I. Purpose

This procedure is required to be performed in subpart S of this part, entitled National Emission Standards for Hazardous Air Pollutants from the Pulp and Paper Industry. Subpart S requires this procedure in § 63.453(p)(3) to be followed during unsafe sampling conditions when it is not practicable to obtain representative samples of hazardous air pollutants (HAP) concentrations from an open biological treatment unit. It is assumed that inlet and outlet HAP concentrations from the open biological treatment unit may be obtained during the unsafe sampling conditions. The purpose of this procedure is to estimate the concentration of HAP within the open biological treatment unit based on information obtained at inlet and outlet sampling locations in units that are not thoroughly mixed and, therefore, have different concentrations of HAP at different locations within the unit.

II. Definitions

Biological treatment unit = wastewater treatment unit designed and operated to promote the growth of bacteria to destroy organic materials in wastewater.

fbio = The fraction of organic compounds in the wastewater biodegraded in a biological treatment unit. Fe = The fraction of applicable organic compounds emitted from the wastewater to the atmosphere. K1 = First-order biodegradation rate constant, L/g mixed liquor volatile suspended solids (MLVSS)-hr KL = Liquid-phase mass transfer coefficient, m/s Ks = Monod biorate constant at half the maximum rate, g/m 3 III. Test Procedure for Determination of fbio for Nonthoroughly Mixed Open Biological Treatment Units Under Unsafe Sampling Conditions

This test procedure is used under unsafe sampling conditions that do not permit practicable sampling of open biological treatment units within the unit itself, but rather relies on sampling at the inlet and outlet locations of the unit. This procedure may be used only under unsafe sampling conditions to estimate fbio. Once the unsafe conditions have passed, then the formal compliance demonstration procedures of fbio based upon measurements within the open biological treatment unit must be completed.

A. Overview of Estimation Procedure

The steps in the estimation procedure include data collection, the estimation of concentrations within the unit, and the use of Form 1 to estimate fbio. The data collection procedure consists of two separate components. The first data collection component demonstrates that the open biological treatment unit can be represented by Monod kinetics and characterizes the effectiveness of the open biological treatment unit as part of the initial performance test, and the second data collection component is used when there are unsafe sampling conditions. These two data collection components are used together in a data calculation procedure based on a Monod kinetic model to estimate the concentrations in each zone of the open biological treatment unit. After the first two components of data collection are completed, the calculation procedures are used to back estimate the zone concentrations, starting with the last zone in the series and ending with the first zone.

B. Data Collection Requirements

This method is based upon modeling the nonthoroughly mixed open biological treatment unit as a series of well-mixed zones with internal recycling between the units and assuming that two Monod biological kinetic parameters can be used to characterize the biological removal rates in each unit. The data collection procedure consists of two separate components. The first data collection component is part of the initial performance test, and the second data collection component is used during unsafe sampling conditions.

1. Initial Performance Test

The objective of the first data collection component is to demonstrate that the open biological treatment unit can be represented by Monod kinetics and to characterize the performance of the open biological treatment unit. An appropriate value of the biorate constant, Ks, is determined using actual sampling data from the open biological treatment unit. This is done during the initial performance test when the open biological treatment unit is operating under normal conditions. This specific Ks value obtained during the initial performance test is used in the calculation procedure to characterize the open biological treatment unit during unsafe sampling conditions. The following open biological treatment unit characterization information is obtained from the first component of the data collection procedure:

(1) The value of the biorate constant, Ks;

(2) The number and characteristics of each zone in the open biological treatment unit (depth, area, characterization parameters for surface aeration, submerged aeration rates, biomass concentration, concentrations of organic compounds, dissolved oxygen (DO), dissolved solids, temperature, and other relevant variables); and

(3) The recycle ratio of internal recirculation between the zones. The number of zones and the above characterization of the zones are also used to determine the performance of the unit under the unsafe sampling conditions of concern.

2. Data Collected Under Unsafe Sampling Conditions

In the second data collection component obtained under unsafe sampling conditions, the measured inlet and outlet HAP concentrations and the biomass concentration are obtained for the open biological treatment unit. After the site specific data collection is completed on the day a parameter excursion occurs, the inlet and outlet concentrations are used with the prior open biological treatment unit characterization to estimate the concentrations of HAP in each zone. The following information on the open biological treatment unit must be available in the second data collection component:

(1) Basic unit variables such as inlet and recycle wastewater flow rates, type of agitation, and operating conditions;

(2) The value of the inlet and outlet HAP concentrations; and

(3) The biomass concentration in the open biological treatment unit.

C. One Time Determination of a Single Value of Ks (Initial Performance Test)

A single value of Ks is calculated using Form 3 for each data set that is collected during the initial performance test. A single composite value of Ks, deemed to be representative of the biological unit, is subsequently selected so that the fbio values calculated by the procedures in this appendix (using this single value of Ks) for the data sets collected during the initial performance test are within 10 percent of the fbio value determined by using Form 1 with these same data sets. The value of Ks meeting these criteria is obtained by the following steps:

(1) Determine the median of the Ks values calculated for each data set;

(2) Estimate fbio for each data set using the selected Ks value (Form 1 and Form 2);

(3) Calculate fbio for each data set using Form 1; and

(4) Compare the fbio values obtained in steps (2) and (3); if the fbio value calculated using step (2) differs from that calculated using step (3) by more than 10 percent, adjust Ks (decrease Ks if the fbio value is lower than that calculated by Form 1 and vice versa) and repeat this procedure starting at step (2). If a negative value is obtained for the values of Ks, then this negative kinetic constant may not be used with the Monod model. If a negative value of Ks is obtained, this test procedure cannot be used for evaluating the performance of the open biological treatment unit.

D. Confirmation of Monod Kinetics (Initial Performance Test)

(1) Confirmation that the unit can be represented by Monod kinetics is made by identifying the following two items:

(i) The zone methanol concentrations measured during the initial performance test; and

(ii) The zone methanol concentrations estimated by the Multiple Zone Concentrations Calculations Procedure based on inlet and outlet concentrations (Column A of Form 2). For each zone, the concentration in item 1 is compared to the concentration in item 2.

(2) For each zone, the estimated value of item 2 must be:

(i) Within 25 percent of item 1 when item 1 exceeds 8 mg/L; or

(ii) Within 2 mg/L of item 1 when item 1 is 8 mg/L or less.

(3) Successful demonstration that the calculated zone concentrations meet these criteria must be achieved for 80 percent of the performance test data sets.

(4) If negative values are obtained for the values of K1 and Ks, then these negative kinetic constants may not be used with the Monod model, even if the criteria are met. If negative values are obtained, this test procedure cannot be used for evaluating the performance of the open biological treatment unit.

E. Determination of KL for Each Zone (Unsafe Sampling Conditions)

(1) A site-specific liquid-phase mass transfer coefficient (KL) must be obtained for each zone during the unsafe sampling conditions. Do not use a default value for KL. The KL value for each zone must be based on the site-specific parameters of the specific unit. The first step in using this procedure is to calculate KL for each zone in the unit using Form 4. Form 4 outlines the procedure to follow for using mass transfer equations to determine KL. Form 4 identifies the appropriate form to use for providing the detailed calculations to support the estimate of the value of KL. Forms 5 and 6 are used to provide individual compound estimates of KL for quiescent and aerated impoundments, respectively. A computer model may be used to perform the calculations. If the WATER8 model or the most recent update to this model is used, then report the computer model input parameters that you used as an attachment to Form 4. In addition, the Bay Area Sewage Toxics Emission (BASTE) model, version 3.0, or equivalent upgrade and the TOXCHEM (Environment Canada's Wastewater Technology Centre and Environmega, Ltd.) model, version 1.10, or equivalent upgrade may also be used to determine KL for the open biological treatment unit with the following stipulations:

(i) The programs must be altered to output a KL value that is based on the site-specific parameters of the unit modeled; and

(ii) The Henry's law value listed in Form 4 must be substituted for the existing Henry's law values in the models.

(2) The Henry's law value listed in Form 4 may be obtained from the following sources:

(i) Values listed by EPA with temperature adjustment if needed;

(ii) Measured values for the system of concern with temperature adjustment; or

(iii) Literature values of Henry's law values for methanol, adjusted for temperature if needed.

(3) Input values used in the model and corresponding output values shall become part of the documentation of the fbio determination. The owner or operator should be aware that these models may not provide equivalent KL values for some types of units. To obtain an equivalent KL value in this situation, the owner or operator shall either use the appropriate procedure on Form 4 or adjust the KL value from the model to the equivalent KL value as described on Form 4.

(4) Report the input parameters that you used in the computer model on Forms 5, 6, and 7 as an attachment to Form 4. If you have submerged air flow in your unit, you must add the value of KL estimated on Form 7 to the value of KL obtained with Forms 5 and 6 before using the value of KL with Form 2.

F. Estimation of Zone Concentrations (Unsafe Sampling Conditions)

Form 2 is used to estimate the zone concentrations of HAP based on the inlet and outlet data. The value of Ks entered on the form is that single composite value of Ks discussed in section III.C of this appendix. This value of Ks is calculated during the Initial Performance Test (and subsequently updated, if necessary). A unique value of the biorate K1 is entered on line 5 of Form 2, and the inlet concentration is estimated in Column A of Form 2. The inlet concentration is located in the row of Form 2 corresponding to zone 0. If there are three zones in the system, n-3 equals 0 for the inlet concentration row. These estimated zone concentrations are then used in Form 1 to estimate f bio for the treatment unit.

G. Quality Control/Quality Assurance (QA/QC)

A QA/QC plan outlining the procedures used to determine the measured inlet and outlet concentrations during unsafe conditions and how the zone characterization data were obtained during the initial performance test shall be prepared and submitted with the initial performance test report. The plan should include, but may not be limited to:

(1) A description of each of the sampling methods that were used (method, procedures, time, method to avoid losses during sampling and holding, and sampling procedures) including simplified schematic drawings;

(2) A description of how that biomass was sampled from the biotreatment unit, including methods, locations, and times;

(3) A description of what conditions (DO, temperature, etc.) are important, what the target values are in the zones, how the factors were controlled, and how they were monitored. These conditions are primarily used to establish that the conditions of the initial performance test correspond to the conditions of the day in question;

(4) A description of how each analytical measurement was conducted, including preparation of solutions, dilution procedures, sampling procedures, monitoring of conditions, etc;

(5) A description of the analytical instrumentation used, how the instruments were calibrated, and a summary of the accuracy and precision for each instrument;

(6) A description of the test methods used to determine HAP concentrations and other measurements. Section 63.457(c)(3) specifies the test methods that must be used to determine HAP concentrations. During unsafe sampling conditions, you do not have to sample over an extended period of time or obtain more than one sample at each sample point.

(7) A description of how data are captured, recorded, and stored; and

(8) A description of the equations used and their solutions for sampling and analysis, including a reference to any software used for calculations and/or curve-fitting.

IV. Calculation of Individual fbio (Unsafe Sampling Conditions)

Use Form 1 with your zone concentration information to estimate the value of f bio under unsafe sampling conditions. Form 1 uses measured concentrations of HAP in the unit inlet and outlet, and Form 1 also uses the estimated concentrations in each zone of the unit obtained from Form 2. This procedure may be used on an open biological treatment unit that has defined zones within the unit. Use Form 1 to determine fbio for each open biological treatment unit as it exists under subpart S of part 63. The first step in using Form 1 is to calculate KL for each zone in the unit using Form 4. Form 7 must also be used if submerged aeration is used. After KL is determined using field data, obtain the concentrations of the HAP in each zone. In this alternative procedure for unsafe sampling conditions, the actual measured concentrations of the HAP in each zone are replaced with the zone concentrations that are estimated with Form 2. After KL and the zone concentrations are determined, Form 1 is used to estimate the overall unit Fe and fbio for methanol.

[65 FR 80765, Dec. 22, 2000]