TSC 02 0442 1 METHOD 314.1 DETERMINATION OF PERCHLORATE IN DRINKING WATER USING INLINE SAMPLE PRE CONCENTRATION/ MATRIX ELIMINATION ION CHROMATOGRAPHY WITH SUPPRESSED CONDUCTIVITY DETECTION RESEARCH SUMMARY April 2005 Herbert P. Wagner ( Lakeshore Engineering Services, Inc.) Barry V. Pepich ( Shaw Environmental, Inc.) Chris Pohl, Douglas Later, Robert Joyce, Kannan Srinivasan, Brian DeBorba, Dave Thomas, and Andy Woodruff ( Dionex, Inc. Sunnyvale, Ca) David J. Munch ( U. S. EPA, Office of Ground Water and Drinking Water)

TECHNICAL SUPPORT CENTER OFFICE OF GROUND WATER AND DRINKING WATER U. S. ENVIRONMENTAL PROTECTION AGENCY CINCINNATI, OHIO 45268 TSC 02 0442 2 TABLE OF CONTENTS TITLE PAGE  .  ...                          .   1 TABLE OF CONTENTS                         ..   . 2 LIST OF ACRONYMS ................................................................................................................ 3 1. INTRODUCTION............................................................................................................. 3 2. INCREASING METHOD SENSITIVITY......................................................................... 5 2.1 COMPARISON OF 2 mm VERSUS 4 mm COLUMNS................................................... 5 2.2 SAMPLE PRE CONCENTRATION/ MATRIX ELIMINATION...................................... 5 2.3 OPTIMIZING THE CRYPTAND CONCENTRATOR COLUMN PROTOCOLS ............ 6 2.3.1 Direction of Load and Rinse Solutions .............................................................................. 6 2.3.2 Comparison of Perchlorate Peak Shape at Room Temperature and 35

C........................... 8 2.3.3 Use of Sodium Ion to Improve Trapping Efficiency........................................................... 8 2.3.4 Concentration and Volume of Rinse Solution. ................................................................... 9 2.3.5 Concentration and Volume of Wash Solution .................................................................... 10 2.3.6 Optimization in the Synthetic Sample Matrix .................................................................... 11 2.3.7 Concentrator Column Trapping Capacity........................................................................... 13 3. PRELIMINARY EVALUATION OF 314.1 PROTOCOLS............................................... 13 4. EVALUATION OF SURROGATES FOR AS16 COLUMNS........................................... 15 4.1 MELLITIC ACID ( MA).................................................................................................... 16 4.2 BENZENESULFONIC ACID ( BSA) ................................................................................ 16 4.3 4 CHLOROBENZENESULFONIC ACID ( 4 Cl BSA) ..................................................... 16 4.4 TRIFLUROBENZOIC ACIDS ( TFBA) ............................................................................ 16 4.5 5 SULFOSALICYLIC ACID ( SSA) ................................................................................. 16 4.6 DINITROBENZOIC ACID ( DNBA) ................................................................................ 16 5. EVALUATION OF THE CRYPTAND ANALYTICAL COLUMN ................................. 18 5.1. SEPARATION OF 4 Cl BSA ON THE CRYPTAND ANALYTICAL COLUMN............ 18 5.2. USE OF LITHIUM AND SODIUM HYDROXIDE ELUENTS........................................ 18 5.2.1. Need for ATC trap Column to Remove Carbonate............................................................. 19 6. IMPROVING METHOD ROBUSTNESS   PHASE 1 ...................................................... 19 6.1 DETERMINATION OF LCMRL...................................................................................... 19 6.2 STERILE FILTRATION................................................................................................... 19 6.2.1 Background Confirmation from Sterile Filtration Devices ................................................. 19 6.3 INCREASING ELUENT CONCENTRATION FROM 50 mM TO 65 mM NaOH........... 20 6.4 CARRYOVER IN GROUNDWATER COMPARED TO SURFACE WATER................. 21 6.5 ADDITION OF A 100 mM NaOH COLUMN CLEANING STEP.................................... 22 7. DEVELOPMENT OF DUAL ELUENT GENERATION.................................................. 23 8. INITIAL ASSESSMENT OF P& A DATA WITH THE AS16 COLUMN......................... 24 8.1 METHOD PROTOCOLS FOR AS16 COLUMN.............................................................. 24 8.2 LCMRL AND P& A RESULTS......................................................................................... 24 8.3 COMPARATIVE STUDY USING EPA METHOD 314.1 AND 331.0 ............................. 25 9. DEVELOPMENT AND EVALUATION OF AS20 CONFIRMATION COLUMN .......... 26 9.1 LCMRL AND P& A RESULTS......................................................................................... 27 10. IMPROVING METHOD ROBUSTNESS   PHASE 2 ...................................................... 27 10.1 EVALUATION OF RINSE TIME AND LSSM CONCENTRATION .............................. 27 10.2 EVALUATION OF DRINKING WATER MATRICES USING 100 mg/ L LSSM............ 28 TSC 02 0442 3 11. FINAL CONCENTRATOR COLUMN EVALUATION................................................... 29 11.1 FINAL CONCENTRATOR COLUMN TRAPPING EFFICIENCY.................................. 29 12. FINAL METHOD PROTOCOLS FOR EPA METHOD 314.1................................................ 30 13. EPA METHOD 314.1 EXPERIMENTAL DATA................................................................... 30 13.1 PRIMARY AS16 COLUMN................................................................................................. 30 13.2 CONFIRMATION AS20 COLUMN..................................................................................... 31 14. REFERENCES ....................................................................................................................... 32 LIST OF ACRONYMS 4 Cl BSA 4 chlorobenzenesulfonic acid BSA Benzene Sulfonic Acid CCC Continuing Calibration Check standards CRATC Continuously Regenerated Anion Trap Column DL Detection Limit DNBA Dinitrobenzoic Acid DQOs Data Quality Objectives EPA Environmental Protection Agency IC Ion Chromatography IC MS Ion Chromatography Mass Spectrometry LCMRL Lowest Concentration Minimum Reporting Level LC MS MS Liquid Chromatography Mass Spectrometry Mass Spectrometry LFSSM Laboratory Fortified Synthetic Sample Matrix LSSM Laboratory Synthetic Sample Matrix MA Mellitic Acid MRL Minimum Reporting Level P& A Precision and Accuracy QC Quality Control RT Retention Time SSA 5 sulfosalicylic Acid TFBA Triflurobutyric Acid UCMR Unregulated Contaminant Monitoring Rule 1. INTRODUCTION EPA Method 314.0, which has been used under Unregulated Contaminant Monitoring Regulation ( UCMR), supports a Minimum Reporting Level ( MRL) of 4.0 µ g/ L. Currently it is the only EPA Method available for monitoring perchlorate in drinking water. New methods were sought that had improved selectivity and sensitivity for perchlorate, particularly in high ionic matrices. TSC 02 0442 4 Up to this point in time, 4 Cl benzensulfonic acid ( 4 Cl BSA), which has been detected in groundwater in the southwest United States, is the only component that has been identified by IC MS to coelute with perchlorate on the AS16 analytical column under EPA Method 314.0 conditions. The Cryptand column technology developed by Dionex offered new possibilities for addressing this analytical problem. Normal IC methods involve ion exchange as the mode of separation with fixed capacity separators. The Cryptand columns, on the other hand, use manipulation of column capacity as part of the mechanism for separation. The cation counter ion in the eluent has a strong influence on both the column capacity and the kinetics of capacity modification. These columns have shown the ability to resolve perchlorate and 4 Cl BSA. 1 The use of confirmation columns to minimize the reporting of false positives is commonly used with gas chromatographic methods that use detectors other than mass spectrometry. The idea behind this technique is to provide a column with different selectivity, thereby minimizing the possibility that any interference could coelute with the analyte of interest on both columns. The preliminary objectives of this work were to develop an automated, suppressed conductivity method with the lowest possible MRL ( goal of 0.50 µ g/ L) while incorporating a confirmation column to minimize the potential for false positives. This work spanned almost 2.5 years and although the objectives did not change during this time, the means to achieve the objectives were altered a couple of times during the development of this method.

Preliminary investigations directed at increasing method sensitivity involved using 2 mm rather than 4 mm columns. An approximate 4 fold increase in sensitivity can be realized in very clean matrices by injecting the same volume onto the 2 mm columns compared to the 4 mm columns. However, most drinking water matrices contain a sufficient quantity of other anions that would prevent this direct injection technique from being applicable to normal drinking water matrices. Consequently, the first stage of research involved investigation of solid phase sample pretreatment clean up cartridges to remove chloride, carbonate/ bicarbonate, residual silver ( from the Ag+ cartridge used to remove chloride) and sulfate prior to direct injection of a large volume of pre treated sample ( 1.3 mL) onto the 2 mm AS16 columns. This technique was successful in providing a method with a MRL for perchlorate of approximately 0.50 µ g/ L in both normal drinking water matrices and the 1000 mg/ L Laboratory Fortified Synthetic Sample Matrices ( LFSSM). The Cryptand columns also provided a similar MRL for the confirmation column. The two disadvantages of these methods were that they involved very extensive sample pretreatment time ( approximately 1 hour/ sample) and the use of 4 different pretreatment cartridges, which dramatically increased the cost of analysis for each sample.

Inline sample pre concentration combined with matrix elimination was investigated as a means to overcome these disadvantages. In this work, a Dionex AS40

autosampler is used to perform the sample pre concentration/ matrix elimination steps on line. The concentrator column is placed in the sample loop position. The AS40 must be used in the proportion concentration mode with the bleed on and the eluent flow MUST be in the same direction for both the concentration and matrix elimination steps. The timing of the autosampler is programmed into the method to allow for two sample vials to be injected for each sample. The first sample vial contains the sample and the second vial contains the rinse solution ( 1.0 mL of 10 mM NaOH), with the filter cap raised to signify a rinse vial. TSC 02 0442 5 A significant amount of data was generated with the Cryptand concentrator and analytical columns. This data was instrumental in focusing the direction of the development work. However, in the end, the Cryptand analytical column was not incorporated into the final method. In order to simplify the method, the AS20 analytical column in combination with the Cryptand concentrator, is being used as the confirmation column.

EPA Method 314.1 incorporates the use of 2x250 mm separator columns with an automated sample pre concentration/ matrix elimination technique using a 4x35 mm Cryptand concentrator column to remove interfering anions and to increase sensitivity. The Cryptand concentrator column is combined with a primary AS16 analytical column and a confirmation AS20 analytical column to minimize the potential for reporting false positives. All positive results for perchlorate above the MRL on the primary column must be confirmed with the confirmation column. EPA Method 314.1 has a perchlorate MRL of 0.50 µ g/ L in both drinking water and high ionic Laboratory Synthetic Sample Matrices ( LSSM) containing up to 1000 mg/ L each of chloride, bicarbonate and sulfate.

2. INCREASING METHOD SENSITIVITY At the start of this work, two alternatives were considered for increasing the method sensitivity using EPA Method 314.0 protocols: the use of a 2 mm column, and sample pre concentration combined with a matrix elimination step.

2.1 COMPARISON OF 2 mm VERSUS 4 mm COLUMNS An approximate 4 fold increase in sensitivity can, in very clean matrices, be realized simply by injecting the same volume onto the 2 mm columns compared to the 4 mm columns. However, most drinking water matrices contain a sufficient quantity of other anions that would prevent this direct injection technique from being applicable to normal drinking water matrices. Consequently, the first stage of research involved investigation of solid phase sample pretreatment clean up cartridges to remove chloride, carbonate/ bicarbonate and sulfate prior to direct injection of a large volume of pre treated sample ( 1.3 mL) onto the 2 mm AS16 columns. This technique was successful in providing a method with a MRL for perchlorate of approximately 0.50 µ g/ L in both normal drinking water matrices and in the 1000 mg/ L LFSSM. The Cryptand columns also provided a similar MRL for the confirmation column. The major disadvantages of this method were that it involved very extensive sample pretreatment time ( approximately 1 hour/ sample) and the use of 4 different pretreatment cartridges that dramatically increased the cost of analysis for each sample. It was envisaged that this method could only be utilized as a last resort. Consequently, column concentration/ matrix elimination was investigated as a way to eliminate the sample pretreatment labor and materials costs.

2.2 SAMPLE PRE CONCENTRATION/ MATRIX ELIMINATION Preliminary investigations using the AS40 autosampler in the concentration mode and an AG11HC or AG16 guard column in the sample loop position showed that the column concentration technique worked well in reagent water ( RW) matrices but not with the LFSSM matrices, which are an integral part of EPA Method 314.0. The high ionic strength of the LFSSM created problems with the trapping and chromatography for TSC 02 0442 6 perchlorate. As a result, it became evident that a matrix elimination step ( background reduction) would be required if the technique was to be successful. Again, incorporating a matrix elimination step with both the AG11HC and AS16 was unsuccessful due to band broadening or failure of the perchlorate to be eluted from the trap column.

The Cryptand column technology developed by Dionex offered new possibilities for addressing this analytical problem. Normal IC methods involve ion exchange as the mode of separation with fixed capacity separators. The Cryptand columns, on the other hand, use manipulation of column capacity as part of the mechanism for separation. The cation counter ion in the eluent has a strong influence on both the concentrator column capacity and the capacity modification kinetics.

2.3 OPTIMIZING THE CRYPTAND CONCENTRATOR COLUMN PROTOCOLS Once the Cryptand concentrator column was available, several parameters were investigated in order to obtain optimal trapping efficiency and performance. These included load/ rinse direction, requirement for the presence of sodium ions, temperature, rinse solution volume and concentration, wash solution volume and concentration, optimization in the synthetic sample matrix, and determination of concentrator column trapping capacity.

2.3.1 Direction of Load and Rinse Solutions The retention time ( RT) and peak shape for perchlorate were not the same when a rinse step ( to remove the interfering anions) was incorporated. The RT was marginally shorter and the peak shape broader when the rinse step was included. This was somewhat surprising but it was finally determined that the normal instrument configuration loaded the sample loop in one direction and eluted the sample from the sample loop in the opposite direction. When the concentrator column was placed in the sample loop position, the concentrated perchlorate was pushed back on the concentrator column during the rinse step and therefore, could experience band broadening on the concentrator column compared to when no rinse step was included. As shown in Figures 1 and 2, this problem was circumvented by changing the ports on the load/ inject valve so that the load and rinse flows were in the same direction. TSC 02 0442 7 Figure 1. Comparison of Direction of Load and Rinse Solutions Figure 2. Comparison of Direction of Load and Rinse Solutions Instrument Offset to Account for CO3 in the LiOH Eluent 0 2.50 5.00 7.50 10.00 12.50 15.00 17.50 20.00 Minutes µ S ClO4  load & elute in same direction ClO4  load & elute in opposite direction 0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0 16.0 18.0 20.0 22.0 24.0 26.0 28.0 30.0 32.0 4.0 10 in opposite direction peak area = 0.3595 uS* min 10 in same direction peak area = 0.4152 uS* min µ S min 21 ClO4

1.0 2.0  0.20 3.0 ug/ L ClO 4  in 50 mg/ L HCO 3  LSSM ug/ L ClO 4  in 50 mg/ L HCO 3  LSSM TSC 02 0442 8 2.3.2 Comparison of Perchlorate Peak Shape at Room Temperature and 35

C As shown in Figure 3, the peak shape for perchlorate was better at 35

C compared to room temperature. Consequently, 35

C was used for all further studies.

Figure 3. Effect of Temperature on Perchlorate Chromatography 2.3.3 Use of Sodium Ion to Improve Trapping Efficiency The Cryptand concentrator capacity is established by the cation counter ion; it is the presence of sodium that establishes the capacity of the concentrator column. This is illustrated in Figure 4, where the concentrator column is used with and without 50 mg/ L of sodium counter ion. Consequently, 50 mg/ L of the LSSM ( made with the sodium salts) was added to all RW and Field Samples prior to analysis. 35C peak area = 42750 ClO4 RT = 6: 23 0 2.00 4.00 6.00 8.00 10.00 12.00 Minutes  0.20 0 0.20 0.40 0.60 0.80 1.00 µ S Room temp peak area = 28365 ClO 4  RT = 9: 70 35

C peak area = 46323 ClO 4  RT = 6: 23 TSC 02 0442 9 Figure 4. Use of Sodium to Improve Perchlorate Peak Shape 2.3.4 Concentration and Volume of Rinse Solution.

The rinse solution is a dilute NaOH solution that is placed in the second autosampler vial for all samples to be injected and is used to rinse any other interfering anions that are trapped on the concentrator column and send them to waste while the perchlorate is retained on the concentrator column. As indicated in Figure 5, the baseline is lowest ( most complete removal of other anionic species) and the peak shape for perchlorate is best ( most symmetrical and least tailing) when incorporating the rinse step using 1.0 mL of 10 mM NaOH. 0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0 16.0 18.0 20.0  0.50  0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 µ S min 1 RW 10 ug/ L ClO 4  + 50 mg/ L Na+

peak area 0.200 RW 10 ug/ LClO 4

peak area 0.101 MA Offset TSC 02 0442 10 Figure 5. Comparison of Rinse Volume 2.3.5 Concentration and Volume of Wash Solution During the preliminary work on this method, the peak shape for perchlorate was always quite broad. This was speculated to be attributed to the band broadening occurring during the concentration, rinse and elution cycles. It was speculated that a very weak wash solution ( e. g., 0.50 mM NaOH) could be used to wash the perchlorate off the concentrator and refocus it at the head of the guard column prior to increasing the eluent strength to separate the perchlorate on the analytical column. This was evaluated by removing the guard and analytical columns from the system and connecting the concentrator column directly to the conductivity detector to observe the time at which all the perchlorate was eluted from the column. In our studies, the perchlorate was completely washed off the concentrator column in about 9 minutes. A 12 minute wash step was incorporated into the method to ensure complete removal of perchlorate and the lowest background conductivity before starting to separate and quantify perchlorate. As indicated in Figure 6, essentially no difference was observed in the peak area using a 15 minute wash time in the 1000 mg/ L LFSSM and therefore a 12 minute wash time was incorporated into the new method. 0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0 16.0 18.0 20.0 22.0 24.0 26.0 28.0 30.0 32.0 321 3.0 3.0 ug/ L ClO4  in 1000 mg/ L HCO3  LSSM no rinse peak area = 0.0547 uS* min 3.0 ug/ L ClO4  in 1000 mg/ L HCO3  LSSM 0.50 mL rinse peak area = 0.0682 uS* min ug/ L ClO4  in 1000 mg/ L HCO 3  LSSM 1.0 mL rinse peak area = 0.0637 uS* min ClO4

 0.20 0.50 1.0 1.5 2.0 2.5 3.0 3.5 4.0 µ S min TSC 02 0442 11 Figure 6. Comparison of 12 and 15 Minute Wash Time 2.3.6 Optimization in the Synthetic Sample Matrix EPA Method 314.0 incorporated a synthetic sample matrix containing 1000 mg/ L of chloride, carbonate and sulfate. In the development of this method, it was determined that the pH of the synthetic matrix used in Method 314.0 was approximately 10.0  an unlikely pH to be experienced in normal finished drinking water matrices. As well, injection of a large volume of solution at this pH has the potential to affect the chromatography in the synthetic sample matrices by increasing the eluent strength and shortening the retention time for perchlorate. When carbonate was replaced with bicarbonate in the 1000 mg/ L LSSM, the pH of this solution was only 8.6. This is a more realistic upper pH for a finished drinking water. As shown in Figure 7, the peak area for perchlorate is approximately 20% lower in the carbonate LSSM compared to the bicarbonate LSSM. The loss in peak area is likely due to the carbonate increasing the eluent strength and the loss of some perchlorate with the other interfering anions. As shown in Figure 8, when the bicarbonate LSSM was adjusted to pH 10 prior to loading, the concentrator column capacity was exceeded sooner ( e. g., less perchlorate was trapped) with the bicarbonate LSSM at pH 10 than at its normal pH of 8.6. Consequently, 1000 mg/ L of bicarbonate was used to replace the 1000 mg/ L carbonate in the LSSM in EPA Method 314.1. 0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0 16.0 18.0 20.0 22.0 24.0 26.0 28.0 30.0 32.0 35.0  0.20 1.0 2.0 3.0 4.0 15 ug/ LClO4  in 1000 mg/ L LSSM 12 min peak area = 0 .4321 uS* min 15 ug/ LClO4  in 1000 mg/ L LSSM 15 min peak area = 0.4187 uS* min µ S min 21 ClO 4  TSC 02 0442 12 Figure 7. Comparison of HCO3  vs. CO3 2 LSSM Figure 8. Comparison of Trapping Efficiency 10  g/ L ClO4  in HCO3  LSSM at pH 8.6 and 10 0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0 16.0 18.0 20.0 22.0 24.0 26.0 28.0 30.0 32.0  0.20 1.0 2.0 3.0 4.0 10 ug/ LClO4  in 1000 mg/ L CO3   in 1000 mg/ L HCO3  LSSM peak area = 0.3194 uS* min µ S min 2 Offset 10% for clarity ClO 4

2 LSSM peak area = 0.2629 uS* min 10 ug/ LClO4 0.0000 0.1000 0.2000 0.3000 0.4000 0.5000 Control 50mL in 50 LSSM 1 2 3 4 5 mL Loaded Peak Area ( uS* Min)

pH = 8.6 pH = 10.0 5 mL in TSC 02 0442 13 2.3.7 Concentrator Column Trapping Capacity Because of the potential for very high ionic matrices to affect the chromatography of perchlorate, an 80% restriction was placed on the trapping capacity of the concentrator column to ensure that the trapping capacity of the concentrator column would not be exceeded when analyzing very high ionic strength drinking water matrices. Prior to use, the capacity of the concentrator column was evaluated to ensure that not more than 80% of the capacity of the concentrator column was exceeded by loading successive volumes of a 5.0 µ g/ L perchlorate standard in the 1000 mg/ L LFSSM and observing when break through occurs ( i. e., no further increase in observed peak area or concentration). Based on the results presented in Figure 9, a 3 mL injection volume was chosen for the method.

Figure 9. Column Capacity Determination for Perchlorate in a 1000 mg/ L LSSM 3. PRELIMINARY EVALUATION OF 314.1 PROTOCOLS After optimizing the preceding parameters, a preliminary evaluation of the new Method 314.1 protocols with the AS16 analytical column was initiated. As indicated in Figure 10, it was established that acceptable performance ( similar peak areas) could be obtained for perchlorate in the 50, 500 and 1000 mg/ L LFSSMs using a 3 mL injection volume with a 1 mL rinse volume of 10 mM NaOH. 0.000 0.050 0.100 0.150 0.200 0.250 0.300 0.350 0.400 Control 5 mL in 50 LSSM 1 2 3 4 5 mL Injected Peak Area ( uS* min) TSC 02 0442 14 Figure 10. Comparison of 3.0 µ g/ L ClO4  in 50, 500 and 1000 mg/ L LSSM The next step involved calibration using calibration standards ranging from 0.20 to 15 µ g/ L ClO4  in the 50 mg/ L LFSSM. As indicated in Figure 11, acceptable correlation coefficients ( 0.9999 to 0.9977) were obtained for calibration curves ranging from 0.20 to 15 µ g/ L ClO4  in 50, 500 and 1000 mg/ L LFSSMs.

Figure 11. Calibration of 0.20 to 15 µ g/ L ClO4  in 50, 500 and 1000 mg/ L LSSM 0.000 0.100 0.200 0.300 0.400 0.00 5.00 10.0015.0020.00 Concentration ( ug/ L) Peak Area ( uS* Min)

50 HIW R2 = 0.9999 500 HIW R2 = 0.9992 100 HIW R2 = 0.9977 LSSM LSSM 1000 LSSM 0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0 16.0 18.0 20.0 22.0 24.0 26.0 28.0 30.0  0.20 1.0 2.0 3.0 4.0 3.0 ug/ L ClO4  in 50 mg/ L LSSM peak area = 0.0666 uS* min 3.0 ug/ L ClO4  in 500 mg/ L LSSM peak area = 0.0660 uS* min 3.0 ug/ L ClO4  in 1000 mg/ L LSSM peak area = 0.0611 uS* min µ S min 321 ClO 4  TSC 02 0442 15 As shown in Figure 12, acceptable peak shape and area was obtained for a 0.20 µ g/ L ClO4

fortification level in the 50 mg/ L LSSM.

Figure 12. 0.20 µ g/ L ClO4  in 50 mg/ L LSSM Preliminary results with the new protocols were very encouraging. However, there was still a desire to identify a surrogate to monitor the trapping efficiency of the concentrator column. The next phase of the project involved the search for a suitable surrogate for the new Method 314.1.

4. EVALUATION OF SURROGATES FOR AS16 COLUMNS Because of the complexity of any sample pre concentration/ matrix elimination technique, it is desirable, if at all possible, to include a surrogate in the method to monitor the efficiency of the trapping and releasing of the analyte of interest from the concentrator column. The ideal surrogate would concentrate and elute from the concentrator column in a similar manner to perchlorate and would have similar chromatographic characteristics to perchlorate on the analytical column, thereby allowing quality control ( QC) protocols to be developed to ensure that Data Quality Objectives ( DQOs) are met. Several compounds were evaluated as potential surrogates. 0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0 16.0 18.0 20.0 22.0 24.0 26.0 28.0 30.0 32.0  0.20 0.00 0.25 0.50 0.75 1.00 1.25 1.50 1.75 2.00 LCMRL 0.20ug/ L ClO 4  in 50 mg/ L HCO 3  LSSM peak area = 0.0049uS* min µ S min ClO 4  TSC 02 0442 16 Since all of the potential surrogates contained a benzene ring structure, an absorbance detector was connected, after the conductivity detector, to provide an additional tool for monitoring the surrogate. Although several compounds were evaluated, no suitable surrogate was found. The complete details and the reasons for the failure of each component are beyond the scope of this report. However, a brief description of the individual components evaluated and the reasons for their failure is included below.

4.1 MELLITIC ACID ( MA)

Preliminary work with MA indicated that this component worked well when using the Cryptand concentrator column with the Cryptand guard and analytical columns but was too strongly retained and not eluted from the AS16 columns with the optimized experimental protocols developed for EPA Method 314.1.

4.2 BENZENESULFONIC ACID ( BSA)

Benzenesulfonic acid was evaluated for its potential as a surrogate. Although concentrated effectively on the concentrator column, BSA eluted with the void volume on the analytical column and therefore was not acceptable as a surrogate.

4.3 4 CHLOROBENZENESULFONIC ACID ( 4 Cl BSA)

Although 4 CL BSA has the potential to coelute with perchlorate on the AS16 columns using EPA Method 314.0 protocols, separation of the two components is achieved with the sample pre concentration/ matrix elimination protocols developed for EPA Method 314.1. However, the presence of a large concentration of 4 Cl BSA as a surrogate, which would be required to prevent QC failures if low concentrations of 4 Cl BSA were present in any field samples, would have the potential to interfere with the quantitation of trace levels of perchlorate. Consequently, 4 Cl BSA was not acceptable as a surrogate for Method 314.1.

4.4 TRIFLUROBENZOIC ACIDS ( TFBA)

Three different isomers 2,3,4, 2,4,5 and 3,4,5 TFBA, were evaluated for their potential to serve a role as the surrogate for Method 314.1. The 2,3,4 and 2,4,5 TFBA isomers eluted with the void volume on the analytical column while the 3,4,5 isomer did not provide acceptable perchlorate/ surrogate recovery ratios. Consequently, these components were eliminated as potential surrogates for EPA Method 314.1.

4.5 5 SULFOSALICYLIC ACID ( SSA)

The SSA was not strongly retained on the concentrator column and experienced significant loss during the rinse step. Consequently, SSA was eliminated as a potential surrogate for EPA Method 314.1.

4.6 DINITROBENZOIC ACID ( DNBA)

The potential to use DNBA as a surrogate showed the most promise and provided very good resolution from perchlorate and response on both the conductivity and absorbance detectors as shown in Figures 13 and 14. TSC 02 0442 17 Figure 13. Conductivity Chromatogram of ClO4 , 4 Cl BSA and DNBA Figure 14. Absorbance Chromatogram of ClO4 , 4 Cl BSA and DNBA 0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0 16.0 18.0 20.0 22.0 24.0 26.0 28.0 30.7  0.05 0.00 0.05 0.10 0.15 0.20 0.25 10 ug/ L ClO4  + 200ug/ L 4 Cl BSA + 100 ug/ L DNBA in 1000 LSSM AU min 4 Cl BSA  25.7 DNBA  28.8 0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0 16.0 18.0 20.0 22.0 24.0 26.0 28.0 31.0  0.50 1.0 2.0 3.0 4.0 10 ug/ L ClO4  + 200 ug/ L 4 Cl BSA + 100 ug/ L DNBA in 1000 LSSM µ S min ClO4   24.5 4 Cl BSA  25.5 DNBA  28.5 TSC 02 0442 18 However, further evaluation indicated that although DNBA did not break through on the concentrator column, it appeared that DNBA was tying up some of the sites on the concentrator column and perchlorate was not being effectively retained on the concentrator column. Consequently, DNBA was eliminated as potential surrogates for EPA Method 314.1.

Once it was established that it would be very unlikely to find a surrogate for a EPA Method 314.1 that would behave similarly to perchlorate on both the concentrator and primary and confirmation columns, the only alternative was to develop QC protocols that would ensure detection of any and all failures in the trapping efficiency and chromatography of perchlorate. As a result, two types of Continuing Calibration Check ( CCC) Standards were added to the method: CCCs prepared in reagent water; and CCCs prepared in the LSSM.

5. EVALUATION OF THE CRYPTAND ANALYTICAL COLUMN The use of confirmation columns to minimize the reporting of false positives is a technique that has commonly been used with gas and liquid chromatographic methods that use detectors other than mass spectrometry. The idea behind this technique is to provide a different separation mechanism with the confirmation column, thereby minimizing the possibility that any interference could coelute with the analyte of interest on both columns. This technique was to be incorporated into EPA Method 314.1.

The Cryptand columns developed by Dionex offered a unique potential to be used for the confirmation method. Normal ion chromatographic ( IC) methods involve ion exchange as the mode of separation with fixed capacity separators. The Cryptand columns, on the other hand, use manipulation of column capacity as part of the mechanism for separation, as discussed above. The cation counter ion in the eluent has a strong influence on both the column capacity and the capacity modification kinetics.

5.1. SEPARATION OF 4 Cl BSA ON THE CRYPTAND ANALYTICAL COLUMN As mentioned previously, 4 Cl BSA is a component that was identified ( IC MS) in groundwater. Under EPA Method 314.0 conditions, it coelutes with perchlorate on the AS16 analytical column. When using the appropriate conditions, the Cryptand columns were shown to have the ability to resolve perchlorate and 4 Cl BSA. 1 5.2. USE OF LITHIUM AND SODIUM HYDROXIDE ELUENTS With the Cryptand columns, the counter ion can be used to manipulate the capacity of the column. The concentration of the counter ion has a similar effect. For example, a sodium ion sets a much higher column capacity than lithium. Therefore, the species of counter ion and its concentration can be manipulated to effectively concentrate the perchlorate on the Cryptand concentrator column and then effect separation on the Cryptand analytical column. Consequently, a two eluent system ( sodium and lithium hydroxide) must be used with the Cryptand analytical column. Because a sodium cartridge was available for the EG50, the preliminary work with the Cryptand analytical column used manuallyprepared lithium hydroxide eluents. TSC 02 0442 19 5.2.1. Need for ATC trap Column to Remove Carbonate Lithium hydroxide, as a granular material, appears to be even more susceptible to carbonate formation due to exposure to the atmosphere than sodium hydroxide. Consequently, a ATC trap column must be used to remove carbonate from the LiOH eluent in order to maintain consistent chromatography. This technology is somewhat cumbersome as it requires that the trap column be frequently removed from the system and regenerated.

Even with the ATC trap column in place, a shift in baseline was observed shortly after the switch from the sodium to lithium eluents. As shown in Figure 4, the rise in baseline of approximately 2.5 µ S, which was attributed to the presence of carbonate in the eluent, was negated using an instrument offset at 8.5 minutes to allow for better visual detection of trace levels of perchlorate.

6. IMPROVING METHOD ROBUSTNESS   PHASE 1 Studies on both the primary AS16 and confirmation Cryptand columns were being conducted simultaneously in both EPA and Dionex laboratories. Having established the preliminary optimal operating conditions and QC requirements for the AS16 column, an attempt to generate the precision and accuracy data was initiated.

6.1 DETERMINATION OF LCMRL The Lowest Concentration Minimum Reporting Level ( LCMRL) was determined according to a procedure described elsewhere. 2 Using unfiltered samples to determine the LCMRL, very promising results were obtained and a LCMRL of approximately 0.13 µ g/ L was calculated for ClO4  in the 50 mg/ L LFSSM.

6.2 STERILE FILTRATION Perchlorate, under certain conditions, can be subject to microbial degradation. Consequently, a sterile filtration step was included in the sample collection protocols for this method.

6.2.1 Background Confirmation from Sterile Filtration Devices When the LCMRL was repeated incorporating the sterile filtration procedure, unacceptable recoveries and precisions were observed. As a result, a much higher LCMRL ( 0.57 µ g/ L) was reported. Eventually the problem was traced to the sterile storage containers which appeared to leach out a contaminant that increased the background conductivity to almost 2.0 µ S* min when perchlorate was eluting compared to about 0.50 µ S* min in the unfiltered samples. Consequently, as shown in Figure 15, trace levels of perchlorate were very hard to detect in the sterile filtered samples by conductivity detection. This problem was eliminated by replacing the sterile containers with an I Chem 125 mL sterile HDPE bottle ( Fisher Cat. No. N411 0125 or equivalent). TSC 02 0442 20 Figure 15. Increase in Background Conductivity with Time ( 0.30  g/ L ClO4  in 50 mg/ L LSSM in Sterile Container for 1, 4 and 7 Days)

6.3 INCREASING ELUENT CONCENTRATION FROM 50 mM TO 65 mM NaOH After establishing the proper sterile filtration protocols, the analysis of 12 samples over 9 hours indicated that occasionally, quantitation problems were being experienced as the result of something else eluting in the RT window for perchlorate. Although the precision was acceptable (% RSD = 6.9), the potential for a sample to be lost due to carryover from a previous sample required further study. Increasing the eluent strength, increasing the flow rate and extending the run time are ways to help ensure that all components are eluted from the analytical column prior to initiating the next run.

Increasing the flow rate caused the perchlorate to elute closer to the void volume. This made integration difficult and was not an acceptable alternative. Extending the run time on a 45 minute analysis time also did not seem to be an attractive alternative. On the other hand, increasing the eluent strength from 50 to 65 mM NaOH for the separation and quantitation of perchlorate only raised the background conductivity marginally and kept the perchlorate peak well away from the trailing edge of the other eluting anions while marginally improving the peak shape and peak area for perchlorate. Consequently, 65 mM NaOH at a flow rate of 0.25 mL per minute became the eluent for the new method. 0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0 16.0 18.0 20.0 22.0 24.0 26.0 28.0 30.0  0.30 1.0 2.0 3.0 4.0 5.0 6.0 µ S min 321 Day 7 Day 4 Day 1 Background increases with days in sterile container ClO4  TSC 02 0442 21 6.4 CARRYOVER IN GROUNDWATER COMPARED TO SURFACE WATER With the new eluent conditions, as shown in Figure 16, a very acceptable precision of 5.8 % RSD ( n= 27 over 21 hours) was obtained for a 0.50 µ g/ L ClO4  fortification of a chlorinated surface water that contained 50 mg/ L of the LSSM.

Figure 16. Chlorinated Surface Water Precision for 0.50  g/ L ClO4  in 50 mg/ L LSSM ( n= 27 over 21 hours)

However, when the same experiment was repeated using a chloraminated ground water, significant problems were encountered. As shown in Figure 17, unacceptable precision of 29.6 % RSD ( n= 27 over 21 hours) was obtained for a 0.50 µ g/ L ClO4  fortification to a chloraminated groundwater containing 50 mg/ L of the LSSM. Again, the background conductivity increased during the analysis and rose above 2.5 µ S* minute when perchlorate was eluting, making quantitation of the trace level of perchlorate extremely difficult. 0.000 0.010 0.020 1 4 7 10 13 16 19 22 25 Replicate Peak Area ( uS* min)

0.030 TSC 02 0442 22 Figure 17. Chloraminated Groundwater Precision for 0.50  g/ L ClO4  in 50 mg/ L LSSM ( n= 27 over 21 hours)

It was felt that the method needed to be further optimized to eliminate the build up of the material that was causing the conductivity to increase during the analysis sequence with normal drinking water matrices.

6.5 ADDITION OF A 100 mM NaOH COLUMN CLEANING STEP It was determined that by adding a step from 65 to 100 mM NaOH just after perchlorate elutes from the analytical column, and continuing the cleaning step for the first 8 minutes of the sample loading step, no carry over was observed in the chloraminated groundwater sample. As shown in Figure 18, acceptable precision of 12.7 % RSD ( n= 27 over 36 hours) was obtained for a 0.50 µ g/ L ClO4  fortification to the same ( Sect. 6.4) chloraminated groundwater containing 50 mg/ L of the LSSM. A power interruption during the run at sample 14 caused about a 15 hour delay in the analysis program. 0.000 0.010 0.020 0.030 1 4 7 10 13 16 19 22 25 Replicates Peak Area ( uS* min) TSC 02 0442 23 Figure 18. Chloraminated Ground Water Precision for 0.50  g/ L ClO4  in 50 mg/ L LSSM ( n= 27 over 36 hours)

7. DEVELOPMENT OF DUAL ELUENT GENERATION As mentioned previously, development of the Cryptand confirmation column work was progressing simultaneously. The focus of this phase of the development work was to circumvent the baseline fluctuation attributed to the presence of carbonate in the manually prepared lithium hydroxide eluent ( Sect. 5.2). Eluent generation using a potassium hydroxide eluent combined with a Continuously Regenerated Anion Trap Column ( CR ATC) to continually remove carbonate from the eluent is a technique developed by Dionex. The second phase of their work involved development of a sodium hydroxide cartridge to generate sodium hydroxide eluents. The sodium hydroxide eluent was required for EPA Method 314.1 use of the Cryptand concentrator column in combination with the AS16 analytical column.

The next step was to determine if it was a viable option to use a lithium hydroxide cartridge with the Cryptand columns and then to determine if a dual column eluent generator could be developed to support the Cryptand confirmation column work for EPA Method 314.1. The development of the dual eluent generator progressed very well but the extremely tight time constraints for completion of the development phase for EPA Method 314.1 required that a parallel search for an alternative confirmation column be initiated. Both of these projects were successfully completed. The optional AS20 confirmation column utilized the same eluent as the primary AS16 column, which significantly simplified the method protocols and therefore, was incorporated into EPA Method 314.1. Although beyond the scope of this Research 0.000 0.010 0.020 0.030 1 4 7 10 13 16 19 22 25 Replicates Peak Area ( uS* min) # 14 liquid on top of sample vial; sample did not inject TSC 02 0442 24 Summary, successful completion of the development of the dual cartridge eluent generator proved to be an integral and vital addition for Cryptand column analyses.

8. INITIAL ASSESSMENT OF P& A DATA WITH THE AS16 COLUMN After modifying and re establishing the optimal operating protocols for the AS16 column, collection of the precision and accuracy data with the AS16 analytical column was repeated.

8.1 METHOD PROTOCOLS FOR AS16 COLUMN The finalized conditions incorporated:   the addition of 50 mg/ L LSSM to all samples   eluent flow rate of 0.25 mL/ minute   3.0 mL loading volume   1.0 mL of 10 mM NaOH rinse solution   0.50 mM NaOH to wash the perchlorate off the concentrator column and refocus it at the head of the AG16 column   65 mM NaOH to separate the perchlorate on the AS16 columns   100 mM NaOH immediately after the elution of perchlorate to clean the AS16 columns and set the capacity of the Cryptand trap column for the next analysis 8.2 LCMRL AND P& A RESULTS With the new operating protocols, including sterile filtration of the samples, the results for the LCMRL were very encouraging with a calculated value of approximately 0.13 µ g/ L for perchlorate. The various P& A matrices were fortified ( n= 7) with 0.50, 1.0 and 5.0 µ g/ L perchlorate, and as shown in Table 1, the precision and accuracy were, in general, acceptable in the 50 and 1000 mg/ L LFSSM, a chlorinated ground water, a chlorinated surface water and a chloraminated surface water. TSC 02 0442 25 TABLE 1. Precision and Accuracy Data for EPA Method 314.1 with AS16 Column Native Spike Spike Spike % % Matrix ( µ g/ L) 0.5 µ g/ L 1.0 µ g/ L 5.0 µ g/ L REC RSD 50 mg/ L LFSSM 0.392 78.4 4.1 1000 mg/ L LFSSM 0.475 94.9 7.3 50 mg/ L LFSSM 5.02 100 1.9 1000 mg/ L LFSSM 5.36 107 5.4 Chlorinated GW < 0.50 Chlorinated GW 1.11 111 5.1 Chlorinated GW 5.39 108 5.3 Chlorinated SW 0.602 4.3 Chlorinated SW 1.64 104 2.8 Chlorinated SW 6.56 120 2.2 High Organic Water 0.421 7.1 High Organic Water 1.52 109 4.9 High Organic Water 6.62 124 2.7 Chloraminated SW < 0.50 Chloraminated SW 0.877 87.7 3.6 Chloraminated SW 5.87 117 4.6 The preliminary precision ( 1.9 to 7.3% RSD) and accuracy ( 78.4 to 124% recovery) results were very encouraging.

8.3 COMPARATIVE STUDY USING EPA METHOD 314.1 AND 331.0 Following the encouraging results with the primary AS16 column, the next step was to evaluate EPA Method 314.1 against the new LC MS MS method ( EPA Method 331.0) using actual drinking water samples. Fifteen different municipal drinking water samples ( ground and surface) were analyzed for their native level of perchlorate and then fortified with 0.50, 2.0 and 5.0 µ g/ L perchlorate and reanalyzed using the two new perchlorate methods.

As shown in Table 2, excellent agreement between the two methods was obtained for the 9 of the 15 samples that had positive hits for perchlorate concentrations above 0.30 µ g/ L. TSC 02 0442 26 TABLE 2. Precision and Accuracy for EPA Method 314.1 with AS16 Column Sample 314.1 µ g/ L ClO4  331.0 µ g/ L ClO4

2 0.42 0.43 7 0.39 0.37 8 0.45 0.50 9 0.31 0.35 10 0.43 0.57 11 0.77 0.85 12 2.07 2.03 14 0.58 0.71 15 0.00 0.39 Although the native levels were in very good agreement, the fortification recoveries with EPA Method 314.1 were higher than anticipated, especially in the 2.0 and 5.0 µ g/ L fortification levels (% recoveries of 114 to 140% and 111 to 147% respectively). The high recoveries in the drinking water fortifications were puzzling, especially in light of the fact that the fortification recoveries were acceptable in the high ionic LFSSM and therefore suggested that the method, as developed, was not performing well in the drinking water matrices. This was addressed further in Section 10 below.

9. DEVELOPMENT AND EVALUATION OF AS20 CONFIRMATION COLUMN The goal was to find a confirmation column with a separation mechanism that is sufficiently different from that of the primary column in order to eliminate potential interferences. The suggested primary column, the IonPac AS16, has a column chemistry that is based on a low cross link vinyl aromatic quaternary monomer. It was designed to provide good chromatographic performance for polarizable inorganic anions such as perchlorate with moderate concentration hydroxide eluents. Anionic species which may exhibit retention characteristics similar to perchlorate on the AS16 column include various relatively rare aromatic anionic species. Although less polarizable than inorganic species such as perchlorate, such aromatic species show enhanced retention due to interaction with the pi electrons of the aromatic backbone. The suggested confirmation column, the IonPac AS20, has a column chemistry that is based on a cross linked quaternary condensation polymer completely free of any pi electron containing substituents. As such, it exhibits selectivity for polarizable anions that is complementary to the AS16, but because of the absence of any pi electron character, retention of aromatic anionic species is greatly diminished relative to that of the AS16.

Because the AS20 confirmation column was developed with many similar characteristics to the primary AS16 column, optimization of the operation protocols was quite simple and required only a 5 minute increase in run time to account for the slightly longer RT for perchlorate on the AS20 column. Having established the preliminary optimal operation conditions and QC requirements for the AS20 column, an attempt to evaluate the precision and accuracy of this column was initiated. TSC 02 0442 27 9.1 LCMRL AND P& A RESULTS With the optimized operating protocols for the AS20 confirmation column, including sterile filtration of the samples, the results for the LCMRL were very encouraging, with a calculated value of approximately 0.12 µ g/ L for perchlorate. The various P& A matrices were fortified ( n= 7) with 0.50, 1.0 and 5.0 µ g/ L perchlorate and as shown in Table 3, the precision and accuracy were acceptable in the 50 and 1000 mg/ L LFSSM, but again showed high recoveries, especially at the 1.0 and 5.0 µ g/ L fortification levels, in the chlorinated surface water and chloraminated surface water.

TABLE 3. Precision and Accuracy for EPA Method 314.1 with AS20 Column Native Spike Spike Spike % % Matrix ( µ g/ L) 0.5 µ g/ L 1.0 µ g/ L 5.0 µ g/ L REC RSD 50 mg/ L LFSSM 0.388 77.6 22.0 1000 mg/ L LFSSM 0.549 110 5.89 50 mg/ L LFSSM 4.65 93.1 10.3 1000 mg/ L LFSSM 5.34 107 7.3 4.00 Chlorinated SW 2.38 3.05 Chlorinated SW 3.88 151 3.62 Chlorinated SW 8.08 161 2.71 Chloraminated SW 0.385 37.5 Chloraminated SW 1.51 113 4.9 Chloraminated SW 6.45 129 3.99 It appeared that fronting on the perchlorate peak in the drinking the water matrices was contributing to the peak area, which would account for the unacceptable high recoveries in the drinking water matrices with the AS20 column.

10. IMPROVING METHOD ROBUSTNESS   PHASE 2 Method performance outlined in Sections 8 and 9 above indicated that the method was still not sufficiently robust and required additional optimization 10.1 EVALUATION OF RINSE TIME AND LSSM CONCENTRATION The reason for the peak fronting and high recoveries in the drinking water matrices was speculated to be attributed to variable retention of perchlorate on the concentrator column in the different strength ionic matrices. It was decided to evaluate a 12 and 15 minute wash time in varying concentrations of the LFSSM containing 5.0 µ g/ L of perchlorate to determine if the perchlorate behaved differently in the varying ionic strength matrices. As shown in Figure 19, the rinse time had essentially no affect on the perchlorate peak area. However, a dramatic increase in peak area was observed between the 50 and 100 TSC 02 0442 28 mg/ L LFSSM and very little difference in the perchlorate peak area in the 100 to 1000 mg/ L LFSSM. It was speculated that the addition of 50 mg/ L of the LSSM to all sample matrices was responsible for a low perchlorate response in the RW calibration standards which contributed to the high recoveries being observed in the normal drinking water matrices. It was thought that the addition of 100 mg/ L to all sample matrices would overcome the problem.

Figure 19. 12 vs. 15 Minute Wash Time for a 5.0  g/ L ClO4  in 50 to 1000 mg/ L LSSM 10.2 EVALUATION OF DRINKING WATER MATRICES USING 100 mg/ L LSSM To ensure use of 100 mg/ L of the LSSM would resolve the high drinking water recoveries, the calibration, LCMRL and P& A data in the chlorinated and chloraminated surface waters were repeated. The LCMRL was calculated to be about 0.13 µ g/ L and as shown in Table 4, much better recoveries were observed in the drinking chlorinated and chloraminated water matrices. 0.000 0.050 0.100 0.150 0 500 1000 mg/ L LSSM 12 min wash 15 min wash TSC 02 0442 29 TABLE 4. Precision and Accuracy for EPA Method 314.1 with 100 mg/ L LFSSM Native Spike Spike Spike % % Matrix ( µ g/ L) 0.5 µ g/ L 1.0 µ g/ L 5.0 µ g/ L REC RSD Chlorinated SW 0.985 4.54 Chlorinated SW 2.16 117 16.6 Chlorinated SW 6.00 100 3.92 Chloraminated SW < 0.50 Chloraminated SW 0.997 99.7 8.2 Chloraminated SW 4.69 93.7 2.1 11. FINAL CONCENTRATOR COLUMN EVALUATION The finalized protocols included one further modification to the Cryptand concentrator column resin in order to ensure manufacturing reproducibility. Consequently, the final concentrator column capacity experiment was repeated using the pre established experimental protocols.

11.1 FINAL CONCENTRATOR COLUMN TRAPPING EFFICIENCY As shown in Figure 20, the final modification to the concentrator column resin resulted in a moderately lower capacity for the concentrator column. The maximum load volume that could be used and still meet the 80% restriction was now 2.0 mL.

Figure 20. Concentrator Column Trapping Efficiency ( 10  g/ L ClO4  in 100 and 1000 mg/ L LSSM 0.000 0.200 0.400 0.600 1 2 2.5 3 4 5 mL LOADED PEAK AREA ( uS / min) 100 mg/ L LSSM 1000 mg/ L LSSM TSC 02 0442 30 12. FINAL METHOD PROTOCOLS FOR EPA METHOD 314.1 The finalized conditions for EPA Method 314.1 are:   the addition of 100 mg/ L LSSM to all samples   2.0 mL loading volume   1.0 mL of 10 mM NaOH rinse solution   eluent flow rate at 0.25 mL/ minute   operation pressure of 2350 psi ( requirement of EG50)   0.50 mM NaOH to wash the perchlorate off the concentrator column and refocus it at the head of the AG16 column   65 mM NaOH to separate the perchlorate on the analytical columns   100 mM NaOH immediately after the elution of perchlorate to clean and prepare the columns and set the capacity of the Cryptand trap column for the next analysis   AS16 as the primary analytical column   AS20 as the confirmation analytical column 13. EPA METHOD 314.1 EXPERIMENTAL DATA After finalizing the experimental protocols, the LCMRL and precision and accuracy data in different matrices were collected for both the primary AS16 and confirmation AS20 analytical columns.

13.1 PRIMARY AS16 COLUMN As shown in Table 5, acceptable LCMRL and DL data was obtained on the primary AS16 column.

TABLE 5. LCMRL Data for EPA Method 314.1 with " Primary" AS16 column Analyte LCMRL a ( µ g/ L) DL* ( µ g/ L) ClO4  0.140 0.031b aLCMRLs were calculated according to the procedure in reference 1 * The DL was calculated from data acquired on a single day bReplicate fortifications at 0.10 µ g/ L TSC 02 0442 31 As shown in Table 6, acceptable precision and accuracy data was obtained on the primary AS16 column.

TABLE 6. Precision and Accuracy Data for EPA Method 314.1 with " Primary" AS16 column ( n= 7)

Matrix Unfortified Concentration ( ug/ L) Fortified Concentration ( ug/ L) Mean % Recovery % RSD 100 mg/ L LFSSM * < MRL 0.50 102 2.6 < MRL 5.0 90.0 3.2 Chlorinated Surface Water 0.63 1.0 82.6 1.5 0.63 5.0 85.8 1.7 Chloraminated Surface Water < MRL 1.0 83.1 3.6 < MRL 5.0 89.3 1.9 Chlorinated Ground Water < MRL 1.0 75.9 5.4 < MRL 5.0 92.4 3.3 100 mg/ L LFSSM * < MRL 0.50 102 2.8 < MRL 5.0 80.9 1.3 * LFSSM = Laboratory Fortified Synthetic Sample Matrix 13.2 CONFIRMATION AS20 COLUMN As shown in Table 7, acceptable LCMRL and DL data was obtained on the confirmation AS20 column.

TABLE 7. LCMRL Data for EPA Method 314.1 with confirmation AS20 column Analyte LCMRL a ( µ g/ L) DL* ( µ g/ L) ClO4  0.130 0.025b aLCMRLs were calculated according to the procedure in reference 1 * The DL was calculated from data acquired on a single day bReplicate fortifications at 0.10 µ g/ L As shown in Table 8, acceptable precision and accuracy data was obtained on the confirmation AS20 column. TSC 02 0442 32 TABLE 8. Precision and Accuracy Data for EPA Method 314.1 with primary AS16 column ( n= 7)

Matrix Unfortified Concentration ( ug/ L) Fortified Concentration ( ug/ L) Mean % Recovery % RSD 100 mg/ L LFSSM * < MRL 0.50 104 5.3 < MRL 5.0 94.2 1.5 Chloraminated Surface Water < MRL 0.50 108 2.2 < MRL 5.0 97.8 2.0 Chlorinated Ground Water 0.22 0.50 96.2 9.4 0.22 5.0 98.0 0.70 100 mg/ L LFSSM * < MRL 0.50 97.4 4.4 < MRL 5.0 86.3 1.3 * LFSSM = Laboratory Fortified Synthetic Sample Matrix 14. REFERENCES 1. Personal Communication.

2. Revisions to the Unregulated Contaminant Monitoring Regulation for Public Water Systems, Proposed Rule, 2004.


[Federal Register Volume 86, Number 192 (Thursday, October 7, 2021)]
[Notices]
[Pages 55891-55893]
[FR Doc No: 2021-21863]

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SECURITIES AND EXCHANGE COMMISSION

[Release No. 34-93234; File No. SR-FICC-2021-007]

Self-Regulatory Organizations; Fixed Income Clearing Corporation;
Order Approving Proposed Rule Change To Remove the Early Unwind
Intraday Charge, Change the Treatment of Short-Term Treasuries, and
Make Other Changes

October 1, 2021.
    On August 13, 2021, Fixed Income Clearing Corporation (``FICC'')
filed with the Securities and Exchange Commission (``Commission''),
pursuant to Section 19(b)(1) of the Securities Exchange Act of 1934
(``Act'') \1\ and Rule 19b-4 thereunder,\2\ proposed rule change SR-
FICC-2021-007 (the ``Proposed Rule Change'') to amend (1) the FICC
Government Securities Division (``GSD'') Rulebook (``Rules'') \3\ in
order to remove the Early Unwind Intraday Charge (``EUIC''), (2) the
GSD Methodology Document--GSD Initial Market Risk Margin Model (``QRM
Methodology Document'') to change the treatment of U.S. Treasury
(``Treasury'') securities with remaining time-to-maturities equal to or
less than a year (``Short-Term Treasuries''), and (3) the Rules and the
QRM Methodology Document to make certain technical changes, as
described more fully below. The Proposed Rule Change was published for
public comment in the Federal Register on August 31, 2021,\4\ and the
Commission received no comment letters regarding the changes proposed
therein. For the reasons discussed below, the Commission is approving
the Proposed Rule Change.
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    \1\ 15 U.S.C. 78s(b)(1).
    \2\ 17 CFR 240.19b-4.
    \3\ Capitalized terms used herein and not defined shall have the
meaning assigned to such terms in the Rules, available at http://www.dtcc.com/legal/rules-and-procedures.aspx.
    \4\ Securities Exchange Act Release No. 92756 (August 25, 2021),
86 FR 48770 (August 31, 2021) (SR-FICC-2021-007) (``Notice'').
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I. Description of the Proposed Rule Change

A. Elimination of the EUIC for the GCF Repo Service

    The GCF Repo service allows members of FICC's Government Securities
Division to trade general collateral finance repos (``GCF Repos'') \5\
throughout the day without requiring intraday, trade-for-trade
settlement on a delivery-versus-payment basis. A key tool that FICC
uses to manage its respective credit exposures to its members is the
daily collection of margin from each member. The aggregated amount of
all members' margin constitutes the Clearing Fund, which FICC would
access should a defaulted member's own margin be insufficient to
satisfy losses to FICC caused by the liquidation of that member's
portfolio. The EUIC was adopted as a component of margin in 2014 and is
generally determined based on the risk posed by underlying collateral
pertaining to GCF Repo positions in FICC's 12 p.m. intraday margin
call. The purpose of the EUIC is to address the under-margined
conditions that can occur in two situations in the GCF Repo service
involving the substitution of securities with cash.\6\ The first
situation may occur when, on an intraday basis, a GCF Repo Member
substitutes cash for the securities that had been used as collateral
for a GCF Repo position the prior day. The second situation may occur
when the GCF Clearing Agent Bank unwound the cash lending side of a GCF
Repo Transaction that occurred on an interbank basis \7\ at
approximately 7:30 a.m.\8\ FICC represents that both of these
situations had the potential to result in higher cash balances in the
underlying collateral of GCF Repo positions at 12:00 p.m. when FICC is
calculating the intraday margin associated with GCF Repo positions.\9\
These situations could cause an under-margined condition because there
is no VaR Charge associated with cash collateral,\10\ and the GCF Repo
Member would likely replace the cash with securities (which would be
subject to the VaR Charge) by end of day.
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    \5\ A GCF Repo is one in which the lender of funds is willing to
accept any of a class of U.S. Treasuries, U.S. government agency
securities, and certain mortgage-backed securities as collateral for
the repurchase obligation. This is in contrast to a specific
collateral repo.
    \6\ Securities Exchange Act Release Nos. 73389 (October 17,
2014), 79 FR 63456 (October 23, 2014) (SR-FICC-2014-01) and 73388
(October 17, 2014), 79 FR 63458 (October 23, 2014) (SR-FICC-2014-
801).
    \7\ At the time of the EUIC approval, the GCF Repo Service was
operating on both an ``interbank'' and ``intrabank'' basis.
``Interbank'' means that the two GCF Repo Members which have been
matched in a GCF Repo transaction each clear at a different clearing
bank. ``Intrabank'' means that the two GCF Repo Members which have
been matched in a GCF Repo transaction clear at the same clearing
bank. The GCF Repo Service now operates on an intrabank basis only
because the interbank service of the GCF Repo service is no longer
available. See Securities Exchange Act Release No. 78206 (June 30,
2016), 81 FR 44388 (July 7, 2016) (SR-FICC-2016-002).
    \8\ All times herein are Eastern Time.
    \9\ Notice, supra note 4, at 48771.
    \10\ The value-at-risk (``VaR'') Charge is designed to capture
the risks related to the movement of market prices associated with
the securities in a member's portfolio, and calculate the potential
losses on a portfolio over a three-day period of risk assumed
necessary to liquidate the portfolio. See Securities Exchange Act
Release No. 90182 (October 14, 2020), 85 FR 66630 (October 20, 2020)
(SR-FICC-2020-009). There is no VaR Charge associated with cash
collateral because there is no need for liquidation.
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    FICC represents that it can address the first situation described
above by applying the Intraday Supplemental Fund Deposit, as updated in
2018,\11\ instead of the EUIC.\12\ The current EUIC is only applied
based on a Netting Member's 12:00 p.m. GCF Repo positions, as the
lesser of (i) the net reduction in the VaR Charge attributable to
either cash substitutions, or (ii) the prior end of day VaR Charge
minus the intraday VaR Charge.\13\ On the other hand, FICC receives
hourly intraday GCF Repo lockup files from 8:00 a.m. to 3:00 p.m. from
The Bank of New York Mellon.\14\ These hourly intraday GCF Repo lockup
files provide FICC with information with respect to the GCF Repo
Members' positions throughout the day that FICC can use to calculate an
intraday VaR Charge. As such, throughout the day, FICC can use the
information in these files to assess the exposure that arises from
collateral substitution (in addition to any other position changes) and
can charge an Intraday Supplemental Fund Deposit amount to the GCF Repo
Member, if necessary, to address this exposure.
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    \11\ See Securities Exchange Act Release No. 83362 (June 1,
2018), 83 FR 26514 (June 7, 2018) (SR-FICC-2018-001) and 83223 (May
1, 2018), 83 FR 23020 (May 17, 2018) (FICC-2018-801).
    \12\ Notice, supra note 4, at 48771.
    \13\ Id.
    \14\ Id.
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    Regarding the second situation described above, the situation no
longer exists because interbank services were suspended in 2016, and
accordingly, the unwind of the cash lending side of a GCF Repo
Transaction that occurred on an interbank basis does not take
place.\15\
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    \15\ See Securities Exchange Act Release No. 78206 (June 30,
2016), 81 FR 44388 (July 7, 2016) (SR-FICC-2016-002).
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B. Treatment of Short-Term Treasuries

    The confidentially filed QRM Methodology Document, which describes
the current GSD margin methodology, does not reflect any special
treatment for determining the margin for transactions in Short-Term
Treasuries. Short-Term Treasuries are margined as part of the entire
portfolio using the sensitivity VaR Charge methodology, and a haircut-
based methodology is used as a backup for Short-Term Treasuries where
sensitivity analytics data is not available. Specifically, Short-Term
Treasuries that do not have sensitivity analytics data are subject to a
single haircut rate calibrated to the volatility of the

Bloomberg/Barclays Index of Treasury securities with remaining time-to-
maturities equal to or less than a year.
    FICC represents that one concern with the current approach is
related to the potentially large impact that market events can have on
the yields of Short-Term Treasuries. Under the current approach, the
VaR Charge calculated for portfolios with a high concentration of
Short-Term Treasuries may not adequately cover the potentially large
impact on the ``short-end'' of the Treasury yield curve.\16\ FICC
represents that another concern with the current approach is that it
may not adequately address the volatility of certain portfolios of
Short-Term Treasuries if the composition of those portfolios differs
greatly from the composition of the Bloomberg/Barclays Index of
Treasury securities described above. Using one haircut rate based on
the volatility of the Bloomberg/Barclays index may not adequately cover
the risk of securities with longer duration maturities in the equal to
or less than one-year.\17\
---------------------------------------------------------------------------

    \16\ Notice, supra note 4, at 48772.
    \17\ Id.
---------------------------------------------------------------------------

    In order to address the concerns above, FICC proposes to use a
haircut methodology to margin all Short-Term Treasuries and not just
for the Short-Term Treasuries without sensitivity analytics data. In
addition, FICC proposes to use two different haircut rates depending on
the time to maturity of the Short-Term Treasuries. The first rate would
apply to Treasury securities with remaining time to maturity equal to
or less than six months with a haircut floor set at 12.5 basis points.
The second rate would apply to Treasury securities with remaining time
to maturity greater than six months but equal to or less than one year
with a haircut floor set at 25 basis points. The haircut charges would
be applied to the absolute value of the net market value of the
Treasury securities in the respective rates, and the correlation offset
would not be applied.
    FICC examined the backtesting results of the current approach, as
applied at a product level, for Short-Term Treasuries.\18\ The results
show that the current approach does not meet FICC's 99% confidence
level standard.\19\ FICC's backtesting results for the period between
January and December 2020 showed that the Proposed Rule Change would
improve the backtesting results from approximately 94.9% to 99.4%.\20\
---------------------------------------------------------------------------

    \18\ FICC filed the backtesting results as a confidential
Exhibit 3 to the Proposed Rule Change pursuant to 17 CFR 240.24b-2.
Backtesting is an ex-post comparison of actual outcomes with
expected outcomes derived from the use of margin methodology.
    \19\ Notice, supra note 4, at 48772.
    \20\ Id.
---------------------------------------------------------------------------

C. Technical Changes

    FICC proposes to make conforming technical changes to renumber the
paragraphs in Section 1b of Rule 4. FICC also proposes to make
technical changes to the QRM Methodology Document. Specifically, FICC
proposes to make clarifying and grammatical changes to a sentence that
describes the indices in a haircut used for short TIPS bonds.

II. Discussion and Commission Findings

    Section 19(b)(2)(C) of the Act \21\ directs the Commission to
approve a proposed rule change of a self-regulatory organization if it
finds that such proposed rule change is consistent with the
requirements of the Act and the rules and regulations thereunder
applicable to such organization. After careful consideration, the
Commission finds that the Proposed Rule Change is consistent with the
requirements of the Act and the rules and regulations applicable to
FICC.\22\ In particular, the Commission finds that the Proposed Rule
Change is consistent with Section 17A(b)(3)(F) \23\ of the Act and
Rules 17Ad-22(e)(4)(i) \24\ and 17Ad-22(e)(6)(i) \25\ thereunder.
---------------------------------------------------------------------------

    \21\ 15 U.S.C. 78s(b)(2)(C).
    \22\ The Commission's findings are based on its review of the
Proposed Rule Change, including its analysis of the backtesting
results, which are summarized in Section I.B. above. See supra note
18 and accompanying text.
    \23\ 15 U.S.C. 78q-1(b)(3)(F).
    \24\ 17 CFR 240.17Ad-22(e)(4)(i).
    \25\ 17 CFR 240.17Ad-22(e)(6)(i).
---------------------------------------------------------------------------

A. Consistency With Section 17A(b)(3)(F) of the Act

    Section 17A(b)(3)(F) \26\ of the Act requires, in part, that the
rules of a clearing agency, such as FICC, be designed to, among other
things, promote the prompt and accurate clearance and settlement of
securities transactions and assure the safeguarding of securities and
funds which are in the custody or control of the clearing agency or for
which it is responsible.
---------------------------------------------------------------------------

    \26\ 15 U.S.C. 78q-1(b)(3)(F).
---------------------------------------------------------------------------

    As described in Section I.A. above, the proposed change to
eliminate the EUIC is designed to provide more accurate coverage by
avoiding potential under-margining due to the two situations described
involving cash substitution. As stated above, the EUIC was established
in 2014 to reduce this risk of potential under-margining. However, in
2018, FICC amended its methodology for determining the VaR Charge and
clarified the nature of the Intraday Supplemental Fund Deposit to more
effectively address market volatility. As described above, the EUIC is
applied based on data produced once per day while the Intraday
Supplemental Fund Deposit is based on hourly information. Accordingly,
the Intraday Supplemental Fund Deposit can more accurately calculate
margin the exposure presented. Furthermore, the second situation
involving interbank transactions no longer exists because inter bank
services were suspended in 2016.
    As described in Section I.B. above, the proposed changes to the QRM
Methodology Document are designed to mitigate the vulnerabilities of
the current GSD margin methodology when it is applied to portfolios
with a high concentration of Short-Term Treasuries. As stated above,
the current GSD Margin methodology does not reflect any special
treatment for determining the margin for Short-Term Treasuries.
Currently, Short-Term Treasuries are margined as part of the entire
portfolio using the sensitivity VaR Charge methodology, and a haircut-
based methodology is used as a backup where sensitivity analytics data
is not available. Pursuant to the Proposed Rule Change, a haircut
methodology would be used to margin all Short-Term Treasuries and two
different haircuts with floors would be used depending on the time to
maturity of the Short-Term Treasuries. The proposed changes would help
FICC to calculate and collect adequate margin for Short-Term Treasuries
from members. Moreover, the backtesting results show that the Proposed
Rule Change would help FICC achieve its backtesting standards, which is
a 99 percent coverage target with 3-days of margin period of risk.
    As described in Section I.C. above, the proposed technical changes
to the QRM Methodology Document would enhance the clarity of the
document for FICC. As the QRM Methodology Document is used by FICC's
risk management personnel regarding the calculation of margin
requirements, the proposed changes would help ensure that FICC's
personnel understand and apply the calculation of the GSD margin
methodology.
    Taken together, the Commission believes that the Proposed Rule
Change would allow FICC to more accurately calculate each member's
margin. This enhancement, in turn, would help FICC to produce margin
levels more commensurate with the risks associated with its members'
portfolios, and more effectively cover its credit exposure to its
members. FICC's collection of margin

amount in a manner that fully manages FICC's applicable credit
exposures should help ensure that, in the event of a member default,
FICC's operations would not be disrupted and non-defaulting members
would not be exposed to losses that they cannot anticipate or control.
Accordingly, the Commission finds that NSCC's Proposed Rule Change is
designed to help promote the prompt and accurate clearance and
settlement of securities transactions, consistent with Section
17A(b)(3)(F) of the Act.\27\ Moreover, FICC's collection of margin
amounts that better limit FICC's credit exposure to members would help
ensure that FICC maintains adequate funds necessary to manage the risks
associated with performing its clearance and settlement functions,
which could, in turn, help reduce the amount of credit losses that
would be distributed to non-defaulting members in the event of a
default. Accordingly, the Commission finds that FICC's Proposed Rule
Change is designed to help promote the prompt and accurate clearance
and settlement of securities transactions and assure the safeguarding
or securities and funds that are in FICC's custody or control.
Therefore, the Commission believes that the Proposed Rule Change is
consistent with Section 17A(b)(3)(F) of the Act.\28\
---------------------------------------------------------------------------

    \27\ Id.
    \28\ Id.
---------------------------------------------------------------------------

B. Consistency With Rule 17Ad-22(e)(4)(i)

    Rule 17Ad-22(e)(4)(i) under the Act \29\ requires a covered
clearing agency to establish, implement, maintain and enforce written
policies and procedures reasonably designed to effectively identify,
measure, monitor, and manage its credit exposures to participants and
those exposures arising from its payment, clearing, and settlement
processes by maintaining sufficient financial resources to cover its
credit exposure to each participant fully with a high degree of
confidence.
---------------------------------------------------------------------------

    \29\ 17 CFR 240.17Ad-22(e)(4)(i).
---------------------------------------------------------------------------

    The proposed change to eliminate the EUIC is designed to more
accurately address the potential under-margining situations described
above. The EUIC is charged once a day, while FICC may charge an
Intraday Supplemental Fund Deposit amount, if necessary, throughout the
day, based on the hourly information that FICC receives regarding GCF
Repo Members' positions. As such, because FICC can continuously assess
its exposure and charge additional margin throughout the day with the
Intraday Supplemental Fund Deposit rather than at one point in time,
the proposed changes would help FICC better measure and monitor its
credit exposures to members.
    The proposed changes to the QRM Methodology Document are designed
to allow FICC to use the haircut methodology to determine the margin
for all Short-Term Treasuries and not just for the Short-Term
Treasuries without sensitivity analytics data, as is the current case.
In addition, FICC would differentiate Short-Term Treasuries based on
the time to maturity, and apply two haircuts. This proposed approach
would address the deficienties with the current approach when it is
applied to portfolios with a high concentration of Short-Term
Treasuries as described above and thereby better enable FICC to limit
its credit exposures to members.
    Therefore, for the reasons discussed above, the Commission believes
that the Proposed Rule Change is consistent with the requirements of
Rule 17Ad-22(e)(4)(i) under the Act.\30\
---------------------------------------------------------------------------

    \30\ Id.
---------------------------------------------------------------------------

C. Consistency With Rule 17Ad-22(e)(6)(i)

    Rule 17Ad-22(e)(6)(i) under the Act \31\ requires a covered
clearing agency to establish, implement, maintain and enforce written
policies and procedures reasonably designed to cover, if the covered
clearing agency provides central counterparty services, its credit
exposures to its participants by establishing a risk-based margin
system that, at a minimum, considers, and produces margin levels
commensurate with, the risks and particular attributes of each relevant
product, portfolio, and market.
---------------------------------------------------------------------------

    \31\ 17 CFR 240.17Ad-22(e)(6)(i).
---------------------------------------------------------------------------

    The proposed change to eliminate the EUIC and thus relying on
Intraday Supplemental Fund Deposit to calculate and collect margins is
designed to cover FICC's credit exposures to its members. As described
above, Intraday Supplemental Fund Deposit would better enable FICC to
consider and produce margin levels commensurate with the risk and
particular attributes of a GCF Repo Member's portfolio and is able to
be more precisely tailored to the risks presented by a particular
portfolio because it allows for more frequent consideration of the
appropriate charge, as opposed to at one point during the day under the
EUIC.
    The proposed changes to the QRM Methodology Document are designed
to cover FICC's credit exposures to its members, especially those
members who have a high concentration of Short-Term Treasuries in their
portfolios because, as described above, this proposed approach would
address two vulnerabilities associated with the current approach when
it is applied to portfolios with a high concentration of Short-Term
Treasuries. By providing targeted margin methodologies for Short-Term
Treasuries and addressing two vulnerabilities, the proposed changes
would enhance NSCC's ability to cover its credit exposures to its
members and produce margin levels commensurate with the risks and
particular attributes of Short-Term Treasuries.
    Therefore, for the reasons discussed above, the Commission believes
that the Proposed Rule Change is consistent with the requiremens of
Rule 17Ad-22(e)(6)(i) under the Act.\32\
---------------------------------------------------------------------------

    \32\ Id.
---------------------------------------------------------------------------

III. Conclusion

    On the basis of the foregoing, the Commission finds that the
Proposed Rule Change is consistent with the requirements of the Act and
in particular with the requirements of Section17A of the Act \33\ and
the rules and regulations promulgated thereunder.
---------------------------------------------------------------------------

    \33\ 15 U.S.C. 78q-1.
---------------------------------------------------------------------------

    It is therefore ordered, pursuant to Section 19(b)(2) of the Act
\34\ that Proposed Rule Change SR-FICC-2021-007, be, and hereby is,
approved.\35\
---------------------------------------------------------------------------

    \34\ 15 U.S.C. 78s(b)(2).
    \35\ In approving the Proposed Rule Change, the Commission
considered the proposals' impact on efficiency, competition, and
capital formation. 15 U.S.C. 78c(f).

    For the Commission, by the Division of Trading and Markets,
pursuant to delegated authority.\36\
---------------------------------------------------------------------------

    \36\ 17 CFR 200.30-3(a)(12).
---------------------------------------------------------------------------

J. Matthew DeLesDernier,
Assistant Secretary.
[FR Doc. 2021-21863 Filed 10-6-21; 8:45 am]
BILLING CODE 8011-01-P


[Federal Register Volume 82, Number 72 (Monday, April 17, 2017)]
[Rules and Regulations]
[Page 18087]
[FR Doc No: 2017-07721]

=======================================================================
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DEPARTMENT OF HOMELAND SECURITY

Coast Guard

33 CFR Part 117

[Docket Number USCG-2017-0179]

Drawbridge Operation Regulation; Upper Mississippi River, Rock
Island, IL

AGENCY: Coast Guard, DHS.

ACTION: Notice of deviation from drawbridge regulation.

-----------------------------------------------------------------------

SUMMARY: The Coast Guard has issued a temporary deviation from the
operating schedule that governs the Rock Island Railroad and Highway
Drawbridge across the Upper Mississippi River, mile 482.9, at Rock
Island, Illinois. The deviation is necessary to allow the Quad City
Heart Walk to cross the bridge. This deviation allows the bridge to be
maintained in the closed-to-navigation position for two and one half
hours.

DATES: This deviation is effective from 8:30 a.m. to 11 a.m. on May 20,
2017.

ADDRESSES: The docket for this deviation, [USCG-2017-0179] is available
at http://www.regulations.gov. Type the docket number in the ``SEARCH''
box and click ``SEARCH.'' Click on Open Docket Folder on the line
associated with this deviation.

FOR FURTHER INFORMATION CONTACT: If you have questions on this
temporary deviation, call or email Eric A. Washburn, Bridge
Administrator, Western Rivers, Coast Guard; telephone<PHONE_NUMBER>,
email<EMAIL_ADDRESS>
SUPPLEMENTARY INFORMATION: The U.S. Army Rock Island Arsenal requested
a temporary deviation for the Rock Island Railroad and Highway
Drawbridge, across the Upper Mississippi River, mile 482.9, at Rock
Island, Illinois to remain in the closed-to-navigation position for a
two and \1/2\ hour period from 8:30 a.m. to 11 a.m., May 20, 2017,
while the Quad Cities Heart Walk is held between the cities of
Davenport, IA and Rock Island, IL.
    The Rock Island Railroad and Highway Drawbridge currently operates
in accordance with 33 CFR 117.5, which states the general requirement
that drawbridges shall open promptly and fully for the passage of
vessels when a request to open is given in accordance with the subpart.
    There are no alternate routes for vessels transiting this section
of the Upper Mississippi River.
    The Rock Island Railroad and Highway Drawbridge has a vertical
clearance of 23.8 feet above normal pool in the closed-to-navigation
position. Navigation on the waterway consists primarily of commercial
tows and recreational watercraft. This temporary deviation has been
coordinated with waterway users. No objections were received.
    In accordance with 33 CFR 117.35(e), the drawbridge must return to
its regular operating schedule immediately at the end of the effective
period of this temporary deviation. This deviation from the operating
regulations is authorized under 33 CFR 117.35.

    Dated: March 31, 2017.
Eric A. Washburn,
Bridge Administrator, Western Rivers.
[FR Doc. 2017-07721 Filed 4-14-17; 8:45 am]
 BILLING CODE 9110-04-P


Comment Info: =================

General Comment:Dear Mr. Zeller:

I am writing as an individual consumer to request an extension of the comment period for the Food and Drug Administration's ("FDA") Proposed Rule Deeming Tobacco Products to be Subject to the Federal Food, Drug, and Cosmetic Act, as amended by the Family Smoking and Prevention and Tobacco Control Act (the "Proposed Rule") published at 79 Fed. Reg. 23,142 and Federal Register No. 2014-09491. On behalf of myself, I am requesting that the comment period for the Proposed Rule be extended by the FDA for an additional 105 days, from its current 75-day period, to 180 days.

The Proposed Rule raises a number of significant issues and questions that are important and relevant to me, as a consumer of products that are proposed for regulation under the Proposed Rule. The Proposed Rule asks about a hundred different questions I might want to respond to. I want to provide my thoughts and comments on many of these issues, but my time to devote to researching and providing thoughtful comments on these important questions is limited. I have already spent many hours researching and dissecting these issues, but they take time. I know that the FDA took many years to even come up with the Proposed Rule, so I do not think it is at all unreasonable to allow the public a mere six months to comment on it. This is our only opportunity, as consumers, to provide our feedback.

I feel very strongly about e-cigarettes as an alternative to combustible cigarettes. Quite simply, I firmly believe that they saved my life and that the FDA has not given enough time nor effort into the fact that these are items are safe and need no help from the government to remain so. I wish to provide you with my personal story, as well as science- and evidence-based responses to your questions so that you can take my comment into account. I realize that the FDA has the authority under 21 CFR 10.40 to extend this time frame and that the FDA has exercised this authority on numerous occasions in the past. I would therefore ask that you do so here, so that all stakeholders have the opportunity to provide their comments on this proposed regulation.

I appreciate your consideration of my request and am happy to discuss this issue with you further.


[Federal Register: August 19, 2009 (Volume 74, Number 159)]
[Notices]
[Page 41967-41968]
[DOCID:fr19au09-109]

=======================================================================
-----------------------------------------------------------------------

DEPARTMENT OF TRANSPORTATION

Office of the Secretary

[Docket Number: DOT-OST-2009-0185]

Request for OMB Clearance of a New Emergency Information
Collection; New Information Collection: ARRA Bonding Assistance Program
Reimbursable Fee Program

AGENCY: Office of the Secretary (OST), Department of Transportation
(DOT).

ACTION: Notice; Letter of public notification of the American Recovery
and Reinvestment Act (ARRA) of 2009, (Pub. L. 111-5) DBE Bonding
Assistance Program. This request is being

submitted to OMB via an Emergency Information Collection Request.

-----------------------------------------------------------------------

SUMMARY: In compliance with the Paperwork Reduction Act of 1995, Public
Law 104-13 (44 U.S.C. 3501 et seq.) this notice announces the
Information Collection Request on DOT Form F4504--Application for
Reimbursement of Bond Fees for this new ARRA DOT program. The notice is
being forwarded to the Office of Management and Budget for Emergency
Action and approval.
    In an effort to assist the Disadvantaged Business Enterprises
(DBEs) obtain transportation and infrastructure contracts at the local,
state and federal levels, the Department of Transportation's (DOT)
Office of the Secretary, Office of Small and Disadvantaged Business
Utilization (OSDBU) has established under the American Recovery and
Reinvestment Act (ARRA) of 2009, the DBE ARRA Bonding Assistance
Program (BAP) Reimbursement Fee Program This program will assist DBEs
become more competitive and perform on more transportation
infrastructure projects receiving ARRA funding assistance from any DOT
mode of transportation, such as Federal Highway Administration, (FHWA),
Federal Transit Administration (FTA), Federal Aviation Administration
(FAA), Federal Railroad Administration (FRA), and the Maritime
Administration (MARAD). The DBE ARRA BAP is financial assistance in the
form of a bonding fee cost reimbursement. DOT will directly reimburse
DBEs the premiums paid to the surety company, usually between 2-3% of
the total bond amount, for performance, payment or bid/proposal bonds.
In the event the DBE also obtains a bond guarantee from Small Business
Administration's (SBA) Surety Bond Guarantee Program (SBGP), the DOT
will also reimburse the DBE for the small business concern (principal)
fee of .729% of the contract price.

FOR FURTHER INFORMATION CONTACT: Nancy Strine, Manager,<PHONE_NUMBER>,
Financial Assistance Division, Office of Small and Disadvantaged
Business Utilization, Office of the Secretary, U.S. Department of
Transportation, 1200 New Jersey Avenue, SE., Room W56-493, Washington,
DC 20590. Office hours are from 9 a.m. to 5 p.m., Monday through
Friday, except holidays.

SUPPLEMENTARY INFORMATION:
    OMB Control Number: OMB Control Number 2105-XXXX.
    Title: ARRA Bonding Assistance Program Reimbursement Fee Program.
    Form Number: DOT F 4504.
    Affected Public: Disadvantaged Business Enterprises--certified by
Title 49 CFR, Part 26.
    Frequency: One-time.
    Estimated Average Burden per Response: 2 hours.
    Estimated Annual Burden Hours: 3,540 hours.
    Abstract: ARRA Bonding Assistance Program Reimbursable Fee Program.
    The information collected will be from the DBE working on
transportation or infrastructure ARRA funded project. The information
collected will be used by DOT OSDBU to verify eligibility, process the
application, and disburse the reimbursement. The information being
collected relates the name of the company; full street address; the Dun
and Bradstreet Number (DUNS); Central Contractor Registration along
with Bank information to process their payment; DOT transportation
related contract information; supporting documentation that shows the
federal project number, bond information along with a copy of their
bond; and proof of payment of the fee. The applicant's eligibility is
determined by submitting a copy of a DBE certification and/or annual
affidavit, if applicable, for bonding fee reimbursement for specific
bonds. This will be verified by OSDBU staff as part of the application
process. Instructions are attached along with a copy of sample letter
to show how to obtain the federal project number. This information is
necessary to be able to reimburse the DBE the financial assistance for
the bond fees.

    Issued in Washington, DC, on August 10, 2009.
Tracey M. Jackson,
Office of the Chief Information Officer.
[FR Doc. E9-19917 Filed 8-18-09; 8:45 am]

BILLING CODE 4910-9X-P


[Federal Register Volume 77, Number 56 (Thursday, March 22, 2012)]
[Rules and Regulations]
[Pages 16668-16669]
[FR Doc No: 2012-6840]

-----------------------------------------------------------------------

DEPARTMENT OF TRANSPORTATION

Federal Aviation Administration

14 CFR Part 71

[Docket No. FAA-2012-0013; Airspace Docket No. 12-ASO-13]

Amendment of Class D and E Airspace; Brooksville, FL

AGENCY: Federal Aviation Administration (FAA), DOT.

ACTION: Final rule, technical amendment.

-----------------------------------------------------------------------

SUMMARY: This action amends Class D and E airspace at Hernando County
Airport, Brooksville, FL. The geographic coordinates of the airport are
being adjusted to coincide with the FAA's aeronautical database, which
shows the correct coordinates. This does not affect the boundaries or
operating requirements of the airspace.

DATES: Effective 0901 UTC March 22, 2012.

FOR FURTHER INFORMATION CONTACT: John Fornito, Operations Support
Group, Eastern Service Center, Federal Aviation Administration, P. O.
Box 20636, Atlanta, Georgia 30320; telephone<PHONE_NUMBER>.

SUPPLEMENTARY INFORMATION:

History

    The FAA is adjusting the geographic location of Hernando County
Airport, Brooksville, FL, to be in concert with the FAAs aeronautical
database, which shows the correct coordinates. This is an
administrative change and does not affect the boundaries or operating
requirements of the airspace, therefore, notice and public procedures
under 5 U.S.C. 553(b) are unnecessary.
    The Class D and E airspace designations are published in Paragraphs
5000, 6002, and 6005 of FAA order 7400.9V, dated August 9, 2011, and
effective September 15, 2011, which is incorporated by reference in 14
CFR 71.1. The Class D and E airspace designations listed in this
document will be published subsequently in the Order.

The Rule

    This amendment to Title 14, Code of Federal Regulations (14 CFR)
part 71 amends the geographic coordinates in the legal description of
Class D airspace, Class E surface airspace, and Class E airspace
extending upward from 700 feet above the surface, for Hernando County
Airport, Brooksville, FL. This update brings the geographic coordinates
of the airport in concert

with the FAA's Aeronautical Products database.
    The FAA has determined that this regulation only involves an
established body of technical regulations for which frequent and
routine amendments are necessary to keep them operationally current, is
non-controversial and unlikely to result in adverse or negative
comments. It, therefore, (1) is not a ``significant regulatory action''
under Executive Order 12866; (2) is not a ``significant rule'' under
DOT Regulatory Policies and Procedures (44 FR 11034; February 26,
1979); and (3) does not warrant preparation of a Regulatory Evaluation
as the anticipated impact is so minimal. Since this is a routine matter
that will only affect air traffic procedures and air navigation, it is
certified that this rule, when promulgated, will not have a significant
economic impact on a substantial number of small entities under the
criteria of the Regulatory Flexibility Act.
    The FAA's authority to issue rules regarding aviation safety is
found in Title 49 of the United States Code. Subtitle I, Section 106
describes the authority of the FAA Administrator. Subtitle VII,
Aviation Programs, describes in more detail the scope of the agency's
authority.
    This rulemaking is promulgated under the authority described in
Subtitle VII, Part A, Subpart I, Section 40103. Under that section, the
FAA is charged with prescribing regulations to assign the use of
airspace necessary to ensure the safety of aircraft and the efficient
use of airspace. This regulation is within the scope of that authority
as it amends controlled airspace at Hernando County Airport,
Brooksville, FL.

Lists of Subjects in 14 CFR Part 71

    Airspace, Incorporation by reference, Navigation (air).

Adoption of the Amendment

    In consideration of the foregoing, the Federal Aviation
Administration amends 14 CFR Part 71 as follows:

PART 71--DESIGNATION OF CLASS A, B, C, D AND E AIRSPACE AREAS; AIR
TRAFFIC SERVICE ROUTES; AND REPORTING POINTS

0
1. The authority citation for Part 71 continues to read as follows:

    Authority:  49 U.S.C. 106(g); 40103, 40113, 40120; E.O. 10854,
24 FR 9565, 3 CFR, 1959-1963 Comp., p. 389.

Sec.  71.1  [Amended]

0
2. The incorporation by reference in 14 CFR 71.1 of Federal Aviation
Administration Order 7400.9V, Airspace Designations and Reporting
Points, dated August 9, 2011, and effective September 15, 2011, is
amended as follows:

Paragraph 5000 Class D airspace.

* * * * *

ASO FL D Brooksville, FL [Amended]

Hernando County Airport, FL
    (Lat. 28[deg]28'25'' N., long. 82[deg]27'20'' W.)

    That airspace extending upward from the surface up to and
including 1,500 feet MSL within a 5.1-mile radius of the Hernando
County Airport. This Class D airspace area is effective during
specific dates and times established in advance by a Notice to
Airmen. The effective date and time will thereafter be continuously
published in the Airport/Facility Directory.

Paragraph 6002 Class E airspace designated as surface areas.

* * * * *

ASO FL E2 Brooksville, FL [Amended]

Hernando County Airport, FL
    (Lat. 28[deg]28'25'' N., long. 82[deg]27'20'' W.)

    That airspace extending from the surface within a 5.1-mile
radius of Hernando County Airport. This Class E airspace area is
effective during specific dates and times established in advance by
a Notice to Airmen. The effective date and time will thereafter be
continuously published in the Airport/Facility Directory.

Paragraph 6005 Class E airspace areas extending upward from 700
feet or more above the surface of the earth.

* * * * *

ASO FL E5 Brooksville, FL [Amended]

Hernando County Airport, FL
    (Lat. 28[deg]28'25'' N., long. 82[deg]27'20'' W.)

    That airspace extending upward from 700 feet above the surface
within a 7.6-mile radius of Hernando County Airport.

    Issued in College Park, Georgia, on March 14, 2012.
Barry A. Knight,
Manager, Operations Support Group, Eastern Service Center, Air Traffic
Organization.
[FR Doc. 2012-6840 Filed 3-21-12; 8:45 am]
BILLING CODE 4910-13-P