATORIES                             iv
                                                  o
LIST OF TABLES                                                  v

LIST OF FIGURES                                                 vi

     I.  INTRODUCTION                                          1

     II. PROCEDURES.   CHROKOLOGICAL DV.1"                       2

     III.FINDINGS AND DISCU3SIOII                               13

     IV. CONCLUSIONS  AIID  RECC^'ZUDAIJ,;. "                        20

BIBLIOGRAPHY                                                    30

APPENDIX                                                        31

     Procedural Details                                         32

     Literature Review                                         35

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                       AOKKOWLEDGE4EHTS






     The time and energy that has been given so graciously in the



inter-laboratory comparison of phosphate determinations,  initiated
                                        *


by the Technical Committee of the Calumet Area-Lake Michigan
                                                 o


Enforcement Conference, is gratefully acknowledged.



     The Laboratory Directors of the Calumet Area-Lake Michigan



Enforcement Conference vishes to extend their thanks and appreciation



to each analyst who participated in the study and to each supervisor



and director who made facilities and services available for these



studies.
                             iii

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     The laboratories and directors participating in the total

phosphate round robin study were:

1.   American Oil Company - Robert J. Austin and Robert Babcock

2.   Cities Service Oil Company - George Jackson

3.   City of Chicago Bureau of Water, Dept. of Water and Sewers -
     Carlton Duke

h.   Gary-Hobart Water Corporation - Herbert L. Plowman, Jr.

5.   Lake Michigan Basin Office - LeRoy E. Scarce

6.   Indiana State Board of Health - Stephen R. Kin

7-   Inland Steel Company - Thomas Voges

8.   Lake Huron Basin Office - Ralph G. Christensen

9.   Lake Ontario Basin Office - Herbert F. Mcore

10.  Metropolitan Sanitary District of Greater Chicago - Alfred W.  Tenny

11.  Robert A. Taft Sanitary Engineering Center - Dwight G.  Ballinger

12.  Milwaukee Sewage Commission - Larry H. Docta

13.  East Chicago Sewage Disposal Plant - Bail Poppa
                             iv

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                         LIST OF TABLES

No.       Title                                                       Page

1         Comparison of Precision and Accuracy of Phosphate           kO
          Determinations

2a, 2b    Phosphate Determinations by Stannous Chloride Without       4i
          Potassium Persulfate, Average Results (mg/l)

3a, 3b    Phosphate Determinations by Stannous Chloride and           43
          Potassium Persulfate, Average Results (mg/l)

h         Phosphate Determinations by Stannous Chloride,              45
          Potassium Persulfate and Extraction, Average Results(mg/l)

5a, 5b    Phosphate Determinations by Potassium Antimony! Tartrate    4g
          and Potassium Persulfate, Average Results (mg/l)

6a, 6b    Phosphate Determinations by Stannous Chloride and           }^Q
          Potassium Persulfate, Average Recoveries (mg/l)

Ja, 7b    Phosphate Determinations by Stannous Chloride               50
          Without Potassium Persulfate, Average Recoveries (mg/l)

8         Phosphate Determinations by Stanncus Chloride, Potassium    52
          Persulfate and Extraction, Average Recoveries (mg/l)

9a, 9"b    Pnosphate Recoveries by Potassium Antimony! Tartrate        53
          and Potassium Persulfate, Average Recoveries (mg/l)

lOa, lOb, Phosphate Determinations by Stannous Chloride Without       55
lOc, lOd, Potassium Persulfate, Original Data (mg/l)
and lOe   (lOe - Individual Laboratory Recoveries)

lla, lib, Pnosphate Determinations by Stannous Chloride and           60
lie, and  Potassium Persulfate, Original Data (mg/l)
lid       (lid - Individual Laboratory Recoveries)

12a, 12b  Phosphate Determinations by Stannous Chloride,              64
          Potassium Persulfate and Extraction,  Original Data (mg/l)
          Vl2b - Individual Laboratory Recoveries)
13s/ 13t>> Phosphate Determinations by Potassium Antimony! Tartrate    66
13c, 13d, and Potassium Persulfate,  Original Data (mg/l)
13e, 13f, (l3h, 13i, and 13j-Individual Laboratory Recoveries)
13i, and
13 j

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                         LIST 07 FIGURES
Mo.    Title                                                      Page

1      Percent Distribution of All Total Phosphate Deter-         22
       minations by Stannous Chloride Without Potassium
       Persulfate; 0.05 mg/l> and 0.05 mg/1 / 2.5 rag/I
       Iron and 0.25 mg/1 Chromium
       Percent Distribution of All Total Phosphate Deter-          23
       minations by Stannous Chloride and Potassium
       Persulfate, 0.03 mg/1 and 0.06 mg/1
3      Percent Distribution of All Total Phosphate Deter-         24
       minations by Stannous Chloride, Potassium Persulfate
       and Extraction, 0.03 mg/1; and Potassium Antimony!
       Tartrate and Potassium Persulfate, 0.00 mg/1 and 0.03 fflg/1

k      Total Phosphate Recoveries from Spiked Lake and River      25
       Samples by Stannous Chloride Without Potassium
       Persulfate, 0.02, 0.06 and 1.0 ng/1

5      Total Fnosphate Recoveries from Spiked Lake and            26
       River Samples by Stannous Chloride and Potassium
       Persulfate, 0.05, 0.06, 0.90 and 1.0 ng/1

6      Total Phosphate Recoveries from Spiked Lake and River      2J
       Samples by Stannous Chloride, Potassium Persulfate
       and Extraction, 0.05 mg/1 and 0.90 mg/1

7      Total Phosphate Recoveries from Spike Lake Samples         28
       by Potassium Antimonyl Tartrate and Potassium
      • Persulfate, 0.02, 0.05 and 0.50 mg/1

8      Total Fnosphate Recoveries from Spiked River Samples       29
       by Potassium Antimonyl Tartrate and Potassium
       Persulfate, 0.80, 0.90, 1.0 and 1.1 mg/1

9      Probability Curve.  Total Phosphate Determination by       76
       Stannous Chloride Without Potassium Persulfate -
       0.05 mg/1 Standard Sample, ?j?,rch 8,  1967

10     Probability Curve.  Total Fnosphate Determination by       77
       Stannous Chloride With Potassium Persulfate -
       0.03 mg/1 Standard Sample, September 19,  1966

11     Probability Curve.  Total Phosphate Determination by       78
       Stannous Chloride With Potassium Persulfate and
       Extraction- 0.03 mg/1 Standard Sample,  October 27,  1966
                              VI

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                          LIST OF FIGURES
No.    Title                                                      Page

12.     Probability Curve.  Total Phosphate Determination          79
       by Potassium Antimonyl Tartrate With Potassium
       Persulfate - 0.03 mg/1 Standard Sample, December 1, 1966

13     Probability Curve.  Recovery of Total Fnosphate,           80
       Determination by Stannous Chloride Without Potassium
       Persulfate - 0.06 mg/1 Lake Sample, March 8, 1967

ih     Probability Curve.  Recovery of Total Fnosphate,           8l
       Determination by Stannous Chloride With Potassium
       Persulfate - 0.05 Eg/1 Lake Sample, October 27, 1966

15     Probability Curve.  Recovery of Total Phosphate,           82
       Determination by Potassium Antimcnyl Tartrate With
       Potassium Persulfate - O.JO mg/1 Lake Sample,
       December 30, 1966

16     Probability Curve.  Recovery of Total Fnosphate,           83
       Determination by Stanncus Chloride With Potassium
       Persulfate - 0.90 mg/1 River Sample, October 27, 1966

17     Probability Curve.  Recovery of Total Fnosphate,           84
       Determination by Stannous Chloride With Potassium
       Persulfate and Extraction - 0.90 mg/1 River Sample,
       October 27, 1966

18     Probability Curve.  Recovery of Total Phosphate,           85
       Determination by Potassium Antimonyl Tartrate With
       Potassium Persulfate - 1.1 mg/1 River Sample,
     -  December 1, 1966
                             Vll

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       A STUDY OF PRECISION AND ACCURACY OF LABORATORIES AND
       METHODS OF ANALYSIS OF PHOSPHATE IN LAKE MICHIGAN WATERS

       A Report to the Technical Committee of the Calumet Area-
                Lake Michigan Enforcement Conference
       The Laboratory Directors of the Calumet Area-Lake Michigan
                         Enforcement Conference

I.   INTRODUCTION

     This is a report of comparison studies performed by cooperating

laboratories concerned with analysis of Lake Michigan waters and stream

waters in the Calumet Area of Indiana and Illinois.

     A series of comparison studies is to be made for determination

of ammonia nitrogen, phosphate, phenol, cyanide,  and threshold odor.

Part I presents the findings from a series of eight comparison studies

on phosphate completed between July 13, 19&6 and April 11,  1967-
                                                   i-
     The objectives of the comparison studies are:

     1.   To determine the reliability (precision and accuracy)

          of the analytical procedures as normally used in the

          desired concentration range.

     2.   To determine if there is a change in the accuracy of these

          procedures arising from departures from prescribed

          analytical routine.

     3.   To determine the degree of variation between the

          participating laboratories.

     4.   To determine the sensitivity of the methods as used.

     5.   To recommend necessary changes in procedures.

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II.  PROCEDURES.  CHRONOLOGICAL DEVELOPMENT


     This section of our report presents a brief chronological commentary-


on the conditions, implied and explicit, which were obtained in the


various Test Series.  It is intended to provide "background for assess-


ment of the results obtained in individual Series and also for comparison


of any or all Series.  All results are summarized in Tables 1 to 13j in


the Appendix.


SERIES I.  July 13, 1966


     Number of samples analyzed:  Two (synthetic)


     Participating laboratories:


     1.   Lake Michigan Basin Office, FtfPCA


     2.   City of Chicago, Bureau of Water, Dept. of Water and Sewers


     3.   Metropolitan Sanitary District of Greater Chicago


     k.   American Oil Company


     5.   Inland Steel Company


     6.   Indiana State Board of Health


     7.   Lake Huron Basin Office, FWPCA


     8.   Lake Ontario Basin Office, F.fPCA


     Conditions:  The following conditions were stipulated by


advance notice to the participating laboratories.


     Stannous Chloride Method:  Standard Methods, 12th Ed., pp.236-237,


except for one modification (the addition of ammonium persulfate).


Samples should be run in triplicate.  Emphasis was placed on the
                                                                   •

cleanliness and pretreatment of glassware, and the importance of using


glassware for phosphate analysis only.

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SERIES II.  September l6, 1966




     Number of samples analyzed:  Five (one synthetic, one lake,




     one lake spiked, one river and. one river spiked)




     Participating laboratories:




     1.   Lake Michigan Basin Office, WPCA




     2.   Gary-Ho"bart Water Corporation




     3.   Metropolitan Sanitary District of Greater Chicago




     4.   Inland Steel Company




     5.   Indiana State Board of Health




     6.   Cities Service Oil Company




     7-   American Oil Company




     8.   Lake Ontario Basin Office, FWTCA




     9-   East Chicago Sewage Disposal Plant




     10.  City of Chicago, Bureau of Water, Dept. of Water and Sewers




     Conditions:  The following conditions were stipulated "by advance




notice to the participating laboratories.




     Stannous Chloride Method:  Standard Methods, 12th Ed., pp.236-237,




except for one modification (the addition of ammonium persulfate).




Samples should be run in triplicate.  Emphasis was placed on the same




items as listed in Series I.




     September 29, 1966




     Calumet Area Laboratory Directors met for the purpose of reviewing




the results obtained from the July 13 "and September 16 Test Series I and




II, respectively.  The results from Series I and II were fairly good for




the synthetic, lake and spiked lake samples.  The river sample and spiked




river samples showed a wide range of results and very poor recoveries.

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 From a review of these




laboratories agreed upo:.




 1.   It was agreed t^r..




      total phosphate.




 2.   It was agreed tr  ,




      analyzed in trip.":..'




      depending upon 1




 3.   It was agreed t'.:-? ,




      persulfate.




 k.   It was agreed tv. ',




      of choice for f j:..




 5.   It was agreed th .-.




      veek of October 17]




      (one spiked with £\




 6.   It was agreed that




      aspects of the prr




      series of the phr .




      Board of Health c/




      work.  All Labc"? -




      Michigan Basin C."




      Basin Office wv.:




      test procedure.




      with the next 5s:-'
 and after considerable discussion,




llowing points:




 terminations would include only




     *



 \aple in each test series would be




 two or more consecutive days,




 capability.




 .-oratories would use potassium








 .brane filter would be the method








 ;posed procedure (to be mailed the




 be accompanied by two river samples




j and interfering substances).




•/•as need for research on various




procedure used in the first two




 aparison test.  Indiana State




 lichigan Basin Office were to do this




Actors were to submit to the Lake




'r suggestions and the lake Michigan




'.sh the official phosphate comparison




 done and the procedure was sent out

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SERIES III.  October 17. 1966




     Number of samples analyzed:  Two (one river sample and one river




     sample spiked with phosphate and interfering substances (Fe and Cr)




     Participating laboratories:




     1.   Lake Michigan Basin Office, FrfPCA




     2.   Gary-Hobart Water Corporation




     3.   City of Chicago, Bureau of Water, Dept. of Water and Sewers




     4.   Inland Steel Company




     5.   Indiana State Board of Health




     6.   East Chicago Sewage Disposal Plant




   .  7.   Lake Huron Basin Office, FWPCA




     Conditions:   All laboratories were to follow the procedure




exactly as outlined.  Each laboratory was to perform analyses in




triplicate each day for five consecutive days.




     Potassium Antimony1 Tartra,te Method:  Determination of Ortho




Phosphate in Fresh and Saline Waters, G.P.Edwards, A.H.Molcf, and




R. W. Schneernan.  Journal American Water Works Association, Vol. 57,




July 1965? PP- 91T-925 (except for the addition of potassium persulfate).



     October 27, 1966




     A meeting of the Calumet Area Laboratory Directors, under the




chairmanship of Mr. LeRoy E. Scarce, was held to discuss phosphate




analytical procedures and the results of the phosphate comparison test




on samples distributed October 17, 1966.

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     The results of the October 17 series were examined and discussed.



It was agreed that the results indicated fairly good precision within



each laboratory, but significant variation between laboratories.  The



results were far better in Series III than those in Series II for the



river sample.



     After a great deal of discussion, no consensus of opinion could



be reached regarding the most preferable method.  It was agreed that



the next comparison series would be analyzed according to the four



methods listed below:



     1.   Standard Methods - stannous chloride with persulfate.



     2.   Standard Methods - stannous chloride, persulfate with



          extraction.



     3«   Stannous chloride, perchloric acid,  without extraction,




          according to method provided by the Ontario Water Resources



          Commission.



     4.   Potassium antimonyl tartrate with persulfate,  using a



          30-minute digestion and read at 15 minutes.



     Sets of five samples were distributed to each Laboratory Director



present,  to be analyzed as specified above.



SERIES IV.  October 2J, 1966



     JMumber of samples analyzed:   Five (one synthetic,  one lake,  one



     lake spiked,  one river and one river spiked).



     Participating laboratories:



     1.   Lake Michigan Basin Office,  FWFCA



     2.   Gary-Hobart Water Corporation

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                                                                      7
     3.   City of Chicago, Bureau of Water, Dept. of Water and Sewers

     k.   Inland Steel Company


     5.   Indiana State Board, of Health


     6.   Cities Service Oil Company

                                                  »
     7-   American Oil Company


     8.   Lake Huron Basin Office, FWPCA


     9.   Lake Ontario Basin Office, F/TPCA


     Conditions:  The synthetic sample, lake sample and spiked lake


sample vsre to be analyzed in duplicate for four days or in triplicate


for two days.  The river and the spiked river samples  were to be run


in triplicate for five days, if possible, or at least two days.


     The following procedures were to be followed:


     1.   Standard Methods^ - stannous chloride with  persulfate.


     2.   Standard Methods - stannous chloride, persulfate with


          extraction.


     3.   Stannous chloride, perchloric acid, without extraction.


     k.   Potassium antimonyl tartrate with persulfate, using 30~Biinute

          digestion and read at 15 minutes.


     December 1, 1966

     A meeting of the Calumet Area Laboratory Directors, under the


chairmanship of Mr. LeRoy Scarce, vas held to discuss phosphate


analytical procedures and the analytical results of  the samples  distributed


October 27,  1966.

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                                                                      8
     Several laboratories failed to provide any data at all, and some


of those returning results were not able to conduct a complete series


of comparisons for even one day.  Therefore, this particular effort


in comparing the four methods was delimited through insufficient data.


     Various laboratory difficulties encountered in making these analyses


were discussed.  After much discussion pertaining to the choice of


method for further comparison series, it was decided that the next


series of samples would be analyzed according to the tartrate method.


     It was agreed that the following modifications be made:


     1.   Ninety minute digestion of all samples.


     2.   Concentration of those samples in the range of 0.00-0.10 mg/1.


SERIES V.  December 1. 1966


     Number of samples analyzed:  Five (one synthetic, one lake, one


     lake spiked, one river and one river spiked).
                                                    <-

     Participating laboratories:


     1.   Lake Michigan Basin Office, FWPCA


     2.   Gary-Eobart Water Corporation


     3.   Metropolitan Sanitary District of Greater Chicago


     k.   City of Chic230,  Bureau of Water,  Dept. of Water and Sewers


     5.   Inland Steel Company


     6.   Indiana State Board of Health


     7.   Lake Huron Program Office,  FWPCA


     8.   Lake Ontario Program Office,  F/rPCA


     9.   East Chicago Sewage Treatment Plant

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      Conditions:   Triplicate analyses wers per.?




 employing the tartrate method.   Samples vere d.'.




 and the  synthetic,  lake and spiked lake s£-T.ple:-




 evaporation.




SERIES VI.  December 30, 1966




     Nusiber of samples  analyzed:  Five  (one  syrr,




     lake spiked, one river and one river spi!;




     Participating laboratories:




     1.   Lake Michigan Basin Office, FWPCA




     2.   Gary-Hobart Water Corporation




     3.   Metropolitan  Sanitary District  of  Gre:




     4.   City of Chicago, Bureau of Water,  Dsp




     5.   Inland Steel  Company




     6.   Indiana State Board of Health




     7.   American Oil  Company




     8.   Lake Huron Basin Office, JVPCA




     9.   Lake Ontario  Basin Office, FVIPCA




     10.  Milwaukee Sewage Commission




     Conditions:  The same as in Series V.



     January 26, 1967




     Calumet Area Laboratory Directors met fo;1




the results obtained from the December  1  Test ,




Test Series VI.  The lake data in Test  Series "




improper mixing in the preparation of samples.




showed a substantial improvement over the prev:
 LI  samples




  90 minutes




 :-n.trated  by
  lake, one
r and Sewers
e of reviewing




i the December 30



r.ed because of



es V and VI



eries.

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                                                                      10
     It was agreed that further analyses, comparing stannous chloride




and tartrate methods, was desirable in order to demonstrate relative




performance when applied to waters containing iron and chromium inter-




fering substances.  It was agreed that the Lake Michigan Basin Office




and Indiana State Board of Health laboratories would analyze a lake




sample and a river sample spiked with interferences and twenty replicas




were run on each sample employing the following methods;  stannous




chloride with persulfate, stannous chloride with persulfate,and extraction




and tartrate with persulfate.  Both laboratories would investigate time




required for color development and the optimum acid strength to be used.




It was further agreed that one more round robin involving all laboratories




would be necessary.




SERIES VII.  March 8, 196?




     Number of samples analyzed:  Six  (one synthetic, one synthetic




     spiked with 2.5 mg/1 of iron and 0.25 fflg/1 of chromium, one lake,




     one lake spiked with phosphate,  one river and one river spiked




     with phosphate).




     Participating laboratories:




     1.   Lake Michigan Basin Office,  F//PCA




     2.   Gary-Hobart Water Corporation




     3.   Metropolitan Sanitary District of Greater Chicago




     4.   City of Chicago,  Bureau of Water,  Dept. of Water and Sewers




     5.   Inland Steel Company




     6.   Indiana State Board of Health




     7«   Cities Services Oil Company




     8.   .American Oil Company




     9.   Lake Huron Basin Office,  FWPCA

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                                                                      11
     10.  Lake Ontario Basin Office, FWPCA.


     11.  East Chicago Sewage Treatment Plant


     12.  Milwaukee Sewage Comroission


     Conditions:  Synthetic samples were to "be concentrated from 200 ml

                                                 o
down to 50 ml, lake samples from 100 nil down to 50 ral and river samples


were to be diluted from 25 ml to 100 ml.  All samples were to be digested


90 minutes and ran in triplicate and,if possible,ten replicas.


     Under the chairmanship of Mr. LeRoy Scarce, the Laboratory Directors


met March 30, 1967.  It was agreed that one more round robin should be


run at extremely low levels as found in Lake Michigan waters.


SERIES VIII.  April 11, 196?


     Number of samples analyzed:  Two (one lake and one lake spiked).


     Participating laboratories:


     1.   Lake Michigan Basin Office, FWPCA


     2.   Metropolitan Sanitary District of Greater Chicago


     3.   City of Chicago, Bureau of Water,  Dept. of Water and Sewers


     k.   Inland Steel Company


     5.   Indiana State Board of Health


     6.   Cities Service Oil Company


     T-   Lake Huron Basin Office,  WPCA


     8.   Lake Ontario Basin Office,  K-/PCA


     9.   Milwaukee Sewage Commission

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                                                                      12
     Conditions:  Lake sample not spiked using the stannous chloride




method were run in triplicate and concentrated from 200 ml down to




50 ml.  Ten replicas were run employing the tratrate method with




persulfate.  Lake sample spiked was run .in the manner as above.  All




samples were digested for 90 minutes.            „




     April 27, 196?




     Calumet Area Laboratory Directors met for the purpose of reviewing




the results obtained from the April 11, 1967 Test Series VIII.  The




potassium antimonyl tartrate method showed greater accuracy and precision.




The stannous chloride method with persulfate and extraction and potassium




antimonyl tartrate with persulfate when applied to lake and river samples




gave equally good results.  It was agreed that Mr. Docta would make a




statistical evaluation of the data end the results will determine if




further analytical work is required.  It was further agreed that Mr. Kin




and Mr. Duke would make a study to determine the limit of detectability




of total phosphate




     May 24, 1967




     A meeting of the Calumet Area Laboratory Directors was held




May 24, 19^7 under the chairmanship of Mr. LeRoy Scarce to discuss the




results of the statistical analysis of the phosphate data and special




studies to determine the minimum detectable limits of total phosphate.




It was unanimously agreed that the phosphate comparison tests should be




terminated and the final report prepared as soon as possible.

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                                                                      13
     Series VIII showed that when all laboratories followed the same




procedure, most of the laboratories obtained a precision of ± 0.01 mg/1




on a lake sample containing O.Co mg/1.  When the lake sample was spiked




with 0.02 mg/1, a.11 laboratories obtained, a precision and an accuracy




of ± 0.01 ing/1, employing both the stannous chloride method without




persulfate and tartrate with persulfate.




     The subject of choice of method was again brought up and the




opinion was expressed that when analyzing lake water there was not




much choice.  On the other hand, when analyzing grossly polluted water,




the tartrate and extraction methods were equally as good, but the




tartrate method was preferred because of ease of manipulation.




     Clean glassware was imperative.  Cleaning glassware with hot 1:1




hydrochloric acid, rinsing with distilled water and treating the glass-




ware with distilled water containing all reagents was found to be the




best method for cleaning.




     This section on procedures indicate"', that with conformity of




procedure, reliable results can be obtained.




     The results of the comparative series are discussed and summarized



in detail in the next section of this report.




III. FINDINGS AHD DISCUSSION




     Stannous Chloride Method Without Potassium ,P_ersul£ate




     As indicated in the preceding section,  Series VIII showed nuch




better agreement of results from the individual laboratories than




Series VII when employing the stannous chloride method without potassium

-------
persulfate.  In Series VIII the results were more consistent and




gave "better indications of the precision and accuracy that can "be




achieved when the recommended procedure is carefully followed.




     Table 1 presents a comparison of precision and accuracy of phosphate




methods.  Table 2 presents individual laboratory average results chrono-




logically and anonymously.  When analyzing a lake sample in Series VII,




a precision of ± 0.03 mg/1 (one standard deviation) was obtained;




whereas in a repeat analysis in Series VIII, a precision of ± 0.01 mg/1




was realized.  A precision and accuracy of ± 0.01 mg/1 was obtained




when analyzing a standard containing 0.05 mg/1 of phosphate.




     Series VIII indicates that equally good precision and accuracy




can be obtained when analyzing lake samples containing 0.06 mg/1 of




phosphate.




     Recoveries of known amounts of phosphate by the stannous chloride




method without potassium persulfate are shown in Table 7«  The precision




and accuracy was ± 0.02 mg/1 and ± 0.01 mg/1 for recoveries of 0.0-5 and




0.02 mg/1,respectively,  of phosphate from Lake Michigan water.  The




precision and accuracy for recovery of 1.0 mg/1 of phosphate from river




water (collected from the Indiana Harbor Canal) was ± 0.26 and 0.33,




respectively.




     Stannous Chloride Method with Potassium Persulf ate




     Table 3 presents individual laboratory average results chrono-




logically and anonymously.  The precisions obtained,  using the stannous




chloride method with potassium persulfate,  in Series I and IV when

-------
analyzing Lake Michigan water and Lake Michigan water spiked with




0.05 mg/1 were ± 0.01 mg/1.  Series II showed a precision of




0.02 mg/1 for the lake sample spiked with 0.06 mg/1 of phosphate.




     The river sample in Series II showed a precision of ± 0.32 mg/1




and the spiked river sample (l.O mg/1) ±O.Vf; whereas in a repeat




analysis in Series IV showed precisions of ± 0.17 end ± 0»33 ^g/1




for the river and river spiked (0.90 ing/l) samples, respectively.




A precision and accuracy of ± 0.01 mg/1 was obtained when analyzing




standards containing 0.03 and 0.06 mg/1 of phosphate.




     Equally good results can be obtained when analyzing Lake Michigan




water, Lake Michigan water spiked and standards.




     Recoveries of known amounts of phosphate by the stannous chloride




method with potassium persulfate are presented in Table 6.  The precision




and accuracy was ± 0.01 and ± 0.02 mg/1 respectively for recoveries of




0.06 mg/1 of phosphates from Lake Michigan water in Series II, whereas




Series IV showed a precision and accuracy of ± 0.01 mg/1.  The precision




and accuracy for recovery of 1.0 mg/1 of phosphate from river water was




± 0.25 and ±0.57 mg/1 respectively in Series II and ± 0.12 and ±0.30 mg/1



in Series IV.




     Stannous Chloride Method With Potassium Persulfate Followed by Extraction




     Table k  presents individual laboratory average results chrono-




logically and anonymously.  When using the stannous chloride method with




potassium persulfate followed by extraction,  the precision and accuracy




was the same as the two preceding methods in case of the standard,  Lake

-------
                                                                      16
Michigan vater and Lake Michigan water spiked.  The precision for

the river and the river spiked samples was considerably better than

the two preceding methods.

     A standard of 0.03 nsg/1 showed a precision and accuracy of ± 0.01 mg/1.


Lake Michigan water and Lake Michigan water spiked with 0.05 mg/l showed

a precision of ± 0.01 and 0.00 mg/1 respectively.  Precisions of ± 0.06

and ± 0.20 rog/1 were observed for river water and river water spiked


with 0.90 mg/1 of phosphate.

     Recoveries of known amoiints of phdsphate by the stannous chloride


method with potassium persulfate followed by extraction are presented in

Table 8.  A precision and accuracy of ± 0.01 mg/1 was obtained for a


Lake Michigan water sample spiked with 0.05 mg/1 of phosphate.  A river

sample spiked with 0.90 mg/1 of phosphate showed a precision of ± 0.11 mg/1


and an accuracy of ± 0.20 mg/1.
                                                    s-
     Potassium Antimony1 Tartrate Method With Potassjura Persulfate

     Table 5 presents individual laboratory average results chrono-

logically and anonymously.  When analyzing a river sanple containing


0.83 to 1.59 mg/1 of phosphate, precisions ranging from ± 0.09 to

± 0.29 mg/1 were obtained.  River water spiked with phosphate ranging

from 0.80 to 1.1 mg/1 gave precisions in the range of ± 0.2^ to ± O.kO mg/1.

Lake Michigan water samples containing 0.0k to 0.70 rag/1 of phosphate gave

precisions ranging from ± 0.01 to ± 0.07 mg/1.  Precisions in the range

of ± 0.02 to ± 0.0k mg/1 were obtained for Lake Michigan water spiked

with phosphate in the range of 0.02 to 0.50 mg/1.  Precision and accuracy

for standards ranging from 0.00 to 0.03 mg/1 was ± 0.01 mg/1.

-------
                                                                      17
     Recoveries of known amounts of phosphate by the potassium anti-

monyl tartrate method with potassium persulfate are presented in Table 9•

Precisions and accuracies of ± 0.01, 0.02 and 0.07 mg/1 were obtained

for Lake Michigan water samples that had been spiked with 0.02, 0.05

and 0.50 mg/1 of phosphate respectively.  River samples spiked with

0.80, 0.90, 1.0, and 1.1 mg/1 of phosphate gave precisions of ± 0.27,

0.13, 0.23 and 0.13 mg/1 and accuracies of + 0.29, 0.14, 0.32 and


0.1^ mg/1 respectively.

                           Data Evaluation


     Figures 1 and 2 summarizes the results from the stannous chloride

method without potassium persulfate in terms of deviation from the known


amounts of total phosphate.  The range of deviation from known amount

and distribution of individual values are presented as percent of all


determinations occurring from all, participating laboratories.  The
                                                    i-
reliability of the method as used in the various laboratories may, in

this manner, be estimated.  Approximately 80 to 85$ of all the deter-

minations for standard samples containing 0.05 nig/1 are within ± 0.01 mg/1

(one standard deviation).  Approximately 55 to 8l$ of all the deter-

minations for spiked lake sesiples ranging from 0.02 to 0.06 mg/1 are

within ± 0.01 mg/1 and for a spiked river sample at the 1.0 mg/1 level,

k$% era vithin ±0.10 mg/1.


     Figures 3 and k summarize the results from the stannous chloride

method with potassium persulfate.  Approximately 65 to 95$ of all the

determinations for standard samples ranging from 0.03 "to 0.06 mg/1

are within ± 0.01 mg/1.  Approximately 52 to 95$ of all the determinations

-------
                                                                      18
for spiked lake samples ranging from 0.05 to 0.06 mg/1 are within



±0.01 mg/1 and for spiked river water samples 4 to 12$ ranging from




0.90 to 1.0 mg/1 were within ± 0.01 rug/1.



     Figure 5 summarises the results from the stannous chloride method



with potassium persulfate followed by extraction.  Approximately $0 to



100$ of all the determinations for a standard containing 0.03 ff-gA



total phosphate values are all within 0.01 mg/1 of the known value.




The same is true for a lake sample spiked with 0.05 Jag/1 of total



phosphate.  Zero to 31$ of the determinations for a river sample spiked



with 0.90 mg/1 of total phosphate are within ± 0.10 iag/1 of the known



value.



     Figure 6 summarizes the results from the potassium antimonyl



tartrate (PAT) method with potassium persulfate.  Forty to 100$ of




fl.li the determinations for standard samples ranging =from 0.00 to



0.03 mg/1 are within ± 0.01 mg/1.  In Figure 7, 17 to 82$ of all the



determinations for spiked lake samples ranging from 0.02 to 0.50 mg/1



are within ± 0.01 mg/1.  In Figure 8, 32 to 66$ of all the deter-



minations for spiked river samples ranging from 0.80 to 1.1 rag/1 are



within ±0.10 mg/1.



     The findings are presented in further graphic detail in Figures 9



through  18, located in the Appendix in the form of probability curves



for selected samples used in the study.

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                                                                      19
                       Laboratory Evaluation




     Since the data are herein presented anonymously, a direct comparison




of laboratory performance in using the four methods is not possible.




However, all laboratories, of course, did not show equal performance.




As indicated in the Procedure Section, consistency of relative achieve-




ment was present at the beginning of these comparisons.  Most of the




laboratories did demonstrate that, with enough effort and special pre-




cautions, the data so generated might be considered as interchangeable




if a standard deviation of ± 0.01 rag/1 for l?,ke samples in the range of




0.00-0.06 mg/1 and a standard deviation of ± 0.10 mg/1 for river samples




in the range of 0.80 to 1.1 mg/1 is allowable.




     Mr. Lawrence H. Docta, Laboratory Supervisor, Milwaukee Sewage




Commission, Milwaukee, Wisconsin did a statistical analysis of LMBO February




data to compare methods, stannous chloride, stannous chloride with ammonium




persulfate and potassium antinonyl tartrate with ammonium persulfate,




and to determine which is the best method.




     Mr. Docta's analysis shows that the PAT method with ammonium




persulfate is far superior to the stainous chloride method in Standard




Methods, Twelfth Edition (1965) and the modified standard methods




procedure employing ammonium persulfate.  The coefficients of variation




are the lowest for the PAT method.  The lower the coefficient of




variation,  the better the method is.  The ideal coefficient of variation




is 1$ and 5$ is considered to be undesirable.

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                                                                      20
     In order to ensure the "best possible results,  only those


laboratories demonstrating ability to meet a precision level of


±0.01 mg/1 should be included in a nutrient monitoring operation.


     In conclusion, this section on procedures  shows that good


results can be obtained by the PAT method for phosphate,  especially


at the low levels encountered in Lake Michigan water, provided that


at great amount of care in preparation and skill in technique are


exercised, and that there is strict adherence to the method outlined


in the Appendix of this report.


IV.  CONCLUSIONS AMD REOTLMENDAIIONS


     1.   This study indicated that an accuracy of  ± 0.01 mg/1 and


          a precision of ± 0.01 rag/1,  both expressed as one standard


          deviation,  can be achieved when analyzing Lake Michigan open


          vater, inshore and harbor samples by the  PAT method.
                                                   i-

     2.   The above results have been obtained by complying strictly


          with the procedure as presented in the Appendix of this report.


     3.   The PAT method was de.: cnstrated to be superior (more accurate,


          greater precision and freer of interferences,especially iron)


          to the stannous chloride method.


     4.   Of the eleven participating laboratories,  the majority  was


          able to achieve the above accuracy using  the PAT method.   These


          results were not achieved on a routine basis, but under conditions


          requiring extraordinary care and precautions.

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                                                                 21
5-   The limit of detectability using the PAT method,  as presented



    ' herein for the detection of total phosphate in Lake Michigan



     waters, appears to "be 0.01 iag/1.



6.   Only those results from laboratories showing the  continuing



     capability to analyze at an accuracy of ± 0.01 mg/1, or better,



     should "be accepted in a monitoring operation when analyzing



     for total phosphate levels below 0.10 mg/1.



7.   Historic data reporting total phosphate levels below 0.10 mg/1



     should be evaluated with extreme caution.  There  appears to be



     no practical way to develop a correction factor to apply to



     the latter data which would provide acceptable correlations



     in the lower concentration ranges.

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                        BIBLIOGRAPHY



1.   Standard Methods for the Examination of Water and Wastevater,




     12th Edition, American Public Health Association, Inc.




     New York, K.Y. 196p.




2.   Edwards, Gail Pj Molof, Alan H.; and Schneeman, Richard W.




     "Determination of Orthophosphate in Fresh and Saline Waters."




     Journal American Water Works Association, July 1965.

-------
APPENDIX

-------
                                                                        32

    ANALYTICAL PROCEDURAL DETAILS FOR THE ANALYSIS OF TOTAL PHOSPHATE



1.   General Discussion

     1.1  'Principle:   Ammonium nolybdate and. potassium antimony! tartrate p/nT
          react in an acid medium with dilute solutions  of ortho-
          phosphate to form  a heteropoly acid (phcsphonolytdic acid)
          which is reduced to the intensely colored  rcclybden-oxi "blue by
          ascorbic acid.

     1.2  Interferences:   Arsenates react with the molybdate reagent to
          produce a blue  color sinilar to that formed with phosphate.
          Concentrations  as  low as 0.10 mg/1 of arsenic  interfere with
          the phosphate determination.  Hexavalent chromium  and nitrite
          interfere to give  results about 3% lev;  at  concentrations of
          1.0 mg/1 and 10-l5£ low at concentrations  of 10 mg/1
        •  chromium and nitrite.  Sulfide (l^S)   and silicate do not
          interfere in concentrations of 1.0 and  10  ing/1.

     1.3  Sampling and preservation:  Samples should be  preserved with
          ^ ml of chloroform per liter at the time of collection to
          inhibit bacterial  activity.

2.   Apparatus

     2.1  Acid-washed glassware:  All glassware used in  the  determination
         -'should be washed with not 1:1 KC1 and rinsed with  distilled
          water".  The acid-washed glassware should be Tilled, with distil-
          led water and treated with all the reagents -to remove the
          last traces of  phosphate that might be  adsorbed on the glass-
          ware.  Preferably, this glassware should be -used only for the
          determination of phosphate and after use it should, be washed
          and kept covered up until needed again.  If -this is dene, the
          treatment with  1:1 HC1 and reagents is  only required occasionally.
          Commercial  detergents jshould never be used .

     2.2  Colorimetric equipment:  A spectrophotometer with  EH infrared
          phototube for use  at 880 r+n, providing  a light path of 1" or .
          longer,  should  be  used.'.

3.   Reagents

     3.1  Sulfuric acid solution, 8N :  Dilute 112 ml  of cone. HgSO^ with
          distilled water to 500 ml.
     3.2  Potassium antimony! tartrate:  Dissolve h.3538  g  KC
          H20 in 200 pi of distilled water.  Store in a dark bottle at

-------
                                                                                 33-
]
            3.3  Ammonium colybdat-e solution: Dissolve 20 g (i'Ki^MoyC^.li H20
                 in 5OO ml cf distilled water.  Store in a plastic bottle at
                 h°c.                                            .

            3«h  Ascorbic acid, 0.11-1:  Dissolve- l.?6 g of ascorbic acid in
                 100 ml of distilled water.  The solution is stable for about
                 a week if stored at li°C.

            3«5>  Combined reagent:  Kbc the above reagents in the following
                 proportions for ICO ml of the combined reagent: $0 ml of
                 8H H^SO]^, 5> *& °£ potassium antimony! tartrate solution,
                 13> ml of arcrr.oniun ir.olybdate solution, and 30 ml of ascorbic
                 acid solution.  Mix after addition of each reagent.  All
                 reagents mist reach room temperature before they are mixed
                 and they should be mixed in the order given.   If turbidity
                 forms in the combined reagent, shake and let it stand for a
                 few minutes until the turbidity disappears before proceeding.
                 The reagent- Is stable for one week if stored at li°C.
3.6  Alcohol, ethyl (£p percent)  or isopropyl.

3.7  Stock phosphate solution:  Dissolve in distilled water
     0.716^ g of potessiun dihydrogen phosphate, KF^POi , which
     has been dried in an oxren at 105°C.  Dilute the solution to
     1000 El.  1 ml equals O.£0 mg
                         phosphate solution:  Dilute 20 ml of st-sck phosphate
                solution to 10CO rol with distilled water.  1 ml ~ 0.01 mg

            3«? Potassium persulTatc, reagent grade.

            lt.0 Strong-acid solution:   Slowly add 3CO ml cone.  HpSO^  to 600 ml
                distilled -Eater.  VJhen cor-1, add U.O ml cone. H1IO_3 and dilute
                to 1 liter,

      It*    Procedure

            lj.1 Make a  spot test en each sample to determine the approxir^ate
                phosphate concentration.  If the color is very  dark,  a proper
                aliquot of  sarrple should be used, diluted to 5>0 ml; if the
                color Is  very light, the sample should be concentrated by
                evaporating 200 ml of sample containing strong-acid and
               - persulfate, down to 50 ml.
                                ___ .  _   Placft appropriate  aliquot of the
                                             sample containing not mere than
                0.6 mg of PO^ in suitable containers  for  digestion.

-------
 3
 1
]
]
]
3
3
3
3
     Iu3  Add 1 drop of phenolphthalein indicator to both the filtered
          and the unfiltered portions.  If a red color develops, add
          strong-acid solution dropwise to just discharge the color.
          Then add 1 ml in excess.

     li.ll  Add 0,U g of potassium persulfate to each container.

     I{.5>  Boil gently for 90 minutes, adding distilled water if neces-
          sary to keep the volume between 25 and $0 ml.

     li.6  Cool, filter the unfiltered aliquot if necessary through a
          membrane filter and transfer both portions to 50 rol nessler
          tubes.

     il.7  Neutralize to a faint pink color with IN NaOH and dilute to
          50 ml with distilled water.

     li.8  Add 2.5 nil of ethyl or isopropyl alcohol and mix thoroughly.

     lt«9  Add 2.5 ml of combined reagent.  Mix thoroughly and allow to
          stand exactly 10 minutes for color development.  Read at 8802-41.
          Samples, standards, and blanks should be read against distilled
          water set at zero op'tical density.  If final volume is not 5>0 ml,
          the volume of reagents used should be adjusted so that the same
          ratio of reagents to sample is maintained.

     ii.10 Standard curve and blanks:  The standards and blanks should be
          processed exactly as the samples.  At least one standard should
          be run either with each set of samples or once each day that
          analyses are performed.  If the standard does not fall very
          close to the curve, then a new calibration curve should be
          prepared.

5«   Calculations

          rng/1 PO^ = O.D. of sample x slope x cone, or dil. factor.

6.   Bibliography

     1.   Standard Methods for the Examination of Water and Wastewater,
          12th Ed., 1965.

     2.   Gail, E.P.,  Molaf, A.H., and Schnuman, R.Vf.  Determination
          of Orthophosphate in Fresh and Saline Waters.  Journal AVJV7A
          57:917 (July 1965).

-------
                                                                                35

To:   A. M. Tenny


From:  G. R. Richardson


Re:  PHOSPHATE LITERATURE REVIEW



In prior years, the primary complication involved in a suitable method for the

determination of phosphate has been the selection of an adequate reducing agent

coupled with the proper selection of pH.

Various methods are based upon the fact that a suitable reducing agent, when

added to an ammonium molybdate solution of proper acidity will produce a blue
                           * '
color if the solution contains phosphate.  Parker and Fudge (1927) showed color

can be developed in five minutes and remain stable for one hour under their

experimental conditions.  Truog and Meyer (1929) improved Denige's colormetric

methods for phosphate and arsenic.  They prepared a stock solution of stannous

chloride by dissolving the pure salt in acidified water, doubled the amount of

ammonium molybdate and increased acidity.  This eliminated the effect of even high

amounts of silica.

A method of extracting phosphomolybdic acid with isobutyl alcohol  was described

by Berenblum and Chain (1938).  This method was later modified by  Pons and Guthrie

(1946) inorder to analyze samples with large, amounts of protein or colored and

turbid extracts.  In (1949) Martin and Doty used equal volumes of  an isobutyl

alcohol and benzene mixture to extract phosphate.  This mixture only required a

single extraction step.

Young and Golledge (1950) found that tannins and their oxidations  products give

a slight color even in the absence of phosphate.  If large quantities of tannins

are present, they may be removed by absorbing and decolorizing with charcoal.

-------
                                       -2-



                                                                                36





They report very little absorption of phosphate though recent work in our laboratory




indicates phosphate is absorbed in charcoal.




Interferences from other ions in the colormetric determination of phosphate has




caused errors.  Greenberg (1950) used sulfamic acid to control nitrite nitrogen.




Ferric iron above 10 ppm not only decreases the intensity of the color it also




produces troublesome greenish tints.  Aluminum, manganese, calcium and magnesium




may be present in concentration equivalent to 1000 P.P.M without any influence on




the color.




The use of stannous chloride as a reducing agent in the molybdenum blue method for




the determination of phosphate in sea water was reviewed by Burton and Riley (1956).




This reagent has a number of disadvantages.  The color fades quite rapidly and




different batches of molybdate reagent give different intensities with the same




amount of phosphorous.  Burton and Riley found P-methylaminophenol sulfate (metol)




used at 100 C for a reducing agent offers a number of advantages over stannous




chloride.




The use of ascorbic acid for the reduction of phosphornobydic acid was first reported




by Ammon and Hinsberg (1936), but their method was modified by several investigators.




A single solution containing ammonium molybdate, ascorbic acid and sulfuric acid was




introduced by Burton and Riley (1958).




The single solution method was modified by Murphy and Riley in (1962), to include




potassium antimonyl tartrate.  The color developed rapidly and the procedure still




maintained the advantages of the original method.




There was no interference by copper, iron, or silicate at concentration many times




greater than their normal concentration in fresh water.




Sletten and Bach (1961)  overcame the weaknesses of the stannous chloride method




due to the instability of the stannous chloride reagent.   They dissolved stannous




chloride in reagent grade glycerine, thus stabilizing the stannous chloride.   Gales,




M. E., Julian, E. C.  and Kroner, R.  C. (1966) described a method of converting meta,

-------
                                       -3-
                                                                                37

pyro, and organic phosphorus into measurable phosphate in natural water.  They used
persulphate for oxidation of the sample followed by reduction in an acid medium.
The colorimetric determination of total phosphate was with stannous chloride.
A rapid, accurate and sensitive automated method for the determination of orthophos-
phate in fresh water was developed by Molof (1965), patterned after the manaul
method using ascorbic acid.

-------
                                                                                33
                                   REFERENCES
AASGP Committee Report, Determination of orthophosphate, hydrolyzable phosphate,
in  total phosphate in surface water.  Jour. Am. Wat. Wk. Assoc. 50:1563, 1958.


Berenblura, I. and Chain, E.  Biochem - Jour. 32:295 1938.


Burton, J. D. and Riley, J. P. "Determination of soluble phosphate and total
phosphate in sea water and total phosphorus in marine muds."
Micro Chim. Acta. 9:1350, 1956.


Edwards, G. P. Molof, A. H. and Schneeman, R. W., "Determination of orthophosp-
hates in fresh and saline water".  Jour. Am. Wat. Wks.
Assoc. 57:917, 1965.


Fontaine, T. D. Spectrophotemetric determination of phosphorus.  Ind. and Eng.
Chem., Anal. Ed. 14:77, 1942.


Gales, M. E. Jr., Julian, E. C. and Kroner, R. C., "Method for quantitative
determination of total phosphorus in water."  Jour. Am, Wat. Wk.
Assoc. 58:1363, 1966.


Greenbert, A. E., Weinberger, S. W. and Sayer, C. N. "Control of nitrates inter-
ference in colorimetric determination of phosphorus".
Anal Chem. 22:499, 1950.


Martin, J. B. and Doty, D.  M. "Determination Inorganic Phosphate". Modification
of  Isobutyl Alcohol Procedure.
Anal Chem. 21:965 1949.
Molof, A. H., Gail, E. P. and Schneeman, R. W.  "An automated analysis for
orthophosphate in fresh and saline waters".  Automation in Analytical Chemistry.
Technician Symposia, 1965,


Murphy, J. and Riley, J. P. " A single solution method for the determination of
soluble phosphate in natural waters".
Jour. Marine Biol. Assoc. UK, 37:9, 1958.


Murphy, J. and Riley, J. P. "A modified single solution method for the determina-
tion of phosphate in natural waters".
Anal. Chem. Acta. 27:31, 1962.

-------
                                       -2-
                                                                                39


Parker and Fudge, Soil Science, 24:109, 1927


Ports,  W. A. and Guthrie, J.  D. "Determination of Inorganic Phosphorus in Plant
Materials".  Ind. Eng. Chem. Anal Ed. 18:184, 1946


Sletten, 0. and Bach, C. M.  "Modified stannous chloride reagent for orthophos-
phate  determination.  Jour.  A. Wat. Wk.  Assoc. 53:1031,  1961.


Young, R. S. and Golledge,  A.  "Determination of hexametaphosphate in water
after  threshold treatment,   Ind.  Chemist 26:13,  1950.

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