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HomeMy WebLinkAboutNC0024970_Wasteload Allocation_19900227NPDES DOCUMENT SCANNING; COVER SHEET NC0024970 McAlpine Creek WWTP NPDES Permit: Document Type: Permit Issuance Wasteload Allocation Authorization to Construct (AtC) Permit Modification Complete File - Historical Engineering Alternatives (EAA) Correspondence Owner Name Change Meeting Notes Instream Assessment (67b) Speculative Limits Environmental Assessment (EA) Document Date: February 27, 1990 This document is printed Girt reuse paper - igriore arty. content Girt the re'erse wide e CAree.4._ PERMIT NO.: NCOO,24q 70 FACILITY NAME: aft)C'.v of it e 6ii5�7 Oral/ vmrf 1-Hodcafioh Facility Status: Permit Status: Major '7 Pipe No.: _ 100 Minor Design Capacity: J() Domestic (% of Flow): 9/ Industrial (% of Flow): 9 /,1 Comments: NPDES WASTE LOAD ALLOCATION aseed rneefl cv%CNw) PLOTTED RECEIVING STREAM: MAO//Ie Cato Class: C Sub -Basin: Q3D$34 Reference USGS Quad: 5/55LC County: freak/Ai/3 Regional Office: /n,Qo Requested by: Prepared by: Reviewed by: 42 1 , (please attach) Date: Date: 0./07,12 /90 Date: z(2 777b Modeler Date Rec. •/ee ula, Drainage Area (mi2 ) 92. c/ Avg. Streamflow (cfs): /39 7Q10 (cfs) /, 3 Winter 7Q10 (cfs) 5, 30Q2 (cfs) 7 V Toxicity Limits: IWC cj$ % Acute hronic Instream MonitorincT: ormhophopne us 043, TZN NOX Tip/ Parameters I • , 0 Jot-abo,ie oul-ra a Upstream Y Locationcz ts Plakoo4 (s) i-k +o„AQ c Q a SC 21.01 Downstream Y Location tij(c qs', r' ofSr, iced cSummet: 3w/wK Por Qo temp c0/X1 PH • -Ixl4xed eo' Fecal. Homily"*. al! a c.5 Effluent 1 Characteristics Summer Winter N!•(3 (mca) 2 4 a) Cm6CI.P) Le t:-S (I / A) 3o ,30 f. (a. (t/ico, i) 20o zoo pH ou) 19-5' (9-9 Cadm1om 061-6 a• b Chitynaim /,ajaJ 5 1 Alic&.1 (i 0 ) Led (Ai?) 24 Comments: kfe fal,' d Toy charge due, i uplatal 7Q(O. Fecal Co fiivm i d recl )1c51L ma4) i 1a J 4d. RECEIVED IliteSPN Of ENVADNIAWAl MANI�EYEM� FEB13 1990 WASTELOAD ALLOCATiO APPROVAL Facility Name: NPDES No.: Type of Waste: Status: Receiving Stream: Classification: Subbasin: County: Regional Office: Requestor: Date of Request: Quad: Fecal usiwAmom Charlotte - Mcalpine NC0024970 91% domestic Existing McAlpine C 030834 Meckle MRO Harfis - 12/19/88 G15SE Creek urg orig. Request No.:5016 Update FORM Creek WWTP Drainage Summer Winter Average RECOMMENDED EFFLUENT LIMITS Cadmium (ug/1) : Chromium (ug/ 1) : Nickel (ug/1) : Lead (ug/l) : Cyanide (ug/1) : Coliform (/100m1): Toxicity Testing Req.: Dly Max 2.0 51 90 26 5.1 clog O C5o) c5o) (a5) (.5) art: 7Q 0: 7Q10: flow: 30Q2: FE0 2 a�yu PERMITS & E,:GIN€[ iN 92.4 1.3 5.8 139 7.4 Mo Avg d r h 200 0000) Chronic/Ceriodaphnia/Quarterly at Upstream (Y/N): Y Downstream (Y/N): Y MONITORING Location: Location: COMMENTS 98% This approval form shows changes in draft permit based on updated 7Q10 information. Fecal coliform change based on new standard. Recommended by: Reviewed by Tech Support Supervisor: Regional Supervisor: Permits & Engineering: RETURN TO TECHNICAL SERVICES BY: 6 Date: a/5/4'a Date: Date: Date: MBAR 10 1990 Qin VW zdq, • 10/89 Facility Name lof'e - � IDtn� C k rp Permit # W1/CbO,2gQ 7d CHRONIC TOXICITY ThS PING REQUIREMENT (QRTRLY) The effluent discharge shall at no time exhibit chronic toxicity in any two consecutive toxicity tests, using test procedures outlined in: 1.) The North Carolina Ceriodaphnia chronic effluent bioassay procedure (North Carolina Chronic Bioassay Procedure - Revised *September 1989) or subsequent versions. The effluent concentration at which there may be no observable inhibition of reproduction or significant mortality is qg 9b (defined as treatment two in the North Carolina procedure document). The permit holder shall perform quartcr/y monitoring using this procedure to establish compliance with the permit condition. The first test will be performed after thirty days from issuance of this permit during the months of Mai Jun Sep, Dec. . Effluent sampling for this testing shall be performed at the WPDES permitted final effluent discharge below all treatment processes. All toxicity testing results required as part of this permit condition will be entered on the Effluent Discharge Monitoring Form (MR-1) for the month in which it was performed, using the parameter code TGP3B. Additionally, DEM Form AT-1 (original) is to be sent to the following address: Attention: Environmental Sciences Branch North Carolina Division of Environmental Management P.O. Box 27687 Raleigh, N.C. 27611 Test data shall be complete and accurate and include all supporting chemical/physical measurements performed in association with the toxicity tests, as well as all dose/response data. Total residual chlorine of the effluent toxicity sample must be measured and reported if chlorine is employed for disinfection of the waste stream. Should any single quarterly monitoring indicate a failure to meet specified limits, then monthly monitoring will begin immediately until such time that a single test is passed. Upon passing, this monthly test requirement will revert to quarterly in the months specified above. Should any test data from this monitoring requirement or tests performed by the North Carolina Division of Environmental Management indicate potential impacts to the receiving stream, this permit may be re -opened and modified to include alternate monitoring requirements or limits. NOTE: Failure to achieve test conditions as specified in the cited document, such as minimum control organism survival and appropriate environmental controls, shall constitute an invalid test and will require immediate retesting(within 30 days of initial monitoring event). Failure to submit suitable test results will constitute noncompliance with monitoring requirements. 7Q10 /,3 cfs Permited Flow '40 MGD Recommended by: IWC% Q7.9 Basin & Sub -basin Cr63y Receiving Stream fricRtptne Cry f C . ,stocu,(11_ County llksc'VenDate 215P0 **Chronic "Toxicity (Ceriodaphnia) P/F at qg %, /t?arJun &p Da , See Part , Condition . gv13ed Lad 04 Maine e Get. '70/0 ebi7.4 . TOXICS REVIEW Facility: Charlotte - McAlpine Creek WWTP NPDES Permit No.: NC0024970 Status (E, P, or M): E Permitted Flow: 40.00 mgd Actual Average Flow: 27.30 mgd Subbasin: 030834 Receiving Stream: McAlpine Creek Stream Classification: C 7Q10: 1.30 as INC: 97.9 % 02/03/90 ver 3.0 =s.=aa=..=._.._..====o P R E T R E A T M E N T EFFLUENT DATA _== I ACTUAL ACTUAL PERMITTED I I or Ind. + Ind. + I ACTUAL ACTUAL I Default ACTUAL Domestic PERMITTED Domestic 1 Maximum Weekly Standard Acute I Removal Allowable Domestic Industrial Total Industrial Total 1 Daily Average Pollutant AL Criteria I Eff. Load Load Load Load Load Load 1 Value Value (ug/1) (ug/1) I t (#/d) (#/d) (#/d) (#/d) (#/d) (#/d) 1 (ug/1) (ug/1) Cadmium S 2.0 1.79 I 92% 5.87 1.99 0.30 2.29 1 12.00 Chromium S 50.0 984 I 76% 48.92 1.99 19.87 21.86 1 79.00 Copper AL 7.0 9.2 I 82% 9.13 5.78 26.70 32.48 1 120.00 Nickel S 88.0 789 I 32% 30.39 5.98 0.95 6.93 1 293.00 Lead S 25.0 34 I 81% 30.90 9.76 8.74 18.50 1 252.00 Zinc AL 50.0 65 I 77% 51.05 29.89 20.36 50.25 1 360.00 Cyanide S 5.0 22.0 I 59% 2.86 3.99 0.21 4.20 Mercury S 0.012 2.4 I 86% 0.02 0.00 0.00 0.00 Silver AL 0.060 1.2 I 94% 0.23 1.00 0.33 1.33 1 30.00 Selenium S S.0 20 I 80% 5.87 Arsenic S 50.0 360 I 80% 58.71 Phenols S NA I I ___-___==_M=_==_====i__.r_..... A N A L Y S IS RE S U L T S....= I I Monitor / Limit / Special Condition* I Allowable Allowable' Predicted Predicted I I Effluent Effluent I on ACTUAL on PERMIT.' Actual Actual I INSTREAM MONITORING Bkg I Conc. Conc. 1 Influent Influent 1 ACTUAL PERMITTED Daily Max. Wk. Avg. I Based on Based on Pollutant Conc. I CHRONIC ACUTE I Data Data 1 Influent Influent Effluent Effluent I Actual Actual (ug/1) I (ug/1) (ug/1) I (ug/1) (ug/1) 1 Loading Loading Data Data I Daily Max. Wk. Avg. I I I I Cadmium S I 2.042 1.828 I 0.804 0.000 I Limit Limit I Monitor Chromium S 4.50 I 50.954 1004.865 I 23.029 0.000 1 Limit Limit I Monitor Copper AL 8.40 I 6.971 9.237 1 25.663 0.000 1 Monitor Special I Monitor Nickel S 1 89.845 805.544 1 20.685 0.000 1 Limit Limit I Monitor Lead S I 25.524 34.488 1 15.429 0.000 1 Limit Limit I Monitor Zinc AL 8.80 I 50.864 66.219 1 50.731 0.000 1 Monitor Special I Monitor Cyanide S 1 5.105 22.461 1 7.559 0.000 1 Limit I Mercury S 1 0.012 2.450 1 0.000 0.000 1 I Silver AL 1 0.061 1.256 1 0.350 0.000 1 Monitor Special I Monitor Selenium S 1 5.105 20.419 1 0.000 0.000 1 I Arsenic S 1 51.048 367.548 1 0.000 0.000 1 I Phenols S 1 0.000 0.000 1 0.000 0.000 1 I Attention: Mr. Trevor Clements January 3, 1990 Page 2 I.C. A Reasonable Compliance Schedule Should Be Provided for New Permit Requirements: CMUD informed DEM that federal Clean Water Act ("CWA"), 33 U.S.C. § 1251 et seq., requirements allow for a reasonable compliance schedule to be included in a permit if a new water -quality permit requirement is imposed upon a permittee (even if the underlying water quality standard has been in existence for over three years), and that EPA Office of General Counsel opinions, EPA regulations and preamble reflect such interpretation. DEM indicated that it would confirm such interpretation with EPA. DEM's November 22, 1989 letter reflected that DEM is still investigating the possibility -of including a compliance schedule in the permit. When DEM agrees to a compliance schedule, CMUD will provide information to DEM regarding appropriate dates. If DEM does not agree to a compliance schedule, 1his i, u +S J� remains unresolved. cJ II. EFFLUENT LIMITATIONS II.A. BOD, 5-Day Effluent Limitation And Monitoring f Requirement Should Be Changed to CBOD: CMUD proposes to use the CBODu test set forth in the enclosed draft section of the new edition of Standard Methods. This would provide for twenty - day CBODu testing of four different daily composites. Also enclosed are articles that discuss the effect of nitrogen -inhibiting substances that may be added to the CBOD test. We propose to use TCMP as an inhibitor, however, we plan to also measure ammonia, nitrate and nitrite at 5-day intervals over the testing period. II.B. Metal Limits: DEM has agreed to review the 7Q10 flow statistics at the gage upstream of the plant and to change the nickel limit to 88 ug/1 to reflect the change to the state water quality standard. DEM's November 22, 1989 letter, however, does not address the discussions pertaining to the analytical detection limit for cyanide. Inasmuch as the 5 ug/1 cyanide limit is below current analytical detection, DEM indicated at the meeting that it will consider providing permit language which allows CMID to use split samples and, if one sample result is below detection and the other split sample result is above detection, for purposes of compliance the sample indicating cyanide below detection would be used (as long as appropriate testing protocols were followed). DEM response to this issue is necessary. iNa 4 CAL OXYGEN DEMAND Lice the 5 day test, the ultimate biochemical oxygen demand (UBOD) determination is an empirical test in which standardized laboratory procedures are used to determine the total oxygen requirements of wastewaters, effluents, and river or estuarine waters. The test estimates the oxygen required for the total biochemical degradation of organic material (ultimate carb- onaceous biochemical demand CBOD). The test may also measure the oxygen necessary to totally oxidize reduced forms of nitrogen (ultimate nitrogenous oxygen demand NOD) . ULTIMATE BIOCHEMICAL OXYGEN DEMAND 1. General Discussion The ultimate oxygen demand values and appropriate kinetic descriptions are needed in water quality modeling studies. There are three separate modeling needs: (a) ultimate BOD to 5- day BOD ratios which are used for relating stream assimilative capacity to - •ES )ar sPDESYpermits, (b) definition of river, estuary, or lake deoxygenation kinetics, which is necessary for initial estimation of model parameters, and (c) instream ultimate CBOD values used for model calibration. The method consists of placing a sample of single dilution in full, air -tight bottles and incubating under specified -2- conditions for a period of time that will vary depending upon wastewater, effluent, river or estuary quality (1). Dissolved oxygen (DO) is measured (with probes) initially and at different times for the duration of the test. This DO time series is used to compute the ultimate BOD by an appropriate statistical analysis. The bottle size and incubation time are of ner7pssity flex- ible to accommodate individual sample characteristics and analytical laboratory limitations. Incubation temperature, however, is specified at 20C. Most effluents and some naturally occurring surface waters will contain more oxygen demanding materials than the amount of DO available in air-saturatr-T3 water. Therefore, it is necessary to dilute the sample or to monitor the DO in the bottles frequently to ensure that low DO or anaerobic conditions do not occur. When DO concentrations approach low levels (2 to 3 mg/1), the sample is reaerated to elevate DO concentrations to values approaching but not ex 111.411111 saturation. Because bacterial growth requires nutrients such as nitr- ogen, phosphorus, and trace metals, these may be added to the dilution water (if used), which is buffered to ensure that pH of the incubated sample remains in a range suitable for bacterial growth. However, if the BDD test is being used to estimate the rate of oxidation of naturally occurring surface waters, then the addition of nutrients and seed would likely accelerate the - 3- decay rate and produce misleading results. However, if only the UHOD is desired, it may be advantageous to add supplemental nutrients which could acrPlerate the decay rate and reduce the duration of the test. When nutrients are used in a sample, they should also be used in the dilution water blank so that their effect on DO is accounted for in the analysis of the time series. The extent of oxidation of nitrogenous mounds during the long term incubation period depends upon the presence of micro- organisms capable of oxidizing these forms. Such organisms may not be in waste waters in numbers to oxidize significant quantities of reduced nitrogen forms. This situation, however, may be reversed in naturally occurring surface waters. Some analysts have obtained erratic results when utilizing nitrification inhibitors in long tern E<JD tests (2) . Three pec:rtC separate effects have been noted: (a) the inhibitor may also 0 inhibit carbonaceous HOD des -ay, (b) the effect of the inhibitor n t) ( P CL pt - diminishPr7 unpredictably with time requiring ring the subsequent addition of fresh inhibitor, and (c) the inhibitor can become a ._A� r lr� Nf S t S r--'6 o OJ� substrate upon repeat addition and increase the BCD. However, S�.e r' others have not observed these effects and have suesfully a. used 2-chlora-6-(trichloromethyl) pyridine (8) ��e method included here specifies that nitrogen inhibitors not be used unless prior experimental evidence on the particular i -4- sample in question suggests otherwise. It is recommended that the nitrogen specie (NO3-N) (Section 418) be monitored with time to compute the oxygen equivalency of the nitrification reaction. When these values are subtracted frum the DO time series, the CBOD time series can be constructed (3). 2. Sampling and Storage Samples for BOD analysis may degrade significantly during storage between collection and analysis, resulting in low BOD values. Minimize reduction of BOD by analyzing the sample promptly or by cooling it to near -freezing temperature (4C) during storage. However, even at low temperatures, keep the holding time to a minimum. Warm the chilled samples to 20 C before analysis; some storage time can be used to accomplish this conveniently. (a) Grab samples: If analysis is initiated within 2 hours of collection, cold storage is unnPc ssary. If analysis is not started within 2 hours of sample collection, keep sample at or below 4 C from the time of collection. Begin analysis within 6 hours of collection; when this is not possible, because the sampling site is di stant fLuln the laboratory, store at or below 4 C and report length and temperature of storage with the results. In no case start analysis more than 24 hours after grab sample collection. When samples are to be used for -5- regulatory purposes make every effort to deliver samples for analysis within 6 hours of collection. (b) Composite samples: Keep samples at or below 4C during ccanpositing. Limit ccanpositing period to 24 hours. Use the same criteria as for storage or grab samples, starting the measurement of holding time frcan the end of the c meriting period. State storage time and conditions as part of the results. 3. Apparatus (a) Incubation bottles: Option 1 2 liter (or larger) capacity glass bottles with ground glass stoppers are desirable. Glass serum bottles in sizes 4 to 10 liters are commercially available at a reasonable cost. Note that a bottle is also necessary for the sample reservoir. Reservoir top 2 liter bottles are also available froaa Wheaton Scientific as a custoaa order. Excellent results, however, have been obtained with non - ground glass bottles using non -biodegradable plastic caps used as a plug insert. The plugs should not be reused when removed from the bottle at the conclusion of a test since discoloration occurs with continued use over long term. The plugs should be replaced every 7 to 14 days. Do not use rubber stoppers since they may exert an oxygen demand. Clean bottles with a laboratory grade detergent and acid wash with dilute (3M) hydrochloric acid, and rinse thoroughly before use. It is also -6- advisable to cover the top of bottles with paper after rinsing to prevent dust from collecting in the bottle. As a precaution against drawing air into the sample bottle during incubation, a water seal is needed. One can be constructed by making a water tight dam around the stopper (or plug) and refilling with the reservoir water as necessary. The dam should be covered with clean aluminum foil to retard evaporation. If the 2 liter Wheaton reservoir top BOD bottles are used, fill the reservoir with *sample and cover with a polyethylene cap prior to incubation. A clean magbar should be placed in each bottle to thoroughly mix the contents prior to DO measurement and removal of sample for nitogen series measuremnts. Each magbar should be dedicated to a sample and not removed until the test is conpleted. A self stirring electrode ccaald also be used. Option 2 300 ml BOD bottles can also be used if larger bottles are not readily available or incubation space is limited. In this option, six (6) or more, depending upon the length of the study, 300 ml HOD bottles are filled with the raw or diluted samples as necessary. Make-up water (for spillage during DO measurenmt and nitrate analysis) is taken from the sixth bottle as necessary. If more make-up is needed, the fifth bottle is sacrificed, etc. When reaeration is needed, all of the sample is poured into a clean vessel, aerated, and the bottles refilled. -7- In either option, if dilution is required, a separate blank sample should be run to properly account for the BOD of the dilution water and added nutrients. (b) Reservoir bottles: A one gallon or larger glass bottle is required. A secure screw plastic cap or non -rubber plug is acceptable. For Option 2, the 300 ml BOD bottles are used as necessary. (c) An incubator or water bath: thermostatically con- trolled at 20C ± 1C. Exclude all light to prevent the possi- bility of photosynthetic production of DO. Scarce analysts have used cleaned glass marbles in lieu of makeup water. Marbles can be a source of carbon if not properly cleaned. If marbles are used to displace water following sample removal for nitrate analysis, the magbar should be omitted. Mixing can be accomplished by inverting the bottles, or by using a self stirring electrode. This technique is applicable to either bottle option selected. 4. Procedure - River Water Samples (a) Fill large BDD bottles (or alternate 300 ml BOD bottles) with sample at 20C. No nutrients, seed, or nitri- fication inhibitor should be used if the in -bottle decay rates are desired to estimate in -stream rates. The sample should not be diluted unless it is ]clown to have a high ultimate BOD (>20 mg/1) . Larger incubation bottles should be used if possible to minimize surface effects. (b) Bacterial seed is not necessary and should not be used. (c) Measure the DO in each bottle, stopper, and make an air tight seal. Incubation should be at 20 C in the dark. (d) Measure the DO in each bottle at intervals of at least 3 to 5 days over a period of at least 30 days (nuninaua of 6 to 8 readings). The DO concentration should not fall below 2 to 3 mg/l. The sample lost by the cap and DO probe displacement can oP be replaced by adding 1 to 2 ml jat sample from the reservoir bottle or by adding 1 or 2 clean glass marbles. (e) When the DO concentration in the bottle approaches 2 to 3 mg/1, reaeration is necessary. Pour a small mount of sample into a clean vessel and reaerate the remaining sample directly in the bottle. Vigorous shaking or bubbling purified air (medical grade) into the bottle can be used for reaeration. The bottle is then refilled and the DO concentration of the bottle measured. This concentration becomes the initial DO for the next measurement. -9- (f) Nitrate plus nitrite nitrogen (NO3 N + NO2-N) (Section 418, 419) analyses are performed on day 0,5,10,15,20,30, and at the end of the test. If the ultimate dew occurs at a time significantly greater than 30 days, additional analyses at 30 day intervals may be appropriate. The sample for these analyses is prepared by removing 10-20 ml from the bottle. Displace the volume created by removing sample by adding sample from the reservoir bottle or by adding a few clean glass marbles. The sample is preserved with sulfuric acid to pH <2 until the analysis can be performed. If the purpose of the test is only to assess the ultimate BOD, the analyst has the option of measuring the nitrate nitrogen concentration at day 0 and on the last day of the test. In this case, kinetic rate estimates are not useful since the progression of the nitrification reaction is not followed. (g) Oxygen consumption during each time interval are calculated. Appropriate corrections are made for the nitrogenous oxygen demand. Most analysts use 4.57 times the nitrate nitrogen produced. (h) When a dilution water blank is used, the DO uptake of the blank should be subtracted frro n the total DO consumed. High quality distilled, deionized water without nutrients will typically constirme a maximum of 1 mg/1 DO in a 30 to 90 day period. -10- (i) When the weekly CO consumption drops below 1 to 2 % of the total accumulative consumption, calculate the ultimate BOD using a non -linear regression method. This procedure will require that the analyst monitor the results of each test to determine if this criterion is met. 5. Procedure - Waste Water Treatment Plant Samples. • (a) High quality distilled-,deionized water is used for dilution water. No nitrification inhibitors should be used if bottle decay rates are desired. If the analyst judges that seed and nutrients are necessary, then the same amounts of each should be added to the dilution water blank. (b) The sample should not be overly diluted. As a general rule -of -thumb, the ultimate BOD of the diluted sample should be in at least the 20 to 30 mg/1 range. Dilution at this level will require 2 or 3 sample reaerations during the incubation period. (c) Use 2 L or larger BOD bottles (or alternate 300 ml BOD bottles) for each dilution to be used. Add the desired volume of sample to each bottle and fill with dilution water to displace all air. -11- (d) Fill a BM bottle with dilution water to serve as a dilution water blank. The blank should be treated the same as all samples. (e) Measure the DO in each bottle, stopper, and make an air tight seal. Incubation should be at 20 C in the dark. (f) Measure the DO in each bottle at intervals .of at least 3 to 5 days over a period of at least 60 days (minimum of 10 to 15 readings). The DO concentration should not fall balm 2 to 3 mg/l. The sample lost by the cap and DO probe displacement can be replaced by adding 1 to 2 ml of sample from the reservoir bottle or by adding 1 to 2 clean glass marbles. (g) When the CO concentration in the bottle approaches 2 to 3 mg/1, reaeration is necessary. Pour a small amount of sample into a clean vessel and reaerate the remaining sample directly in the bottle. Vigorous shaking or bubbling purified air (medical grade) into the bottle can be used for reaeration. The bottle is then refilled and the CO concentration of the bottle measured. This concentration becomes the initial CO for the next measurement. (h) When a dilution water blank is used, the DO uptake of this sample should be subtracted from the total DO consumed. High quality distilled, deionized water without nutrients will • -12- v typically consume a maximum of 1 mg/1 DO in a 30 to 90 day period. (i) Nitrate plus nitrite nitrogen (NO3 N + NON) (Section 418, 419) analyses are performed on day 0,5,10,15,20,30,60 and at the end of the test. The sample for these analyses is prepared by removing 10-20 ml from the bottle. Displace the volume created by removing sample by adding sample from the reservoir bottle or by adding a few clean glass marbles. The sample is preserved with sulfuric acid to pH <2 until the analysis can be performed. If the purpose of the test is only to assess the ultimate BOD, the analyst has the option of measuring the nitrate nitrogen concentration at day 0 and on the last day of the test. In this case, kinetic rate estimates are not useful since the progression of the nitrification reaction is not followed. (j) Oxygen consunnption during each time interval are calculated. Appropriate corrections are made for the nitrogenous oxygen demand. Most analysts use 4.57 times the nitrate nitrogen produced. (k) When the weekly DO consumption drops below 1 to 2 % of the total accumulative consumption, calculate the ultimate BOD using a non -linear regression method. This procedure will require that the analyst monitor the results of each test to determine if this criterion is met. -13- 5. Sample Data Set and Analysis Procedure Example Analysis Wastewater sample, undiluted, no seed, no nutrient. Day DO Blank DO Accmwlated NO3-N NBOD CBOD (mg/1) (mg/1) DO Consulted (mg/1) (mg/1) (mg/1) By Sample _(1)___(2)____(mg/1) (3) _ !4j a5}_. 6) 0 8.1 - 0 0.0 0 0 3 5.6 - 2.5 - 0 2.5 5 3.5/8 - 4.6 0.0 0 4.6 7 6.2 - 6.4 - 0.23 6.2 10 3.2/8/2 - 9.4 0.10 0.46 8.9 15 • 4.3 - 13.3 - 0.58 12.7 18 2.7/8.1 - 14.9 0.15 0.69 14.2 20 6.6 - 16.4 - 0.80 15.6 25 5.4 - 17.6 0.20 0.92 16.7 30 2.6/8.2 - 20.4 - 0.92 19.5 40 5.3 - 23.3 0.20 0.92 22.4 50 3.1/8.0 - 25.5 - 0.92 24.6 60 4.5 - 29.0 - 0.92 28.1 70 3.3/8.1 - 30.2 - 0.92 29.3 90 5.4 - 32.9 0.20 0.92 -32.0 NODES: (1) Average DO in bottles, / represents reaeration (2) Average DO in dilution water blank [in this cage, none was used] (3) Columm (1) - blank correction (in this case, none is needed). (4) Average nitrate nitrogen concentration (mg/1 as Nj (5) Column (4) X 4.57 (linear interpolation between values) (6) [Column (3) - Column (5)] x dilution factor Ultimate MOD - 34.5 mg/1 CBOD Decay Rate - 0.03/day The analysis was performed with a non -linear regression technique applied to a first order model (6) . The use of a first order kinetic model, however, is not always the best choice. Significantly better statistical fits are usually obtained with alternative kinetic models including s1.un of two first order and logistic function models (1,2,3). Analysts . -14- are encouraged to pursue these options since computer software is commercially available to assist in these analyscz. At least one state agency currently employs this analysis procedure (7). 6. Precision and Accuracy • The precision of the long term BOD test was assessed with a series of replicate tests summarized below. This approach was taken because formal inter -laboratory studies have not been conducted. Study Replicate Ultimate BOD Precision Summary (ma/1) A(2) 1 154 Mean 151 mg/1 2 154 Coefficient 3 145 of Variation 3.5% B(4) 1 10.3 2 11.1 3 -9.6 Mean 10.0 mg/1 4 9.9 Coefficient 5 9.8 of Variation 5.8% 6 9.6 C(5) 1 12.8 Mean 12.4 mg/1 2 12.6 Coefficient 3 12.6 of Variation 4.4% 4 11.6 Measurement accuracy was assessed by determining the BOD of a known concentration of glucose and glutamic acid. The ultimate carbonaceous BOD of the control was made up of 150 mg/1 glucose and 150 mg/1 glutamic acid. This solution has an -15- c ultimate BOD of 321 mg/1 to 308 mg/1 depending on the extent of the oxidation of nitrogen. The results of the study conducted in triplicate was (1): Estimate Theoretical Percent of BOD (mg/1) BOD (mg/1) Difference 276 308/321-10/-14 310 308/321 +1/-3 303 308/321 -2/-6 (1) Marton, C.H. , "Studies Related to the Determination of Bio-degradability and Long Term BOD", M.S. Thesis, Tufts University, Dept. of Civil Engineering, Medford, Massachusetts (June, 1976). (2) National Council of the Paper Irilustry for Air and Stream Inprovement, Inc., "A Review of the Separation of Carbonaceous and Nitrogenous BOD in Lang -therm BOD Measurements, Technical Bulletin No. 461 (May, 1986). National Council of the Paper Industry for Air and Stream Improvement, Inc., "A Review of Ultimate BOD and Its Kinetic Fonmalation for Pulp and Paper Mill Effluents", Technical. Bulletin No. 382 (October, 1982) . (4) National Council of the Paper Industry for Air and Stream Improvement, Inc., "A Proposal to Examine the Effect of Mixing or Long Tenn BOD Test", NE82-01 (May, 1982). (5) National Council of the Paper Industry for Air and Stream Improvement, Inc., " A Study of the Selection, Calibration, and Verificationof Mathematical Water Quality Models", Technical Bulletin No. 367 (March, 1982). (6) Barnwell, T., "Least Squares Estimates of BOD Parameters", ASCE, EE6 (1980) . (3) (7) Private Communication, Roy Burke, Georgia EPD, Atlanta, Georgia (January, 1987) . (8) PrivateCommunication, B. Fenske and D. Patterson; Wisconsin Department of Natural Resources, Madison, Wisconsin (November, 1987). 1~ MCALP%NE (mo/L) AVERAGE DETECTION INFLUENT 11,19/89 2/6/89 3/13/89 4/3/89 5/1/89 6/27/89 7/10/89 8/14/Bg 9/11/99 LIMITS Cooper 0.043 0.065 0.030 0.213 0.088 0.063 0.058 0.105 0.070 0.1391 <O.OlO Chromium 0.075 0.015 0.013 0.043 0.025 0.008 0.010 0.028 0.005 0.088 <0.010 Zinc 0.060 0'093 0.045 0.320 0.048 0.093 0.340 0.230 0.135 0.311 <0.050 Nickel 0.078 0.003 0.060 0.030 0.040 0.293 0.018 0.038 0.023 0.042 <O.UGO Lead 0.023 0'014 0.013 0.035 0.013 0.024 0.015 0.025 O.O%B 0.094 <0.050 Cadmium 0.01--13 0.005 0.003 0.005 0.005 0.005 0.005 0.010 0.008 0.015 <0.030 Silver 0.003 0.005 0.0134 0.030 0.001 0.004 0.008 0.0213 0.005 0.010 <O.O1O Aluminum 0.800 1.760 0.400 2.250 0.375 1.530 2.140 2.470 1.933 1.545 <O,lOO EFFLUENT %EFFICIE/\' Copper 0.028 0.015 0.010 0.023 0.053 0.088 0.098 0.018 0.012 0.022 <O.OlO 76.0 Chromium 0.032 0.013 0.015 0.015 0.020 0.000 0.008 0.013 0.003 0.024 <O.O%O 71.8 Zino 0.055 0.060 0.055 0.100 0.043 0.050 0.048 0.045 0.123 0.101 <0.050 67.5 Nickel 0.055 0.013 0.023 0.018 0.038 1.260 0.018 0.013 0.025 0.062 <0.050 0.0 Lead 0.032 0.019 0.015 0.020 0.018 0.028 0.008 0.005 0.018 0'1345 <0.050 51.8 Cadmium 0.003 0'008 0.003 0.003 0.008 O.O[B 0.005 0.003 0.008 0.006 <0'030 62'2 Silver 0.01114 0'004 0.004 0.008 0.002 .0.001 0.003 0.003 0.003 0.004 <O.OlO 62.0 Aluminum 13.250 0.180 0.100 0.500 0.260 0.030 0.170 0.220 0.103 0.235 <O'lOO 84'0 MCALpINE Cn�^�� "/ � INFLUENT 3/3/07 3/11/87 3/25/87 5/20/87 6/9/87 7/14187 8/4/87 9/2/87 10/6/87 11/4/87 12/1/87 Copper 13.095 0.138 0.075 0.058 0.105 0.063 0.138 0.090 0.120 0.100 0.185 0.130 Chromium 0.219 0,143 0.055 0'035 0.092 0.313 0.130 0.093 0.010 0.270 0.815 0.055 Zinc 0'344 0'493 0.178 0.275 0.348 0.373 0.298 0.348 0.900 0.318 0'460 0.200 Nickel 0.035 0.035 0'013 0.010 0.038 0.060 0.068 0.0513 0.073 0.025 0.043 0.018 Lead 0.178-1 0.276 0.058 0.122 0.082 0.084 0.108 0.184 0.054 0.279 0.128 0.056 Cadmium 0.015 0.010 0.000 0.003 0'010 0'019 0.012 0.013 0.003 0.008 0.213 0.010 Silver Aluminum EFFLUENT Copper 0.015 0.018 0.055 0.025 0.023 0.015 0.015 0.018 0.018 O.O%O 0.013 0'010 Chromium 13.02O 0.028 O.055 13.0113 0.000 0.028 0.028 0.018 0.002 0.015 0.035 0.030 Zino 0.274 0.136 0.135 0.121 0.083 13.070 0.115 0.1513 0.073 0.000 0'103 0.085 Nickel 0'015 0.008 O'O1B 0-023 0.020 0.028 0.063 0.053 0.025 0.013 0.018 0'015 Lead 0.060 0.044 0.056 0.070 0.044 0'027 0.113 0.146 13.060 0'149 0'034 0.034 Cadmium 0'003 0.000 0.0135 0.005 0.008 0.005 0.013 O.00B 0'003 0'008 0'005 O'OOQ Silver MCALPINE INFLUENT 1 / 12/88 2/3/8O 3/ 1 O/88 4 /6/88 5/12/88 6/9/88 7/ 11 /88 8/8/88 9/7/88 10/4/88 11/7/88 12/5/88 Copper 0.058 0.130 0.123 0.093 0.075 0.080 0.063 0.045 0.120 0.013 0.068 Chromium 0.075 0.045 0.185 0.123 0.098 0.053 0.045 0.040 0.079 0.058 0.015 Zinc 0.270 0.400 0.680 0.450 0.453 0.613 0.258 0.703 0.348 0.360 0.115 Nickel 0.023 0.010 0.023 0.003 0.043 0.045 0.025 0.030 0.023 0.028 0.020 Lead 0.063 O.O85 0.127 0.140 0.213 0.064 0.051 0.017 0.252 0.180 0.046 Cadmium 0.000 0.005 0.010 0.005 0.008 0.043 0.008 0.010 0.010 0.012 0.005 Silver Aluminum 1.79O EFFLUENT Copper 0.023 0.010 0.018 0.028 0.020 0.028 0.035 0.018 0.013 O.0.02 0.020 0.018 Chromium 0.020 0.030 0.053 0.063 0.005 0.055 0.058 0.020 0.024 0.035 0.023 0.015 Zinc 0.028 0.063 0.230 0.105 0.083 0.245 0.030 0.258 0.053 0.044 0.093 0.083 Nickel O.018 0.O13 0.018 0.030 0.018 0.043 0.023 0.015 0.025 0.018 0.023 0.023 Lead 0.039 0.059 0.040 0.049 0.045 0.046 0.047 0.013 0.028 0.041 0.046 0.045 Cadmium 0.1000 0.005 0.008 0.005 0.008 0.015 0.008 0.005 0.003 0.003 0.005 0.000 Silver Aluminum 0.428 0.340