REPORT TO THE CONFEREES OF THE THIRD SESSION OF THE
             CONFERENCE IN THE MATTER OF POLLUTION OF THE
            INTERSTATE WATERS OF THE  ESCAMBIA RIVER  BASIN
             (ALABAMA-FLORIDA) AND THE INTRASTATE PORTIONS
           OF THE ESCAMBIA BASIN WITHIN THE STATE OF FLORIDA
                   WASTE  SOURCE STUDY
                             AND
REVIEW OF  WASTE TREATMENT  AND CONTROL  PRACTICES
           AIR  PRODUCTS  AND CHEMICALS,  INC.
                    PENSACOLA, FLORIDA
                           May, 1972

                    Environmental  Protection Agency
                    Surveillance and Analytis Division
                         Athens, Georgia

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     The planning and operation of this project was carried out under




the supervision of B. H. Adams, Chief, Engineering Services Branch.






     Mr. C. A. Sweatt was Project Engineer and principal author of




this report.







     All Environmental Protection Agency personnel are attached to the




Surveillance and Analysis Division located at Athens, Georgia.  The




Division is under the direction of J. A. Little.

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                          TABLE OF CONTENTS





Title                                                     Page No.




INTRODUCTION	   1




PROBLEM SUMMARY 	   2




SUMMARY AND CONCLUSIONS 	   3




RECOMMENDATIONS 	   9




PLANT DESCRIPTION	12




     GENERAL	12




     PLANT PROCESSES	12




     WASTE TREATMENT FACILITIES 	  15




PREVIOUS WASTEWATER STUDIES 	  20




     REPORT REVIEWS 	  20




     SOURCE CONTROLS	23




STUDY FINDINGS	26




     GENERAL DISCUSSION	26




     COMPARISON OF 1969 AND 1972 DATA	29




          Biochemical Oxygen Demand 	  29




          Phosphorus	.30




          Nitrogen	30




          Metals	31




          Organic Compounds 	  31




          Ground water	< .	33




          DNT, Urea and Ammonia Nitrate Waste	34




          Ammonia Waste 	  38




          Amines Waste	38
                                   ii

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          PVC and Nitric Acid Waste	   39




          Well Water	   39




TREATMENT ALTERNATIVES AND SUGGESTIONS	   41




     TREATMENT METHODS	   42




          Ion Exchange	   42




          Spray  Irrigation	   43




          Deep Well Disposal	   43




          Ammonia Stripping  	   43




          Biological Treatment	   44




REFERENCES	   45




APPENDIX A, PROJECT PERSONNEL



APPENDIX B, ANALYTICAL METHODOLOGY AND STUDY PLAN




APPENDIX C, WATER SAMPLING DATA




APPENDIX D, CORRESPONDENCE
                                   iii

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                           LIST OF TABLES


Table No.                   Title                           Page No.

   I             SAMPLING STATIONS AND LOCATIONS	27

  II             AVERAGE ANALYTICAL DATA FOR INPLANT
                 WASTE STREAMS	28

 III             ORGANIC COMPOUND DATA	32

  IV             MONTHLY SUMMARY OF AIR PRODUCT
                 MONITORING DATA	35

   V             WELL WATER NITROGEN DATA	40
                                  iv

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                          LIST OF FIGURES







Figure No.                 Title                            Page No.




   1            PROJECT STUDY AREA	   13




   2            LAYOUT AND TREATMENT FACILITIES PLANT. ...   14




   3            TOTAL NITROGEN (LBS/DAY) LOADS 	   36




   4            NITROGEN WASTE LOADS 	   37

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                          INTRODUCTION






     This report presents an evaluation of waste treatment and waste




control practices at the Air Products and Chemicals, Inc. plant located




near Pensacola, Florida.  The study, conducted by the Environmental




Protection Agency during March 6-12, 1972, was requested by the con-




ferees of the third session of the Federal-State Escambia Bay Enforcement




Conference held on January 24-25, 1972.




     The study objectives outlined in this report are to:






        •  Characterize and quantify all plant wastes discharged into




           receiving waters;




        •  Evaluate and document current waste treatment and control




           practices, and




        •  Propose alternatives for the best available technology




           for waste treatment.






     The assistance and cooperation of the Florida Department of Pollution




Control, Escambia County Health Department, and Air Products and Chemicals,




Inc. are gratefully acknowledged.

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                         PROBLEM SUMMARY









     As a result of continuing numerous fish kills and general degradation




of the water quality in Escambia Bay,  the State of Florida in mid-1969




served Air Products and Chemicals,  Inc. a citation and orders specifying




a 90 percent minimum treatment of their liquid discharges.  At a Federal-




State Enforcement Conference held in January 1970, the company was directed




to further reduce carbonaceous and  nitrogenous wastes by 94 percent and




phosphorus wastes by 90 percent.(1)  During the February 1971 session of




the enforcement conference,  allowable daily limits of 17 pounds of 5-day




Biochemical Oxygen Demand (8005), 477 pounds of total nitrogen and 35




pounds of total phosphorus were established for compliance by December 31,




1972.(2)   It was also recommended that should the specified reductions




fail to minimize the problems of excessive enrichment of Escambia Bay,




plans should be developed to remove all waste discharges from the bay.




The Florida Department of Pollution Control (FDPC) concluded that complete




removal was necessary and on December 15, 1971, issued an order to Air




Products and Chemicals, Inc., advising the company that no wastewaters




containing pollutants or contaminants would be discharged into Escambia




Bay after December 31, 1972.(3)

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                    SUMMARY AND CONCLUSIONS


1. Wastewater discharges into Escambia Bay from Air Products and

   Chemicals, Inc., Escambia Plant, do not presently meet conference

   established limits.  It is very doubtful that the company will meet

   the conference recommendations by December 31, 1972.  Significant

   reductions in waste loads have been accomplished through source con-

   trols and the closing of two plant processes (NPK and methanol).

   However, pollution abatement efforts within the past three years

   have been partially offset by a two-fold increase in the production of

   nitrogenous materials.  The success of pollution abatement efforts,

   as they relate to conference recommendations, are demonstrated by

   the following comparisons:


                  Waste Load (Ibs/day)	      Percent Removals
1969 1969
Parameter Base Load Study
Conf.
Limits
Present
Study
Base Conf,
Load Recom.
I/ 21 21
Total 15,100^-
Nitrogen
BOD5
Total
Phosphorus —

5,650
290

320

477
17

35
(3,190)-
2,610
185

39
(79)-'
83 94
94

90
Since
1969 Study
21
(44)^
54
40

88
Flow (MGD)   —         5.2    —      1.84
I/  The 1969 base load was established by the company in correspondence
    with the State of Florida Department of Air & Water Pollution Control.

2]  Estimated added effect on the plant effluent of wastes presently being
    retained in Echo Pond, assuming a 60 percent nitrogen removal.

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2. The dominant pollutants in the plant effluent are nitrogenous com-




   pounds.  The final waste effluent is a neutral, unheated liquid con-




   taining relatively low concentrations of carbonaceous material and




   nonfilterable residue.  Relatively low concentrations of organic com-




   pounds from the dinitrotuluene operations were detected in the discharge




   into Escambia Bay.  Some of these compounds are known to be toxic to




   fish at concentrations greatly in excess of levels found in the




   effluent and the effects of other compounds on aquatic life are unknown.




   Other contaminants observed in the effluent were in low concentrations




   and are not believed to adversely effect water quality in Escambia Bay.






3. Process wastes at the Escambia Plant are collected in a network of open




   ditches flowing to treatment ponds consisting of four biological ponds




   (total area - 65 acres), two settling ponds (total area - 4 acres), and




   one percolation pond containing 14 acres.  Wastes from the treatment




   system flows through a common discharge into Escambia Bay.






4. Alpha, Bravo and Charlie Ponds are unlined ponds constructed on pervious




   material and, therefore, unsuitable for the treatment or storage of




   concentrated nitrogenous waste.  However, the ponds do intercept a




   portion of the contaminated groundwater and surface drainage and provide




   limited regulation of pond discharge.  The ponds are located in the




   natural drainage of a small watershed which tend to flush out during




   periods of heavy rainfall.  Flood gates have been installed on Bravo and




   Charlie Ponds, creating approximately 75 additional acre feet of storage




   for discharge regulation.

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5.  Nitrogenous wastes are difficult to treat effectively and the problem




   is compounded by contaminated groundwater.  Contaminated groundwater




   seepage, the most complicated aspect of the problem, accounts for over




   50 percent of the total nitrogen in the plant effluent.   Study data




   showed a 720 percent increase in the total nitrogen concentration from




   the effluent of Charlie Pond to the effluent of Alpha Pond — no wastes




   are discharged between these points.  The groundwater contamination is




   primarily due to past waste control practices; however,  the amines waste




   percolated through George Pond and the DNT waste seepage from Delta Pond




   are existing contributors.  This problem must be controlled to signif-




   icantly reduce the nitrogen discharged into Escambia Bay.  Although the




   company has previously installed approximately 85 shallow well points




   for monitoring groundwater quality, additional investigations will be




   required to determine the dispersion of wastes in the contaminated




   groundwater zone and feasibility of corrective methods.






6.  The diverse nature of the various plants operated within the complex




   complicates the development of an effective treatment system.  Several




   methods of waste treatment were examined in preparation of this report.




   Some of the methods examined include those previously investigated by




   Air Products and reported to the FDPC.  Methods investigated were ion




   exchange, spray irrigation, deep well disposal, ammonia stripping, and




   biological (nitrification-denitrification) treatment.  The following




   conclusions were reached:

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      •  Ion exchange would produce a waste stream unusable for product




         recovery due to high concentrations of salts other than ammonium




         nitrate.  Disposal of the concentrated waste stream would present




         a difficult problem.




      0  Spray-irrigation has limited use in the area due to heavy rain-




         fall during the growing season.  Over applications of nitrogen




         wastes would leach rapidly through the pervious soil causing




         groundwater contamination.




      •  Deep well disposal was determined by the company to be unsuitable




         for the total plant effluent due to the large volume of waste and




         the 90 percent reduction requirement of the FDPC.  Although EPA




         does not encourage this disposal practice, this method could




         possibly be used for disposal of the treated process wastes,




         which would not include seepage, runoff, etc.




      •  Stripping of ammonia with air or steam may be suitable for treat-




         ment of the amines and interceptor ditch waste.  Steam stripping




         with ammonia recovery or distillation may be necessary for air




         quality protection.




      •  Biological denitrification for nitrate removal in combination




         with ammonia stripping is considered to be the best alternative.





7.  In-plant survey data and discussions with company personnel indicate




   that it would be feasible to reroute the following plant waste streams




   for more effective treatment:

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   •  The amines plant waste stream is a very alkaline waste  (pH 11.4)




      with high nitrogen and carbon concentrations.  This waste,




      presently discharged at an average rate of 225 gpm into the




      percolation pond and contributing to the groundwater contamination




      problem, could probably be effectively treated in Echo Pond.  The




      excess alkalinity could be used for neutralization of the acidic




      DNT waste, now being neutralized by caustic.  This stream would




      also provide a carbon source necessary for biological treatment.




      The high ammonia concentration should be reduced, possibly by




      stripping prior to neutralization.




   •  The ammonia plant waste stream, a very alkaline waste (pH 11.9)




      now flowing into Charlie Pond at an average discharge of 88 gpm,




      could be combined with the amines waste, piped to the DNT plant




      for neutralization and treated in Echo Pond.




   •  Wastes from the PVC plant could be routed through Echo Pond pro-




      viding a necessary phosphorus supply for the microbial population.





This arrangement appears to be suitable for treatment of the combined




streams for nitrogen and carbon removal in Echo Pond plus utilization




of the alkalinity and acidity of individual streams for neutralization.




The combined flow would average approximately 600 gpm with a COD:N03:




T^tal P ratio of 230 to 31 to 1.  One potential problem with this




scheme of treatment is the unknown biological treatability problems




associated with the nitroCompounds in the DNT waste.  If these com-
pounds greatly retard biological action, as might be suspected, extended

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                                 8
   holding periods or removal of the compounds at the source may be




   required.  Activated carbon adsorption, a method previously tested




   by the company, would probably be an effective method of removal.






   Studies to determine the compatibility and treatability of these waste




   streams can be accomplished through the use of jar studies now being




   conducted by the company and through plant-scale operations with Echo




   Pond which was recently placed into service.






8. At the present rate of discharge, the BOD5 effluent concentration would




   have to be reduced to 1.1 mg/1 to meet conference recommendations.  A




   seven-day average effluent 6005 concentration of 10 to 15 mg/1 (155 to




   230 Ibs/day), with maximum daily fluctuations of 125 percent, is a much




   more reasonable, achievable limit.

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                      RECOMMENDATIONS






1. The company should intensify their source control program which has




   accomplished significant results to date.






2. Alpha, Bravo, and Charlie Ponds should be operated primarily as polish-




   ing ponds and not for the treatment of concentrated nitrogen wastes.






3. All untreated DNT waste leaks should be eliminated from Delta Pond.






4. The use of George Pond, a percolation pond treating wastes from the




   amines plant, should be discontinued.






5. The company should investigate the following compatibility and treat-




   ability modifications and submit a report of the findings to the con-




   ferees by June 1, 1973:





     •  Combine the waste streams from the amines and ammonia plants.




        Air strip or otherwise remove the ammonia from the combined stream




        and pipe the treated stream to the DNT plant to neutralize the




        acidic DNT waste.  Treat the combined waste in Echo Pond for nitrate




        removal.  The amines and ammonia waste should provide a necessary




        source of carbon.  Treatment of the amines discharge in this manner




        would also eliminate George Pond, a percolation pond which is




        contributing to the groundwater contamination problem.




     •  Divert Fox Trot Pond effluent to Echo Pond.  This stream will




        provide part of the phosphorus necessary for proper microbial




        growth in Echo Pond.

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                                10
     •  Investigate the treatability of the nitro compounds in Echo Pond.




        If these compounds prove to seriously inhibit microbial growth,




        consideration should be given to removal at the source by use of




        activated carbon or other methods.




     •  Additional clay-lined ponding capacity may be required.  An




        aerated treatment pond or another form of aerobic treatment may




        be desirable following treatment in Echo Pond.





6. The company should conduct an investigation of the groundwater con-




   tamination problem and submit a report of the finding to the conferees




   by June 1, 1973.  The report should include:






     •  The extent of the contaminated groundwater zone showing vertical




        and horizontal concentration profiles.




     •  Flow patterns of the contaminated groundwater.




     •  Alternatives for reducing or eliminating this nitrogen contri-




        bution to the Bay.




     •  A specific implementation schedule for the selected alternative.





7. A groundwater monitoring system should be established to determine




   the long-term changes in groundwater nitrogen concentrations.  Monthly




   samples should be collected from a minimum of three points located




   between Area "B" and the bay.  Samples should be analyzed for TKN,




   NH3, N02~N03 and reported to the FDPC.






8. In general, all surface water runoff from the drainage basin should be




   routed around the treatment system.  An exception should be made in any

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                                  11
    immediate plant areas where runoff contains high nitrogen concentra-

    tions or other contaminants.  Wastes from these areas should be col-

    lected and treated with process waste.


 9. The conferees should increase the allowable BOD 5 effluent limit from

    17 to 200 pounds per day.  Established loadings should apply as seven-

    day average values with average daily loads permitted to vary up to

    125 percent of this value.  The following effluent criteria would

    apply:


                                      Maximum Effluent Loadings (Ibs/day)
    Parameter                           7-day Average    Maximum Daily

    5-day Biochemical Oxygen Demand          200              250

    Total Nitrogen                           477              600

    Total Phosphorus                          35               44


10. Spray irrigation appears to be one of the most promising schemes for  «££>

    utilizing the waste and should receive further consideration in spite

    of apparent problems.

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                                  12







                        PLANT DESCRIPTION





GENERAL




     The Air Products and Chemicals, Inc., Escambia Plant, was originally




constructed in 1955 on a 1600-acre tract of land located north of Pensacola




near Pace, Florida (Figure 1).  The plant produces ammonium nitrate, ammonia,




nitric acid, amines, urea, dinitrotoluene, and polyvinyl chloride.  Total




plant production of nitrogenous materials has approximately doubled in the




past three years.  Since the 1970 Enforcement Conference, the methanol and




mixed fertilizer (NPK) plants have been closed.  The company reported that




the methanol operation was temporarily shut down because of a shortage of




natural gas and the NPK operation was terminated because of the difficulty




and expense of controlling the nutrient waste load.  Treated process wastes




are discharged through a common outfall into the upper northeastern area




of Escambia Bay (Figure 1).  Domestic wastes are treated in several septic




tank systems and discharged to subsurface drain fields.




     Operations are grouped into  two separate areas approximately one




mile apart (Figure 2).  The complex of plants to the north are con-




tained in Area "A" and the plants to the south in Area "B".  Separate




grouping of the processes was required by insurance companies for




safety reasons.





PLANT PROCESSES




Ammonia  - Natural gas is reformed and reacted with atmospheric nitrogen




to produce ammonia which is used  in other plant processes.  Additional




ammonia is shipped in to augment  plant usage.

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                                     13
                                                                                     FIGURE  I
                                                                                •<'<
                                   PROJECT   STUDY AREA
                                                                             VICINITY  MAP
     I  ,i MARfMO COUftTt WTP

            s
—	1
                                                                   US ENVIRONMENTAL PROTECTION AGENCY
                                                                             REGION 13
                                                                    ESCAMBIA RIVER STUDY
                                                                         MARCH, 1972
                                                                    SURVEILLANCE AND ANALYSIS DIVISION
                                                                  ATHENS                 GEORGIA

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                                  14
                                                                         FIGURE  2
                PLANT LAYOUT AND TREATMENT FACILITIES
                    AIR PRODUCTS  AND CHEMICALS INC.

                      Cloy Pit ond Sonilory Landfill
                                    AREA "A" PLANT SITE

                                      i—Neutralization 8
                                    "7 \ Phosphorus Removal
                                                      Main Administration Building
                                 Sul Acid Cone
                                 DNT
                                 Once Through Cooling Water
Escombio Boy
                   SCALE IN FEET
              500  0  500 1,000 1,500 2,000
                                                    US. ENVIRONMENTAL PROTECTION AGENCY
                                                               REGION Iff
ESCAMBIA  BAY STUDY
     MARCH, 1972
                                                     SURVEILLANCE AND ANALYSIS DIVISION
                                                    ATHENS                  GEORGIA

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                                 15
Amines - Methanol and ammonia are used to produce mono-, di-^ and tri-




methylamines.  These are intermediates used by other companies in pro-




duction of various products*






Nitric Acid - This product is a major component in the production of




ammonium nitrate, and is produced by oxidizing ammonia.






PVC - Vinyl chloride is imported, polymerized and shipped to other pro-




cessors.  This operation is not integrally connected with other plant




operations since nitrogenous materials are not utilized.






Ammonium Nitrate - Ammonia and nitric acid are reacted to form ammonium




nitrate, which is used principally for fertilizer.






Urea - Ammonia is reacted with carbon dioxide to form urea.  This product




has a high nitrogen content and is used for fertilizer, protein feed




supplement and other uses.






Dinitrotoluene - Toluene is imported and reacted with a mixture of nitric




and sulfuric acid to form dinitrotoluene.  The product is sold for use




in the production of urethane products.






NPK - The NPK plant is now permanently closed, but formerly produced




mixed agricultural fertilizers containing nitrogen, phosphate and potash.






WASTE TREATMENT FACILITIES




     The existing treatment facilities (Figure 2) consist of a system of




settling, percolation and biological treatment ponds.  Waste is conveyed

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                                  16
from Area "A" to the treatment ponds by two paved ditches.  Prior to con-




struction of Alpha, Bravo and Charlie Ponds in 1971, the total plant




effluent, with only source control treatment, was discharged into the




swampy area where the ponds are now located.  Echo Pond was recently con-




structed for aerobic/anaerobic biological treatment of the concentrated




waste from the DNT plant.  Delta and Fox Trot ponds were designed primarily




for settling while George Pond was designed for percolation.




     Alpha, Bravo and Charlie Ponds encompass 9, 33, and 16 acres,




respectively.  Construction on the ponds began in late 1970, and the




system was placed in service during March 1971.  The ponds, constructed




in the natural drainage of a watershed, were formed by constructing




dikes on the typical lowland muck.  Bottom material permits a free inter-




change of groundwater and wastewater.  Waste streams discharge into Charlie




Pond through two paved ditches from the PVC and ammonia plants; each carry




100 to 150 gptn of waste.  The company reported that approximately 700 gpm




of once-through cooling water from Area "B" also discharges into Charlie




Pond.  These are the only surface discharges flowing into the three ponds;




however, a considerable amount of contaminated groundwater apparently does




infiltrate into this system.  Groundwater infilteration is evident by both




the increased volume of wastewater and the increased nitrogen concentration




levels as the waste flows through the pond system.  At the present time,




Echo Pond is being filled and has no discharge.  When it begins overflowing




later this summer,  the discharge will be into Charlie Pond.




     These ponds are located in the natural drainage of a watershed and




are susceptible to flushing from heavy rainfall.  To help alleviate this

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                                 17
 problem,  the State of Florida required the company to install floodgates




 above the weirs in Charlie and Bravo Ponds which increases the storage by




 approximately 75 acre feet.   The installation of floodgates has prevented




 complete  flushing; however,  the flow varies considerably with rainfall.




      The  failure to clear the pond area of trees and other vegetation




 prior to  construction has initiated a need for the frequent removal




 of  floating debris.   However,  the vegetation removal accounts for some




 nitrogen  reduction.   The heavy growth of algae and duck weed in the




 ponds cause a noticeable green color.  Prior to pond construction,




 the total plant effluent flowed across the muck area where the ponds




 are now located.   Leaching of waste materials from the pond bottoms




 will continue to occur until the system is stabilized.




      Delta Pond,  a two-acre  asphalt-lined pond,  provides a holding period




 for the DNT waste.   At the time of the survey,  the lining above the liquid




 level was badly cracked.   The yellow color of the waste in the interceptor




 ditch below Delta Pond and the presence of toluene compounds in the




 effluent  of Alpha Pond indicated that seepage was occurring.  Water from




 Delta Pond is pumped into Echo Pond for biological treatment.  An emergency




 overflow  is provided from Delta to Charlie Ponds.




     The  interceptor ditch is  a  shallow  excavation  immediately above  the




northwest  portion of Charlie and Bravo Ponds.  The  pond  dikes  form  the




lower bank of  the collection ditch  (Figure 2).  The primary  purpose of




this ditch  is  to intercept contaminated  groundwater which seeps from  the




slope below Area "B".  Approximately  70  gallons per hour of waste discharged




from the urea and ammonia nitrate operations  flow into this  collection

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                                  18
 ditch along with surface runoff frpm Area JIB" and some groundwater seepage.




 A pump,  installed in the northwest end of the ditch, pumps waste into Echo




 Pond.  It appears that a large portion of the infiltration into Bravo and




 Charlie  Ponds comes from the collection ditch.   Since the water level in the




 ditch is normally higher than the water surface in the ponds,  a positive




 head  is  available for flow through and under the dike.  An emergency




 spillway is provided from the ditch to Bravo and Charlie Ponds.




      The company has approximately 85 shallow monitoring wells distributed




 around the property.   Company information indicates  that nitrogen levels




 within the wells are very sporadic,  varying  from trace concentrations up




 to 1,000 mg/1.   This  condition was probably  caused by former indiscrim-




 inate discharge  practices,  including leaking flumes,  plant leaks,  spills,




 leakage  from Delta  Pond  and the amines percolation pond.




      Echo  Pond is a newly constructed 7.2 acre,  clay-lined pond.   Wastes




 from  Delta Pond  and the  collection ditch  are pumped  through a  common




 four-inch  header to this new facility.  At the  time  of this study,  the




 pond  was being filled  and had  no  discharge.   The pond is  designed  for




 nitrification-denitrification,  neutralization and  biological oxidation




 of the concentrated nitrogen waste.   After treatment,  the effluent  will




 flow  into  Charlie Pond.




      Fox Trot Pond  is  a  two-acre,  clay-lined pond  designed to  settle




material from the PVC  operation.   Pretreatment  of  this waste is




 accomplished  by  the addition of magnesium oxide for  phosphate  precipi-




 tation.  The  polymers  and magnesium  oxide slurry from this operation

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                                 19
settle rather easily, and the first section of the pond has a pronounced




blanket of white solids visible through the water.  Cooling water from




the nitric acid plant is also discharged to this pond.  After settling




and biological treatment, the waste flows via a paved ditch into




Charlie Pond.




     George Pond is an unlined, 14-acre pond constructed of sand.  It




is designed, as a percolation pond for the amines waste and undoubtedly




contributes heavily to the nitrogen problem in the groundwater.  Although




the upper end of the ditch conveying the amines water is lined, the




lower portion is unlined permitting loss of some of the waste before it




reaches the pond.




     Waste from the ammonia plant flows into Charlie Pond through a




concrete-lined ditch.  This ditch is in need of repair and permits




the loss of some waste before it reaches Charlie Pond.

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                                  20
                   PREVIOUS WASTEWATER STUDIES






REPORT REVIEWS




     Two wastewater studies were performed for the Company by Black,




Crow and Eidsness, Inc., consulting engineers, located in Gainesville,




Florida.(4)(5)  The first report, dated October 8, 1969, resulted from




a citation issued by the Florida Air and Water Pollution Control Board




charging the Company with the pollution of Escambia Bay.  The directive




required the company to submit to the Board within 45 days an engineering




report on proposed waste treatment.  Major conclusions and recommendations




of this report were:




     •  Treatment facilities at Air Products consisted of source




        controls, a percolation system and an impoundment.




     •  Process wastewater flow was about 5.0 MGD with nitrogen and




        Chemical Oxygen Demand loadings ahead of source controls about




        14,800 and 58,900 pounds per day,  respectively.




     •  Estimated treatement removals,  in percent were:




                                               Nitrogen    COD




            Source control equipment only        62        59




            Overall system                       62        97





     •  Recommended additional studies:




            A.   Wastewater characterization




            B.   Evaluation of treatment methods,  including:




                       1.   Additional source controls




                       2.   Spray percolation

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                                   21
                        3.   Spray  irrigation;  and




                        4.   Subsurface  disposal




             C.   Treatability  and  pilot plant  studies.




             D.   Design, engineering, construction, and startup.




      f   The  proposed  program  could be  accomplished in 35 months with a




         target  date of  October, 1972.






      The second report, dated June 12, 1970, was in response to a




directive  from  the Florida  Department  of Air  and Water Pollution Control




to report  on accomplishments and  proposed further actions.  Major con-




clusions were:




      *   All  improvements proposed for  installation by January 1, 1970



         had  been accomplished,




      •   Existing waste control improvements afforded 89 percent nitrogen




         removal from plant wastewater streams,




      •   Overall nitrogen removal  at the outfall had been reduced to




         about 68 percent due to seepage.




      •   Estimated loading due to seepage were:






                                                  Amount




                   Flow                            1.3 MG




                   Nitrogen (total)              3,400 Ibs.




                   Phosphorus (total)              250 Ibs.




                   Potassium                      410 Ibs.




     The Company, with the assistance  of  their consultant, Investigated




and reported findings  on various waste treatment methods in a 1971 report

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                                  22
to the FDPC.(6)  Listed below are the conclusions taken directly from




the report.





     Spray Irrigation Problems




     1.  Nitrogen must be applied at rates vegetation can assimilate it.




         Water volume must be applied at rates that can hydrologically




         be handled.




     2.  In the case of the Escambia Plant, hydrological considerations




         will govern irrigation application.  The land area and reservoir




         requirements make the entire approach impractical.




     3.  The Escambia Plant area experiences some 80 inches of rainfall




         per year.  The greater portion of this rainfall coincides with




         the local agricultural growing season.




     Ion Exchange Application Problems




     1.  Ion exchange of the outfall would generate 28,800 gallons per




         day of 15% salt solution which cannot be disposed of.




     2.  Ion exchange results in a 50-fold increase in ion concentration.




     3.  Chloride concentrations in the outfall exceed permissible limits




         for safely concentrating the regenerant stream.




     4.  The regenerant solution would contain 60% of salts other than




         ammonium nitrate, excluding recycle to process.




     Subsurface Disposal Application Problems




     1.  Escambia must inject its entire outfall to achieve desired




         treatability.

-------
                                   23
      2.   Based  on data  developed  from Monsanto's  injection well,  limited




          receiving aquifier  permeability  precludes  subsurface  disposal  of




          Escambia's entire outfall.




      3.   Recent legislation  may require 90%  treatment  prior to injection.




      Ac t ivated  Carbon Applj.cation Problems




      1.   The  removal of DNT  plant wastewater  COD  load  was  achieved.




      2.   Activated carbon did  not significantly reduce the total  nitrogen




          load of  the wastewater.




      3,   The  expanded biological  pond system  is anticipated to require




          this carbon source  to achieve the maximum  nitrogen treatability.




      4.   A source-control project has resulted in a 50% reduction of  the




          DNT  plant total N-load.






SOURCE CONTROLS




      This report will not attempt to discuss  fully  the  in-plant controls




which have resulted  in  waste load and flow reductions;  however, a listing




of the controls and  resulting reductions  are  shown.  This  listing was




provided  by a company letter dated April  24,  1972,  which is included  in




Appendix D.






              Escambia  Plant Source-Control Program




Timetable     Proj ec t




Pre-1970      1.   Cooling towers.




              2.  Catalytic  combustion on HN03 plant.




              3.   Ammonia recovery from copper liquor system.

-------
                                  24
               4.  Aqua ammonia stripper and vaporizer system,

               5.  Methanol by-product disposal (to boilers).

               6.  Compressor building oil recovery and disposal.

               7.  Amines by-product disposal (flare).

               8.  Nitric acid oil recovery and disposal.

               9.  Methyl methacrylate effluent pH control.

              10.  Methyl methacrylate effluent stabilization basin.

              11.  Ammonium nitrate remelt and reclaim system.
After Jan.
  1970         1.  NPK recycle pond,
               2.  Recovery of weak aqua ammonia from percolation.

               3.  HNOg concentrator recycle and reclaim system.

               4.  HN03 plant start-up weak acid recovery and recycle.

               5.  NPK plant shutdown.

               6.  DNT organics recovery and recycle.

               7.  Ammonia condensate stripper.

               8.  Ammonia cascade cooler on cooling tower recycle.

               9.  Nitric acid recovery and recycle from DNT spent acid

                   stripper.

              10.  Methanol distillation system put on reboilers.

              11.  Methanol still bottoms recycled as cooling tower makeup.

              12,  Ammonium nitrate solutions recovery and recycle.

              13.  Totally enclosed ammonium nitrate prill loading and

                   bulk conveyor system,

              14.  NPK gypsum pond removal for agricultural use.

              15.  Cooling towers.

-------
                                   25
     Load  reductions  reported  by  the  Company in their  1971  report to




 the FDPC from  source  control werei






                    Flow                          1.31  mgd




                    COD                      50,300  Ibs/day




                    Total Nitrogen           12,800  Ibs/day




                    Heat                      3.5 mm BTU/hr






     Because of difficulties in treating nitrogen waste  and  in  particular




a mixture of nitrogen waste from  several different  processes, this area




merits careful study for possible further development.   Air  Products and




Chemicals reported, in the 1971 report to the FDPC,  that 99.706  percent




of the total nitrogen handled  is contained as product  and 0.294  percent




is lost to the effluent.(6)

-------
                                  26
                         STUDY FINDINGS






GENERAL DISCU SSION




     Sampling began on March 7, 1972, and continued for five consecutive




days.  Twenty-four hour composite samples were collected with automatic




sampling equipment provided by the company at seven in-plant stations.




Station locations are described in Table I and plotted in Figure 2.




Automatic samplers and flow measuring equipment are permanently installed




at these stations since the company routinely samples these locations.




Equal aliquots of samples were collected at roughly 30-minute intervals




and pumped into a 2-1/2 gallon jug packed in ice.  The sample collected at




Station AP-4 was an exception since it was collected by a dripping faucet




via a tube attached to the glass jug.  This arrangement was necessary




because the sample was taken from a force main, and conventional automatic




samplers could not be used.  All samples were divided at the point of




collection for duplicate analysis by the company.  Samples collected at




Stations AP-1 and AP-4 were also split with the FDPC.  Two grab samples




of well water were collected.  The study plan listing the sample stations




and analysis for each sample is included in Appendix E.  Table II contains




the tabulated data obtained from this study.




     Weather conditions were variable during the study, typical of spring-




time.  Temperatures averaged 4°F below normal with a maximum temperature




of 72°F and a minimum of 40°F.  Rainfall recorded at the Pensacola air-




port totaled 0.58 inches and occurred on March 8.  The company reported




0.55 inches of rain on March 7 and 0.07 inches on March 8 at the plant

-------
                                27
                            Table I

                SAMPLING STATIONS AND LOCATIONS
                AIR PRODUCTS AND CHEMICALS, INC,


AP-1        Effluent from Alpha Pond

AP-2        Effluent from Bravo Pond

AP-3        Effluent from Charlie Pond

AP-4        Open ditch in Area "B" between the plant and ponds

AP-5        East ditch flowing from Area "A" to the ponds

AP-6        Ditch flowing from Amines Plant to George Pond

AP-7        Effluent from Fox Trot Pond

AP-8        Well water supply
site.  Waste flows during the first part of the study were still being

influenced by runoff from a 1.85 inch rain which occurred on March  2.

The flood control gates installed above the weirs on Bravo and Charlie

Ponds provide a considerable amount of extra storage (up to approximately

1.5 feet head) which slowly drains out with the normal plant effluent.

This condition makes the flow measuring devices installed at the discharge

of Bravo and Charlie Ponds inoperative.  It also creates a non-steady state

condition which makes it difficult to relate influent to effluent for the

three pond system.

     Chemical analysis of samples split with the company were in good

agreement with the exception of the nitrogen series, particularly the

N02-N03 concentrations.  Subsequent resampling of AP-1 through AP-7

-------
                      TABLE II


AVERAGE ANALYTICAL DATA FOK INPLANT WASTE  STHEAMS
      •»•• AIR PHOOUCTS AND CHEMICALS  INC.  ••*«
                 MARCH 7-12.  1972


STATION
AP-1
AP-2
AP-3
AP-4
AP-S
AP-6
AP-7
Ap-a
.

AP-l
AP-J
AP-3
AP-4
AP-5
AP-6
AP-7
AP-B
•••**•••*


STATION
AP-1
»P-<4
AP-5
AP-6
AP-7


AP-1
AP-4
AP-S
AP-b
AP-7
FLOW
RATE
GPM
1372
_.
—
119
88
225
124
~
RESDUE
DISS-105
C MG/L
755
463
340
5906
769
769
399
21
'*••••»*•*'
FLOW
RATE
GPM
1273
130
88
225
124
RESOUE
DISS-105
C L6/D
11829
9606
35<*0
1993
444
T Acorn
CAC03
MG/L
36
32
10
115
0
0
0
14
RESOUE
VOL FLT
MG/L
366
131
49
954
100
100
83
9
»*«>4B**>
T ACUITY
CAC03
LH/0
549
152
0
0
0
BESDUE
VOL FLT
LB/0
6173.0 1
1307.6
315.0
265.4
122.6
T ALK
CAC03
MG/L
23
30
43
73
2553
1664
121
9
N03-N
TOTAL
MG/L
B3.4
67.4
9.8
556.0
9.2
1.0
6.3
1.8
«»*•**»»«
T ALK
CAC03
LB/0
351
127
2094
4435
179
N03-N
TOTAL
LB/0
280.32
845.90
a. 23
2.70
9.22
BOD
5 OAY
MG/L
11.4
24.5
41.0
107.3
57.0
_-
134.5
"
WATER
TEMP
CENT
14.5
16.0
17.4
—
23.1
46.9
20.2
— —
>***•**«»*
BOO
5 DAY
LB/0
184.6
146.7
62.7

233.4







COO
HI LEV
MG/L
52
49
27
4B7
119
1974
51
6
PH
SU
6.6
6.7
7.1
5.8
11.9
11.4
9,6
5.8
»*«»**«•*»•»»
COO
HI LEV
LB/D
800
823
126
5476
77







T ORG C
C
MG/L
13.4
12.0
7.4
161.8
64.8
662.4
11.8
"










»«*»•»»•«»••
T ORG C
C
L8/D
206.9
266.2
53.5
1823. 2
17,8







PrtOS-T
P-WET
MG/L
2.64
3.69
1.95
5.14
1.00
0.05
12.09












PHOS-T
P-WET
LB/D
38.71
7.22
1.03
0.12
17.92







RESDUE
V NFLT
MG/L
12
9
B
22
15
— -
9












BESDUE
V NFJ.T
LB/D
190
38
18
—
13







HESOUE «ESDUE BESOUE
T NFLT TOTAL T VOL
MG/L MG/L MG/L
17 772 398
9 470 135
8 348 56
56 5962 971
44 3672 398
14 783 100
19 314 90
21 7











HESDUE RESDUE RESCUE
T NFLT TOTAL T VOL
LH/0 LB/D LH/D
260 12089 636Z.93
91 9698 0362.93
52 3592 332.59
37 2030 265.36
22 466 131.94







T KJEL
N
MG/L
86.2
67.9
13.7
231.1
26.4
269.7
9.1
1.8











T KJEL
N
LH/D
1326.23
132t>.22
36.54
734.78
14.09







NH3-N
TOTAL
MG/L
84.9
65.9
11.0
230.6
23.8
139.6
6.2
1.6











NH3-N
TOTAL
LB/0
1305
1305
33
380
9







                                                                                                        10
                                                                                                        00

-------
                                  29
produced comparable results between the two laboratories and also compared

very closely with company results on the original surveys  EPA and company

sample collection and laboratory procedures were thoroughly reviewed and

no explanation for the wide variation could be determined.  Since the

original company results agreed very closely with both EPA and company

results from a sample collected later at each of the sampling locations,

it was decided to use company results for the nitrogen series.


COMPARISON OF 1969 AND 1972 DATA (PLANT EFFLUENT)
     The 1969 Federal report identified Air Products and Chemicals, Inc.

(formerly Escambia Chemicals) as a major contributor of nitrogen and

phosphorus wastes discharged into Escambia Bay.  A comparative tabulation

of data is shown below:


                                                            Total  Total
      Flow   BOD5      TOC     TKN-N    NH3-N   N02-N03-N     N    Phos-P
      mgd   Ibs/day  Ibs/day  Ibs/day  Ibs/day   lbs/d_ay_   Ibs/day Ibs/day

1969  5.2

1972  1.84
290
ife
-105

194
207
+13
Biochemical
3,
1,
-1,
,270
,327
,943
Oxygen
2,
1,
-
280
306
974
2
1
-1
,380
,281
,099
5
2
-3
,650
,608
,042
320
if
-281
Demand
     Considerable variation (2.0 to 23 mg/1) was noted in the BOD5 dis-

charged into Escambia Bay.  The final daily discharge contained 185 pounds

of BODij — 168 pounds greater than the conference recommended limit.  At

the present rate of discharge (1.84 MGD), the BOD5 effluent concentration

would have to be reduced to 1.1 mg/1 to meet the 17 pounds per day limit

recommended.  A seven-day average effluent BOD5 concentration of  10 to 15

-------
                                  30
mg/1 (155 to 230 pounds per day), with a maximum daily fluctuation of 125




percent, is a much more reasonable, achievable limit.




     Except for the amines plant discharge, BOD5 concentrations generated




by plant processes are rather minor.  Concentrations of BOD 5 in excess of




800 mg/1 were noted in the amines plant discharge into George Pond, the




percolation pond.  The discharge from Fox Trot Pond, which receives the




PVC plant waste was the largest single direct contributor of BODc (233




Ibs/day) to the pond system.  The urea and ammonia nitrate operation




(Station AP-4) was the second largest contributor with an average of 147




pounds of BOD 5 discharged daily into Echo Pond.






                           Phosphorus




     Significant reductions have been achieved in phosphorus removal




(88 percent).  The total phosphorus load has been reduced from 320 pounds




per day to 39 pounds per day.  Reductions have resulted primarily from




closing the NPK operation.  Pretreatment of the PVC waste with magnesium




oxide before discharge to Fox Trot Pond also reduced the effluent phos-




phorus load.  At the time of the recent study, the average phosphorus




load from all plant processes was 26 pounds per day.






                            Nitrogen




     Nitrogen reductions for the same period have been less dramatic than




phosphorus reductions.  A complicating factor in comparing the two sets




of data is the waste being retained in Echo Pond.  Since this pond was




recently (November 1971) placed into operation and is not yet full, the

-------
                                  31
plant effluent measured at Station AP-1 did not reflect this waste.,  Waste




from the two ponds and the collection ditch which receives waste from the




urea and ammonium nitrate operations plus groundwater seepage is diverted




to Echo Pond.  During the survey, the flow into Echo Pond averaged 0.173




MGD with the following loads in pounds per day:  BOD - 138; TOC - 266;




TKN - 295; NH3 - 359; N03-N - 1,154, and total phosphorus - 7.2.  It is




impossible to accurately predict the effect of the Echo Pond discharge




on the total plant effluent.  However, for comparison purposes, it is




assumed that 60 percent of the nitrogen entering Echo Pond will be removed,




resulting in an adjusted plant effluent of 3,214 pounds per day or a




43 percent reduction from the 1969 load.  This reduction is attributed




to closing of the NPK and methanol plant, additional source controls, and




treatment in the biological pond system.






                             Metals




     Analyses were made for specific metals by atomic adsorption on




samples collected from Stations AP-1, AP-4, and AP-8.  In addition, a metals




scan was performed by the spark source mass spectrometer on samples from




Stations AP-1 and AP-4.  The plant effluent (Station AP-1) contained




1.2 pounds per day of chromium, 1.5 pounds per day of zinc, and 3 pounds




per day of manganese as well as many other metals in low concentrations.




The contribution of metals from Air Products and Chemicals, Inc., to




Escambia Bay is very small.





                        Organic Compounds




     An organic scan was performed on samples collected from Stations

-------
                                   32
AP-1, AP-4, and AP-8 (Table III).  Results indicated low concentrations

(.03 mg/1) of organic compounds from the DNT operation in the plant

effluent.
Station No.
   AP-1
   AP-4
   AP-8
            Table III

     ORGANIC COMPOUND DATA


    Compound
Concentration
   (mg/1)
0-Nitrotoluene                               0.012
2,6-Dinitrotoluene                           0.02
15 other unidentified compounds were
   observed in the 0.01-1.0 mg/1 range.

0-Nitrotoluene                               7.8
P-Nitrotoluene                               8.8
2,4-Dinitrotoluene                           190
2,6-Dinitrotoluene                           150
3,4-Dinitrotoluene                            40
10 other organic compounds were also
   detected in the 0.01-5.0 mg/1 range.

No compounds greater than 0.01 mg/1 detected.
     Concentrations of organic compounds in the plant effluent were low;

however, the waste from Station AP-4 is presently being retained on site

in Echo Pond.  When this pond starts overflowing later this year, an

increase in the concentration of organics from the DNT operation may be

observed.  Although fish toxicity for dinitrotoluene is unknown, concen-

trations of 0-Nitrotoluene in the range of 18 to 40 mg/1 were observed

to be lethal for minnows.(7)

     Nitro compounds are subject to biochemical oxidation in dilute con-

centrations; however, higher concentrations retard biological growth.

-------
                                   33
Trinitrotoluene (TNT) has a deleterious effect at concentrations greater




than 1.0 mg/l.(5)  The biological toxicity limits for nitrotoluene and




dinitrotoluene are not known, but it is likely that toxicity will occur




at relatively low concentrations.  This may severely limit the treat-




ability of this waste in conventional biological ponds requiring much




greater retention times.





                          Groundwater




     Groundwater seepage was a major factor in the total nitrogen load




discharged from the plant.  Studies performed by the company have shown




that nitrogen concentrations in the upper zones of the groundwater in




Area "B" ranged up to 1,000 mg/1 of total nitrogen.  This situation  is




caused by poor waste control practices in the past.  Source controls,




waste treatment, better materials handling, and awareness of groundwater




contamination problems by company personnel should greatly reduce this




problem in the future.  The U. S. Geological Survey reports that the




average rate of movement of groundwater in the Fensacola area  is approx-




imately 100 feet per year. (8)  The distance from Area "B" to  the upper




dikes of the ponds is approximately 1,000 feet, and the approximate




distance to the final pond effluent is 3,000 feet.  It is theorized  that




water in the upper ground water zone should move considerably  faster than




100 feet per year.  Contributions of nitrogen from the ground  water  will




likely be present for several years.




     The groundwater problem becomes apparent when a flow or materials




balance is attempted on the treatment system.  Data, reported  by the

-------
                                   34
company to the FDPC, tabulated in Table IV and plotted  in Figure  3,




illustrate this problem.  These data show approximately a 60 percent




increase in flow and 240 percent increase in total nitrogen through the




three pond system.  Results of the recent EPA survey indicated a  28




percent increase in flow (1.3 vs 1.83 mgd) and a 4,000  percent increase




in nitrogen (66 vs 2,603 pounds per day of total nitrogen)  (Figure 4).




These figures do not include the 694 pounds per day discharged into the




percolation pond or the 1,515 pounds per day retained in Echo Pond.




The 1 MGD of once-through cooling water from the DNT operation was not




sampled; however, company spokesman stated that no additives or con-




taminants were added through the process.






              DNT, Urea, and Ammonia Nitrate Waste




     During the survey, the pump in the interceptor ditch ran continuously




while the pump in Delta Pond ran intermittently.  The two composite




samples collected at Station AP-4 on March 9-10 and 11-12 represent only




waste from the ditch since the Delta Pond pump did not  operate during this




period.  Data indicate a considerable difference in the character of the




two wastes (Appendix C).  Waste from Delta Pond, which  receives the DNT




waste, is a concentrated dark brown liquid containing approximately




15,000 mg/1 of total residue and 1,500 mg/1 of COD.  Most of the nitrogen




discharged from this operation is in the form of nitrate nitrogen with




concentrations of about 1,000 mg/1.  The high solids concentration is due




primarily to the soda ash wash operation used to purify the dinitrotoluene




and to caustic neutralization of the wastes.  A 380 rag/1 dinitrotoluene




concentration was observed in the combined flow at Station AP-4.

-------
                                                    TABLE  IV

                       MONTHLY SUMMARY OF AIR PRODUCTS & CHEMICALS.  INC.
                                        JUNE 1970 THROUGH  FEBRUARY  1972
MONTORING DATA


FLOW *
COD
NITROGEN:
AMMONIA
ORGANIC
MTRATE
NITROGEN TOTAL
PHOPHORUS TOTAL
POTASSIUM



FLOW •
coo
NITROGEN:
AMMONIA
OPOAMIC
NITRATE
NITROGEN TOTAL
PHOPHORUS TOTAL
POTASSIUM
(1970)
JUNE
INF EFF
4.13 6.39
7763 4357

841 3755
286 894
1658 3304
2735 7909
134 676
160 993
(1971)
JANUARY
" INF EFF
3.73 5.26
6683 3960

478 4314
317 243
982 4139
1797 8597
128 604
31 833
JULY
INF EFF
3.55 5.97
3714 2563

571 2886
204 • 329
465 2329
1232 5490
50 478
61 466

FEBRUARY
INF EFF
3.87 5.74
7508 4586

396 3960
153 208
811 4905
1360 8817
112 348
42 366
AUGUST
INF
4.07
8113

583
340
532
1399
113
71

EFF
6.87
2422

3063
318
2764
6064
581
609

MARCH
INF
3.03
7471

894
283
1380
2558
55
174
EFF
4.42
2341

4066
217
4646
9010
402
733
SEPTEMBER
INF
3.82
9553

487
456
513
1457
124
72

EFF
6.07
1944

2406
273
1985
4665
492
485

APRIL
INF
2.28
7811

1936
466
1203
3604
249
122
EFF
3.69
3175

3393
319
2981
6687
359
537
OCTOBER
INF
4.50
11843

639
253
964
1B58
343
75

MAY
INF
2.27
7992

1463
109
2415
4649
290
167
EFF
7.94
3847

4963
362
3561
8886
581
678

NOVEMBER
INF
3.98
14511

576
508
238
1323
95
36

ENF
7.68
4486

5003
167
3509
8684
409
693

JUNE
EFF
3.77
2323

3039
233
2744
5893
441
404
INF
2.32
. 18336

247
213
1128
1588
8
19
ENF
3.78
2649

1742
282
1094
3109
185
195
DECEMBER
INF ENF
3.49 6.98
5107 3721

540 4465
224 374
546 3682
1611 8521
65 957
36 408

JULY
INF ENF
2.24 3.91
5529 2184

287 1691
168 343
871 961
1323 3005
36 168
27 205
(19731


PLOW •
coo
NITROGENS
AMMONIA
ORGANIC
NITRATE
NITROGEN TOTAL
PHOPHORUS TOTAL
POTASSIUM
AUGUST
INF EFF
2.39 4.05
8191 1956

684 1956
146 221
833 1659
1521 3S36
23 138
59 246
SEPTEMBER
INF EFF
2.29 5.06
7033 2177

877 2352
318 297
777 2408
1959 5049
__ __
•*• — — .
OCTOBER
INF
i 	
__

__
__
_.»
—
__
•~
EFF
2.43
1144

1248
90
1290
2628
__
~—
NOVEMBER
INF
__
--

—
_-
_.
--
--
*~
EFF
1.58
967

1174
46
1161
2362
—
™ —
DECEMBER
INF
—
--

— -
—
--
—
—

EFF
1.75
938

1209
45
1231
2484
--

JANUARY
INF
—
—

—
--
—
~ —
—

ENF
1.89
903

1493
64
1211
2764
—

FEBRUARY
INF ENF
~ 2.05
858

— 1469
21
-- 1272
— 2759
__

                                                                                                                             u>
                                                                                                                             On
 •  FLO* REPORTED AS MGO»  ALL OTHER VALUES ARE LBS/OAY
(DATA THROUGH AUGUST 1971 WAS TAKEN FROM COMPANY REPORT
OATEO OCTOBER 1« 1971 TO THE FOPC. LATER DATA WAS
OBTAINED FROM COMPANY PREPARED REPORTS TO THE FOPC.)

-------
                                                           FIGURE 3

                                            TOTAL NITROGEN (LBS/ DAY) LOADS

                                             AIR  PRODUCTS AND CHEMICALS INC.
   10,000
I
"V
CD
GO
o
cc
     5,000
           ~~ \
                                                                    -ALPHA, BRAVO 8 CHARLIE

                                                                    PONDS PLACED IN OPERATION
                                                              ECHO POND PLACED IN OPERATION
                                    TOTAL PLANT DISCHARGE TO BAY
                                                                                                               U>
                                             -WASTE STREAM INFLUENT


                                              TO TREATMENT SYSTEM
              \	

               NOTE: Doto Obtained from Company Reports to the FDPC and Included in Appendix C
                                                                                            ALLOWABLE LOAD - 477 LBS / DAY
                                                                                                        I     I      I
8     9     10    II





     1970
                                             12
23456


        MONTHS

                      1971
                                                                                            8     9    10     II     12     I
                                                                                                                          1972

-------
                            37
                                                      FIGURE  4
                  NITROGEN  WASTE LOADS
            AIR PRODUCTS AND CHEMICALS INC.
             1,000 r
 3,000
 2,500
 Z.OOO
•,
• i
  I.5OO
  1,000
  500
 Escambio Bay
                                                             355
                                           Total Nitrogen - N

                                           NOj-N
                                           NH3-N
                                     U.S. ENVIRONMENTAL PROTECTION AGENCY
                                               REGION 1C
                                       ESCAMBIA BAY STUDY
                                            MARCH, 1972
                                      SURVEILLANCE AND ANALYSIS DIVISION
                                     ATHENS                GEORGIA

-------
                                  38
Considering the time that each pump was. in operation, a concentration of




700 to 800 mg/1 of dinitrotoluene in Delta Pond was estimated..  The inter-




ceptor ditch receives approximately 500 gallons per hour of condensate




waste and barometric condenser condensate from the urea and ammonia




nitrate operations with the remainder of the flow being surface runoff




and ground water infiltration.  This waste had an approximate ammonia and




nitrate concentration of 350 mg/1 and 385 mg/1, respectively, with an




average flow of 84 gpm.  Since the combined flow from Delta Pond and the




interceptor ditch represents 67 percent of the total nitrogen load from




process discharges, the company has isolated this waste for additional




treatment in Echo Pond.






                          Ammonia Waste




     The ammonia waste flows through the concrete lined East Ditch to




Charlie Pond (Station AP-5).  This is a highly alkaline waste (2,550 mg/1




as CaC03) with an average pH of 11.9.  The average total nitrogen concen-




tration is relatively low at 26 mg/1 with 23 mg/1 as ammonia.  This waste




stream contains 2 percent of the total nitrogen waste loading from process




operations.






                          Amines Waste




     Waste from the amines plant is clear with an average temperature of




47°C and pH of 11.4 (Station AP-6).  Average concentrations are:




alkalinity - 1,664 mg/1 as CaCC^; BOD5 - greater than 808 mg/1 (company




reported one value of 2,463 mg/1); COD - 2,368 mg/1; TOC - 750 mg/1;

-------
                                   39
and total nitrogen as N - 694 mg/1.  This source accounts for 30 percent




of the total nitrogen discharged from plant processes and is probably




a large contributor of nitrogen seepage into the lower pond system.




The 1969 report by Black, Crow and Eidsness, Inc., states that "The




data tend to indicate that the  Amines plants effluent, discharged into




the percolation area with an estimated nitrogen loading of 872 pounds




per day, appears at the outfall."






                      PVC and Nitric Acid Waste
     The discharge from Fox Trot Pond (Station AP-7) is slightly alkaline




with an average pH of 8.8.  The waste is well settled and presents no




significant nitrogen load to the lower pond system.  Nitrogen contributions




from this source represent one percent of the total from process operations,




This stream is the only direct process discharge of phosphorus to Charlie




Pond.  The load is 18 pounds per day.






                             Well Water




     Air Products is presently using three 150-foot deep wells to supply




the plant's water requirements.  One well, located in Plant Area "B",




supplies the cooling water requirements of this area.  The other two wells




are located east of the Area "A" (Figure 2).  Two grab samples were col-




lected from these wells during the survey (Station AP-8).  Because of




discrepancies in the nitrogen data, two more grab samples were collected




in April.  All Parameters analyzed, other than nitrogen, were in good




agreement with well samples taken from the same general area.  Nitrogen

-------
                                   40
concentrations were higher than concentrations in samples taken outside

the plant area.

     Analysis of well water samples taken at American Cyanamid's Santa

Rosa Plant, located only a few miles away, showed nitrogen concentrations

less than 1 mg/1 of total nitrogen.  By contrast, these results indicate

that nitrogen waste from the Air Products Plant have spread through a

relatively large area of the ground water (Table V).



                               Table V

                      WELL WATER NITROGEN DATA


                   Well No. 1      Well No.  3       Well No. 5
                   4/13   4/14     4/13   4/14      4/13   4/14

     TKN (mg/1)     4.2    3.7      1.1    1.0       0.6    0.0

     NH3-N (mg/1)   4.2    3.7      1.1    1.0       0.4    0.0

     N03-N (mg/1)   0.7    0.6      5.1    3.6       0.2    0.2

     Total N (mg/1) 4.9    4.3      6.2    4.6       0.8    0.2

-------
                                   41
            TREATMENT ALTERNATIVES AND SUGGESTIONS






     The major objective in waste treatment considerations at Air Products




is further reduction in the nitrogen discharge.  Nitrogen in the plant




effluent originates from two principal sources — the total discharge from




the individual plant processes and contaminated groundwater seepage into




the treatment system.  During the recent survey, 46 pounds per day of




nitrogen were discharged into the three-pond system, and 2,610 pounds




were discharged from the ponds.  However, process wastes being stored in




Echo Pond accounted for the unusually low nitrogen load (46 Ibs/day) dis-




charged into the ponds.  During the study, water was being released from




stors ,e in the three-pond system; however, the major portion of this




difference must be attributed to groundwater seepage.  It is reasonable




to assume that roughly 700 pounds per day comes directly from the per-




colation pond and the remaining 1,800 pounds per day comes from contami-




nated groundwater and seepage from the Delta Pond.




     Because of geophysical characteristics of the plant area, such as the




porous surface sand zone, the shallow water table, and existing problems




encountered with contaminated groundwater, all waste transmission and




treatment facilities should be as leakproof as possible.  The following




are suggestions for improving waste handling procedures:




          •  Eliminate George (percolation) Pond.




          •  Reline Delta Pond.




          •  Line future ponds with clay or other impervious materials.

-------
          •  Use unlined Alpha,  Bravo, and Charlie Ponds only for polishing




             pretreated wastes.,




          •  Transport all waste (especially from Area "A")  in water-tight




             pipes or channels.




          •  Re-evaluate in-plant handling procedures to prevent any nitrogen




             spillage of intermediate or finished products.






TREATMENT METHODS




     The following alternative methods of waste treatment were considered:




          •  Ion exchange




          •  Spray irrigation




          •  Deep well disposal




          •  Ammonia stripping




          •  Biological ponds






                            Ion Exchange




     Initially, the ion exchange process designed by Chemical Separations




Corporation for Farmers Chemical Association, Inc., in Chattanooga,




Tennessee, appeared to provide a possible solution for the problems at Air




Products.  After discussions with Chemical Separations and Air Products




personnel, it was learned that methods have been studied to adapt this




system.  However, the high concentrations of salts, other than ammonium




nitrate, would produce a waste stream unusable for product recovery.




Disposal of this unusable waste stream  (estimated by Air Products to be




28,800 gpd) would present a problem of  the same magnitude as disposing




of the original waste.

-------
                                43
                          Sgray Irrigation




     Spray irrigation provides some possibilities; however, it needs




additional study.   It is doubtful that this method could be used for




disposal of the total plant effluent, including ground water seepage to




the ponds, because of the large volume (2 to 4 MGD); however, it could




possibly be used for ultimate disposal of the process waste.






                         Deep Well Disposal




     The company has determined that deep well disposal is not suitable




for disposal of the total effluent because of the large waste volume and




the 90 percent FDPC reduction requirement.  This method could, however,




be used for disposal after treatment of the process waste.






                         Ammonia Stripping




     Stripping appears feasible for removal of the 355 pounds per day of




ammonia in the amines plant waste.  The existing high pH and temperature




make this waste suitable without pre-conditioning for stripping.  Steam




stripping or distillation with ammonia recovery may be necessary in order




to prevent air pollution problems.  Any of these methods should remove




virtually all of the ammonia which accounts for roughly 50 percent of the




total nitrogen in this stream.  Ammonia stripping of the other large




source of ammonia waste (DNT and the interceptor ditch) would require pre-




conditioning since the pH is 5.8.  If ammonia stripping is used, it would




probably be advantageous to separate these two wastes streams since the




major portion of the ammonia comes from the interceptor ditch.  The pH




of the waste in the interceptor ditch averaged 4.4.

-------
                                  44
                        Biological Treatment




     Air Products has placed in operation a system of biological ponds




for treatment of the total plant waste.  Because of the problems encoun-




tered with previously-discussed treatment methods, biological treatment




combined with ammonia stripping appears to be the more promising.  For




example, Dr. William Oswald has stated that "Input-output balances show




disappearance of up to 80 percent of the total input nitrogen in a single




faculative pond treating domestic waste."(9)  Laboratory results from the




report prepared by Associated Water and Air Resources Engineers, Inc.




for Farmers Chemicals Association, Inc., indicated that 80 to 85 percent




of the nitrate nitrogen could be removed in an anaerobic unit in 10 to 35




days providing the proper nutrient balance was maintained for bacterial




growth.(10)




     The organic nitro compounds from  the DNT operation will probably




retard biological growth in Echo Pond.  If given  sufficient time, these




compounds will break down; however, a  sizable increase in ponding




capacity may be required.

-------
                                 45
                            REFERENCES
 1.  Proceedings of  the . .Confer ence_ jln  tjieMatter  of  Pollution  of  Inter-
     state Waters of the Escambia  River  Basin  (Alabama-Florida) and  the
     Interstate Portions of  the  Escamb.ia B_as_in_Wi_l:hin tine  State of Florida,
     USDI, FWPCA, Gulf Breeze, Florida,  January 21-22,  1970.

 2.  proceedings of  the Second Session of the  Conference  in  the Matter oj^
     Pollution of Interstate Waters of the Escambia  River  Basin  (Alabama-
     Florida) and the Interstate Portions of. j:jie_  Escambia  Basin Within
     the State of Florida, EPA,  Pensacola, Florida,  February 23-24,  1971.

 3.  Case No. IW-226-69, Order No. 356,  "Orders for  Corrective Action,"
     the Florida Department  of Pollution Control, December 15, 1971.

 4.  Preliminary Report to^ Escambia Chemical Corporation  on Wastewater
     Treatment, Black, Crow  and  Eidsness, Inc., Engineers, Gainesville,
     Florida, October 1969.

 5.  Report to Escambia Chemical Corporation on Wastewater Studies,  Black,
     Crow and Eidsness, Inc., Engineers, Gainesville, Florida, June  1970.

 6.  Report to the Florida Department  of Pollution Control on  Final  Phase
     of Wastewater Studies,  Air  Products and Chemicals, Inc.,  October,1971.

 7.  Water Quality Criteria, California  Water  Resources Control Board,
     Publ. 3-A, 2nd  Ed., 1963.

 8.  Water Resources of Escambia and Santa Rosa Counties,  Florida. U. S.
     Geological Survey, Report of  Investigation No.  40, Tallahassee,
     Florida, 1965.

 9.  Oswald, William J., "Status of Oxidation  Pond Processes."  Presented
     at the conference, Southeast Water  Laboratory,  Athens, Georgia,
     "Advances in Treatment  of Domestic  Wastes."  October  18,  1972.

10.  Laboratory Investigations into the  Removal and  Control of High Con-
     centrations of Nitrogenous Compounds^ Associated Water and Air
     Resources Engineers, Inc., Nashville, Tennessee, May  1970.

-------
APPENDICES

-------
            APPENDIX A
ACKNOWLEDGMENT & PROJECT PERSONNEL

-------
                           APPENDIX A






ACKNOWLEDGMENT




     Appreciation is expressed to Mr. Phil Doherty and  his  staff  at




the FDPC Gulf Breeze Laboratory for their able assistance in conducting




this study by providing laboratory space and field personnel for




assisting in sample collection.  Company reports provided by the  FDPC




were very useful in obtaining background information on previous




pollution abatement activities.  Company assistance and cooperation




were outstanding.  Mr. Roy Duggan and his crew made available the




Company's automatic sampling and flow measuring equipment for this




survey.






EPA FIELD PERSONNEL




     Rod Davis - Field Chemist




     Charles Sweatt - Sanitary Engineer




     Tom Bennett - Chemist




     Pat Lawless - Chemist






FDPC FIELD PERSONNEL




     Ron Breeding - Technician

-------
      APPENDIX B
ANALYTICAL METHODOLOGY

-------
                                  B-l






                       ANALYTICAL METHODS





     All chemical analysis will be done in accordance with those methods




listed in Methods for Chemical Analysis of Water and Wastes 1971.






 1.  Acidity - Listed on page 5, uses a NaOH titration to an end-




     point of pH 8.3.  Results are reported as mg/1 CaC03.




 2.  Alkalinity - Listed in Standard Methods for the Examination of




     Water and Wastewater. 13th Edition, p. 52, Method 102 (1971).




 3.  Biochemical Oxygen Demand (3005) - Standard Methods for the




     Examination of Water and Wastewater, 13th Edition, p. 489, Method




     219 (1971).




 4.  Chemical Oxygen Demand - Standard Methods for the Examination of




     Water and Wastewater, 13th Edition, p. 495, Method 220 (1971).




 5.  Cyanide - EPA Methods for Chemical Analysis _o_f_Wa_ter_and_Wastes




     1971, p. 42.




 6.  Metals - EPA Methods for Chemical Analysis of Water and Wastes 1971,




     p. 83.




 7.  Nitrogen-Ammonia - (Automated Method) EPA Methods for^ Chemical




     Analysis of Water and Wastes 1971, p. 141.




 8.  Nitrogen - Total Kjeldahl - (Automated Phenolate Method)




     EPA Methods of Chemical Analysis of Water and Wastes 1971, p. 157.




 9.  Nitrogen, Nitrate-Nitrite - (Automated Cadmium Reduction Method)




     EPA Methods for Chemical Analysis of Water and Wastes^ 1971, p. 175.




10.  Oil and Grease - Hexane Extraction - EPA Methods of Chemical Analysis




     ofChemical Analysis of Water and Wastes 1971, p. 217.




11.  Total Organic Carbon - Carbonaceous Analyzer - EPA Methods of




     Chemical Analysis of Water and Wastes 1971, p. 221.

-------
                                 B-2
12.  Phenolics - (Automated 4-AAP Method with. Distillation)




     Standard Methods for the Examination of Water and Wastewater,




     13th Edition,  pp. 501-510, Method 222 through 222E (1971),




     Modified for Automation.




13.  Phosphorus - (Automated Single Reagent Method) Ej?AJMethpds  of




     Chemical Analysis of Water and Wastes 1971, p. 246.




14.  Solids, Filterable (Dissolved) - EPA Methods of Chemical Analysis




     of Water and Wastes 1971, p. 275.




15.  Solids, Total - EPA Methods of Chemical Analysis of Water and




     Wastes 1971, p. 280.




16.  Solids, Non-Filterable  (Suspended) - By difference between total




     and filterable solids.




17.  Solids, Volatile - EPA Methods for Chemical Analysis of Water and




     Wastes 1971, p. 282.

-------
                                 B-3
                 PROCEDURE FOR ORGANIC ANALYSES






     Samples AP-1, AP-4, and AP-8 were approximately neutral pH




when received.  They were extracted with 15% methylene chloride




in hexane, made strongly basic with KOH and re-extracted with 15%




methylene chloride in hexane, acidified with sulfuric acid and




extracted for the third time with methylene chloride.  The samples




were dried by passing through glass wool and then concentrated to




1 ml in a Kuderna-Danish concentrator.  The acid extract was esterified




using diazomethane.  All extracts were injected into a gas chromatograph




equipped with a flame ionization detector.  The column was glass




6'x2.5 mm I.D. packed with 3% SE-30 on Chromosorb W, HP.  The oven




was programmed from 75°-240° @ 10°/min.  We attempted to identify any




peaks detected using the Finnigan GC/MS Model 1015 system.  The com-




pounds listed were confirmed by injecting a known standard into the




GC/MS.  Quantitation was done on the gas chromatograph.




     All samples were extracted in duplicate and the concentrations




found represent the average of the duplicates.  Concentrations found




should be considered minimum concentrations as the percent recovery




of each compound from water is unknown.

-------
                                       METHODS OF CHEMICAL ANALYSES
 PARAMETER

 Acidity

 Alkalinity

 Ammonia

 Biochemical  Oxygen
     Demand

 Chemical Oxygen Demand

 Chromium, To tal

 Cobalt

 Copper

 Dissolved Solids


 Cyanides

Manganese

Nitrate-Nitrite

Oil and Grease

PH

Phenols
                Water and Wastewater

METHOD                                REFERENCE

Volumetric, NaOH Titration                1

    11       H2S04 Titration               1

Automated Phenolate Method                2

Winkler D.O., 5-day                      1,2


Acid-Dichromate Oxidation                 2

Atomic Absorption                        1,2

Atomic Absorption                        1,2

Atomic Absorption                        1,2

Difference Between Total and
Suspended Solids

Pyridine-Pyrazolone                    1,2,4

Atomic Absorption                        1,2

Copper-Cadmium Reduction, Automated       2

Solvent Extraction                        1

Electrometric                             1

4-Aminoantipyrine                         1
MODIFICATION
Potentiometric Endpoint
None

Azide Modification Formula "C"
Dilution Water w/Sewage Sed.

None

HC1-HN03 Digestion

HC1-HN03 Digestion

HC1-HN03 Digestion
CO
Distillation Cleanup

HC1-HN03 Digestion

None

None

None

Distillation, Automated
Colorimetric Analysis

-------
                                                   (Con't)
PARAMETER

Phosphorus

Suspended Solids

Thiocyanates

Total Kjeldahl Nitrogen

Total Organic Carbon

Total Solids

Turbidity

Volatile Suspended
    Solids

Volatile Total Solids

Zinc

Titanium

Vanadium
METHOD
Ascorbic Acid Method

Gravimetric

Ferric Nitrate Complex

Automated Phenolate Method

Carbon Analyzer

Gravimetric, 105°C

Hellige Turbidimeter

Gravimetric, 550°C


Gravimetric, 550°C

Atomic Absorption

Atomic Absorption

Atomic Absorption
REFERENCE      MODIFICATION

    2          Automated, Manual Digestion

    1          None

    3

    2          None

    2          None

    1          None

    2          None

    1          None


    1          None

   1,2         HC1-HN03 Digestion

   1,2         HC1-HN03 Digestion

   1,2         HC1-HN03 Digestion
                                                                                     t
                                                                                     Ui
References

1.  Standard Methods for Examination of Water and Wastewater, 13th Edition, 1971.
2."  EPA Manual of Methods for Chemical Analyses of Water and Wastes, 1971.
3!  Colorimetric Methods of Analysis, Vol. 11A, 1959, Snell and Snell.
4.  ASTM Book of Standards, Part 23, 1971.

-------
     APPENDIX C
WASTE SAMPLING DATA

-------
ST03ET RETRIEVAL DATE  72/06/10
AIR PRODUCTS AND CHEMICALS INC.
ESCAMBIA RIVER STUDY
641050
ESCAMBIA R. AIR
12 FLORIDA
SOUTHEAST
ESCAMBIA RIVER
1113SOOO
00058 00435
DATE TIME DEPTH FLOW T flCDITY
FROM OF RATE CAC03
TO OAY FEET GPM MG/L
72/03/07 09 27
CPIT1-G 1382.00 28
72/03/08 08 00
72/03/08 09 30
CP(T)-G 1382.00 38
72/03/09 09 30
72/03/09 09 35
CP(TI-G 1417.00 39
72/03/10 09 30
72/03/10 09 35
CPU1-G 1208.00 46
72/03/11 09 15
72/03/11 09 45
CP(T)-G 972.00 27
72/03/12 09 15
00500 00505
DATE TIME DEPTH RESIDUE RESIDUE
FROM OF TOTAL TOT VOL
TO OAY FEET MG/L MG/L
72/03/07 09 27
14 45
72/03/07 09 27
CP
-------
       RETRIEVAL DATE  72/06/10
                                                                  6*1053
                 AP-02
r-i13-47
AIR PRODUCTS AND CHEMICALS INC.
ESCAMBIA RIVER STUDY
ESCAM8IA R. AIR PRODUCTS 4 CHEH.
12 FLORIDA
SOUTHEAST
ESCAMBIA RIVER
1113SOOO             2444220

DATE TIME DEPTH
FROM OF
TO DAY FEET
72/03/07 09 SO
CP(T»-G
73/03/08 08 05
72/03/08 09 45
CP-6
72/03/08 08 05
72/03/09 09 45
72/03/08 09 45
CPIH-G
72/03/09 09 45
72/03/10 09 45
72/03/09 09 45
CP
-------
STORE! RETRIEVAL DATE 72/06/10
                                                                   641054
                                                                                  AP-03
F-U3-48
AIR PRODUCTS AND CHEMICALS INC.
ESCAMBIA RIVER STUDY
                                                                  ESCAMBIA R. AIR PRODUCTS & CHEM.
                                                                  12 FLORIDA
                                                                  SOUTHEAST
                                                                  ESCAMBIA RIVER
                                                                  1113SOOO             244<>220
00058 00435 00410
DATE TIME DEPTH FLOW T ACDITY T ALK
FROM OF RATE CAC03 CAC03
TO DAY FEET GPM MG/L MG/L
72/03/07 10 13
CP(T)-G 8 52
72/03/00 10 05
72/03/OB 10 08
CP-G 252 72 13.900
72/03/08 10 05
72/03/08 10 08
CP(T)-G 260 66 13.600
72/03/09 09 15
09 50
72/03/10 10 00
72/03/09 10 00
CP(T)-G 250 36 lb.000
72/03/10 10 00
72/03/11 10 05
72/03/10 10 05
CP«T)-G 234 60 13.900
72/03/11 10 05
72/03/12 10 15
72/03/11 10 15
CP(T)-G 245 44 12.200
72/03/12 10 15
00310
BOD
5 DAY
MG/L

72. OK


68. OK


41.0


65. OK


68. OK

00610
NH3-N
TOTAL
MG/L




11.600


11.100




11.600



10.500


10.000

00340
COO
HI LEVEL
MG/L

17


24


26


35


32

00515
RESIDUE
DISS-105
C MG/L




241


254




244



226


233

00660
T ORG C
C
MG/L

6.0


6.0


8.0


8.0


9.0

00520
RESIDUE
VOL FLT
MG/L




64


61




36



53


33

00665
PHOS-T
P-WET
MG/L

1.65


1.70


2.30


1.69


2.00

00620
N03-N
TOTAL
MG/L




8.60


9.70




11.30



10.40


9.10

00535
RESIDUE
VOL NFLT
MG/L

8


5


5K


7


11

00010
WATER
TEMP
CENT
17.0
18.5
18.0






15.5
17.0



17.5



18.5


00530
RESIDUE
TOT NFLT
MG/L

9


6


6


a


12

00403
LAB
PH
SU




7.2


7.3




7.1



6.9


7.2

                                                                                                                               o
                                                                                                                                I
                                                                                                                               OJ

-------
STORET RETRIEVAL DATE  72/06/10
                                                                   641056
                 AP-04
F-113-49
AIR PRODUCTS AND CHEMICALS INC.
ESCAMBIA RIVER STUDY
ESCAMBIA R. AIR PRODUCTS S. CHEM.
12 FLORIDA
SOUTHEAST
ESCAMBIA RIVER
11135000             2^44220

DATE TIME DEPTH
FKOM OF
TO DAY FEET
72/03/07 10 35
CP(T)-G
72/03/08 10 20
72/03/08 10 25
CP(Tt-G
72/03/09 10 10
72/03/09 10 20
CP(T)-G
72/03/10 10 15
72/03/10 10 20
CP(T)-G
72/03/11 10 20
72/03/11 10 30
CP(T)-G
72/03/12 10 20

DATE TIME DEPTH
FROM OF
TO DAY FEET
72/03/07 10 35
CP(T)-G
72/03/08 10 20
72/03/08 10 25
CP t T ) -G
72/03/09 10 10
72/03/09 10 20
CP
-------
STORET RETRIEVAL DATE 73/06/10
AIR PRODUCTS AND CHEMICALS INC.
ESCAMBIA RIVER STUDY
                                                                  641058
                                                                                  AP-05
                                                                 ESCAM8IA R. AIR PRODUCTS
                                                                 12 FLORIDA
                                                                 SOUTHEAST
                                                                 ESCAMBIA RIVER
                                                                 1H3SOOO             2444220
                                                                                               F-l13-50


                                                                                            CHEM.
DATE
FROM
TO
72/03/07
CPUI-G
72/03/08
72/03/08
CPIT)-G
72/03/09
72/03/09
CPCTJ-C
72/03/10
72/03/10
CP(T)-G
72/03/11
72/03/11
CPtT)-G
72/03/12

DATE
FROM
TO
72/03/07

72/03/08
72/03/07
CPtT)-G
72/03/08
72/03/09
72/03/08
CP
-------
STORET RETRIEVAL DATE 72/06/10
AIR PRODUCTS AND CHEMICALS INC.
ESCAMBIA RIVER STUDY
                                                                   641060
                  AP-06
                               F-113-S1
ESCAMBIA R. AIR PRODUCTS «. CHEM.
12 FLORIDA
SOUTHEAST
ESCAMBIA RIVER
1113SOOO
00058 00435
DATE TIME DEPTH FLOW T ACDITY
FROM OF RATE CAC03
TO DAY FEET GPM MG/L
72/03/07 11 12
CP«T)-G 245.00 0
72/03/08 11 25
72/03/08 11 33
CP(T)-G 240.00 0
72/03/09 11 20
72/03/09 11 25
CP(T)-G 217.00 0
72/03/10 11 05
72/03/10 11 10
CP-G 282 30
72/03/10 11 05
72/03/11 11 00
72/03/10 11 10
CPlTJ-G 1430 103
72/03/H 11 00
72/03/12 IQ SO
72/03/11 11 10
CP(T)-G 1660 201
72/03/12 10 50
00410
T ALK
CAC03
MG/L

810


1810


1600


2200


1900

0062S
TOT KJEL
N
MG/L



255.600



356.500



369.200



249.500



117.500

00310
BOD
5 DAY
MG/L

830. OL


810. OL


820. OL


740. OL


840. OL

00610
NH3-N
TOTAL
MG/L



127.500



179.100



214.600



117.500



59.300

00340 00680
COD T ORG C
HI LEVEL C
MG/L MG/L

3210 800.0


2570 1000.0


1960 600.0


1730 600.0


402 312.0

00515 00520
RESIDUE RESIDUE
DISS-10S VOL FLT
C MG/L MG/L



251 80



261 84



272 30



1415 103



1648 201

00665 00535
PHOS-T RESIDUE
P-WET VOL NFLT
MG/L MG/L

0.01 5K


0.03 5K


0.0 IK 5K


0.02 5K


0.13 SK

00620 00010
N03-N WATER
TOTAL TEMP
MG/L CENT
44.0
40.0

1.50

43.0

1.10

44.5

0.80

56.0

0.70

S4.0

0.80

00530
RESIDUE
TOT NFLT
MG/L

22


9


10


15


12

00403
LAB
PH
SU



11.2



11. 0



U.I



11.7



11.9

                                                                                                                            o
                                                                                                                             I

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ST.ORE.1
                OME  12/06/10
AIR PRODUCTS AND CHEMICALS INC.
ESCAMBIA RIVER STUDY
                                                                                   AP-07
                                                                                                F-113-5Z
                                                                  ESCAMBIA R. AIR PRODUCTS  &  CHEM.
                                                                  12 FLORIDA
                                                                  SOUTHEAST
                                                                  ESCAHBIA RIVER
                                                                  11135000              2444220

DATE TIME DEPTH
FROM OF
TO DAY FEET
72/03/07 11 50
72/03/08 11 50
CP
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STORET RETRIEVAL DATE 72/06/10
                                                                   641064
                 AP-08
F-113-53
AIR PRODUCTS AND CHEMICALS INC.
ESCAMBIA RIVER STUDY
CSCAMBIA R. AIR PRODUCTS & CHEM.
12 FLORIDA
SOUTHEAST
ESCAMBIA RIVER
11135000             2444220

DATE TIME DEPTH
FROM OF
TO DAY FEET
72/03/09 11 45
72/03/10 11 25
00058
FLOW
RATE
GPM


00435
T ACDITY
CAC03
MG/L
14
14
00410
T ALK
CAC03
MG/L
6
12
00310
BOD
5 DAY
MG/L


00310
BOD
5 DAY
MG/L


00340
COD
HI LEVEL
MG/L
5
6
00680
T ORG C
C
MG/L
l.OK
l.OK
                                                                                   00665      00535     00530
                                                                                  PHOS-T    RESIDUE   RESIDUE
                                                                                  P-WET     VOL  NFLT  TOT NFLT
                                                                                   MG/L       MG/L      MG/L
                                                                                     0.01K
                                                                                     0.01K
                                5K
                                5K
            5K
            5K
o
I
oo
                       00500
   DATE   TIME DEPTH RESIDUE
   FROM    OF         TOTAL
    TO    DAY  FEET    MG/L

 72/03/09 11 45
 72/03/10 11 25
 72/04/13
 72/04/14
0
E


23
18


00505
RESIDUE
TOT VOL
MG/L
5
9


00625
TOT KJEL
N
MG/L


2.000
1.600
00610
NH3-N
TOTAL
MG/L


1.900
1.600
00515
RESIDUE
DISS-105
C MG/L
23
18


00520
RESIDUE
VOL FLT
MG/L
5K
9


00620
N03-N
TOTAL
MG/L


00010
WATER
TEMP
CENT


00403
LAB
PH
SU
5.5
6.0
                   2.00
                   1.50

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                                    C-9

                      ELEMENTS IN WASTEWATER STREAMS
                     AIR PRODUCTS AND CHEMICALS,  INC.
                              ESGAMBIA PLANT
                             MARCH 6-12,  1972
Silver
Rhodium
Molybdenum
Zirconium
Strontium
Rubidium
Bromine
Selenium
Arsenic
Zinc
Copper
Nickel
Cobalt
Iron
Manganese
Chromium
Vanadium
Titanium
Calcium
Potassium
Chlorine
Sulfur
Phosphorus
Silicon
 Elements detected by spark source-mass spectrometer scan:

                    Final Pond Effluent (Station AP-1)
 Lead
 Cerium
 Lanthanum
 Barium
 Cesium
 Tin
 Lead
 Terbium
 Gadolinium
 Neodymium
 Praseodymium
 Cerium
 Lanthanum
 Borow
                     Echo Pond  Influent  (Station AP-4)
Barium
Cesium
Antimony
Ruthenium
Molybdenum
Niobium
Strontium
Fluoride
Rubidium
Bromine
Selenium
Arsenic
Gallium
Zinc
Copper
Magnesium
Nickel
Cobalt
Iron
Manganese
Chromium
Vanadium
Calcium
Potassium
Chlorine
Sulfur
Phosphorus
Silicon
Aluminum
Sodium
                                                    Aluminum
                                                    Magnesium
                                                    Sodium
                                                    Fluorine
                                                    Boron
Metal concentrations determined by atomic asorption methods:

     Station AP-1              Station AP-4              Station AP-8
Parameter   Cone  (M*g/l)   Parameter   Gone (u-g/1)   Parameter   Cone (iig/1)
Chromium
Cobalt
Copper
Manganese
Titanium
Vanadium
Zinc
  80
<100
 <50
 200
<500
<500
 100
Chromium
Cobalt
Copper
Manganese
Titanium
Vanadium
Zinc
2,150
 <100
  <50
1,050
 <500
 <500
  420
Chromium
Cobalt
Copper
Manganese
Titanium
Vanadium
Zinc
 <50
<100
 <50
 <50
<500
<500

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  APPENDIX D
CORRESPONDENCE

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                                               INC.
                            ESCAMBIA PLANT
                   P.O. Box 467. Pensacolo. Florida 325O2
                            April 24,  1972
Mr. Charles Sweatt
Environmental Protection Agency
Surveillance & Analysis Division
College Station Road
Athens, Ga. 30601

       Re:     Escambia Plant, Air Products and Chemicals, Inc. -
               Source-Control Program	

Dear Mr. Sweatt:

       Per your request of April 19,  1972 at the Escambia Plant meeting
for reviewing the wastewater survey,  I have  worked up the following list
of source-control projects.  These projects are organized as before and
after 19VO,  according to your request.

               Escambia Plant Source-Control Program

Timetable	Project	

Pre-1970      1.      Cooling towers.
               2.      Catalytic combustor on HNO3 plant.
               3.      Ammonia recovery from copper liquor system.
               4.      Aqua ammonia  stripper and vaporizer system.
               5.      Methanol by-product disposal (to boilers).
               6.      Compressor building oil recovery and disposal.
               7.      Amines by-product disposal (flare).
               8.      Nitric acid oil recovery and disposal.
               9.      Methyl methacrylate effluent pH control.
             10.      Methyl methacrylate effluent stabilization basin.
             11.      Ammonium nitrate  remelt and reclaim system.

After Jan.     1.      NPK recycle pond.
   1970         2.      Recovery of weak aqua ammonia from percolation.
               3.      HNO3 concentrator recycle and  reclaim system.
               4.      HNO3 plant start-up weak acid recovery and recycle.
               5.      NPK plant shutdown.
               6.      DNT organics recovery and recycle.
               7.      Ammonia condensate stripper.

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Mr. Charles Sweatt
                    -2-
April 24,  1972
Timetable

After Jan.
   1970
  (cont'd)
                        Project
 8.      Ammonia cascade cooler on cooling tower recycle.
 9.      Nitric acid recovery and recycle from DNT spent
         acid stripper.
10.      Methanol distillation system put on reboilers,
11.      Methanol still bottoms recycled as cooling tower
         makeup.
12.      Ammonium nitrate solutions recovery and recycle.
13.      Totally enclosed ammonium nitrate prill loading
         and bulk conveyor system.
14.      NPK gyp pond removal for agricultural use.
15.      Cooling towers.
The above list of projects details source-control projects and not treatment
projects (i.e., bi ological ponds, chemical treatment, percolation,  etc.).
Should you require additional information,  please let us know.

                                    Very truly yours,

                                    AIR PRODUCTS AND CHEMICALS, INC.
                                    Escambia Plant
RLD/as
                                    R.
                                    Environmental Engineer

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