National United States Regulations 40 CFR PART 430—THE PULP, PAPER, AND PAPERBOARD POINT SOURCE CATEGORY PART 430—THE PULP, PAPER, AND PAPERBOARD POINT SOURCE CATEGORY ---- Authority: Sections 301, 304, 306, 307, 308, 402, and 501 of the Clean Water Act, as amended, (33 U.S.C. 1311, 1314, 1316, 1317, 1318, 1342, and 1361), and Section 112 of the Clean Air Act, as amended (42 U.S.C. 7412). Source: 63 FR 18635, Apr. 15, 1998, unless otherwise noted. General Provisions top § 430.00 Applicability. top (a) This part applies to any pulp, paper, or paperboard mill that discharges or may discharge process wastewater pollutants to the waters of the United States, or that introduces or may introduce process wastewater pollutants into a publicly owned treatment works. (b) The following table presents the subcategorization scheme codified in this part, with references to former subpart designations contained in the 1997 edition of 40 CFR parts 425 through 699: Subcategorization Scheme With References to Former Subparts Contained in the July 1, 1997 Edition of 40 CFR Parts 425 Through 699 ---------------------------------------------------------------------------------------------------------------- Final codified subpart Final subcategorization scheme Types of products covered in the subpart ---------------------------------------------------------------------------------------------------------------- A......................... Dissolving Kraft.............. Dissolving pulp at kraft mills (F\a\) B......................... Bleached Papergrade Kraft and Market pulp at bleached kraft mills (G\a\); Soda. paperboard, coarse paper, and tissue paper at bleached kraft mills (H\a\); pulp and fine papers at bleached kraft mills (I\a\); and pulp and paper at soda mills (P\a\). C......................... Unbleached Kraft.............. Pulp and paper at unbleached kraft mills including linerboard or bag paper and other mixed products (A\a\); pulp and paper using the unbleached kraft- neutral sulfite semi-chemical (cross recovery) process (D\a\); and pulp and paper at combined unbleached kraft and semi-chemical mills, wherein the spent semi-chemical cooking liquor is burned within the unbleached kraft chemical recovery system (V\a\). D......................... Dissolving Sulfite............ Pulp at dissolving sulfite mills for the following grades: nitration, viscose, cellophane, and acetate (K\a\). E......................... Papergrade Sulfite............ Pulp and paper at papergrade sulfite mills where _Calcium-, Magnesium-, or blow pit pulp washing techniques are used (J\a\) Sodium-based pulps. and pulp and paper at papergrade sulfite mills _Ammonium-based pulps......... where vacuum or pressure drums are used to wash _Specialty grade pulps........ pulp (U\a\). F......................... Semi-Chemical................. Pulp and paper at semi-chemical mills using an ammonia base or a sodium base (B\a\). G......................... Mechanical Pulp............... Pulp and paper at groundwood chemi-mechanical mills (L\a\); pulp and paper at groundwood mills through the application of the thermo-mechanical process (M\a\); pulp and coarse paper, molded pulp products, and newsprint at groundwood mills (N\a\); and pulp and fine paper at groundwood mills (O\a\). H......................... Non-Wood Chemical Pulp........ Pulp and paper at non-wood chemical pulp mills. I......................... Secondary Fiber Deink......... Pulp and paper at deink mills including fine papers, tissue papers, or newsprint (Q\a\). J......................... Secondary Fiber Non-Deink..... Paperboard from wastepaper from noncorrugating medium furnish or from corrugating medium furnish (E\a\); tissue paper from wastepaper without deinking at secondary fiber mills (T\a\); molded products from wastepaper without deinking (W\a\); and builders' paper and roofing felt from wastepaper (40 CFR Part 431, Subpart A \a\). K......................... Fine and Lightweight Papers Fine Papers at nonintegrated mills using wood fiber from Purchased Pulp. furnish or cotton fiber furnish (R\a\); and lightweight papers at nonintegrated mills or lightweight electrical papers at nonintegrated mills (X\a\). L......................... Tissue, Filter, Non-woven, and Tissue papers at nonintegrated mills (S\a\); filter Paperboard from Purchased and non-woven papers at nonintegrated mills (Y\a\); Pulp. and paperboard at nonintegrated mills (Z\a\). ---------------------------------------------------------------------------------------------------------------- \a\ This subpart is contained in the 40 CFR parts 425 through 699, edition revised as of July 1, 1997. § 430.01 General definitions. top In addition to the definitions set forth in 40 CFR part 401 and 40 CFR 403.3, the following definitions apply to this part: (a) Adsorbable organic halides (AOX). A bulk parameter that measures the total mass of chlorinated organic matter in water and wastewater. (b) Annual average. The mean concentration, mass loading or production-normalized mass loading of a pollutant over a period of 365 consecutive days (or such other period of time determined by the permitting authority to be sufficiently long to encompass expected variability of the concentration, mass loading, or production-normalized mass loading at the relevant point of measurement). (c) Bleach plant. All process equipment used for bleaching beginning with the first application of bleaching agents (e.g., chlorine, chlorine dioxide, ozone, sodium or calcium hypochlorite, or peroxide), each subsequent extraction stage, and each subsequent stage where bleaching agents are applied to the pulp. For mills in subpart E of this part producing specialty grades of pulp, the bleach plant includes process equipment used for the hydrolysis or extraction stages prior to the first application of bleaching agents. Process equipment used for oxygen delignification prior to the application of bleaching agents is not part of the bleach plant. (d) Bleach plant effluent. The total discharge of process wastewaters from the bleach plant from each physical bleach line operated at the mill, comprising separate acid and alkaline filtrates or the combination thereof. (e) Chemical oxygen demand (COD). A bulk parameter that measures the oxygen-consuming capacity of organic and inorganic matter present in water or wastewater. It is expressed as the amount of oxygen consumed from a chemical oxidant in a specific test. (f) Elemental chlorine-free (ECF). Any process for bleaching pulps in the absence of elemental chlorine and hypochlorite that uses exclusively chlorine dioxide as the only chlorine-containing bleaching agent. (g) End of the pipe. The point at which final mill effluent is discharged to waters of the United States or introduced to a POTW. (h) Fiber line. A series of operations employed to convert wood or other fibrous raw material into pulp. If the final product is bleached pulp, the fiber line encompasses pulping, de-knotting, brownstock washing, pulp screening, centrifugal cleaning, and multiple bleaching and washing stages. (i) Minimum level (ML). The level at which the analytical system gives recognizable signals and an acceptable calibration point. The following minimum levels apply to pollutants in this part: ------------------------------------------------------------------------ Pollutant Method Minimum level ------------------------------------------------------------------------ 2,3,7,8-TCDD...................... 1613 10 pg/L \a\ 2,3,7,8-TCDF...................... 1613 10 pg/L \a\ Trichlorosyringol................. 1653 2.5 ug/L \b\ 3,4,5-Trichlorocatechol........... 1653 5.0 ug/L \b\ 3,4,6-Trichlorocatechol........... 1653 5.0 ug/L \b\ 3,4,5-Trichloroguaiacol........... 1653 2.5 ug/L \b\ 3,4,6-Trichloroguaiacol........... 1653 2.5 ug/L \b\ 4,5,6-Trichloroguaiacol........... 1653 2.5 ug/L \b\ 2,4,5-Trichlorophenol............. 1653 2.5 ug/L \b\ 2,4,6-Trichlorophenol............. 1653 2.5 ug/L \b\ Tetrachlorocatechol............... 1653 5.0 ug/L \b\ Tetrachloroguaiacol............... 1653 5.0 ug/L \b\ 2,3,4,6-Tetrachlorophenol......... 1653 2.5 ug/L \b\ Pentachlorophenol................. 1653 5.0 ug/L \b\ AOX............................... 1650 20 ug/L \b\ ------------------------------------------------------------------------ \a\ Picograms per liter. \b\ Micrograms per liter. (j) New source. (1) Notwithstanding the criteria codified at 40 CFR 122.29(b)(1), a source subject to subpart B or E of this part is a “new source” if it meets the definition of “new source” at 40 CFR 122.2 and: (i) It is constructed at a site at which no other source is located; or (ii) It totally replaces the process or production equipment that causes the discharge of pollutants at an existing source, including the total replacement of a fiber line that causes the discharge of pollutants at an existing source, except as provided in paragraph (j)(2) of this section; or (iii) Its processes are substantially independent of an existing source at the same site. In determining whether these processes are substantially independent, the Director shall consider such factors as the extent to which the new facility is integrated with the existing plant; and the extent to which the new facility is engaged in the same general type of activity as the existing source. (2) The following are examples of changes made by mills subject to subparts B or E of this part that alone do not cause an existing mill to become a “new source”: (i) Upgrades of existing pulping operations; (ii) Upgrades or replacement of pulp screening and washing operations; (iii) Installation of extended cooking and/or oxygen delignification systems or other post-digester, pre-bleaching delignification systems; (iv) Bleach plant modifications including changes in methods or amounts of chemical applications, new chemical applications, installation of new bleaching towers to facilitate replacement of sodium or calcium hypochlorite, and installation of new pulp washing systems; or (v) Total replacement of process or production equipment that causes the discharge of pollutants at an existing source (including a replacement fiber line), but only if such replacement is performed for the purpose of achieving limitations that have been included in the discharger's NPDES permit pursuant to §430.24(b). (k) Non-continuous discharger. (1) Except as provided in paragraph (k)(2) of this section, a non-continuous discharger is a mill which is prohibited by the NPDES authority from discharging pollutants during specific periods of time for reasons other than treatment plant upset control, such periods being at least 24 hours in duration. A mill shall not be deemed a non-continuous discharger unless its permit, in addition to setting forth the prohibition described above, requires compliance with the effluent limitations established for non-continuous dischargers and also requires compliance with maximum day and average of 30 consecutive days effluent limitations. Such maximum day and average of 30 consecutive days effluent limitations for non-continuous dischargers shall be established by the NPDES authority in the form of concentrations which reflect wastewater treatment levels that are representative of the application of the best practicable control technology currently available, the best conventional pollutant control technology, or new source performance standards in lieu of the maximum day and average of 30 consecutive days effluent limitations for conventional pollutants set forth in each subpart. (2) A mill is a non-continuous discharger for the purposes of determining applicable effluent limitations under subpart B or E of this part (other than conventional limits for existing sources) if, for reasons other than treatment plant upset control (e.g., protecting receiving water quality), the mill is prohibited by the NPDES authority from discharging pollutants during specific periods of time or if it is required to release its discharge on a variable flow or pollutant loading rate basis. (l) POTW. Publicly owned treatment works as defined at 40 CFR 403.3(o). (m) Process wastewater. For subparts B and E only, process wastewater is any water that, during manufacturing or processing, comes into direct contact with or results from the production or use of any raw material, intermediate product, finished product, byproduct, or waste product. For purposes of subparts B and E of this part, process wastewater includes boiler blowdown; wastewaters from water treatment and other utility operations; blowdowns from high rate (e.g., greater than 98 percent) recycled non-contact cooling water systems to the extent they are mixed and co-treated with other process wastewaters; wastewater, including leachates, from landfills owned by pulp and paper mills subject to subpart B or E of this part if the wastewater is commingled with wastewater from the mill's manufacturing or processing facility; and storm waters from the immediate process areas to the extent they are mixed and co-treated with other process wastewaters. For purposes of this part, contaminated groundwaters from on-site or off-site groundwater remediation projects are not process wastewater. (n) Production. (1) For all limitations and standards specified in this part except those pertaining to AOX and chloroform: Production shall be defined as the annual off-the-machine production (including off-the-machine coating where applicable) divided by the number of operating days during that year. Paper and paperboard production shall be measured at the off-the-machine moisture content, except for subpart C of this part (as it pertains to pulp and paperboard production at unbleached kraft mills including linerboard or bag paper and other mixed products, and to pulp and paperboard production using the unbleached kraft neutral sulfite semi-chemical (cross recovery) process), and subparts F and J of this part (as they pertain to paperboard production from wastepaper from noncorrugating medium furnish or from corrugating medium furnish) where paper and paperboard production shall be measured in air-dry-tons (10% moisture content). Market pulp shall be measured in air-dry tons (10% moisture). Production shall be determined for each mill based upon past production practices, present trends, or committed growth. (2) For AOX and chloroform limitations and standards specified in subparts B and E of this part: Production shall be defined as the annual unbleached pulp production entering the first stage of the bleach plant divided by the number of operating days during that year. Unbleached pulp production shall be measured in air-dried-metric-tons (10% moisture) of brownstock pulp entering the bleach plant at the stage during which chlorine or chlorine-containing compounds are first applied to the pulp. In the case of bleach plants that use totally chlorine free bleaching processes, unbleached pulp production shall be measured in air-dried-metric tons (10% moisture) of brownstock pulp entering the first stage of the bleach plant from which wastewater is discharged. Production shall be determined for each mill based upon past production practices, present trends, or committed growth. (o) TCDD. 2,3,7,8-tetrachlorodibenzo-p-dioxin. (p) TCDF. 2,3,7,8-tetrachlorodibenzofuran. (q) Totally chlorine-free (TCF) bleaching. Pulp bleaching operations that are performed without the use of chlorine, sodium hypochlorite, calcium hypochlorite, chlorine dioxide, chlorine monoxide, or any other chlorine-containing compound. (r) Wet Barking. Wet barking operations shall be defined to include hydraulic barking operations and wet drum barking operations which are those drum barking operations that use substantial quantities of water in either water sprays in the barking drums or in a partial submersion of the drums in a “tub” of water. [63 FR 18635, Apr. 15, 1998; 63 FR 42239, Aug. 7, 1998] § 430.02 Monitoring requirements. top This section establishes minimum monitoring frequencies for certain pollutants. Where no monitoring frequency is specified in this section or where the duration of the minimum monitoring frequency has expired under paragraphs (b) through (e) of this section, the permit writer or pretreatment control authority shall determine the appropriate monitoring frequency in accordance with 40 CFR 122.44(i) or 40 CFR part 403, as applicable. (a) BAT, NSPS, PSES, and PSNS monitoring frequency for chlorinated organic pollutants. The following monitoring frequencies apply to discharges subject to subpart B or subpart E of this part: ---------------------------------------------------------------------------------------------------------------- Minimum monitoring frequency CAS number Pollutant ------------------------------------------------------------ Non-TCF \a\ TCF \b\ ---------------------------------------------------------------------------------------------------------------- 1198556.................. Tetrachlorocatechol..... Monthly...................... (\c\) 2539175.................. Tetrachloroguaiacol..... Monthly...................... (\c\) 2539266.................. Trichlorosyringol....... Monthly...................... (\c\) 2668248.................. 4,5,6-trichloroguaiacol. Monthly...................... (\c\) 32139723................. 3,4,6-trichlorocatechol. Monthly...................... (\c\) 56961207................. 3,4,5-trichlorocatechol. Monthly...................... (\c\) 57057837................. 3,4,5-trichloroguaiacol. Monthly...................... (\c\) 58902.................... 2,3,4,6- Monthly...................... (\c\) tetrachlorophenol. 60712449................. 3,4,6-trichloroguaiacol. Monthly...................... (\c\) 87865.................... Pentachlorophenol \d\... Monthly...................... (\c\) 88062.................... 2,4,6-trichlorophenol Monthly...................... (\c\) \d\. 95954.................... 2,4,5-trichlorophenol Monthly...................... (\c\) \d\. 1746016.................. 2,3,7,8-TCDD............ Monthly...................... (\c\) 51207319................. 2,3,7,8-TCDF............ Monthly...................... (\c\) 67663.................... chloroform \e\.......... Weekly....................... (\c\) 59473040................. AOX \f\................. Daily........................ None specified. ---------------------------------------------------------------------------------------------------------------- \a\ Non-TCF: Pertains to any fiber line that does not use exclusively TCF bleaching processes. \b\ TCF: Pertains to any fiber line that uses exclusively TCF bleaching processes, as disclosed by the discharger in its permit application under 40 CFR 122.21(g)(3) and certified under 40 CFR 122.22 or, for indirect dischargers, as reported to the pretreatment control authority under 40 CFR 403.12 (b), (d), or (e). \c\ This regulation does not specify a limit for this pollutant for TCF bleaching processes. \d\ Monitoring frequency does not apply to this compound when used as a biocide. The permitting or pretreatment control authority must determine the appropriate monitoring frequency for this compound, when used as a biocide, under 40 CFR 122.44(i) or 40 CFR part 403, as applicable. \e\ This regulation does not specify a limit for this pollutant for Subpart E mills. \f\ This regulation does not specify a limit for this pollutant for the ammonium-based or specialty grade sulfite pulp segments of Subpart E. (b) Duration of required monitoring for BAT, NSPS, PSES, and PSNS. The monitoring frequencies specified in paragraph (a) of this section apply for the following time periods: (1) For direct dischargers, a duration of 5 years commencing on the date the applicable limitations or standards from subpart B or subpart E of this part are first included in the discharger's NPDES permit; (2) For existing indirect dischargers, until April 17, 2006; (3) For new indirect dischargers, a duration of 5 years commencing on the date the indirect discharger commences operation. (c) Reduced monitoring frequencies for bleach plant pollutants under the Voluntary Advanced Technology Incentives Program. The following monitoring frequencies apply to mills enrolled in the Voluntary Advanced Technology Incentives Program established under subpart B of this part for a duration of 5 years commencing after achievement of the applicable BAT limitations specified in §430.24(b)(3) or NSPS specified in §430.25(c)(1) for the following pollutants, except as noted in footnote f: ---------------------------------------------------------------------------------------------------------------- Minimum monitoring frequency CAS number Pollutant -------------------------------------------------------------------------- Non-ECF \a\ Advanced ECF \b,f\ TCF \c\ ---------------------------------------------------------------------------------------------------------------- 1198556.......... Tetrachlorocatecho Monthly................ Monthly (\d\) l. 2539175.......... Tetrachloroguiacol Monthly................ Monthly (\d\) 2539266.......... Trichlorosyringol. Monthly................ Monthly (\d\) 2668248.......... 4,5,6- Monthly................ Monthly (\d\) trichloroguaiacol. 32139723......... 3,4,6- Monthly................ Monthly (\d\) trichlorocatechol. 56961207......... 3,4,5- Monthly................ Monthly (\d\) trichlorocatechol. 57057837......... 3,4,5- Monthly................ Monthly (\d\) trichloroguaiacol. 58902............ 2,3,4,6- Monthly................ Monthly (\d\) tetrachlorophenol. 60712449......... 3,4,6- Monthly................ Monthly (\d\) trichloroguaiacol. 87865............ Pentachlorophenol Monthly................ Monthly (\d\) \e\. 88062............ 2,4,6- Monthly................ Monthly (\d\) trichlorophenol \e\. 95954............ 2,4,5- Monthly................ Monthly (\d\) trichlorophenol \e\. 1746016.......... 2,3,7,8-TCDD...... Monthly................ Monthly (\d\) 51207319......... 2,3,7,8-TCDF...... Monthly................ Monthly (\d\) 67663............ Chloroform........ Weekly................. Monthly (\d\) ---------------------------------------------------------------------------------------------------------------- \a\ Non-ECF: Pertains to any fiber line that does not use exclusively ECF or TCF bleaching processes. \b\ Advanced ECF: Pertains to any fiber line that uses exclusively Advanced ECF bleaching processes, or exclusively ECF and TCF bleaching processes as disclosed by the discharger in its permit application under 40 CFR 122.21(g)(3) and certified under 40 CFR 122.22. Advanced ECF consists of the use of extended delignification or other technologies that achieve at least the Tier I performance levels specified in § 430.24(b)(4)(i). \c\ TCF: Pertains to any fiber line that uses exclusively TCF bleaching processes, as disclosed by the discharger in its permit application under 40 CFR 122.21(g)(3) and certified under 40 CFR 122.22. \d\ This regulation does not specify a limit for this pollutant for TCF bleaching processes. \e\ Monitoring frequency does not apply to this compound when used as a biocide. The permitting authority must determine the appropriate monitoring frequency for this compound, when used as a biocide, under 40 CFR 122.44(i). \f\ Monitoring requirements for these pollutants by mills certifying as Advanced ECF in their NPDES permit application or other communication to the permitting authority will be suspended after one year of monitoring. The permitting authority must determine the appropriate monitoring frequency for these pollutants beyond that time under 40 CFR 122.44(i). (d) Reduced monitoring frequencies for AOX under the Voluntary Advanced Technology Incentives Program (year one). The following monitoring frequencies apply to direct dischargers enrolled in the Voluntary Advanced Technology Incentives Program established under Subpart B of this part for a duration of one year after achievement of the applicable BAT limitations specified in §430.24(b)(4)(i) or NSPS specified in §430.25(c)(2): ---------------------------------------------------------------------------------------------------------------- Advanced ECF, any tier CAS number Pollutant Non-ECF, any tier \a\ \b\ TCF, any tier \c\ ---------------------------------------------------------------------------------------------------------------- 59473040......... AOX............... Daily.................. Weekly................. None specified. ---------------------------------------------------------------------------------------------------------------- \a\ Non-ECF: Pertains to any fiber line that does not use exclusively ECF or TCF bleaching processes. \b\ Advanced ECF: Pertains to any fiber line that uses exclusively Advanced ECF bleaching processes or exclusively ECF and TCF bleaching processes, as disclosed by the discharger in its permit application under 40 CFR 122.21(g)(3) and certified under 40 CFR 122.22. Advanced ECF consists of the use of extended delignification or other technologies that achieve at least the Tier I performance levels specified in § 430.24(b)(4)(i). \c\ TCF: Pertains to any fiber line that uses exclusively TCF bleaching processes, as disclosed by the discharger in its permit application under 40 CFR 122.21(g)(3) and certified under 40 CFR 122.22. (e) Reduced monitoring frequencies for AOX under the Voluntary Advanced Technology Incentives Program (years two through five). The following monitoring frequencies apply to mills enrolled in the Voluntary Advanced Technology Incentives Program established under Subpart B of this part for a duration of four years starting one year after achievement of the applicable BAT limitations specified in §430.24(b)(4)(i) or NSPS specified in §430.25(c)(2): -------------------------------------------------------------------------------------------------------------------------------------------------------- Advanced ECF_tier I Advanced ECF_tier II Advanced ECF_tier CAS number Pollutant Non-ECF any tier \a\ \b\ \b\ III \b\ TCF_ any tier \c\ -------------------------------------------------------------------------------------------------------------------------------------------------------- 59473040.......... AOX.................. Daily................ Monthly............. Quarterly........... Annually............ None specified. -------------------------------------------------------------------------------------------------------------------------------------------------------- \a\ Non-ECF: Pertains to any fiber line that does not use exclusively ECF or TCF bleaching processes. \b\ Advanced ECF: Pertains to any fiber line that uses exclusively Advanced ECF bleaching processes or exclusively ECF and TCF bleaching processes, as disclosed by the discharger in its permit application under 40 CFR 122.21(g)(3) and certified under 40 CFR 122.22. Advanced ECF consists of the use of extended delignification or other technologies that achieve at least the Tier I performance levels specified in § 430.24(b)(4)(i). \c\ TCF: Pertains to any fiber line that uses exclusively TCF bleaching processes, as disclosed by the discharger in its permit application under 40 CFR 122.21(g)(3) and certified under 40 CFR 122.22. (f) Certification in Lieu of Monitoring for Chloroform—(1) Under what circumstances may a discharger be exempt from the minimum monitoring requirements of this section for chloroform? A discharger subject to limitations or standards for chloroform under subpart B of this part is not subject to the minimum monitoring requirements specified in this section for chloroform at a fiber line to which the limitations or standards apply if the discharger meets the requirements of this section. (2) How do I qualify for the exemption? At the time you request an exemption from the minimum monitoring requirements of this section for chloroform from your permitting authority or pretreatment control authority for a fiber line, you must: (i) Demonstrate, based on 104 measurements taken over a period of not less than two years of monitoring conducted in accordance with paragraph (a) of this section, that you are complying with the applicable limitations or standards for chloroform; (ii) Certify that you will maintain a record of the maximum value for each of the following process and operating conditions for the fiber line that was recorded during the collection of each of the samples used to make the demonstration required under paragraph (f)(2)(i) of this section. (A) The pH of the first chlorine dioxide bleaching stage; (B) The chlorine (Cl2) content of chlorine dioxide (ClO2) used on the bleach line; (C) The kappa factor of the first chlorine dioxide bleaching stage; and (D) The total bleach line chlorine dioxide application rate; (iii) Identify the chlorine-containing compound used for bleaching during the collection of samples used to make the demonstration required under paragraph (f)(2)(i) of this section; and (iv) Certify that the fiber line does not use either elemental chlorine or hypochlorite as bleaching agents. (3) What happens if I change the process and operating conditions on the fiber line so that one or more exceeds the maximum value recorded under paragraph (f)(2)(ii) of this section for that process and operating condition? If you wish to continue your exemption from the minimum monitoring requirements of this section for chloroform, you must: (i) Demonstrate, based on monitoring conducted at a frequency similar to that required in paragraph (a) of this section and for a duration determined by the permitting or pretreatment control authority, that you are complying with the applicable limitations or standards for chloroform; (ii) Certify that you will maintain a record of the maximum value for each of the following process and operating conditions for the fiber line that was recorded during the collection of each of the samples used to make the demonstration required under paragraph (f)(6)(i) of this section: (A) The pH of the first chlorine dioxide bleaching stage; (B) The chlorine (Cl2) content of chlorine dioxide (ClO2) used on the bleach line; (C) The kappa factor of the first chlorine dioxide bleaching stage; and (D) The total bleach line chlorine dioxide application rate; (iii) Identify the chlorine-containing compound used for bleaching during the collection of each sample used to make the demonstration required under paragraph (f)(3)(i) of this section; and (iv) Certify that the fiber line does not use either elemental chlorine or hypochlorite as bleaching agents. (4) What are my reporting obligations? You must certify in reports required under §122.41(l)(4) or §403.12(b) of this chapter, as appropriate, that the chlorine-containing compounds used for bleaching are unchanged from those identified under paragraph (f)(2)(iii) of this section and that the following process and operating conditions maintained on the fiber line during the reporting period have not exceeded the maximum value recorded for each such condition during the collection of the samples used to make the demonstration required under paragraphs (f)(2)(i) or (f)(3)(i) of this section: (i) The pH of the first chlorine dioxide bleaching stage; (ii) The chlorine (Cl2) content of chlorine dioxide (ClO2) used on the bleach line; (iii) The kappa factor of the first chlorine dioxide bleaching stage; and (iv) The total bleach line chlorine dioxide application rate. (5) What happens if I fail to maintain the records described in paragraphs (f)(2)(ii) and (f)(3)(ii) of this section? You will be required to comply with the minimum monitoring requirements of this section for chloroform. (6) What happens if I exceed the maximum value recorded under paragraphs (f)(2)(ii) or (f)(3)(ii) of this section for any of the process and operating conditions identified in that section? (i) If for any reason (e.g., intentionally or due to process upset) you fail to maintain process and operating conditions at values equal to or less than the maximum value recorded under paragraphs (f)(2)(ii) or (f)(3)(ii) of this section for each such condition, you will be in violation of the applicable chloroform limitation or standard unless: (A) Within 30 days, you notify your permitting or pretreatment control authority in writing of the exceedance; and (B) You demonstrate compliance with the applicable chloroform limitation or standard by immediately monitoring the bleach plant effluent for chloroform at a frequency similar to that required in paragraph (a) of this section and for a duration determined by the permit or pretreatment control authority. (ii) In order to continue your exemption from the minimum monitoring requirements of this section for chloroform, you must meet the requirements of paragraph (f)(6)(i) of this section and you must recertify that the fiber line process and operating conditions do not exceed the maximum value recorded under paragraphs (f)(2)(ii) or (f)(3)(ii) of this section for each of the parameters identified in those paragraphs. (7) Definitions: (i) Kappa factor—the ratio of available chlorine (total equivalent chlorine, as percent on oven dry pulp) to the kappa number of the pulp. Kappa number is the lignin content of pulp, as measured by a modified permanganate test corrected to 50 percent consumption of the chemical. (ii) Total bleach line chlorine dioxide application rate—mass of chlorine dioxide applied in all stages of the bleach line per mass of unbleached pulp (i.e., lb/ton or kg/kkg). (iii) Chlorine-containing compounds—compounds containing chlorine used in the bleach plant for bleaching, brightening, whitening, or viscosity control. These compounds include but are not limited to chlorine (Cl2), sodium hypochlorite (NaOCl), chlorine dioxide (ClO2) and chlorine monoxide (Cl2O). [63 FR 18635, Apr. 15, 1998, as amended at 67 FR 58997, Sept. 19, 2002] § 430.03 Best management practices (BMPs) for spent pulping liquor, soap, and turpentine management, spill prevention, and control. top (a) Applicability. This section applies to direct and indirect discharging pulp, paper, and paperboard mills with pulp production in subparts B (Bleached Papergrade Kraft and Soda) and E (Papergrade Sulfite). (b) Specialized definitions—(1) Action Level: A daily pollutant loading that when exceeded triggers investigative or corrective action. Mills determine action levels by a statistical analysis of six months of daily measurements collected at the mill. For example, the lower action level may be the 75th percentile of the running seven-day averages (that value exceeded by 25 percent of the running seven-day averages) and the upper action level may be the 90th percentile of the running seven-day averages (that value exceeded by 10 percent of the running seven-day averages). (2) Equipment Items in Spent Pulping Liquor, Soap, and Turpentine Service: Any process vessel, storage tank, pumping system, evaporator, heat exchanger, recovery furnace or boiler, pipeline, valve, fitting, or other device that contains, processes, transports, or comes into contact with spent pulping liquor, soap, or turpentine. Sometimes referred to as “equipment items.” (3) Immediate Process Area: The location at the mill where pulping, screening, knotting, pulp washing, pulping liquor concentration, pulping liquor processing, and chemical recovery facilities are located, generally the battery limits of the aforementioned processes. “Immediate process area” includes spent pulping liquor storage and spill control tanks located at the mill, whether or not they are located in the immediate process area. (4) Intentional Diversion: The planned removal of spent pulping liquor, soap, or turpentine from equipment items in spent pulping liquor, soap, or turpentine service by the mill for any purpose including, but not limited to, maintenance, grade changes, or process shutdowns. (5) Mill: The owner or operator of a direct or indirect discharging pulp, paper, or paperboard manufacturing facility subject to this section. (6) Senior Technical Manager: The person designated by the mill manager to review the BMP Plan. The senior technical manager shall be the chief engineer at the mill, the manager of pulping and chemical recovery operations, or other such responsible person designated by the mill manager who has knowledge of and responsibility for pulping and chemical recovery operations. (7) Soap: The product of reaction between the alkali in kraft pulping liquor and fatty acid portions of the wood, which precipitate out when water is evaporated from the spent pulping liquor. (8) Spent Pulping Liquor: For kraft and soda mills “spent pulping liquor” means black liquor that is used, generated, stored, or processed at any point in the pulping and chemical recovery processes. For sulfite mills “spent pulping liquor” means any intermediate, final, or used chemical solution that is used, generated, stored, or processed at any point in the sulfite pulping and chemical recovery processes (e.g., ammonium-, calcium-, magnesium-, or sodium-based sulfite liquors). (9) Turpentine: A mixture of terpenes, principally pinene, obtained by the steam distillation of pine gum recovered from the condensation of digester relief gases from the cooking of softwoods by the kraft pulping process. Sometimes referred to as sulfate turpentine. (c) Requirement to implement Best Management Practices. Each mill subject to this section must implement the Best Management Practices (BMPs) specified in paragraphs (c)(1) through (10) of this section. The primary objective of the BMPs is to prevent leaks and spills of spent pulping liquors, soap, and turpentine. The secondary objective is to contain, collect, and recover at the immediate process area, or otherwise control, those leaks, spills, and intentional diversions of spent pulping liquor, soap, and turpentine that do occur. BMPs must be developed according to best engineering practices and must be implemented in a manner that takes into account the specific circumstances at each mill. The BMPs are as follows: (1) The mill must return spilled or diverted spent pulping liquors, soap, and turpentine to the process to the maximum extent practicable as determined by the mill, recover such materials outside the process, or discharge spilled or diverted material at a rate that does not disrupt the receiving wastewater treatment system. (2) The mill must establish a program to identify and repair leaking equipment items. This program must include: (i) Regular visual inspections (e.g., once per day) of process areas with equipment items in spent pulping liquor, soap, and turpentine service; (ii) Immediate repairs of leaking equipment items, when possible. Leaking equipment items that cannot be repaired during normal operations must be identified, temporary means for mitigating the leaks must be provided, and the leaking equipment items repaired during the next maintenance outage; (iii) Identification of conditions under which production will be curtailed or halted to repair leaking equipment items or to prevent pulping liquor, soap, and turpentine leaks and spills; and (iv) A means for tracking repairs over time to identify those equipment items where upgrade or replacement may be warranted based on frequency and severity of leaks, spills, or failures. (3) The mill must operate continuous, automatic monitoring systems that the mill determines are necessary to detect and control leaks, spills, and intentional diversions of spent pulping liquor, soap, and turpentine. These monitoring systems should be integrated with the mill process control system and may include, e.g., high level monitors and alarms on storage tanks; process area conductivity (or pH) monitors and alarms; and process area sewer, process wastewater, and wastewater treatment plant conductivity (or pH) monitors and alarms. (4) The mill must establish a program of initial and refresher training of operators, maintenance personnel, and other technical and supervisory personnel who have responsibility for operating, maintaining, or supervising the operation and maintenance of equipment items in spent pulping liquor, soap, and turpentine service. The refresher training must be conducted at least annually and the training program must be documented. (5) The mill must prepare a brief report that evaluates each spill of spent pulping liquor, soap, or turpentine that is not contained at the immediate process area and any intentional diversion of spent pulping liquor, soap, or turpentine that is not contained at the immediate process area. The report must describe the equipment items involved, the circumstances leading to the incident, the effectiveness of the corrective actions taken to contain and recover the spill or intentional diversion, and plans to develop changes to equipment and operating and maintenance practices as necessary to prevent recurrence. Discussion of the reports must be included as part of the annual refresher training. (6) The mill must establish a program to review any planned modifications to the pulping and chemical recovery facilities and any construction activities in the pulping and chemical recovery areas before these activities commence. The purpose of such review is to prevent leaks and spills of spent pulping liquor, soap, and turpentine during the planned modifications, and to ensure that construction and supervisory personnel are aware of possible liquor diversions and of the requirement to prevent leaks and spills of spent pulping liquors, soap, and turpentine during construction. (7) The mill must install and maintain secondary containment (i.e., containment constructed of materials impervious to pulping liquors) for spent pulping liquor bulk storage tanks equivalent to the volume of the largest tank plus sufficient freeboard for precipitation. An annual tank integrity testing program, if coupled with other containment or diversion structures, may be substituted for secondary containment for spent pulping liquor bulk storage tanks. (8) The mill must install and maintain secondary containment for turpentine bulk storage tanks. (9) The mill must install and maintain curbing, diking or other means of isolating soap and turpentine processing and loading areas from the wastewater treatment facilities. (10) The mill must conduct wastewater monitoring to detect leaks and spills, to track the effectiveness of the BMPs, and to detect trends in spent pulping liquor losses. Such monitoring must be performed in accordance with paragraph (i) of this section. (d) Requirement to develop a BMP Plan. (1) Each mill subject to this section must prepare and implement a BMP Plan. The BMP Plan must be based on a detailed engineering review as described in paragraphs (d)(2) and (3) of this section. The BMP Plan must specify the procedures and the practices required for each mill to meet the requirements of paragraph (c) of this section, the construction the mill determines is necessary to meet those requirements including a schedule for such construction, and the monitoring program (including the statistically derived action levels) that will be used to meet the requirements of paragraph (i) of this section. The BMP Plan also must specify the period of time that the mill determines the action levels established under paragraph (h) of this section may be exceeded without triggering the responses specified in paragraph (i) of this section. (2) Each mill subject to this section must conduct a detailed engineering review of the pulping and chemical recovery operations—including but not limited to process equipment, storage tanks, pipelines and pumping systems, loading and unloading facilities, and other appurtenant pulping and chemical recovery equipment items in spent pulping liquor, soap, and turpentine service—for the purpose of determining the magnitude and routing of potential leaks, spills, and intentional diversions of spent pulping liquors, soap, and turpentine during the following periods of operation: (i) Process start-ups and shut downs; (ii) Maintenance; (iii) Production grade changes; (iv) Storm or other weather events; (v) Power failures; and (vi) Normal operations. (3) As part of the engineering review, the mill must determine whether existing spent pulping liquor containment facilities are of adequate capacity for collection and storage of anticipated intentional liquor diversions with sufficient contingency for collection and containment of spills. The engineering review must also consider: (i) The need for continuous, automatic monitoring systems to detect and control leaks and spills of spent pulping liquor, soap, and turpentine; (ii) The need for process wastewater diversion facilities to protect end-of-pipe wastewater treatment facilities from adverse effects of spills and diversions of spent pulping liquors, soap, and turpentine; (iii) The potential for contamination of storm water from the immediate process areas; and (iv) The extent to which segregation and/or collection and treatment of contaminated storm water from the immediate process areas is appropriate. (e) Amendment of BMP Plan. (1) Each mill subject to this section must amend its BMP Plan whenever there is a change in mill design, construction, operation, or maintenance that materially affects the potential for leaks or spills of spent pulping liquor, turpentine, or soap from the immediate process areas. (2) Each mill subject to this section must complete a review and evaluation of the BMP Plan five years after the first BMP Plan is prepared and, except as provided in paragraph (e)(1) of this section, once every five years thereafter. As a result of this review and evaluation, the mill must amend the BMP Plan within three months of the review if the mill determines that any new or modified management practices and engineered controls are necessary to reduce significantly the likelihood of spent pulping liquor, soap, and turpentine leaks, spills, or intentional diversions from the immediate process areas, including a schedule for implementation of such practices and controls. (f) Review and certification of BMP Plan. The BMP Plan, and any amendments thereto, must be reviewed by the senior technical manager at the mill and approved and signed by the mill manager. Any person signing the BMP Plan or its amendments must certify to the permitting or pretreatment control authority under penalty of law that the BMP Plan (or its amendments) has been prepared in accordance with good engineering practices and in accordance with this regulation. The mill is not required to obtain approval from the permitting or pretreatment control authority of the BMP Plan or any amendments thereto. (g) Record keeping requirements. (1) Each mill subject to this section must maintain on its premises a complete copy of the current BMP Plan and the records specified in paragraph (g)(2) of this section and must make such BMP Plan and records available to the permitting or pretreatment control authority and the Regional Administrator or his or her designee for review upon request. (2) The mill must maintain the following records for 3 years from the date they are created: (i) Records tracking the repairs performed in accordance with the repair program described in paragraph (c)(2) of this section; (ii) Records of initial and refresher training conducted in accordance with paragraph (c)(4) of this section; (iii) Reports prepared in accordance with paragraph (c)(5) of this section; and (iv) Records of monitoring required by paragraphs (c)(10) and (i) of this section. (h) Establishment of wastewater treatment system influent action levels. (1) Each mill subject to this section must conduct a monitoring program, described in paragraph (h)(2) of this section, for the purpose of defining wastewater treatment system influent characteristics (or action levels), described in paragraph (h)(3) of this section, that will trigger requirements to initiate investigations on BMP effectiveness and to take corrective action. (2) Each mill subject to this section must employ the following procedures in order to develop the action levels required by paragraph (h) of this section: (i) Monitoring parameters. The mill must collect 24-hour composite samples and analyze the samples for a measure of organic content (e.g., Chemical Oxygen Demand (COD) or Total Organic Carbon (TOC)). Alternatively, the mill may use a measure related to spent pulping liquor losses measured continuously and averaged over 24 hours (e.g., specific conductivity or color). (ii) Monitoring locations. For direct dischargers, monitoring must be conducted at the point influent enters the wastewater treatment system. For indirect dischargers monitoring must be conducted at the point of discharge to the POTW. For the purposes of this requirement, the mill may select alternate monitoring point(s) in order to isolate possible sources of spent pulping liquor, soap, or turpentine from other possible sources of organic wastewaters that are tributary to the wastewater treatment facilities (e.g., bleach plants, paper machines and secondary fiber operations). (3) By the date prescribed in paragraph (j)(1)(iii) of this section, each existing discharger subject to this section must complete an initial six-month monitoring program using the procedures specified in paragraph (h)(2) of this section and must establish initial action levels based on the results of that program. A wastewater treatment influent action level is a statistically determined pollutant loading determined by a statistical analysis of six months of daily measurements. The action levels must consist of a lower action level, which if exceeded will trigger the investigation requirements described in paragraph (i) of this section, and an upper action level, which if exceeded will trigger the corrective action requirements described in paragraph (i) of this section. (4) By the date prescribed in paragraph (j)(1)(vi) of this section, each existing discharger must complete a second six-month monitoring program using the procedures specified in paragraph (h)(2) of this section and must establish revised action levels based on the results of that program. The initial action levels shall remain in effect until replaced by revised action levels. (5) By the date prescribed in paragraph (j)(2) of this section, each new source subject to this section must complete a six-month monitoring program using the procedures specified in paragraph (h)(2) of this section and must develop a lower action level and an upper action level based on the results of that program. (6) Action levels developed under this paragraph must be revised using six months of monitoring data after any change in mill design, construction, operation, or maintenance that materially affects the potential for leaks or spills of spent pulping liquor, soap, or turpentine from the immediate process areas. (i) Monitoring, corrective action, and reporting requirements. (1) Each mill subject to this section must conduct daily monitoring of the influent to the wastewater treatment system in accordance with the procedures described in paragraph (h)(2) of this section for the purpose of detecting leaks and spills, tracking the effectiveness of the BMPs, and detecting trends in spent pulping liquor losses. (2) Whenever monitoring results exceed the lower action level for the period of time specified in the BMP Plan, the mill must conduct an investigation to determine the cause of such exceedance. Whenever monitoring results exceed the upper action level for the period of time specified in the BMP Plan, the mill must complete corrective action to bring the wastewater treatment system influent mass loading below the lower action level as soon as practicable. (3) Although exceedances of the action levels will not constitute violations of an NPDES permit or pretreatment standard, failure to take the actions required by paragraph (i)(2) of this section as soon as practicable will be a permit or pretreatment standard violation. (4) Each mill subject to this section must report to the NPDES permitting or pretreatment control authority the results of the daily monitoring conducted pursuant to paragraph (i)(1) of this section. Such reports must include a summary of the monitoring results, the number and dates of exceedances of the applicable action levels, and brief descriptions of any corrective actions taken to respond to such exceedances. Submission of such reports shall be at the frequency established by the NPDES permitting or pretreatment control authority, but in no case less than once per year. (j) Compliance deadlines—(1) Existing direct and indirect dischargers. Except as provided in paragraph (j)(2) of this section for new sources, indirect discharging mills subject to this section must meet the deadlines set forth below. Except as provided in paragraph (j)(2) of this section for new sources, NPDES permits must require direct discharging mills subject to this section to meet the deadlines set forth below. If a deadline set forth below has passed at the time the NPDES permit containing the BMP requirement is issued, the NPDES permit must require immediate compliance with such BMP requirement(s). (i) Prepare BMP Plans and certify to the permitting or pretreatment authority that the BMP Plan has been prepared in accordance with this regulation not later than April 15, 1999; (ii) Implement all BMPs specified in paragraph (c) of this section that do not require the construction of containment or diversion structures or the installation of monitoring and alarm systems not later than April 15, 1999. (iii) Establish initial action levels required by paragraph (h)(3) of this section not later than April 15, 1999. (iv) Commence operation of any new or upgraded continuous, automatic monitoring systems that the mill determines to be necessary under paragraph (c)(3) of this section (other than those associated with construction of containment or diversion structures) not later than April 17, 2000. (v) Complete construction and commence operation of any spent pulping liquor, collection, containment, diversion, or other facilities, including any associated continuous monitoring systems, necessary to fully implement BMPs specified in paragraph (c) of this section not later than April 16, 2001. (vi) Establish revised action levels required by paragraph (h)(4) of this section as soon as possible after fully implementing the BMPs specified in paragraph (c) of this section, but not later than January 15, 2002. (2) New sources. Upon commencing discharge, new sources subject to this section must implement all of the BMPs specified in paragraph (c) of this section, prepare the BMP Plan required by paragraph (d) of this section, and certify to the permitting or pretreatment authority that the BMP Plan has been prepared in accordance with this regulation as required by paragraph (f) of this section, except that the action levels required by paragraph (h)(5) of this section must be established not later than 12 months after commencement of discharge, based on six months of monitoring data obtained prior to that date in accordance with the procedures specified in paragraph (h)(2) of this section. (k) The provisions of paragraphs (c) through (j) of this section do not apply to the bleached papergrade kraft mill, commonly known as the Androscoggin Mill, that is owned by International Paper and located in Jay, Maine. In lieu of imposing the requirements specified in those paragraphs, the permitting authority shall establish conditions for the discharge of COD and color for this mill on the basis of best professional judgment. [63 FR 18635, Apr. 15, 1998, as amended at 65 FR 46108, July 27, 2000] Subpart A—Dissolving Kraft Subcategory top § 430.10 Applicability; description of the dissolving kraft subcategory. top The provisions of this subpart apply to discharges resulting from the production of dissolving pulp at kraft mills. § 430.11 Specialized definitions. top For the purpose of this subpart, the general definitions, abbreviations, and methods of analysis set forth in 40 CFR part 401 and §430.01 of this part shall apply to this subpart. § 430.12 Effluent limitations representing the degree of effluent reduction attainable by the application of the best practicable control technology currently available (BPT). top (a) Except as provided in 40 CFR 125.30 through 125.32, any existing point source subject to this subpart must achieve the following effluent limitations representing the degree of effluent reduction attainable by the application of the best practicable control technology currently available (BPT), except that non-continuous dischargers shall not be subject to the maximum day and average of 30 consecutive days limitations but shall be subject to annual average effluent limitations: Subpart A [BPT effluent limitations] ------------------------------------------------------------------------ Kg/kkg (or pounds per 1,000 lb) of product -------------------------------------- Continuous dischargers -------------------------- Pollutant or pollutant property Average of daily Non- Maximum for values for continuous any 1 day 30 dischargers consecutive days ------------------------------------------------------------------------ BOD5............................. 23.6 12.25 6.88 TSS.............................. 37.3 20.05 11.02 pH............................... (\1\) (\1\) (\1\) ------------------------------------------------------------------------ \1\ Within the range of 5.0 to 9.0 at all times. (b) The following limitations establish the quantity or quality of pollutants or pollutant properties, controlled by this section, resulting from the use of wet barking operations, which may be discharged by a point source subject to the provisions of this subpart. These limitations are in addition to the limitations set forth in paragraph (a) of this section and shall be calculated using the proportion of the mill's total production due to use of logs which are subject to such operations. Non-continuous dischargers shall not be subject to the maximum day and average of 30 consecutive days limitations, but shall be subject to annual average effluent limitations: Subpart A [BPT effluent limitations] ------------------------------------------------------------------------ Kg/kkg (or pounds per 1,000 lb) of product ---------------------------------------- Continuous dischargers --------------------------- Non- Pollutant or pollutant property Average of continuous daily values dischargers Maximum for for 30 (annual any 1 day consecutive average) days ------------------------------------------------------------------------ BOD5........................... 3.2 1.7 0.95 TSS............................ 6.9 3.75 2.0 pH............................. (\1\) (\1\) (\1\) ------------------------------------------------------------------------ \1\ Within the range of 5.0 to 9.0 at all times. (c) The following limitations establish the quantity or quality of pollutants or pollutant parameters, controlled by this section, resulting from the use of log washing or chip washing operations, which may be discharged by a point source subject to the provisions of this subpart. These limitations are in addition to the limitations set forth in paragraph (a) of this section and shall be calculated using the proportion of the mill's total production due to use of logs and/or chips which are subject to such operations. Non-continuous dischargers shall not be subject to the maximum day and average of 30 consecutive days limitations, but shall be subject to the annual average effluent limitations: Subpart A [BPT effluent limitations] ------------------------------------------------------------------------ Kg/kkg (or pounds per 1,000 lb) of product -------------------------------------- Continuous dischargers -------------------------- Pollutant or pollutant property Average of Non- daily continuous Maximum for values for dischargers any 1 day 30 (annual consecutive average) days ------------------------------------------------------------------------ BOD5............................. 0.35 0.2 0.1 TSS.............................. 0.70 0.4 0.2 pH............................... (\1\) (\1\) (\1\) ------------------------------------------------------------------------ \1\ Within the range of 5.0 to 9.0 at all times. (d) The following limitations establish the quantity or quality of pollutants or pollutant properties, controlled by this section, resulting from the use of log flumes or log ponds, which may be discharged by a point source subject to the provisions of this subpart. These limitations are in addition to the limitations set forth in paragraph (a) of this section and shall be calculated using the proportion of the mill's total production due to use of logs which are subject to such operations. Non-continuous dischargers shall not be subject to the maximum day and average of 30 consecutive days limitations but shall be subject to the annual average effluent limitations: Subpart A [BPT effluent limitations] ------------------------------------------------------------------------ Kg/kkg (or pounds per 1,000 lb) of product ---------------------------------------- Continuous dischargers ---------------------------- Non- Pollutant or pollutant property Average of continuous daily values dischargers Maximum for for 30 (annual any 1 day consecutive average) days ------------------------------------------------------------------------ BOD5........................... 0.6 0.35 0.2 TSS............................ 1.45 0.8 0.4 pH............................. (\1\) (\1\) (\1\) ------------------------------------------------------------------------ \1\ Within the range of 5.0 to 9.0 at all times. § 430.13 Effluent limitations guidelines representing the degree of effluent reduction attainable by the application of the best conventional pollutant control technology (BCT). top Except as provided in 40 CFR 125.30 through 125.32, any existing point source subject to this subpart shall achieve the following effluent limitations representing the degree of effluent reduction attainable by the application of the best conventional pollutant control technology (BCT): The limitations shall be the same as those specified for conventional pollutants (which are defined in 40 CFR 401.16) in §430.12 of this subpart for the best practicable control technology currently available (BPT). § 430.14 Effluent limitations representing the degree of effluent reduction attainable by the application of the best available technology economically achievable (BAT). top Except as provided in 40 CFR 125.30 through 125.32, any existing point source subject to this subpart where chlorophenolic-containing biocides are used must achieve the following effluent limitations representing the degree of effluent reduction attainable by the application of the best available technology economically achievable (BAT). Non-continuous dischargers shall not be subject to the maximum day mass limitations in kg/kkg (lb/1000 lb) but shall be subject to concentration limitations. Concentration limitations are only applicable to non-continuous dischargers. Permittees not using chlorophenolic-containing biocides must certify to the permit-issuing authority that they are not using these biocides: Subpart A [BAT effluent limitations] ------------------------------------------------------------------------ Maximum for any 1 day ------------------------------------------ Pollutant or pollutant Kg/kkg (or property pounds per 1,000 lb) of Milligrams/liter product ------------------------------------------------------------------------ Pentachlorophenol............ 0.0025 (0.011)(55.1)/y Trichlorophenol.............. 0.016 (0.068)(55.1)/y y = wastewater discharged in kgal per ton of product. ------------------------------------------------------------------------ § 430.15 New source performance standards (NSPS). top Any new source subject to this subpart must achieve the following new source performance standards (NSPS), except that non-continuous dischargers shall not be subject to the maximum day and average of 30 consecutive days effluent limitations for BOD5 and TSS, but shall be subject to annual average effluent limitations. Also, for non-continuous dischargers, concentration limitations (mg/l) shall apply, where provided. Concentration limitations will only apply to non-continuous dischargers. Only facilities where chlorophenolic-containing biocides are used shall be subject to pentachlorophenol and trichlorophenol limitations. Permittees not using chlorophenolic-containing biocides must certify to the permit-issuing authority that they are not using these biocides: Subpart A [NSPS] ------------------------------------------------------------------------ Kg/kkg (or pounds per 1,000 lb) of product -------------------------------------- Continuous dischargers -------------------------- Pollutant or pollutant property Average of Non- daily continuous Maximum for values for dischargers any 1 day 30 (annual consecutive average) days ------------------------------------------------------------------------ BOD5............................. 15.6 8.4 4.4 TSS.............................. 27.3 14.3 7.5 pH............................... (\1\) (\1\) (\1\) ------------------------------------------------------------------------ Maximum for any 1 day ---------------------------------------------------------------- Kg/kkg (or pounds per 1,000 lb) Milligrams/liter of product ---------------------------------------------------------------------------------------------------------------- Pentachlorophenol.............................. 0.0025 (0.012)(50.7)/y Trichlorophenol................................ 0.016 (0.074)(50.7)/y y = wastewater discharged in kgal per ton at all times. ---------------------------------------------------------------------------------------------------------------- \1\ Within the range of 5.0 to 9.0 at all times. § 430.16 Pretreatment standards for existing sources (PSES). top Except as provided in 40 CFR 403.7 and 403.13, any existing source subject to this subpart that introduces pollutants into a publicly owned treatment works must: comply with 40 CFR part 403; and achieve the following pretreatment standards for existing sources (PSES) if it uses chlorophenolic-containing biocides. Permittees not using chlorophenolic-containing biocides must certify to the permit-issuing authority that they are not using these biocides. PSES must be attained on or before July 1, 1984: Subpart A [PSES] ---------------------------------------------------------------------------------------------------------------- Maximum for any 1 day ----------------------------------------------------------------- Kg/kkg (or Pollutant or pollutant property pounds per Milligrams/liter (mg/l) 1,000 lb) of product \a\ ---------------------------------------------------------------------------------------------------------------- Pentachlorophenol............................. (0.011)(55.1)/y................................... 0.0025 Trichlorophenol............................... (0.082)(55.1)/y................................... 0.019 y = wastewater discharged in kgal per ton of product. ---------------------------------------------------------------------------------------------------------------- \a\ The following equivalent mass limitations are provided as guidance in cases when POTWs find it necessary to impose mass effluent limitations. § 430.17 Pretreatment standards for new sources (PSNS). top Except as provided in 40 CFR 403.7, any new source subject to this subpart that introduces pollutants into a publicly owned treatment works must: comply with 40 CFR part 403; and achieve the following pretreatment standards for new sources (PSNS) if it uses chlorophenolic-containing biocides. Permittees not using chlorophenolic-containing biocides must certify to the permit-issuing authority that they are not using these biocides: Subpart A [PSNS] ---------------------------------------------------------------------------------------------------------------- Maximum for any 1 day ----------------------------------------------------------------- Kg/kkg (or Pollutant or pollutant property pounds per Milligrams/liter (mg/l) 1,000 lb) of product \a\ ---------------------------------------------------------------------------------------------------------------- Pentachlorophenol............................. (0.012)(50.7)/y................................... 0.0025 Trichlorophenol............................... (0.089)(50.7)/y................................... 0.019 y = wastewater discharged in kgal per ton of product. ---------------------------------------------------------------------------------------------------------------- \a\ The following equivalent mass limitations are provided as guidance in cases when POTWs find it necessary to impose mass effluent limitations. Subpart B—Bleached Papergrade Kraft and Soda Subcategory top § 430.20 Applicability; description of the bleached papergrade kraft and soda subcategory. top The provisions of this subpart apply to discharges resulting from: The production of market pulp at bleached kraft mills; the integrated production of paperboard, coarse paper, and tissue paper at bleached kraft mills; the integrated production of pulp and fine papers at bleached kraft mills; and the integrated production of pulp and paper at soda mills. § 430.21 Specialized definitions. top (a) The general definitions, abbreviations, and methods of analysis set forth in 40 CFR part 401 and §430.01 of this part apply to this subpart. (b) Baseline BAT limitations or NSPS means the BAT limitations specified in §430.24(a) (1) or (2), as applicable, and the NSPS specified in §430.25(b) (1) or (2), as applicable, that apply to any direct discharger that is not “enrolled” in the “Voluntary Advanced Technology Incentives Program.” (c) Enroll means to notify the permitting authority that a mill intends to participate in the “Voluntary Advanced Technology Incentives Program.” A mill can enroll by indicating its intention to participate in the program either as part of its application for a National Pollutant Discharge Elimination System (NPDES) permit, or through separate correspondence to the permitting authority as long as the mill signs the correspondence in accordance with 40 CFR 122.22. (d) Existing effluent quality means the level at which the pollutants identified in §430.24(a)(1) are present in the effluent of a mill “enrolled” in the “Voluntary Advanced Technology Incentives Program.” (e) Kappa number is a measure of the lignin content in unbleached pulp, determined after pulping and prior to bleaching. (f) Voluntary Advanced Technology Incentives Program is the program established under §430.24(b) (for existing direct dischargers) and §430.25(c) (for new direct dischargers) whereby participating mills agree to accept enforceable effluent limitations and conditions in their NPDES permits that are more stringent than the “baseline BAT limitations or NSPS” that would otherwise apply, in exchange for regulatory- and enforcement-related rewards and incentives. § 430.22 Effluent limitations representing the degree of effluent reduction attainable by the application of the best practicable control technology currently available (BPT). top (a) Except as provided in 40 CFR 125.30 through 125.32, any existing point source subject to this subpart must achieve the following effluent limitations representing the degree of effluent reduction attainable by the application of the best practicable control technology currently available (BPT): Subpart B [BPT effluent limitations for bleached kraft facilities where market pulp is produced] ------------------------------------------------------------------------ Kg/kkg (or pounds per 1,000 lb) of product ---------------------------------------- Continuous dischargers Pollutant or pollutant ---------------------------- Non- parameter Average of continuous daily values dischargers Maximum for for 30 (annual any 1 day consecutive average) days ------------------------------------------------------------------------ BOD5........................... 15.45 8.05 4.52 TSS............................ 30.4 16.4 9.01 pH............................. (\1\) (\1\) (\1\) ------------------------------------------------------------------------ \1\ Within the range of 5.0 to 9.0 at all times. Subpart B [BPT effluent limitations for bleached kraft facilities where paperboard, coarse paper, and tissue paper are produced] ------------------------------------------------------------------------ Kg/kkg (or pounds per 1,000 lb) of product --------------------------------------- Continuous dischargers --------------------------- Pollutant or pollutant parameter Average of Non- daily continuous Maximum for values for dischargers any 1 day 30 (annual consecutive average) days ------------------------------------------------------------------------ BOD5............................ 13.65 7.1 3.99 TSS............................. 24.0 12.9 7.09 pH.............................. (\1\) (\1\) (\1\) ------------------------------------------------------------------------ \1\ Within the range of 5.0 to 9.0 at all times. Subpart B [BPT effluent limitations for bleached kraft facilities where pulp and fine papers are produced] ------------------------------------------------------------------------ Kg/kkg (or pounds per 1,000 lb) of product -------------------------------------- Continuous dischargers -------------------------- Pollutant or pollutant parameter Average of Non- daily continuous Maximum for values for dischargers any 1 day 30 (annual consecutive average) days ------------------------------------------------------------------------ BOD5............................. 10.6 5.5 3.09 TSS.............................. 22.15 11.9 6.54 pH............................... (\1\) (\1\) (\1\) ------------------------------------------------------------------------ \1\ Within the range of 5.0 to 9.0 at all times. Subpart B [BPT effluent limitations for soda facilities where pulp and paper are produced] ------------------------------------------------------------------------ Kg/kkg (or pounds per 1,000 lb) of product -------------------------------------- Continuous dischargers -------------------------- Pollutant or pollutant parameter Average of Non- daily continuous Maximum for values for dischargers any 1 day 30 (annual consecutive average) days ------------------------------------------------------------------------ BOD5............................. 13.7 7.1 3.99 TSS.............................. 24.5 13.2 7.25 pH............................... (\1\) (\1\) (\1\) ------------------------------------------------------------------------ \1\ Within the range of 5.0 to 9.0 at all times. (b) The following limitations establish the quantity or quality of pollutants or pollutant properties, controlled by this section, resulting from the use of wet barking operations, which may be discharged by a point source subject to the provisions of this subpart. These limitations are in addition to the limitations set forth in paragraph (a) of this section and shall be calculated using the proportion of the mill's total production due to use of logs which are subject to such operations: Subpart B [BPT effluent limitations for bleached kraft facilities where market pulp is produced] ------------------------------------------------------------------------ Kg/kkg (or pounds per 1,000 lb) of product --------------------------------------- Continuous dischargers --------------------------- Non- Pollutant or pollutant parameter Average of continuous daily values dischargers Maximum for for 30 (annual any 1 day consecutive average) days ------------------------------------------------------------------------ BOD5............................ 2.3 1.2 0.70 TSS............................. 5.3 2.85 1.55 pH.............................. (\1\) (\1\) (\1\) ------------------------------------------------------------------------ \1\ Within the range of 5.0 to 9.0 at all times. Subpart B [BPT effluent limitations for bleached kraft facilities where paperboard, coarse paper, and tissue paper are produced] ------------------------------------------------------------------------ Kg/kkg (or pounds per 1,000 lb) of product -------------------------------------- Continuous dischargers -------------------------- Pollutant or pollutant parameter Average of Non- daily continuous Maximum for values for dischargers any 1 day 30 (annual consecutive average) days ------------------------------------------------------------------------ BOD5............................. 2.25 1.2 0.65 TSS.............................. 5.75 3.1 1.70 pH............................... (\1\) (\1\) (\1\) ------------------------------------------------------------------------ \1\1 Within the range of 5.0 to 9.0 at all times. Subpart B [BPT effluent limitations for bleached kraft facilities where pulp and fine papers are produced] ------------------------------------------------------------------------ Kg/kkg (or pounds per 1,000 lb) of product ---------------------------------------- Continuous dischargers Pollutant or pollutant ---------------------------- Non- parameter Average of continuous daily values dischargers Maximum for for 30 (annual any 1 day consecutive average) days ------------------------------------------------------------------------ BOD5........................... 1.95 1.0 0.55 TSS............................ 5.3 2.85 1.55 pH............................. (\1\) (\1\) (\1\) ------------------------------------------------------------------------ \1\ Within the range of 5.0 to 9.0 at all times. Subpart B [BPT effluent limitations for soda facilities where pulp and papers are produced] ------------------------------------------------------------------------ Kg/kkg (or pounds per 1,000 lb) of product ---------------------------------------- Continuous dischargers Pollutant or pollutant ---------------------------- Non- parameter Average of continuous daily values dischargers Maximum for for 30 (annual any 1 day consecutive average) days ------------------------------------------------------------------------ BOD5........................... 2.05 1.1 0.60 TSS............................ 5.25 2.8 1.55 pH............................. (\1\) (\1\) (\1\) ------------------------------------------------------------------------ \1\ Within the range of 5.0 to 9.0 at all times. (c) The following limitations establish the quantity or quality of pollutants or pollutant parameters, controlled by this section, resulting from the use of log washing or chip washing operations, which may be discharged by a point source subject to the provisions of this subpart. These limitations are in addition to the limitations set forth in paragraph (a) of this section and shall be calculated using the proportion of the mill's total production due to use of logs and/or chips which are subject to such operations: Subpart B [BPT effluent limitations for bleached kraft facilities where market pulp is produced] ------------------------------------------------------------------------ Kg/kkg (or pounds per 1,000 lb) of product ---------------------------------------- Continuous dischargers Pollutant or pollutant ---------------------------- Non- parameter Average of continuous daily values dischargers Maximum for for 30 (annual any 1 day consecutive average) days ------------------------------------------------------------------------ BOD5........................... 0.2 0.1 0.1 TSS............................ 0.6 0.3 0.15 pH............................. (\1\) (\1\) (\1\) ------------------------------------------------------------------------ \1\ Within the range of 5.0 to 9.0 at all times. Subpart B [BPT effluent limitations for bleached kraft facilities where paperboard, coarse paper, and tissue paper are produced] ------------------------------------------------------------------------ Kg/kkg (or pounds per 1,000 lb) of product ---------------------------------------- Continuous dischargers Pollutant or pollutant ---------------------------- Non- parameter Average of continuous daily values dischargers Maximum for for 30 (annual any 1 day consecutive average) days ------------------------------------------------------------------------ BOD5........................... 0.25 0.15 0.05 TSS............................ 0.65 0.35 0.20 pH............................. (\1\) (\1\) (\1\) ------------------------------------------------------------------------ \1\ Within the range of 5.0 to 9.0 at all times. Subpart B [BPT effluent limitations for bleached kraft facilities where pulp and fine papers are produced] ------------------------------------------------------------------------ Kg/kkg (or pounds per 1,000 lb) of product ---------------------------------------- Continuous dischargers Pollutant or pollutant ---------------------------- Non- parameter Average of continuous daily values dischargers Maximum for for 30 (annual any 1 day consecutive average) days ------------------------------------------------------------------------ BOD5........................... 0.2 0.1 0.05 TSS............................ 0.55 0.3 0.15 pH............................. (\1\) (\1\) (\1\) ------------------------------------------------------------------------ \1\ Within the range of 5.0 to 9.0 at all times. Subpart B [BPT effluent limitations for soda facilities where pulp and papers are produced] ------------------------------------------------------------------------ Kg/kkg (or pounds per 1,000 lb) of product ---------------------------------------- Continuous dischargers Pollutant or pollutant ---------------------------- Non- parameter Average of continuous daily values dischargers Maximum for for 30 (annual any 1 day consecutive average) days ------------------------------------------------------------------------ BOD5........................... 0.15 0.1 0.05 TSS............................ 0.5 0.25 0.15 pH............................. (\1\) (\1\) (\1\) ------------------------------------------------------------------------ \1\ Within the range of 5.0 to 9.0 at all times. (d) The following limitations establish the quantity or quality of pollutants or pollutant properties, controlled by this section, resulting from the use of log flumes or log ponds, which may be discharged by a point source subject to the provisions of this subpart. These limitations are in addition to the limitations set forth in paragraph (a) of this section and shall be calculated using the proportion of the mill's total production due to use of logs which are subject to such operations: Subpart B [BPT effluent limitations for bleached kraft facilities where market pulp is produced] ------------------------------------------------------------------------ Kg/kkg (or pounds per 1,000 lb) of product ---------------------------------------- Continuous dischargers Pollutant or pollutant ---------------------------- Non- parameter Average of continuous daily values dischargers Maximum for for 30 (annual any 1 day consecutive average) days ------------------------------------------------------------------------ BOD5........................... 0.4 0.2 0.15 TSS............................ 1.15 0.6 0.35 pH............................. (\1\) (\1\) (\1\) ------------------------------------------------------------------------ \1\ Within the range of 5.0 to 9.0 at all times. Subpart B [BPT effluent limitations for bleached kraft facilities where paperboard, coarse paper, and tissue paper are produced] ------------------------------------------------------------------------ Kg/kkg (or pounds per 1,000 lb) of product ---------------------------------------- Continuous dischargers Pollutant or pollutant ---------------------------- Non- parameter Average of continuous daily values dischargers Maximum for for 30 (annual any 1 day consecutive average) days ------------------------------------------------------------------------ BOD5........................... 0.45 0.25 0.10 TSS............................ 1.25 0.7 0.35 pH............................. (\1\) (\1\) (\1\) ------------------------------------------------------------------------ \1\ Within the range of 5.0 to 9.0 at all times. Subpart B [BPT effluent limitations for bleached kraft facilities where pulp and fine papers are produced] ------------------------------------------------------------------------ Kg/kkg (or pounds per 1,000 lb) of product -------------------------------------- Continuous dischargers -------------------------- Pollutant or pollutant parameter Average of Non- daily continuous Maximum for values for dischargers any 1 day 30 (annual consecutive average) days ------------------------------------------------------------------------ BOD5............................. 0.35 0.2 0.10 TSS.............................. 1.15 0.6 0.30 pH............................... (\1\) (\1\) (\1\) ------------------------------------------------------------------------ \1\ Within the range of 5.0 to 9.0 at all times. Subpart B [BPT effluent limitations for soda facilities where pulp and papers are produced] ------------------------------------------------------------------------ Kg/kkg (or pounds per 1,000 lb) of product -------------------------------------- Continuous dischargers -------------------------- Pollutant or pollutant parameter Average of Non- daily continuous Maximum for values for dischargers any 1 day 30 (annual consecutive average) days ------------------------------------------------------------------------ BOD5............................. 0.3 0.2 0.10 TSS.............................. 1.1 0.55 0.35 pH............................... (\1\) (\1\) (\1\) ------------------------------------------------------------------------ \1\Within the range of 5.0 to 9.0 at all times. § 430.23 Effluent limitations representing the degree of effluent reduction attainable by the application of the best conventional pollutant control technology (BCT). top Except as provided in 40 CFR 125.30 through 125.32, any existing point source subject to this subpart must achieve the following effluent limitations representing the degree of effluent reduction attainable by the application of the best conventional pollutant control technology (BCT). The limitations shall be the same as those specified in §430.22 of this subpart for the best practicable control technology currently available (BPT). § 430.24 Effluent limitations representing the degree of effluent reduction attainable by the application of best available technology economically achievable (BAT). top Except as provided in 40 CFR 125.30 through 125.32, any existing point source subject to this subpart must achieve the following effluent limitations representing the degree of effluent reduction attainable by the application of the best available technology economically achievable (BAT). (a) Except as provided in paragraph (b) of this section— (1) The following effluent limitations apply with respect to each fiber line that does not use an exclusively TCF bleaching process, as disclosed by the discharger in its NPDES permit application under 40 CFR 122.21(g)(3) and certified under 40 CFR 122.22: Subpart B ---------------------------------------------------------------------------------------------------------------- BAT effluent limitations ---------------------------------------------------- Pollutant or pollutant property Monthly Maximum for any 1 day average ---------------------------------------------------------------------------------------------------------------- TCDD....................................................... greater than % percent 18.1.2 Alphabetical characters. cm centimeter g gram h hour ID inside diameter in inch L liter m meter mg milligram min minute mL milliliter mm millimeter N normal; gram molecular weight of solute divided by hydrogen equivalent of solute, per liter of solution OD outside diameter ppb part-per-billion ppm part-per-million ppt part-per-trillion psig pounds-per-square inch gauge v/v volume per unit volume w/v weight per unit volume 18.2 Definitions and acronyms (in alphabetical order). Analyte: AOX tested for by this method. Calibration standard (CAL): A solution prepared from a secondary standard and/or stock solution which is used to calibrate the response of the instrument with respect to analyte concentration. Calibration verification standard (VER): The mid-point calibration standard (CS3) that is used to verify calibration. Field blank: An aliquot of reagent water or other reference matrix that is placed in a sample container in the laboratory or the field, and treated as a sample in all respects, including exposure to sampling site conditions, storage, preservation, and all analytical procedures. The purpose of the field blank is to determine if the field or sample transporting procedures and environments have contaminated the sample. IPR: Initial precision and recovery; four aliquots of the diluted PAR standard analyzed to establish the ability to generate acceptable precision and accuracy. An IPR is performed prior to the first time this method is used and any time the method or instrumentation is modified. Laboratory blank: See Method blank. Laboratory control sample (LCS): See Ongoing precision and recovery sample (OPR). Laboratory reagent blank: See Method blank. May: This action, activity, or procedural step is neither required nor prohibited. May not: This action, activity, or procedural step is prohibited. Method blank: An aliquot of reagent water that is treated exactly as a sample including exposure to all glassware, equipment, solvents, reagents, internal standards, and surrogates that are used with samples. The method blank is used to determine if analytes or interferences are present in the laboratory environment, the reagents, or the apparatus. Minimum level (ML): The level at which the entire analytical system must give a recognizable signal and acceptable calibration point for the analyte. It is equivalent to the concentration of the lowest calibration standard, assuming that all method-specified sample weights, volumes, and cleanup procedures have been employed. Must: This action, activity, or procedural step is required. OPR: Ongoing precision and recovery standard; a laboratory blank spiked with a known quantity of analyte. The OPR is analyzed exactly like a sample. Its purpose is to assure that the results produced by the laboratory remain within the limits specified in this method for precision and recovery. PAR: Precision and recovery standard; secondary standard that is diluted and spiked to form the IPR and OPR. Preparation blank: See Method blank. Primary dilution standard: A solution containing the specified analytes that is purchased or prepared from stock solutions and diluted as needed to prepare calibration solutions and other solutions. Quality control check sample (QCS): A sample containing all or a subset of the analytes at known concentrations. The QCS is obtained from a source external to the laboratory or is prepared from a source of standards different from the source of calibration standards. It is used to check laboratory performance with test materials prepared external to the normal preparation process. Reagent water: Water demonstrated to be free from the analyte of interest and potentially interfering substances at the method detection limit for the analyte. Relative standard deviation (RSD): The standard deviation multiplied by 100, divided by the mean. RSD: See Relative standard deviation. Should: This action, activity, or procedural step is suggested but not required. Stock solution: A solution containing an analyte that is prepared using a reference material traceable to EPA, the National Institute of Science and Technology (NIST), or a source that will attest to the purity and authenticity of the reference material. VER: See Calibration verification standard. Method 1653—Chlorinated Phenolics in Wastewater by In Situ Acetylation and GCMS 1.0 Scope and Application 1.1 This method is for determination of chlorinated phenolics (chlorinated phenols, guaiacols, catechols, vanillins, syringaldehydes) and other compounds associated with the Clean Water Act; the Resource Conservation and Recovery Act; and the Comprehensive Environmental Response, Compensation, and Liability Act; and that are amenable to in situ acetylation, extraction, and analysis by capillary column gas chromatography/mass spectrometry (GCMS). This method is based on existing methods for determination of chlorophenolics in pulp and paper industry wastewaters (References 1 and 2). 1.2 The chemical compounds listed in Table 1 may be determined in waters and, specifically, in in-process streams and wastewaters associated with the pulp and paper industry. The method is designed to meet the survey and monitoring requirements of the Environmental Protection Agency (EPA). 1.3 The detection limit of this method is usually dependent on the level of interferences rather than instrumental limitations. The method detection limits (MDLs) in Table 2 typify the minimum quantity that can be detected with no interferences present. 1.4 The GCMS portions of this method are for use only by persons experienced with GCMS or under the close supervision of such qualified persons. Laboratories unfamiliar with analyses of environmental samples by GCMS should run the performance tests in Reference 3 before beginning. 1.5 Any modification of the method beyond those expressly permitted is subject to the application and approval of alternative test procedures under 40 CFR Parts 136.4 and 136.5. 2.0 Summary of Method 2.1 A 1000-mL aliquot of water is spiked with stable isotopically labeled analogs of the compounds of interest and an internal standard. The solution is adjusted to neutral pH, potassium carbonate buffer is added, and the pH is raised to 9–11.5. The chlorophenolics are converted in situ to acetates by the addition of acetic anhydride. After acetylation, the solution is extracted with hexane. The hexane is concentrated to a final volume of 0.5 mL, an instrument internal standard is added, and an aliquot of the concentrated extract is injected into the gas chromatograph (GC). The compounds are separated by GC and detected by a mass spectrometer (MS). The labeled compounds and internal standard serve to correct the variability of the analytical technique. 2.2 Identification of a pollutant (qualitative analysis) is performed by comparing the relative retention time and mass spectrum to that of an authentic standard. A compound is identified when its relative retention time and mass spectrum agree. 2.3 Quantitative analysis is performed in one of two ways by GCMS using extracted ion-current profile (EICP) areas: (1) For those compounds listed in Table 1 for which standards and labeled analogs are available, the GCMS system is calibrated and the compound concentration is determined using an isotope dilution technique; (2) for those compounds listed in Table 1 for which authentic standards but no labeled compounds are available, the GCMS system is calibrated and the compound concentration is determined using an internal standard technique. 2.4 Quality is assured through reproducible calibration and testing of the extraction and GCMS systems. 3.0 Definitions 3.1 Chlorinated phenolics are the chlorinated phenols, guaiacols, catechols, vanillins, syringaldehydes and other compounds amenable to in situ acetylation, extraction, and determination by GCMS using this method. 3.2 Definitions for other terms used in this method are given in the glossary at the end of the method (Section 20.0). 4.0 Interferences 4.1 Solvents, reagents, glassware, and other sample processing hardware may yield artifacts and/or elevated baselines, causing misinterpretation of chromatograms and spectra. All materials used in the analysis shall be demonstrated to be free from interferences under the conditions of analysis by running method blanks initially and with each sample batch (samples started through the extraction process on a given eight-hour shift, to a maximum of 20). Specific selection of reagents and purification of solvents by distillation in all-glass systems may be required. Glassware and, where possible, reagents are cleaned by using solvent rinse and baking at 450 °C for a minimum of one hour. 4.2 Interferences co-extracted from samples will vary considerably from source to source, depending on the diversity of the site being sampled. Industry experience suggests that high levels of non-chlorinated phenols may cause poor recovery of the compounds of interest, particularly in samples collected in the vicinity of a source of creosote, such as a wood-preserving plant (Reference 1). 4.3 The internal standard, 3,4,5-trichlorophenol, has been reported to be an anaerobic degradation product of 2,3,4,5-tetrachlorophenol and/or pentachlorophenol (Reference 1). When an interference with this or another compound occurs, labeled pentachlorophenol or another labeled compound may be used as an alternative internal standard; otherwise, the internal standards and reference compounds must be used as specified in this method. 4.4 Blank contamination by pentachlorophenol has been reported (Reference 1) to be traceable to potassium carbonate; it has also been reported that this contamination may be removed by baking overnight at 400 to 500 °C. 4.5 Catechols are susceptible to degradation by active sites on injection port liners and columns, and are subject to oxidation to the corresponding chloro-o-benzoquinones (Reference 2). A small amount of ascorbic acid may be added to samples to prevent auto-oxidation (Reference 2; also see Section 11.1.6). For pulp and paper industry samples, ascorbic acid may be added to treated effluent samples only. 5.0 Safety 5.1 The toxicity or carcinogenicity of each compound or reagent used in this method has not been precisely determined; however, each chemical compound should be treated as a potential health hazard. Exposure to these compounds should be reduced to the lowest possible level. The laboratory is responsible for maintaining a current awareness file of OSHA regulations regarding the safe handling of the chemicals specified in this method. A reference file of materials safety data sheets (MSDSs) should be made available to all personnel involved in these analyses. Additional information on laboratory safety can be found in References 4 through 6. 5.2 Samples may contain high concentrations of toxic compounds, and should be handled with gloves and a hood opened to prevent exposure. 6.0 Equipment and Supplies Note: Brand names, suppliers, and part numbers are for illustrative purposes only. No endorsement is implied. Equivalent performance may be achieved using apparatus and materials other than those specified here, but demonstration of equivalent performance that meets the requirements of this method is the responsibility of the laboratory. 6.1 Sampling equipment for discrete or composite sampling. 6.1.1 Sample bottles and caps. 6.1.1.1 Sample bottle: Amber glass, 1000-mL minimum, with screw-cap. If amber bottles are not available, samples shall be protected from light. 6.1.1.2 Bottle caps: Threaded to fit sample bottles. Caps shall be lined with PTFE. 6.1.1.3 Cleaning bottles: Detergent water wash, cap with aluminum foil, and bake at 450 °C for a minimum of one hour before use. 6.1.1.4 Cleaning liners: Detergent water wash, reagent water (Section 7.4) and solvent rinse, and bake at approximately 200 °C for a minimum of 1 hour prior to use. 6.1.1.5 Bottles and liners must be lot-certified to be free of chlorophenolics by running blanks according to this method. If blanks from bottles and/or liners without cleaning or with fewer cleaning steps show no detectable chlorophenolics, the bottle and liner cleaning steps that do not eliminate chlorophenolics may be omitted. 6.1.2 Compositing equipment: Automatic or manual compositing system incorporating glass containers cleaned per bottle cleaning procedure above. Sample containers are kept at 0 to 4 °C during sampling. Glass or PTFE tubing only shall be used. If the sampler uses a peristaltic pump, a minimum length of compressible silicone rubber tubing may be used in the pump only. Before use, the tubing shall be thoroughly rinsed with methanol, followed by repeated rinsing with reagent water (Section 7.4) to minimize sample contamination. An integrating flow meter is used to collect proportional composite samples. 6.2 Extraction apparatus. 6.2.1 Bottle or beaker: 1500-to 2000-mL capacity. 6.2.2 Separatory funnel: 500-to 2000-mL, glass, with PTFE stopcock. 6.2.3 Magnetic stirrer: Corning Model 320, or equivalent, with stirring bar. 6.3 Polyethylene gloves: For handling samples and extraction equipment (Fisher 11–394–110–B, or equivalent). 6.4 Graduated cylinders: 1000-mL, 100-mL, and 10-mL nominal. 6.5 Centrifuge: Capable of accepting 50-mL centrifuge tubes and achieving 3000 RPM. 6.5.1 Centrifuge tubes. 6.5.1.1 35-mL nominal, with PTFE-lined screw-cap. 6.5.1.2 15-mL nominal, conical graduated, with ground-glass stopper. 6.6 Concentration apparatus. 6.6.1 Kuderna-Danish (K-D) concentrator tube: 10-mL, graduated (Kontes K-570050–1025, or equivalent) with calibration verified. Ground-glass stopper (size 19/22 joint) is used to prevent evaporation of extracts. 6.6.2 Kuderna-Danish (K-D) evaporation flask: 1000-mL (Kontes K-570001–1000, or equivalent), attached to concentrator tube with springs (Kontes K-662750–0012). 6.6.3 Snyder column: Three-ball macro (Kontes K-503000–0232, or equivalent). 6.6.4 Snyder column: Two-ball micro (Kontes K-469002–0219, or equivalent). 6.6.5 Boiling chips: Approximately 10/40 mesh, extracted with methylene chloride and baked at 450 °C for a minimum of one hour. 6.6.6 Nitrogen evaporation apparatus: Equipped with a water bath controlled at 35 to 40 °C (N-Evap, Organomation Associates, Inc., South Berlin, MA, or equivalent), installed in a fume hood. This device may be used in place of the micro-Snyder column concentrator in Section 6.6.4 above. 6.7 Water bath: Heated, with concentric ring cover, capable of temperature control (±2 °C), installed in a fume hood. 6.8 Sample vials: Amber glass, 1- to 3-mL, with PTFE-lined screw-cap. 6.9 Balances. 6.9.1 Analytical: Capable of weighing 0.1 mg. 6.9.2 Top loading: Capable of weighing 10 mg. 6.10 pH meter. 6.11 Gas chromatograph: Shall have splitless or on-column injection port for capillary column, temperature program with 50 °C hold, and shall meet all of the performance specifications in Section 9. 6.12 Gas chromatographic column: 30 m (±5 m) × 0.25 mm (±0.02 mm) I.D. × 0.25 micron, 5% phenyl, 94% methyl, 1% vinyl silicone bonded-phase fused-silica capillary column (J & W DB–5, or equivalent). 6.13 Mass spectrometer: 70 eV electron impact ionization, shall repetitively scan from 42 to 450 amu in 0.95 to 1.00 second, and shall produce a unit resolution (valleys between m/z 441–442 less than 10% of the height of the 441 peak), background-corrected mass spectrum from 50 ng decafluorotriphenylphosphine (DFTPP) introduced through the GC inlet. The spectrum shall meet the mass-intensity criteria in Table 3 (Reference 7). The mass spectrometer shall be interfaced to the GC such that the end of the capillary column terminates within 1 cm of the ion source, but does not intercept the electron or ion beams. All portions of the column which connect the GC to the ion source shall remain at or above the column temperature during analysis to preclude condensation of less volatile compounds. 6.14 Data system: Shall collect and record MS data, store mass-intensity data in spectral libraries, process GCMS data, generate reports, and compute and record response factors. 6.14.1 Data acquisition: Mass spectra shall be collected continuously throughout the analysis and stored on a mass storage device. 6.14.2 Mass spectral libraries: User-created libraries containing mass spectra obtained from analysis of authentic standards shall be employed to reverse search GCMS runs for the compounds of interest (Section 10.2). 6.14.3 Data processing: The data system shall be used to search, locate, identify, and quantify the compounds of interest in each GCMS analysis. Software routines shall be employed to compute retention times, and to compute peak areas at the m/z's specified (Table 4). Displays of spectra, mass chromatograms, and library comparisons are required to verify results. 6.14.4 Response factors and multi-point calibrations: The data system shall be used to record and maintain lists of response factors (response ratios for isotope dilution) and multi-point calibration curves (Section 10). Computations of relative standard deviation (coefficient of variation) are used for testing calibration linearity. Statistics on initial (Section 9.3.2) and ongoing (Section 9.6) performance shall be computed and maintained. 7.0 Reagents and Standards 7.1 Reagents for adjusting sample pH. 7.1.1 Sodium hydroxide: Reagent grade, 6 N in reagent water. 7.1.2 Sulfuric acid: Reagent grade, 6 N in reagent water. 7.2 Reagents for sample preservation. 7.2.1 Sodium thiosulfate (Na2S2O3) solution (1 N): Weigh 79 g Na2S2O3 in a 1–L volumetric flask and dilute to the mark with reagent water. 7.2.2 Ascorbic acid solution: Prepare a solution of ascorbic acid in reagent water at a concentration of 0.1 g/mL. This solution must be prepared fresh on each day when derivatizations will be performed. Therefore, do not prepare more than will be used that day. (A 50-mL volume is sufficient for ten analyses). 7.3 Solvents: Hexane, acetone, and methanol. Distilled in glass (Burdick and Jackson, or equivalent). 7.4 Reagent water: Water in which the compounds of interest and interfering compounds are not detected by this method. 7.5 Reagents for derivatization. 7.5.1 Potassium carbonate (K2CO3). 7.5.1.1 Purification: Spread in a shallow baking dish, heat overnight at 400 to 500 °C. 7.5.1.2 Solution: Dissolve 150 g purified K2CO3 in 250 mL reagent water. 7.5.2 Acetic anhydride: Redistilled reagent grade. 7.6 Analytical standards. 7.6.1 Derivatization: Because the chlorinated phenolics are determined as their acetate derivatives after in situ acetylation, the method requires that the calibration standards be prepared by spiking the underivatized materials into reagent water and carrying the spiked reagent water aliquot through the entire derivatization and extraction procedure that is applied to the field samples. 7.6.2 Standard solutions: Purchased as solutions or mixtures with certification to their purity, concentration, and authenticity, or prepared from materials of known purity and composition. If chemical purity of a compound is 98% or greater, the weight may be used without correction to compute the concentration of the standard. When not being used, standards are stored in the dark at -20 to -10 °C in screw-capped vials with PTFE-lined lids. A mark is placed on the vial at the level of the solution so that solvent evaporation loss can be detected. The vials are brought to room temperature prior to use. 7.6.3 If the chemical purity of any standard does not meet the 98% requirement above, the laboratory must correct all calculations, calibrations, etc., for the difference in purity. 7.7 Preparation of stock solutions: Prepare chlorovanillins and chlorosyringaldehydes in acetone, as these compounds are subject to degradation in methanol. Prepare the remaining chlorophenolics in methanol. Prepare all standards per the steps below. Observe the safety precautions in Section 5. 7.7.1 Dissolve an appropriate amount of assayed reference material in a suitable solvent. For example, weigh 50 mg (±0.1 mg) of pentachlorophenol in a 10-mL ground-glass-stoppered volumetric flask and fill to the mark with methanol. After the pentachlorophenol is completely dissolved, transfer the solution to a 15-mL vial with PTFE-lined cap. 7.7.2 Stock solutions should be checked for signs of degradation prior to the preparation of calibration or performance test standards and shall be replaced after six months, or sooner if comparison with quality control check standards indicates a change in concentration. 7.8 Labeled compound spiking solution: From stock solutions prepared as above, or from mixtures, prepare one spiking solution to contain the labeled chlorovanillin in acetone and a second spiking solution to contain the remaining chlorophenolics, including the 3,4,5-trichlorophenol sample matrix internal standard (SMIS), in methanol. The labeled compounds and SMIS are each at a concentration of 12.5 µg/mL. 7.9 Secondary standards for calibration: Using stock solutions (Section 7.7), prepare one secondary standard containing the chlorovanillins and chlorsyringaldehydes listed in Table 1 in acetone and a second secondary standard containing the remaining chlorophenolics in methanol. The monochlorinated phenol, guaiacol, and catechol are included at a concentration of 25 µg/mL; the trichlorinated catechols, tetrachlorinated guaiacol and catechol, pentachlorophenol, 5,6-dichlorovanillin, and 2,6-dichlorosyringaldehyde are included at a concentration of 100 µg/mL; and the remaining compounds are included at a concentration of 50 µg/mL, each in their respective solutions. 7.10 Instrument internal standard (IIS): Prepare a solution of 2,2'-difluorobiphenyl (DFB) at a concentration of 2.5 mg/mL in hexane. 7.11 DFTPP solution: Prepare a solution of DFTPP at 50 µg/mL in acetone. 7.12 Solutions for obtaining authentic mass spectra (Section 10.2): Prepare mixtures of compounds at concentrations which will assure authentic spectra are obtained for storage in libraries. 7.13 Preparation of calibration solutions. 7.13.1 Into five 1000-mL aliquots of reagent water, spike 50, 100, 200, 500 and 1000 µL of each of the two solutions in Section 7.9. Spike 1.00 mL of each of the two labeled compound spiking solutions (Section 7.8) into each of the five aliquots. 7.13.2 Using the procedure in Section 11, derivatize and extract each solution, and concentrate the extract to a final volume of 0.50 mL. This will produce calibration solutions of nominal 5, 10, 20, 50, and 100 µg/mL of the native chlorophenolics and a constant concentration of 25 µg/mL of each labeled compound and the SMIS (assuming 100% derivatization and recovery). As noted in Section 11.1.6, ascorbic acid is added to all samples of final effluents to stabilize chlorocatechols, but is not added to samples of pulp and paper in-process wastewaters. Therefore, it is necessary to prepare separate sets of five initial calibration standards with and without the addition of ascorbic acid. Also, in the event that the laboratory is extracting final effluent samples by both the stir-bar and separatory funnel procedures (see Section 11.3), initial calibration standards should be prepared by both methods. 7.13.3 These solutions permit the relative response (labeled to unlabeled) and the response factor to be measured as a function of concentration (Sections 10.4 and 10.5). 7.13.4 The nominal 50 µg/mL standard may also be used as a calibration verification standard (see Section 9.6). 7.14 Ongoing precision and recovery (OPR) standard: Used for determination of initial (Section 9.3.2) and ongoing (Section 9.6) precision and recovery. This solution is prepared by spiking 500 µL of each the two solutions of the secondary calibration standards (Section 7.9) and 1 mL of each of the two labeled compound spiking solutions (Section 7.8) into 1000 mL of reagent water. 7.15 Stability of solutions: All standard solutions (Sections 7.7 through 7.14) shall be analyzed within 48 hours of preparation and on a monthly basis thereafter for signs of degradation. Standards will remain acceptable if the peak area at the quantitation m/z relative to the DFB internal standard remains within ±15% of the area obtained in the initial analysis of the standard. 8.0 Sample Collection, Preservation, and Storage 8.1 Collect samples in glass containers (Section 6.1) following conventional sampling practices (Reference 9). Aqueous samples are collected in refrigerated bottles using automatic sampling equipment. 8.2 Sample preservation. 8.2.1 Residual chlorine: If the sample contains residual chlorine, the chlorine must be reduced to eliminate positive interference resulting from continued chlorination reactions. Immediately after sampling, test for residual chlorine using the following method or an alternative EPA method (Reference 10). 8.2.1.1 Dissolve a few crystals of potassium iodide in the sample and add three to five drops of a 1% starch solution. A blue color indicates the presence of residual chlorine. 8.2.1.2 If residual chlorine is found, add 1 mL of sodium thiosulfate solution (Section 7.2.1) for each 2.5 ppm of free chlorine or until the blue color disappears. 8.2.2 Acidification: Adjust pH of all aqueous samples to <2 with sulfuric acid (Section 7.1.2). Failure to acidify samples may result in positive interferences from continued chlorination reactions. 8.2.3 Refrigeration: Maintain sample temperature at 0 to 4 °C from time of collection until extraction, and maintain extracts at a temperature of 0 to 4 °C from time of extraction until analysis. 8.3 Collect a minimum of 2000 mL of sample. This will provide a sufficient amount for all testing. Smaller amounts may be collected if the stream is known to contain high levels of chlorophenolics. 8.4 All samples must be acetylated and extracted within 30 days of collection, and must be analyzed within 30 days of acetylation. If labeled compound recoveries for a sample do not meet the acceptance criteria in Table 5 and the 30-day holding time is not met, a new sample must be collected. 9.0 Quality Control 9.1 Each laboratory that uses this method is required to operate a formal quality assurance program (Reference 8). The minimum requirements of this program consist of an initial demonstration of laboratory capability, analysis of samples spiked with labeled compounds to evaluate and document data quality, and analysis of standards and blanks as tests of continued performance. Laboratory performance is compared to established performance criteria to determine if the results of analyses meet the performance characteristics of the method. 9.1.1 DFTPP spectrum validity shall be checked at the beginning of each eight-hour shift during which analyses are performed. This test is described in Section 9.2. 9.1.2 The laboratory shall make an initial demonstration of the ability to generate acceptable results with this method. This ability is established as described in Section 9.3. 9.1.3 The laboratory is permitted to modify this method to improve separations or lower the costs of measurements, provided all performance specifications are met. Each time a modification is made to the method, the laboratory is required to repeat the procedures in Sections 10.3 and 9.3.2 to demonstrate method performance. If the detection limits for the analytes in this method will be affected by the modification, the laboratory should demonstrate that each MDL (40 CFR 136, Appendix B) is less than or equal to the MDL in this method or one-third the regulatory compliance level, whichever is higher. 9.1.4 The laboratory shall spike all samples with labeled compounds and the sample matrix internal standard (SMIS) to monitor method performance. This test is described in Section 9.4. When results of these spikes indicate atypical method performance for samples, the samples are diluted to bring method performance within acceptable limits (Section 13). 9.1.5 Analyses of blanks are required to demonstrate freedom from contamination. The procedures and criteria for analysis of a blank are described in Section 9.5. 9.1.6 The laboratory shall, on an ongoing basis, demonstrate through analysis of the ongoing precision and recovery standard (Section 7.14) that the analysis system is in control. These procedures are described in Section 9.6. 9.1.7 The laboratory shall maintain records to define the quality of data that is generated. Development of accuracy statements is described in Section 9.4.4 and 9.6.3. 9.2 DFTPP spectrum validity: Inject 1 µL of the DFTPP solution (Section 7.11) either separately or within a few seconds of injection of the OPR standard (Section 9.6) analyzed at the beginning of each shift. The criteria in Table 3 shall be met. 9.3 Initial demonstration of laboratory capability. 9.3.1 Method Detection Limit (MDL): To establish the ability to detect the analytes in this method, the laboratory should determine the MDL per the procedure in 40 CFR 136, Appendix B using the apparatus, reagents, and standards that will be used in the practice of this method. MDLs less than or equal to the MDLs in Table 2 should be achieved prior to the practice of this method. 9.3.2 Initial precision and recovery (IPR): To establish the ability to demonstrate control over the analysis system and to generate acceptable precision and accuracy, the laboratory shall perform the following operations: 9.3.2.1 Derivatize, extract, concentrate, and analyze four 1000-mL aliquots of the ongoing precision and recovery standard (OPR; Section 7.14), according to the procedure in Section 11. Separate sets of IPR aliquots must be prepared with the addition of ascorbic acid and without. 9.3.2.2 Using results of the four analyses, compute the average percent recovery (X) and the relative standard deviation of the recovery (s) for each compound, by isotope dilution for pollutants with a labeled analog, and by internal standard for pollutants with no labeled analog and for the labeled compounds and the SMIS. 9.3.2.3 For each compound, compare s and X with the corresponding limits for initial precision and recovery in Table 5. If s and X for all compounds meet the acceptance criteria, system performance is acceptable and analysis of blanks and samples may begin. If, however, any individual s exceeds the precision limit or any individual X falls outside the range for recovery, system performance is unacceptable for that compound. In this event, correct the problem and repeat the test (Section 9.3.2). 9.4 Labeled compound recovery: The laboratory shall spike all samples with labeled compounds and the sample matrix internal standard (SMIS) to assess method performance on the sample matrix. 9.4.1 Analyze each sample according to the method beginning in Section 11. 9.4.2 Compute the percent recovery (P) of the labeled compounds and the SMIS using the internal standard method (Section 14.3) with 2,2'-difluorobiphenyl as the reference compound. 9.4.3 Compare the labeled compound and SMIS recovery for each compound with the corresponding limits in Table 5. If the recovery of any compound falls outside its warning limit, method performance is unacceptable for that compound in that sample. Therefore, the sample is complex. The sample is diluted and reanalyzed per Section 13. 9.4.4 As part of the QA program for the laboratory, it is suggested, but not required, that method accuracy for samples be assessed and records maintained. After the analysis of five samples for which the labeled compounds pass the tests in Section 9.4.3, compute the average percent recovery (P) and the standard deviation of the percent recovery (sp) for the labeled compounds only. Express the accuracy assessment as a percent recovery interval from P-2sp to P = 2sp for each matrix. For example, if P = 90% and sp = 10%, the accuracy interval is expressed as 70 to 110%. Update the accuracy assessment for each compound on a regular basis (e.g., after each 20 to 30 new accuracy measurements). 9.5 Blanks: Reagent water blanks are analyzed to demonstrate freedom from contamination. 9.5.1 Extract and concentrate a 1000-mL reagent water blank with each sample batch (samples started through the extraction process on the same eight-hour shift, to a maximum of 20 samples). Blanks associated with samples to which ascorbic acid is added must be prepared with ascorbic acid, and blanks associated with samples to which ascorbic acid is not added must be prepared without ascorbic acid. Analyze the blank immediately after analysis of the OPR (Section 7.14) to demonstrate freedom from contamination. 9.5.2 If any of the compounds of interest (Table 1) or any potentially interfering compound is found in an aqueous blank at greater than 5 µg/L (assuming a response factor of one relative to the sample matrix internal standard for compounds not listed in Table 1), analysis of samples is halted until the source of contamination is eliminated and a blank shows no evidence of contamination at this level. 9.6 Calibration verification and ongoing precision and recovery: At the beginning of each eight-hour shift during which analyses are performed, analytical system performance is verified for all compounds. Analysis of DFTPP (Section 9.2) and the nominal 50 µg/mL OPR (Section 11.1.5) is used to verify all performance criteria. Adjustment and/or recalibration, per Section 10, shall be performed until all performance criteria are met. Only after all performance criteria are met may samples and blanks be analyzed. 9.6.1 Analyze the extract of the OPR (Section 11.1.5) at the beginning of each eight-hour shift and prior to analysis of samples from the same batch. Alternatively, a separate calibration verification may be performed using an aliquot of the midpoint calibration standard from Section 7.13 (with a nominal concentration of 50 µg/mL). This alternative may be used to check instrument performance on failure of an OPR, or when samples extracted with an OPR aliquot are not analyzed within the same eight-hour analysis shift. 9.6.1.1 Retention times: The absolute retention time of 2,2'-difluorobiphenyl shall be within the range of 765 to 885 seconds, and the relative retention times of all pollutants and labeled compounds shall fall within the limits given in Table 2. 9.6.1.2 GC resolution: The valley height between 4,6-dichloroguaiacol and 3,4-dichloroguaiacol at m/z 192 shall not exceed 10% of the height of the taller of the two peaks. 9.6.1.3 Multiple peaks: Each compound injected shall give a single, distinct GC peak. 9.6.2 Compute the percent recovery of each pollutant (Table 1) by isotope dilution (Section 10.4) for those compounds that have labeled analogs. Compute the percent recovery of each pollutant that has no labeled analog by the internal standard method (Section 10.5), using the 3,4,5-trichlorophenol (SMIS) as the internal standard. Compute the percent recovery of the labeled compounds and the SMIS by the internal standard method, using the 2,2'-difluorobiphenyl as the internal standard. 9.6.2.1 For each compound, compare the recovery with the limits for ongoing precision and recovery in Table 5. If all compounds meet the acceptance criteria, system performance is acceptable and analysis of blanks and samples may proceed. If, however, any individual recovery falls outside of the range given, system performance is unacceptable for that compound. In this event, there may be a problem with the GCMS or with the derivatization/extraction/concentration systems. 9.6.2.2 GCMS system: To determine if the failure of the OPR test (Section 9.6.2.1) is due to instrument drift, analyze the current calibration verification extract (Section 7.13.4), calculate the percent recoveries of all compounds, and compare with the OPR recovery limits in Table 5. If all compounds meet these criteria, GCMS performance/stability is verified, and the failure of the OPR analysis is attributed to problems in the derivatization/extraction/concentration of the OPR. In this case, analysis of the sample extracts may proceed. However, failure of any of the recovery criteria in the analysis of a sample extract requires rederivatization of that sample (Sections 13.3.1 and 13.3.2). If, however, the performance/stability of the GCMS is not verified by analysis of the calibration verification extract, the GCMS requires recalibration and all extracts associated with the failed OPR must be reanalyzed. 9.6.3 Add results that pass the specifications in Section 9.6.2.1 to initial and previous ongoing data for each compound. Update QC charts to form a graphic representation of continued laboratory performance. Develop a statement of laboratory accuracy for each pollutant and labeled compound in each matrix type (reagent water, C-stage filtrate, E-stage filtrate, final effluent, etc.) by calculating the average percent recovery (R) and the standard deviation of percent recovery (sr). Express the accuracy as a recovery interval from R- 2sr to R = 2sr. For example, if R = 95% and sr = 5%, the accuracy is 85 to 105%. 9.7 The specifications contained in this method can be met if the apparatus used is calibrated properly, then maintained in a calibrated state. The standards used for calibration (Section 10) and for initial (Section 9.3.2) and ongoing (Section 9.6) precision and recovery should be identical, so that the most precise results will be obtained. The GCMS instrument in particular will provide the most reproducible results if dedicated to the settings and conditions required for the analyses of chlorophenolics by this method. 9.8 Depending on specific program requirements, field replicates may be collected to determine the precision of the sampling technique, and spiked samples may be required to determine the accuracy of the analysis when the internal standard method is used. 10.0 Calibration and Standardization 10.1 Assemble the GCMS and establish the operating conditions in Section 12. Analyze standards per the procedure in Section 12 to demonstrate that the analytical system meets the minimum levels in Table 2, and the mass-intensity criteria in Table 3 for 50 ng DFTPP. 10.2 Mass-spectral libraries: Detection and identification of compounds of interest are dependent upon spectra stored in user-created libraries. 10.2.1 Obtain a mass spectrum of the acetyl derivative of each chlorophenolic compound (pollutant, labeled compound, and the sample matrix internal standard) by derivatizing and analyzing an authentic standard either singly or as part of a mixture in which there is no interference between closely eluting components. That only a single compound is present is determined by examination of the spectrum. Fragments not attributable to the compound under study indicate the presence of an interfering compound. 10.2.2 Adjust the analytical conditions and scan rate (for this test only) to produce an undistorted spectrum at the GC peak maximum. An undistorted spectrum will usually be obtained if five complete spectra are collected across the upper half of the GC peak. Software algorithms designed to “enhance” the spectrum may eliminate distortion, but may also eliminate authentic m/z's or introduce other distortion. 10.2.3 The authentic reference spectrum is obtained under DFTPP tuning conditions (Section 10.1 and Table 3) to normalize it to spectra from other instruments. 10.2.4 The spectrum is edited by removing all peaks in the m/z 42 to 45 range, and saving the five most intense mass spectral peaks and all other mass spectral peaks greater than 10% of the base peak (excluding the peaks in the m/z 42 to 45 range). The spectrum may be further edited to remove common interfering m/z's. The spectrum obtained is stored for reverse search and for compound confirmation. 10.3 Minimum level: Demonstrate that the chlorophenolics are detectable at the minimum level (per all criteria in Section 14). The nominal 5 µg/mL calibration standard (Section 7.13) can be used to demonstrate this performance. 10.4 Calibration with isotope dilution: Isotope dilution is used when (1) labeled compounds are available, (2) interferences do not preclude its use, and (3) the quantitation m/z (Table 4) extracted ion-current profile (EICP) area for the compound is in the calibration range. Alternative labeled compounds and quantitation m/z's may be used based on availability. If any of the above conditions preclude isotope dilution, the internal standard calibration method (Section 10.5) is used. 10.4.1 A calibration curve encompassing the concentration range is prepared for each compound to be determined. The relative response (pollutant to labeled) vs. concentration in standard solutions is plotted or computed using a linear regression. The example in Figure 1 shows a calibration curve for phenol using phenol-d5 as the isotopic diluent. Also shown are the ±10% error limits (dotted lines). Relative response (RR) is determined according to the procedures described below. A minimum of five data points are employed for calibration. 10.4.2 The relative response of a pollutant to its labeled analog is determined from isotope ratio values computed from acquired data. Three isotope ratios are used in this process: Rx = the isotope ratio measured for the pure pollutant. Ry = the isotope ratio measured for the labeled compound. Rm = the isotope ratio of an analytical mixture of pollutant and labeled compounds. The m/z's are selected such that Rx>Ry. If Rm is not between 2Ry and 0.5Rx, the method does not apply and the sample is analyzed by the internal standard method. 10.4.3 Capillary columns sometimes separate the pollutant-labeled pair when deuterium labeled compounds are used, with the labeled compound eluted first (Figure 2). For this case, 10.4.4 When the pollutant-labeled pair is not separated (as occurs with carbon-13-labeled compounds), or when another labeled compound with interfering spectral masses overlaps the pollutant (a case which can occur with isomeric compounds), it is necessary to determine the contributions of the pollutant and labeled compound to the respective EICP areas. If the peaks are separated well enough to permit the data system or operator to remove the contributions of the compounds to each other, the equations in Section 10.4.3 apply. This usually occurs when the height of the valley between the two GC peaks at the same m/z is less than 70 to 90% of the height of the shorter of the two peaks. If significant GC and spectral overlap occur, RR is computed using the following equation: Where: Rx is measured as shown in figure 3A, Ry is measured as shown in figure 3B, Rm is measured as shown in figure 3C. For example, Rx = 46100/4780 = 9.644; Ry = 2650/43600 = 0.0608; Rm = 49200/48300 = 1.1019; thus, RR = 1.114. 10.4.5 To calibrate the analytical system by isotope dilution, analyze a 1-µL aliquot of each of the calibration standards (Section 7.13) using the procedure in Section 12. Compute the RR at each concentration. 10.4.6 Linearity: If the ratio of relative response to concentration for any compound is constant (less than 20% coefficient of variation) over the five-point calibration range, an averaged relative response/concentration ratio may be used for that compound; otherwise, the complete calibration curve for that compound shall be used over the five-point calibration range. 10.5 Calibration by internal standard: The method contains two types of internal standards, the sample matrix internal standard (SMIS) and the instrument internal standard (IIS), and they are used for different quantitative purposes. The 3,4,5-trichlorophenol sample matrix internal standard (SMIS) is used for measurement of all pollutants with no labeled analog and when the criteria for isotope dilution (Section 10.4) cannot be met. The 2,2'-difluorobiphenyl instrument internal standard (IIS) is used for determination of the labeled compounds and the SMIS. The results are used for intralaboratory statistics (Sections 9.4.4 and 9.6.3). 10.5.1 Response factors: Calibration requires the determination of response factors (RF) for both the pollutants with no labeled analog and for the labeled compounds and the SMIS. The response factor is defined by the following equation: Where: As=the area of the characteristic mass for the compound in the daily standard. Ais=the area of the characteristic mass for the internal standard. Cis=the concentration of the internal standard (µg/mL). Cs=is the concentration of the compound in the calibration standard (µg/mL). When this equation is used to determine the response factors for pollutant compounds without labeled analogs, use the area (Ais) and concentration (Cis) of 3,4,5-trichlorophenol (SMIS) as the internal standard. When this equation is used to determine the response factors for the labeled analogs and the SMIS, use the area (Ais) and concentration (Cis) of 2,2'-difluorobiphenyl as the internal standard. 10.5.2 The response factor is determined for at least five concentrations appropriate to the response of each compound (Section 7.13); nominally, 5, 10, 20, 50, and 100 µg/mL. The amount of SMIS added to each solution is the same (25 µg/mL) so that Cis remains constant. Likewise, the concentration of IIS is constant in each solution. The area ratio (As/Ais) is plotted versus the concentration ratio (Cs/Cis) for each compound in the standard to produce a calibration curve. 10.5.3 Linearity: If the response factor (RF) for any compound is constant (less than 35% coefficient of variation) over the five-point calibration range, an averaged response factor may be used for that compound; otherwise, the complete calibration curve for that compound shall be used over the five-point range. 10.6 Combined calibration: By using calibration solutions (Section 7.13) containing the pollutants, labeled compounds, and the internal standards, a single set of analyses can be used to produce calibration curves for the isotope dilution and internal standard methods. These curves are verified each shift (Section 9) by analyzing the OPR standard, or an optional calibration verification (VER) standard. Recalibration is required only if OPR criteria (Section 9.6 and Table 5) cannot be met. 11.0 Sample Derivatization, Extraction, and Concentration The procedure described in this section uses a stir-bar in a beaker for the derivatization. The extraction procedures applied to samples depend on the type of sample being analyzed. Extraction of samples from in-process wastewaters is performed using a separatory funnel procedure. All calibrations, IPR, OPR, and blank analyses associated with in-process wastewater samples must be performed by the separatory funnel procedure. Extraction of samples of final effluents and raw water may be performed using either the stir-bar procedure or the separatory funnel procedure. However, all calibrations, IPR, OPR, blank, and sample analyses must be performed using the same procedure. Both procedures are described below. 11.1 Preparation of all sample types for stir-bar derivatization. 11.1.1 Allow sample to warm to room temperature. 11.1.2 Immediately prior to measuring, shake sample vigorously to insure homogeneity. 11.1.3 Measure 1000 mL (±10 mL) of sample into a clean 2000-mL beaker. Label the beaker with the sample number. 11.1.4 Dilute aliquot(s). 11.1.4.1 Complex samples: For samples that are expected to be difficult to derivatize, concentrate, or are expected to overload the GC column or mass spectrometer, measure an additional 100 mL (±1 mL) into a clean 2000-mL beaker and dilute to a final volume of 1000-mL (±50 mL) with reagent water. Label with the sample number and as the dilute aliquot. However, to ensure adequate sensitivity, a 1000-mL aliquot must always be prepared and analyzed. 11.1.4.2 Pulp and paper industry samples: For in-process streams such as E-stage and C-stage filtrates and other in-process wastewaters, it may be necessary to prepare an aliquot at an additional level of dilution. In this case, dilute 10 mL (±0.1 mL) of sample to 1000-mL (±50 mL). 11.1.5 QC aliquots: For a batch of samples of the same type to be extracted at the same time (to a maximum of 20), place two 1000-mL (±10 mL) aliquots of reagent water in clean 2000-mL beakers. Label one beaker as the blank and the other as the ongoing precision and recovery (OPR) aliquot. Because final effluent samples are treated with ascorbic acid and in-process wastewater samples are not (see Section 11.1.6), prepare an OPR aliquot and a blank for the final effluent and a separate pair for the in-process samples. Treat these QC aliquots in the same fashion as the associated samples, adding ascorbic acid to the pair associated with the final effluents, and not adding ascorbic acid to the pair associated with the in-process samples. 11.1.6 Ascorbic acid: Added to stabilize chlorocatechols. However, for pulp and paper industry in-process streams and other in-process wastewaters, the addition of ascorbic acid may convert chloro-o-quinones to catechols if these quinones are present. Separate calibration curves must be prepared with and without the addition of ascorbic acid (Section 7.13.2). 11.1.6.1 Spike 5 to 6 mL of the ascorbic acid solution (Section 7.2.2) into each final effluent sample, and the associated calibration standards, IPR and OPR aliquots, and blank. 11.1.6.2 For pulp and paper industry C-stage filtrates, E-stage filtrates, and untreated effluents, omit the ascorbic acid to prevent the conversion of chloro-o-quinones to catechols. Prepare calibration standards, IPR and OPR aliquots, and blanks associated with these samples without ascorbic acid as well. 11.1.7 Spike 1000 µL of the labeled compound spiking solution (Section 7.8) into the sample and QC aliquots. 11.1.8 Spike 500 µL of the nominal 50 µg/mL calibration solution (Section 7.13.4) into the OPR aliquot. 11.1.9 Adjust the pH of the sample aliquots to between 7.0 and 7.1. For calibration standards, IPR and OPR aliquots, and blanks, pH adjustment is not required. 11.1.10 Equilibrate all sample and QC solutions for approximately 15 minutes, with occasional stirring. 11.2 Derivatization: Because derivatization must proceed rapidly, particularly upon the addition of the K2CO3 buffer, it is necessary to work with one sample at a time until the derivatization step (Section 11.2.3) is complete. 11.2.1 Place a beaker containing a sample or QC aliquot on the magnetic stirrer in a fume hood, drop a clean stirring bar into the beaker, and increase the speed of the stirring bar until the vortex is drawn to the bottom of the beaker. 11.2.2 Measure 25 to 26 mL of K2CO3 buffer into a graduated cylinder or other container and 25 to 26 mL of acetic acid into another. 11.2.3 Add the K2CO3 buffer to the sample or QC aliquot, immediately (within one to three seconds) add the acetic anhydride, and stir for three to five minutes to complete the derivatization. 11.3 Extraction: Two procedures are described below for the extraction of derivatized samples. The choice of extraction procedure will depend on the sample type. For final effluent samples, either of two procedures may be utilized for extraction of derivatized samples. For samples of in-process wastewaters, the separatory funnel extraction procedure must be used. Note: Whichever procedure is employed, the same extraction procedure must be used for calibration standards, IPR aliquots, OPR aliquots, blanks, and the associated field samples. 11.3.1 Stir-bar extraction of final effluents. 11.3.1.1 Add 200 mL (±20 mL) of hexane to the beaker and stir for three to five minutes, drawing the vortex to the bottom of the beaker. 11.3.1.2 Stop the stirring and drain the hexane and a portion of the water into a 500-to 1000-mL separatory funnel. Allow the layers to separate. 11.3.1.3 Drain the aqueous layer back into the beaker. 11.3.1.4 The formation of emulsions can be expected in any solvent extraction procedure. If an emulsion forms, the laboratory must take steps to break the emulsion before proceeding. Mechanical means of breaking the emulsion include the use of a glass stirring rod, filtration through glass wool, and other techniques. For emulsions that resist these techniques, centrifugation is nearly 100% effective. If centrifugation is employed to break the emulsion, drain the organic layer into a centrifuge tube, cap the tube, and centrifuge for two to three minutes or until the phases separate. If the emulsion cannot be completely broken, collect as much of the organic phase as possible, and measure and record the volume of the organic phase collected. If all efforts to break the emulsion fail, including centrifugation, and none of the organic phase can be collected, proceed with the dilute aliquot (Section 11.1.4.2). However, use of the dilute aliquot will sacrifice the sensitivity of the method, and may not be appropriate in all cases. 11.3.1.5 Drain the organic layer into a Kuderna-Danish (K-D) apparatus equipped with a 10-mL concentrator tube. Label the K-D apparatus. It may be necessary to pour the organic layer through a funnel containing anhydrous sodium sulfate to remove any traces of water from the extract. 11.3.1.6 Repeat the extraction (Section 11.3.1.1 through 11.3.1.5) two more times using another 200-mL of hexane for each extraction, combining the extracts in the K-D apparatus. 11.3.1.7 Proceed with concentration of the extract, as described in Section 11.4. 11.3.2 Separatory funnel extraction of either final effluents or in-process wastewaters. 11.3.2.1 Transfer the derivatized sample or QC aliquot to a 2-L separatory funnel. 11.3.2.2 Add 200 mL (±20 mL) of hexane to the separatory funnel. Cap the funnel and extract the sample by shaking the funnel for two to three minutes with periodic venting. 11.3.2.3 Allow the organic layer to separate from the water phase for a minimum of 10 minutes. 11.3.2.4 Drain the lower aqueous layer into the beaker used for derivatization (Section 11.2), or into a second clean 2-L separatory funnel. Transfer the solvent to a 1000-mL K-D flask. It may be necessary to pour the organic layer through a funnel containing anhydrous sodium sulfate to remove any traces of water from the extract. 11.3.2.5 The formation of emulsions can be expected in any solvent extraction procedure. If an emulsion forms, the laboratory must take steps to break the emulsion before proceeding. Mechanical means of breaking the emulsion include the use of a glass stirring rod, filtration through glass wool, and other techniques. For emulsions that resist these techniques, centrifugation may be required. If centrifugation is employed to break the emulsion, drain the organic layer into a centrifuge tube, cap the tube, and centrifuge for two to three minutes or until the phases separate. If the emulsion cannot be completely broken, collect as much of the organic phase as possible, and measure and record the volume of the organic phase collected. If all efforts to break the emulsion, including centrifugation, fail and none of the organic phase can be collected, proceed with the dilute aliquot (Section 11.1.4.2). However, use of the dilute aliquot will sacrifice the sensitivity of the method, and may not be appropriate in all cases. 11.3.2.6 If drained into a beaker, transfer the aqueous layer to the 2-L separatory funnel (Section 11.3.2.1). Perform a second extraction using another 200 mL of fresh solvent. 11.3.2.7 Transfer the extract to the 1000-mL K-D flask in Section 11.3.2.4. 11.3.2.8 Perform a third extraction in the same fashion as above. 11.3.2.9 Proceed with concentration of the extract, as described in Section 11.4. 11.4 Macro concentration: Concentrate the extracts in separate 1000-mL K-D flasks equipped with 10-mL concentrator tubes. Add one to two clean boiling chips to the flask and attach a three-ball macro-Snyder column. Prewet the column by adding approximately 1 mL of hexane through the top. Place the K-D apparatus in a hot water bath so that the entire lower rounded surface of the flask is bathed with steam. Adjust the vertical position of the apparatus and the water temperature as required to complete the concentration in 15 to 20 minutes. At the proper rate of distillation, the balls of the column will actively chatter but the chambers will not flood. When the liquid has reached an apparent volume of 1 mL, remove the K-D apparatus from the bath and allow the solvent to drain and cool for at least 10 minutes. Remove the Snyder column and rinse the flask and its lower joint into the concentrator tube with 1 to 2 mL of hexane. A 5-mL syringe is recommended for this operation. 11.5 Micro-concentration: Final concentration of the extracts may be accomplished using either a micro-Snyder column or nitrogen evaporation. 11.5.1 Micro-Snyder column: Add a clean boiling chip and attach a two-ball micro-Snyder column to the concentrator tube. Prewet the column by adding approximately 0.5 mL hexane through the top. Place the apparatus in the hot water bath. Adjust the vertical position and the water temperature as required to complete the concentration in 5 to 10 minutes. At the proper rate of distillation, the balls of the column will actively chatter but the chambers will not flood. When the liquid reaches an apparent volume of approximately 0.2 mL, remove the apparatus from the water bath and allow to drain and cool for at least 10 minutes. Remove the micro-Snyder column and rinse its lower joint into the concentrator tube with approximately 0.2 mL of hexane. Adjust to a final volume of 0.5 mL. 11.5.2 Nitrogen evaporation: Transfer the concentrator tube to a nitrogen evaporation device and direct a gentle stream of clean dry nitrogen into the concentrator. Rinse the sides of the concentrator tube with small volumes of hexane, and concentrate the extract to a final volume of 0.5 mL. 11.6 Spike each extract with 10 µL of the 2,2'-difluorobiphenyl IIS (Section 7.10) and transfer the concentrated extract to a clean screw-cap vial using hexane to rinse the concentrator tube. Seal the vial with a PTFE-lined lid, and mark the level on the vial. Label with the sample number and store in the dark at -20 to -10 °C until ready for analysis. 12.0 GCMS Analysis 12.1 Establish the following operating conditions: Carrier gas flow: Helium at 30 cm/sec at 50 °C Injector temperature: 300 °C Initial temperature: 50 °C Temperature program: 8 °C/min to 270 °C Final hold: Until after 2,6-dichlorosyringaldehyde elutes Adjust the GC conditions to meet the requirements in Section 9.6.1.1 and Table 2 for analyte separation and sensitivity. Once optimized, the same GC conditions must be used for the analysis of all standards, blanks, IPR and OPR aliquots, and samples. 12.2 Bring the concentrated extract (Section 11.6) or standard (Sections 7.13 and 7.14) to room temperature and verify that any precipitate has redissolved. Verify the level on the extract (Sections 7.13, 7.14, and 11.6) and bring to the mark with solvent if required. 12.3 Inject a 1-µL volume of the standard solution or extract using on-column or splitless injection. For 0.5 mL extracts, this 1-µL injection volume will contain 50 ng of the DFB internal standard. If an injection volume other than 1 µL is used, that volume must contain 50 ng of DFB. 12.4 Start the GC column temperature ramp upon injection. Start MS data collection after the solvent peak elutes. Stop data collection after the 2,6-dichlorosyringaldehyde peak elutes. Return the column to the initial temperature for analysis of the next sample. 13.0 Analysis of Complex Samples Some samples may contain high levels (>1000 µg/L) of the compounds of interest, interfering compounds, and/or other phenolic materials. Some samples will not concentrate to 0.5 mL (Section 11.5); others will overload the GC column and/or mass spectrometer; others may contain amounts of phenols that may exceed the capacity of the derivatizing agent. 13.1 Analyze the dilute aliquot (Section 11.1.4) when the sample will not concentrate to 0.5 mL. If a dilute aliquot was not extracted, and the sample holding time (Section 8.4) has not been exceeded, dilute an aliquot of sample with reagent water, and derivatize and extract it (Section 11.1.4). Otherwise, dilute the extract (Section 14.7.3) and quantitate it by the internal standard method (Section 14.3). 13.2 Recovery of the 2,2'-difluorobiphenyl instrument internal standard: The EICP area of the internal standard should be within a factor of two of the area in the OPR or VER standard (Section 9.6). If the absolute areas of the labeled compounds and the SMIS are within a factor of two of the respective areas in the OPR or VER standard, and the DFB internal standard area is less than one-half of its respective area, then internal standard loss in the extract has occurred. In this case, analyze the extract from the dilute aliquot (Section 11.1.4). 13.3 Recovery of labeled compounds and the sample matrix internal standard (SMIS): SMIS and labeled compound recovery specifications have been developed for samples with and without the addition of ascorbic acid. Compare the recoveries to the appropriate limits in Table 5. 13.3.1 If SMIS or labeled compound recoveries are outside the limits given in Table 5 and the associated OPR analysis meets the recovery criteria, the extract from the dilute aliquot (Section 11.1.4) is analyzed as in Section 14.7. 13.3.2 If labeled compound or SMIS recovery is outside the limits given in Table 5 and the associated OPR analysis did not meet recovery criteria, a problem in the derivatization/extraction/concentration of the sample is indicated, and the sample must be rederivatized and reanalyzed. 14.0 Data Analysis and Calculations 14.1 Qualitative determination: Identification is accomplished by comparison of data from analysis of a sample or blank with data stored in the mass spectral libraries. Identification of a compound is confirmed when the following criteria are met: 14.1.1 The signals for m/z 43 (to indicate the presence of the acetyl derivative) and all characteristic m/z's stored in the spectral library (Section 10.2.4) shall be present and shall maximize within the same two consecutive scans. 14.1.2 Either (1) the background corrected EICP areas, or (2) the corrected relative intensities of the mass spectral peaks at the GC peak maximum shall agree within a factor of two (0.5 to 2 times) for all m/z's stored in the library. 14.1.3 The relative retention time shall be within the window specified in Table 2. 14.1.4 The m/z's present in the mass spectrum from the component in the sample that are not present in the reference mass spectrum shall be accounted for by contaminant or background ions. If the mass spectrum is contaminated, an experienced spectrometrist (Section 1.4) shall determine the presence or absence of the compound. 14.2 Quantitative determination by isotope dilution: By adding a known amount of a labeled compound to every sample prior to derivatization and extraction, correction for recovery of the pollutant can be made because the pollutant and its labeled analog exhibit the same effects upon derivatization, extraction, concentration, and gas chromatography. Relative response (RR) values for sample mixtures are used in conjunction with calibration curves described in Section 10.4 to determine concentrations directly, so long as labeled compound spiking levels are constant. For the phenol example given in Figure 1 (Section 10.4.1), RR would be equal to 1.114. For this RR value, the phenol calibration curve given in Figure 1 indicates a concentration of 27 µg/mL in the sample extract (Cex). 14.2.1 Compute the concentration in the extract using the response ratio determined from calibration data (Section 10.4) and the following equation: Where: Cex = concentration of the pollutant in the extract. An = area of the characteristic m/z for the pollutant. Cl = concentration of the labeled compound in the extract. Al = area of the characteristic m/z for the labeled compound. RR = response ratio from the initial calibration. 14.2.2 For the IPR (Section 9.3.2) and OPR (Section 9.6), compute the percent recovery of each pollutant using the equation in Section 14.6. The percent recovery is used for the evaluation of method and laboratory performance, in the form of IPR (Section 9.3.2) and OPR (Section 9.6). 14.3 Quantitative determination by internal standard: Compute the concentration using the response factor determined from calibration data (Section 10.5) and the following equation: Where: Cex = concentration of the pollutant in the extract. As = area of the characteristic m/z for the pollutant. Cis = concentration of the internal standard in the extract (see note below). Ais = area of the characteristic m/z for the internal standard. RF = response factor from the initial calibration. Note: When this equation is used to compute the extract concentrations of native compounds without labeled analogs, use the area (Ais) and concentration (Cis) of 3,4,5-trichlorophenol (SMIS) as the internal standard. For the IPR (Section 9.3.2) and OPR (Section 9.6), compute the percent recovery using the equation in Section 14.6. Note: Separate calibration curves will be required for samples with and without the addition of ascorbic acid, and also for both extraction procedures (stir-bar and separatory funnel) where applicable. 14.4 Compute the concentration of the labeled compounds and the SMIS using the equation in Section 14.3, but using the area and concentration of the 2,2'-difluorobiphenyl as the internal standard, and the area of the labeled compound or SMIS as As. 14.5 Compute the concentration of each pollutant compound in the sample using the following equation: Where: Cs = Concentration of the pollutant in the sample. Cex = Concentration of the pollutant in the extract. Vex = Volume of the concentrated extract (typically 0.5 mL). Vo = Volume of the original sample in liters. 14.6 Compute the recovery of each labeled compound and the SMIS as the ratio of concentration (or amount) found to the concentration (or amount) spiked, using the following equation: These percent recoveries are used to assess method performance according to Sections 9 and 13. 14.7 If the EICP area at the quantitation m/z for any compound exceeds the calibration range of the system, three approaches are used to obtain results within the calibration range. 14.7.1 If the recoveries of all the labeled compounds in the original sample aliquot meet the limits in Table 5, then the extract of the sample may be diluted by a maximum of a factor of 10, and the diluted extract reanalyzed. 14.7.2 If the recovery of any labeled compound is outside its limits in Table 5, or if a tenfold dilution of the extract will not bring the pollutant within the calibration range, then extract and analyze a dilute aliquot of the sample (Section 11). Dilute 100 mL, 10 mL, or an appropriate volume of sample to 1000 mL with reagent water and extract per Section 11. 14.7.3 If the recoveries of all labeled compounds in the original sample aliquot (Section 14.7.1) meet the limits in Table 5, and if the sample holding time has been exceeded, then the original sample extract is diluted by successive factors of 10, the DFB internal standard is added to give a concentration of 50 µg/mL in the diluted extract, and the diluted extract is analyzed. Quantitation of all analytes is performed using the DFB internal standard. 14.7.4 If the recoveries of all labeled compounds in the original sample aliquot (Section 14.7.1) or in the dilute aliquot (Section 14.7.2) (if a dilute aliquot was analyzed) do not meet the limits in Table 5, and if the holding time has been exceeded, re-sampling is required. 14.8 Results are reported for all pollutants, labeled compounds, and the sample matrix internal standard in standards, blanks, and samples, in units of µg/L. 14.8.1 Results for samples which have been diluted are reported at the least dilute level at which the area at the quantitation m/z is within the calibration range (Section 14.7). 14.8.2 For compounds having a labeled analog, results are reported at the least dilute level at which the area at the quantitation m/z is within the calibration range (Section 14.7) and the labeled compound recovery is within the normal range for the method (Section 13.3). 15.0 Method Performance 15.1 Single laboratory performance for this method is detailed in References 1, 2, and 11. Acceptance criteria were established from multiple laboratory use of the draft method. 15.2 A chromatogram of the ongoing precision and recovery standard (Section 7.14) is shown in Figure 4. 16.0 Pollution Prevention 16.1 The solvents used in this method pose little threat to the environment when recycled and managed properly. 16.2 Standards should be prepared in volumes consistent with laboratory use to minimize the volume of expired standards to be disposed. 17.0 Waste Management 17.1 It is the laboratory's responsibility to comply with all federal, state, and local regulations governing waste management, particularly the hazardous waste identification rules and land disposal restrictions, and to protect the air, water, and land by minimizing and controlling all releases from fume hoods and bench operations. Compliance with all sewage discharge permits and regulations is also required. 17.2 Samples preserved with HCl or H2SO4 to pH < 2 are hazardous and must be neutralized before being disposed, or must be handled as hazardous waste. 17.3 For further information on waste management, consult “The Waste Management Manual for Laboratory Personnel”, and “Less is Better: Laboratory Chemical Management for Waste Reduction”, both available from the American Chemical Society's Department of Government Relations and Science Policy, 1155 16th Street N.W., Washington, DC 20036. 18.0 References 18.1 “Chlorinated Phenolics in Water by In Situ Acetylation/GC/MS Determination,” Method CP–86.01, National Council of the Paper Industry for Air and Stream Improvement, Inc., 260 Madison Avenue, New York, NY 10016 (July 1986). 18.2 “6240-Chlorinated Phenolics (Interim Standard),” Draft Version, U.S. Environmental Protection Agency, Manchester Laboratory, Manchester, Washington. 18.3 “Performance Tests for the Evaluation of Computerized Gas Chromatography/Mass Spectrometry Equipment and Laboratories,” USEPA, EMSL Cincinnati, OH 45268, EPA–600/4–80–025 (April 1980). 18.4 “Working with Carcinogens,” DHEW, PHS, CDC, NIOSH, Publication 77–206 (August 1977). 18.5 “OSHA Safety and Health Standards, General Industry,” OSHA 2206, 29 CFR 1910 (January 1976). 18.6 “Safety in Academic Chemistry Laboratories,” ACS Committee on Chemical Safety (1979). 18.7 “Interlaboratory Validation of U. S. Environmental Protection Agency Method 1625A, Addendum Report,” SRI International, Prepared for Analysis and Evaluation Division (WH–557), USEPA, 401 M St., SW., Washington, DC 20460 (January 1985). 18.8 “Handbook of Analytical Quality Control in Water and Wastewater Laboratories,” USEPA, EMSL, Cincinnati, OH 45268, EPA–600/4–79–019 (March 1979). 18.9 “Standard Practice for Sampling Water,” ASTM Annual Book of Standards, ASTM, Philadelphia, PA, 76 (1980). 18.10 “Methods 330.4 and 330.5 for Total Residual Chlorine,” USEPA, EMSL, Cincinnati, OH 45268, EPA 600/4–70–020 (March 1979). 18.11 “Determination of Chlorophenolics, Special Analytical Services Contract 1047, Episode 1886,” Analytical Technologies, Inc., Prepared for W. A. Telliard, Industrial Technology Division (WH–552), USEPA, 401 M St., SW., Washington, DC 20460 (June 1990). 18.12 “Determination of Chlorophenolics by GCMS, Development of Method 1653,” Analytical Technologies, Inc., Prepared for W. A. Telliard, Industrial Technology Division (WH–552), USEPA, 401 M St., SW., Washington, DC 20460 (May 1991). 19.0 Tables and Figures Table 1_Chlorophenolic Compounds Determined by GCMS Using Isotope Dilution and Internal Standard Techniques ---------------------------------------------------------------------------------------------------------------- Pollutant Labeled compound Compound ----------------------------------------------------------------------------- CAS registry EPA-EGD Analog CAS registry EPA-EGD ---------------------------------------------------------------------------------------------------------------- 4-chlorophenol.................... 106-48-9 1001 2,4-dichlorophenol................ 120-83-2 1002 d3 93951-74-7 1102 2,6-dichlorophenol................ 87-65-0 1003 2,4,5-trichlorophenol............. 95-95-4 1004 2,4,6-trichlorophenol............. 88-06-2 1005 2,3,4,6-tetrachlorophenol......... 58-90-2 1006 pentachlorophenol................. 87-86-5 1007 \13\C6 85380-74-1 1107 4-chloroguaiacol.................. 16766-30-6 1008 \13\C6 136955-39-0 1108 3,4-dichloroguaiacol.............. 77102-94-4 1009 4,5-dichloroguaiacol.............. 2460-49-3 1010 4,6-dichloroguaiacol.............. 16766-31-7 1011 3,4,5-trichloroguaiacol........... 57057-83-7 1012 3,4,6-trichloroguaiacol........... 60712-44-9 1013 4,5,6-trichloroguaiacol........... 2668-24-8 1014 \13\C6 136955-40-3 1114 tetrachloroguaiacol............... 2539-17-5 1015 \13\C6 136955-41-4 1115 4-chlorocatechol.................. 2138-22-9 1016 3,4-dichlorocatechol.............. 3978-67-4 1017 3,6-dichlorocatechol.............. 3938-16-7 1018 4,5-dichlorocatechol.............. 3428-24-8 1019 \13\C6 136955-42-5 1119 3,4,5-trichlorocatechol........... 56961-20-7 1020 3,4,6-trichlorocatechol........... 32139-72-3 1021 tetrachlorocatechol............... 1198-55-6 1022 \13\C6 136955-43-6 1122 5-chlorovanillin.................. 19463-48-0 1023 \13\C6 136955-44-7 1123 6-chlorovanillin.................. 18268-76-3 1024 5,6-dichlorovanillin.............. 18268-69-4 1025 2-chlorosyringaldehyde............ 76341-69-0 1026 2,6-dichlorosyringaldehyde........ 76330-06-8 1027 trichlorosyringol................. 2539-26-6 1028 Sample matrix internal standard (SMIS) 3,4,5-trichlorophenol............. 609-19-8 184 Instrument internal standard (IIS) 2,2[prime]-difluorobiphenyl....... 388-82-9 164 ---------------------------------------------------------------------------------------------------------------- Table 2_Gas Chromatography and Method Detection Limits for Chlorophenolics ---------------------------------------------------------------------------------------------------------------- Minimum Retention EGD ref level \4\ MDL \5\ EGD No. \1\ Compound time mean No. RRT window \3\ (µg/ (µg/ (sec) \2\ L) L) ---------------------------------------------------------------------------------------------------------------- 1001........................... 4-chlorophenol... 691 184 0.651-0.681 1.25 1.11 1003........................... 2,6- 796 184 0.757-0.779 2.5 1.39 dichlorophenol. 1102........................... 2,4- 818 164 0.986-0.998 dichlorophenol- d3. 1202........................... 2,4- 819 1102 0.997-1.006 2.5 0.15 dichlorophenol. 164............................ 2,2[prime]- 825 164 1.000 difluorobiphenyl (I.S.). 1108........................... 4-chloroguaiacol- 900 164 1.077-1.103 \13\C6. 1208........................... 4-chloroguaiacol. 900 1108 0.998-1.002 1.25 0.09 1005........................... 2,4,6- 920 184 0.879-0.895 2.5 0.71 trichlorophenol. 1004........................... 2,4,5- 979 184 0.936-0.952 2.5 0.57 trichlorophenol. 1016........................... 4-chlorocatechol. 1004 184 0.961-0.975 1.25 0.59 1011........................... 4,6- 1021 184 0.979-0.991 2.5 0.45 dichloroguaiacol. 1009........................... 3,4- 1029 184 0.986-0.998 2.5 0.52 dichloroguaiacol. 184............................ 3,4,5- 1037 164 1.242-1.272 trichlorophenol (I.S.). 1010........................... 4,5- 1071 184 1.026-1.040 2.5 0.52 dichloroguaiacol. 1018........................... 3,6- 1084 184 1.037-1.053 2.5 0.57 dichlorocatechol. 1006........................... 2,3,4,6- 1103 184 1.050-1.078 2.5 0.38 tetrachloropheno l. 1123........................... 5-chlorovanillin- 1111 164 1.327-1.367 \13\C6. 1223........................... 5-chlorovanillin. 1111 1123 0.998-1.001 2.5 1.01 1013........................... 3,4,6- 1118 184 1.066-1.090 2.5 0.46 trichloroguaiaco l. 1024........................... 6-chlorovanillin. 1122 184 1.070-1.094 2.5 0.94 1017........................... 3,4- 1136 184 1.083-1.105 2.5 0.60 dichlorocatechol. 1119........................... 4,5- 1158 164 1.384-1.424 dichlorocatechol- \13\C6. 1219........................... 4,5- 1158 1119 0.998-1.001 2.5 0.24 dichlorocatechol. 1012........................... 3,4,5- 1177 184 1.120-1.160 2.5 0.49 trichloroguaiaco l. 1114........................... 4,5,6- 1208 164 1.444-1.484 trichloroguaiaco l-\13\C6. 1214........................... 4,5,6- 1208 1114 0.998-1.002 2.5 0.25 trichloroguaiaco l. 1021........................... 3,4,6- 1213 184 1.155-1.185 5.0 0.44 trichlorocatecho l. 1025........................... 5,6- 1246 184 1.182-1.222 5.0 0.80 dichlorovanillin. 1026........................... 2- 1255 184 1.190-1.230 2.5 0.87 chlorosyringalde hyde. 1107........................... pentachlorophenol- 1267 164 1.511-1.561 \13\C6. 1207........................... pentachlorophenol 1268 1107 0.998-1.002 5.0 0.28 1020........................... 3,4,5- 1268 184 1.208-1.238 5.0 0.53 trichlorocatecho l. 1115........................... tetrachloroguaiac 1289 164 1.537-1.587 ol-\13\C6. 1215........................... tetrachloroguaiac 1290 1115 0.998-1.002 5.0 0.23 ol. 1028........................... trichlorosyringol 1301 184 1.240-1.270 2.5 0.64 1122........................... tetrachlorocatech 1365 164 1.630-1.690 ol-\13\C6. 1222........................... tetrachlorocatech 1365 1122 0.998-1.002 5.0 0.76 ol. 1027........................... 2,6- 1378 184 1.309-1.349 5.0 1.13 dichlorosyringal dehyde. ---------------------------------------------------------------------------------------------------------------- \1\ Four digit numbers beginning with 10 indicate a pollutant quantified by the internal standard method; four digit numbers beginning with 11 indicate a labeled compound quantified by the internal standard method; four digit numbers beginning with 12 indicate a pollutant quantified by isotope dilution. \2\ The retention times in this column are based on data from a single laboratory (reference 12), utilizing the GC conditions in Section 11. \3\ Relative retention time windows are estimated from EPA Method 1625. \4\ The minimum level (ML) is defined as the level at which the entire analytical system must give a recognizable signal and acceptable calibration point for the analyte. It is equivalent to the concentration of the lowest calibration standard, assuming that all method-specified sample weights, volumes, and cleanup procedures have been employed. \5\ 40 CFR Part 136, Appendix B; from reference 2. Table 3_DFTPP Mass Intensity Specifications \1\ ------------------------------------------------------------------------ Mass Intensity required ------------------------------------------------------------------------ 51........................... 8 to 82% of m/z 198. 68........................... Less than 2% of m/z 69. 69........................... 11 to 91% of m/z 198. 70........................... Less than 2% of m/z 69. 127.......................... 32 to 59% of m/z 198. 197.......................... Less than 1% of m/z 198. 198.......................... Base peak, 100% abundance. 199.......................... 4 to 9% of m/z 198. 275.......................... 11 to 30% of m/z 198. 441.......................... 44 to 110% of m/z 443. 442.......................... 30 to 86% of m/z 198. 443.......................... 14 to 24% of m/z 442. ------------------------------------------------------------------------ \1\ Reference 7. Table 4_Characteristic M/Z's of Chlorophenolic Compounds ------------------------------------------------------------------------ Compound Primary m/z ------------------------------------------------------------------------ 4-chlorophenol.......................................... 128 2,4-dichlorophenol...................................... 162 2,4-dichlorophenol-d3................................... 167 2,6-dichlorophenol...................................... 162 2,4,5-trichlorophenol................................... 196 2,4,6-trichlorophenol................................... 196 2,3,4,6-tetrachlorophenol............................... 232 pentachlorophenol....................................... 266 pentachlorophenol-13C6.................................. 272 4-chloroguaiacol........................................ 158 4-chloroguaiacol-13C6................................... 164 3,4-dichloroguaiacol.................................... 192 4,5-dichloroguaiacol.................................... 192 4,6-dichloroguaiacol.................................... 192 3,4,5-trichloroguaiacol................................. 226 3,4,6-trichloroguaiacol................................. 226 4,5,6-trichloroguaiacol................................. 226 4,5,6-trichloroguaiacol-13C6............................ 234 tetrachloroguaiacol..................................... 262 tetrachloroguaiacol-13C6................................ 268 4-chlorocatechol........................................ 144 3,4-dichlorocatechol.................................... 178 3,6-dichlorocatechol.................................... 178 4,5-dichlorocatechol.................................... 178 4,5-dichlorocatechol-13C6............................... 184 3,4,5-trichlorocatechol................................. 212 3,4,6-trichlorocatechol................................. 212 tetrachlorocatechol..................................... 248 tetrachlorocatechol-13C6................................ 254 5-chlorovanillin........................................ 186 5-chlorovanillin-13C6................................... 192 6-chlorovanillin........................................ 186 5,6-dichlorovanillin.................................... 220 2-chlorosyringaldehyde.................................. 216 2,6-dichlorosyringaldehyde.............................. 250 trichlorosyringol....................................... 256 Sample Matrix Internal Standard (SMIS) 3,4,5-trichlorophenol................................... 196 Instrument Internal Standard (IIS) 2,2[prime]-difluorobiphenyl............................. 190 ------------------------------------------------------------------------ Table 5_Acceptance Criteria for Performance Tests \1\ ---------------------------------------------------------------------------------------------------------------- Initial precision Labeled compound and and recovery sec. SMIS recovery sec. Test conc. 9.3.2 (percent) Ongoing 9.4 and 14.6 \3\ ---------------------- recovery --------------------- EGD No. \2\ Compound (µg/ sec. 9.6 With Without mL) (percent) ascorbic ascorbic s X acid P acid P (%) (%) ---------------------------------------------------------------------------------------------------------------- 1001........................ 4-chlorophenol. 25 64 72-144 40-236 1202........................ 2,4- 50 14 84-120 84-118 dichlorophenol. 1102........................ 2,4- 25 54 64-160 56-170 58-135 27-143 dichlorophenol- d3. 1003........................ 2,6- 50 20 66-148 58-170 dichlorophenol. 1004........................ 2,4,5- 50 14 78-140 82-128 trichloropheno l. 1005........................ 2,4,6- 50 20 72-142 72-146 trichloropheno l. 1006........................ 2,3,4,6- 50 14 80-132 82-132 tetrachlorophe nol. 1207........................ pentachlorophen 100 6 90-111 84-120 ol. 1107........................ pentachlorophen 25 21 58-169 61-157 8-143 27-167 ol-\13\C6. 1208........................ 4- 25 20 88-120 88-120 chloroguaiacol. 1108........................ 4- 25 104 68-148 64-152 59-121 43-168 chloroguaiacol- \13\C6. 1009........................ 3,4- 50 18 80-126 82-126 dichloroguaiac o \4\. 1010........................ 4,5- 50 14 82-121 80-128 dichloroguaiac ol. 1011........................ 4,6- 50 16 82-126 86-120 dichloroguaiac ol. 1012........................ 3,4,5- 50 16 78-130 80-134 trichloroguaia col. 1013........................ 3,4,6- 50 16 64-152 74-140 trichloroguaia col. 1214........................ 4,5,6- 50 14 92-106 88-116 trichloroguaia col. 1114........................ 4,5,6- 25 48 66-146 74-140 48-131 51-139 trichloroguaia col-\13\C6. 1215........................ tetrachloroguai 100 7 84-115 81-126 acol. 1115........................ tetrachloroguai 25 22 57-173 65-161 35-120 27-161 acol-\13\C6. 1016........................ 4- 25 48 76-140 80-124 chlorocatechol. 1017........................ 3,4- 50 24 66-154 78-134 dichlorocatech ol. 1018........................ 3,6- 50 16 78-136 84-126 dichlorocatech ol. 1219........................ 4,5- 50 8 84-118 86-122 dichlorocatech ol. 1119........................ 4,5- 25 78 68-144 66-142 33-129 0-190 dichlorocatech ol-\13\C6. 1020........................ 3,4,5- 100 17 60-166 72-128 trichlorocatec hol. 1021........................ 3,4,6- 100 17 74-138 64-149 trichlorocatec hol \4\. 1222........................ tetrachlorocate 100 29 46-234 81-132 chol. 1122........................ tetrachlorocate 25 39 48-227 63-152 14-118 0-184 chol-\13\C6. 1223........................ 5- 50 20 94-208 84-118 chlorovanillin. 1123........................ 5- 25 84 68-160 70-144 51-126 32-254 chlorovanillin- \13\C6. 1024........................ 6- 50 22 82-128 80-126 chlorovanillin. 1025........................ 5,6- 100 9 67-146 77-140 dichlorovanill in. 1026........................ 2- 50 28 76-130 72-156 chlorosyringal dehyde. 1027........................ 2,6- 100 14 82-129 60-183 ......... ......... dichlorosyring aldehyde. 1028........................ trichlorosyring 50 18 76-136 66-174 ol. Sample Matrix Internal Standard ---------------------------------------------------------------------------------------------------------------- 184......................... 3,4,5- 100 47 62-185 68-144 56-116 24-167 trichloropheno l. ---------------------------------------------------------------------------------------------------------------- \1\ Specifications derived from multi-laboratory testing of draft method. \2\ Four-digit numbers beginning with 10 indicate a pollutant quantified by the internal standard method; four- digit numbers beginning with 11 indicate a labeled compound quantified by the internal standard method; four- digit numbers beginning with 12 indicate a pollutant quantified by isotope dilution. \3\ Test concentrations are in units of µg/mL. \4\ Specification derived from isomer. View or download PDF View or download PDF View or download PDF View or download PDF 20.0 Glossary of Definitions and Purposes These definitions and purposes are specific to this method but have been conformed to common usage as much as possible. 20.1 Units of weight and measure and their abbreviations 20.1.1 Symbols. °C degrees Celsius µL microliter < less than > greater than % percent 20.1.2 Alphabetical characters. cm centimeter g gram h hour ID inside diameter in. inch L liter M Molecular ion m meter mg milligram min minute mL milliliter mm millimeter m/z mass-to-charge ratio N normal; gram molecular weight of solute divided by hydrogen equivalent of solute, per liter of solution OD outside diameter pg picogram ppb part-per-billion ppm part-per-million ppt part-per-trillion psig pounds-per-square inch gauge v/v volume per unit volume w/v weight per unit volume 20.2 Definitions and acronyms (in alphabetical order). Analyte: A chlorophenolic tested for by this method. The analytes are listed in Table 1. Calibration standard (CAL): A solution prepared from a secondary standard and/or stock solutions and used to calibrate the response of the instrument with respect to analyte concentration. Calibration verification standard (VER): The mid-point calibration standard (CS3) that is used to verify calibration. See Table 4. Chlorophenolics: collectively, the analytes listed in Table 1. CS1, CS2, CS3, CS4, CS5: See Calibration standards and Table 4. Field blank: An aliquot of reagent water or other reference matrix that is placed in a sample container in the laboratory or the field, and treated as a sample in all respects, including exposure to sampling site conditions, storage, preservation, and all analytical procedures. The purpose of the field blank is to determine if the field or sample transporting procedures and environments have contaminated the sample. GC: Gas chromatograph or gas chromatography. HRGC: High resolution GC. IPR: Initial precision and recovery; four aliquots of the diluted PAR standard analyzed to establish the ability to generate acceptable precision and accuracy. An IPR is performed prior to the first time this method is used and any time the method or instrumentation is modified. K-D: Kuderna-Danish concentrator; a device used to concentrate the analytes in a solvent. Laboratory blank: See Method blank. Laboratory control sample (LCS): See Ongoing precision and recovery standard (OPR). Laboratory reagent blank: See Method blank. May: This action, activity, or procedural step is neither required nor prohibited. May not: This action, activity, or procedural step is prohibited. Method blank: An aliquot of reagent water that is treated exactly as a sample including exposure to all glassware, equipment, solvents, reagents, internal standards, and surrogates that are used with samples. The method blank is used to determine if analytes or interferences are present in the laboratory environment, the reagents, or the apparatus. Minimum level (ML): The level at which the entire analytical system must give a recognizable signal and acceptable calibration point for the analyte. It is equivalent to the concentration of the lowest calibration standard, assuming that all method-specified sample weights, volumes, and cleanup procedures have been employed. MS: Mass spectrometer or mass spectrometry. Must: This action, activity, or procedural step is required. OPR: Ongoing precision and recovery standard (OPR); a laboratory blank spiked with known quantities of analytes. The OPR is analyzed exactly like a sample. Its purpose is to assure that the results produced by the laboratory remain within the limits specified in this method for precision and recovery. PAR: Precision and recovery standard; secondary standard that is diluted and spiked to form the IPR and OPR. Preparation blank: See Method blank. Primary dilution standard: A solution containing the specified analytes that is purchased or prepared from stock solutions and diluted as needed to prepare calibration solutions and other solutions. Quality control check sample (QCS): A sample containing all or a subset of the analytes at known concentrations. The QCS is obtained from a source external to the laboratory or is prepared from a source of standards different from the source of calibration standards. It is used to check laboratory performance with test materials prepared external to the normal preparation process. Reagent water: Water demonstrated to be free from the analytes of interest and potentially interfering substances at the method detection limit for the analyte. Relative standard deviation (RSD): The standard deviation times 100 divided by the mean. RF: Response factor. See Section 10.5.1. RR: Relative response. See Section 10.4.4. RSD: See Relative standard deviation. Should: This action, activity, or procedural step is suggested but not required. Stock solution: A solution containing an analyte that is prepared using a reference material traceable to EPA, the National Institute of Science and Technology (NIST), or a source that will attest to the purity and authenticity of the reference material. VER: See Calibration verification standard.