California Department of Food and Agriculture EM 62.9 Center for Analytical Chemistry Revision:2 Environmental Analysis Section Revision Date:1/09/09 3292 Meadowview Road Original Date: 7/21/1999 Sacramento, CA 95832 Page 1 of 26



### Title: Determination of Atrazine, Bromacil, Cyanazine, Diuron, Hexazinone, Metribuzin, Norflurazon, Prometon, Prometryn, Simazi ne, Deethyl Atrazine (DEA), Deisopropyl Atrazine ( ACET), Diamino Chlorotraizine ( DACT), Tebuthiuron and the metabolites Tebuthiuron-104, Tebuthiuron- 106, Tebuthiuron-107 and Tebut hiuron-108 in Well Water and River Water By Liquid Chromatography- Atmospheric Pressure Chemical Ionization Mass Spectrometry

1. Scope :

This modified section method (SM) is applicable to the analysis of Atrazine, Bromacil, Cyanazine, Diuron, Hexazinone, Metribuzin , Norflurazon, Prometon, Prometryn, Simazine, Deethyl Atrazine (DEA), Deis opropyl Atrazine ( ACET), and Diamino Chlorotraizine ( DACT) in well water and rive r water using APCI/LC/MS/MS. Desmethyl Norflurazon Tebuthiuron, Tebuthiuron-104 , Tebuthiuron-106, Tebuthiuron-107 and Tebuthiuron-108 method detection limit and validation data for well water was added later. The reporting limit for all chemicals is 0.05 ppb.

2. Principle :

Two conditioned Water Oasis ® MCX Cartridges connected in tandem are used to retain the analytes from well water and river water samples. The cartridges are placed under vacuum to eliminate any remaining wa ter. The chemicals are eluted with 5% ammonium hydroxide in methanol. The eluant is then filtered, concentrated, reconstituted in 1:3 methanol/wat er and analyzed by APCI/LC/MS/MS.

3. Safety :

All general laboratory safety rules for sample preparation and analysis shall be followed.

4. Interferences :

There were no matrix interferences that caused quantitative problems during method development and validation

5. Apparatus and Equipment :

5.1 Nitrogen Evaporator (Mey er N-EVAP Organomation Model #112 or equivalent) 5.2 Balance (Mettler PC 4400 or equivalent) 5.3 Vortex-vibrating mixer 5.4 Solid phase extraction manifold, Supelco Visiprep TM24 or equivalentCalifornia Department of Food and Agriculture EM 62.9 Center for Analytical Chemistry Revision:2 Environmental Analysis Section Revision Date:1/09/09 3292 Meadowview Road Original Date: 7/21/1999 Sacramento, CA 95832 Page 2 of 26



### 5.5 Solid phase extraction manifold accesso ries: vacuum source, vacuum chamber, vacuum controller, cartridge fittings (tube adapters) and connectors,sample delivery tubing with stainless steel wei ght, sample collection tubes and rack. 5.6 Sample filtration apparatus 5.7 Liquid Chromatograph equip ped with an ion trap (LCMS)

6. Reagents and Supplies :

6.1 Diamino Chlorotriazine (DACT) CAS#3397-62-4 6.2 Deisopropyl Atrazine (ACET) CAS#11007-28-9 6.3 Deethyl Atrazine (D EA) CAS#6190-65-4 6.4 Metribuzin CAS#21087-64-9 6.5 Bromacil CAS#314-40-9 6.6 Atrazine CAS#1912-24-9 6.7 Norflurazon CAS#27314-13-2 6.8 Cyanazine CAS#21725-46-2 6.9 Simazine CAS#122-34-9 6.10 Hexazinone CAS#51235-04-2 6.11 Diuron CAS#330-54-1 6.12 Prometon CAS#1610-18-0 6.13 Prometryn CAS#7287-19-6 6.14 Propazine (surrogat e) CAS#139-40-2 6.15 Desmethyl-Norflurz on CAS#23576-24-1 6.16 Tebuthiuron CAS#34014-18-1 6.17 Tebuthiuron 108 CAS# 6.18 Tebuthiuron 107 CAS# 6.19 Tebuthiuron 106 CAS# 6.20 Tebuthiuron 104 CAS# 6.21 Methanol, MS grade, Burd ick & Jackson or equivalent 6.22 Water, MS grade, Burdi ck & Jackson or equivalent 6.23 Formic acid, HPLC grade 6.24 Ammonium formate 1.0 M 6.25 Ammonium hydroxide, reagent grade or equivalent

. 

### 6.26 Elution reagent: 5% amm onium hydroxide in methanol. 6.27 Hydrochloric acid 6 N 6.28 Reconstitution reagent: 1:3 methanol/water 6.29 Mobil phase A: For 500 mL, mix 470 ± 2m L water, 25 ± 0.5 mL methanol, 4.50 ± 0.25 mL 1 M ammonium formate and 0.5 ± 0.05 mL formic acid. 6.30 Mobil phase B: For 500mL, mix 450 ± 2m L methanol and 45 ± 0.5 mL water with 4.50 ± 0.25 mL 1 M amm onium formate and 0.5 ± 0.05 mL formic acid.California Department of Food and Agriculture EM 62.9 Center for Analytical Chemistry Revision:2 Environmental Analysis Section Revision Date:1/09/09 3292 Meadowview Road Original Date: 7/21/1999 Sacramento, CA 95832 Page 3 of 26



### 6.31 Solid phase extraction cartridges: Wate rs Oasis® MCX 6 cc (150 mg), 60-micron particle size cartridge. 6.32 Nylon Acrodisc ®, 0.2 micron, Gelman Sciences 6.33 Syringe and plunger for filtration, 10mL 6.34 Graduated test tube, 15 mL (ca librated at 0.5mL with methanol) 6.35 Fiberglass f ilters, 1um x 47 mm.

6.36 LCMS Columns: Analytical column: Waters SymmetryShieldRP 18 

### 5 μ m, 3.9 x 150 mm column (part # 186000108) or equivalent Guard column: Waters SymmetryShieldRP 18 

### 5 μ m, 3.9 x 20 mm cartridge (Part # 186000107) or equivalent Guard column holder: Waters Sentry guard holder universal. (Part # wat064610)

7. Standards Preparation:

7.1 A combination stock standard of 0.1 mg/m L for all the triazines except propazine was obtained from the CDFA/CAC Standards Reposit ory. Propazine was received at a concentration of 1 mg/mL and was diluted to 1.0 ug/mL in methanol for spiking as a surrogate. Tebuthiuron and metabolites were received at a concentration of 1 mg/mL and were diluted with the combination triazine standard to 1.0 ug/mL in methanol for spiking.

A combination standard of 10 μg/mL was prepared with 1:3 methanol/water from the combination 0.1mg/mL standard, T ebuthuiron, metabolites and propazine standards. The combination working st andard was diluted to the following concentrations: 0.025, 0.05, 0.1, 0.2, 0.5, and 1 μ g/mL in 1:3 methanol/water for instrument calibration.

7.2 Keep all standards in the designated refrig erator for storage.

7.3 The expiration date of each standard is six m onths from the preparat ion date or the expira tion date of the stock standar ds which ever comes first.

8. Sample Preservation and Storage :

Store all samples waiting for extracti on in a separate refrigerator (32-40 ° F).California Department of Food and Agriculture EM 62.9 Center for Analytical Chemistry Revision:2 Environmental Analysis Section Revision Date:1/09/09 3292 Meadowview Road Original Date: 7/21/1999 Sacramento, CA 95832 Page 4 of 26



### 9. Test Sample Preparation :

9.1 Background Preparation

The Department of Pesticide Regulati on (DPR) provided the surface water and well water for background to be used in method validation and QC.

9.2 Preparation of blank and spike

Matrix blank: Weigh out 500 g of background water and follow the test sample extraction procedure.

Matrix spike: Weigh out 500 g of backgr ound water. Spike a client requested amount of herbicides into the background water and let it stand for 1 minute. Follow the test sample extraction procedure.

9.3 Test Sample Extraction

9.3.1 Remove sample from refrigerator and allow them to come to ambient temperature.

9.3.2 Weigh 500 ± 0.5 g of water sample into a 600 mL beaker.

9.3.3 Add 0.1 μg propazine ( 100 μL of 1 ng/μL spiking solution) as a surrogate to each sample except blank. Note: the volume of methanol in spiking solution added to the sample should be 0.1% or less of the sample volume.

9.3.4 Filter the surface water sample through a 1 μm x 47mm fiberglass filter. Note: no filtration is need for well water sample.

9.3.5 Adjust pH to 2.5 – 3.0 with 3 N HCL.

9.3.6 Two MCX cartridges are connected together in tandem and connected to the vacuum manifold. (Fill the 1 st 

### MCX cartridge reservoir with methanol and attach it to the solid phase ex traction manifold. Stack the 2 nd 

### MCXCalifornia Department of Food and Agriculture EM 62.9 Center for Analytical Chemistry Revision:2 Environmental Analysis Section Revision Date:1/09/09 3292 Meadowview Road Original Date: 7/21/1999 Sacramento, CA 95832 Page 5 of 26



### cartridge to the 1 st 

### MCX cartridge with fitting connec tor. Add methanol to 2 nd 

### reservoir.)

9.3.7 Condition the cartridges wit h total ~15 mL of methanol at a flow rate ~ 8 mL/minutes followed by ~ 15 mL of D.I. water by applying vacuum.

9.3.8 Turn off the vacuum when the D. I. water has just passed through the cartridges. Refill MCX cartridges with D.I. water. Attach the sample delivery tubes to the 2 nd 

### cartridge and place weighted tube ends into water sample.

9.3.9 Allow the sample to pass thr ough the conditioned cartridges by applying vacuum. Adjust the flow rate to ~ 8 mL/minute

9.3.10 After all of the water sample has passed through the cartridges, increase the vacuum to ~ 20 psi for about 2 mi nutes. Detach the sample delivery tube from MCX cartridge. Shake out any excess water in the cartridge reservoir. Reverse the stacking order of the MCX cartridges on the vacuum manifold.

9.3.11 Place the graduated test tubes into the vacuum manifold.

9.3.12 Elute and collect all chemicals with 15 ± 0.5 mL of 5% ammonium hydroxide in methanol at a fl ow rate of ~8 mL/minutes.

9.3.13 Concentrate the eluant to ~10 mL in a water bath at 38 ± 2 °C under a gentle stream of nitrogen.

9.3.14 Filter the eluant through a 0.2 μ m Acrodisc into a 15 mL graduated test tube, which has been calibrated at 0.5 mL. Rinse the test tube with ~ 2 mL of Methanol and filter t he rinsate. Add filtered rinsate to eluant. Rinse the filter and syringe and add to eluant.

9.3.15 Concentrate the eluant to ~0.2 mL in a water bath at 38 ± 2 °C under a gentle stream of nitrogen. Bring to a final volume of 0.5 mL with reconstitution reagent (1:3, water/me thanol). Vortex for 30 seconds. Transfer the extract into two autosampl er vials with inserts. Analyzed by APCI/LC/MS/MS.

10. Instrument Calibration :California Department of Food and Agriculture EM 62.9 Center for Analytical Chemistry Revision:2 Environmental Analysis Section Revision Date:1/09/09 3292 Meadowview Road Original Date: 7/21/1999 Sacramento, CA 95832 Page 6 of 26



### 10.1 The calibration standard curve consists of a minimum of three levels. The lowest level must be at or below t he corresponding reporting limits.

10.2 The LCMS calibration curves we re obtained using linear regression.

11. Analysis:

11.1 HPLC-MS

11.1.1 HPLC Instrument: Waters model 2695 HPLC and auto-sampler with column heater and remote control through Thermo Finnigan Xcalibur system. Column: Waters SymmetrySheid RP 18 

### 5 μm, 3.9 x 150 mm column Column Temperature: 40 °C

Mobile Phase: Gradient Time(min) Flow rate Mobile Phase A Mobile Phase B 

### 0 0.75 85.0 15.0 3.0 0.75 85.0 15.0 4.0 0.75 50.0 50.0 10.0 0.75 50.0 50.0 21.0 0.75 25.0 75.0 22.0 0.75 5.0 95.0 26.0 0.75 85.0 15.0 30.0 0.75 85.0 15.0 Injection Volume: 30 μL

11.1.2 Liquid Chromatograph Mass s pectrometer (LC-MS) and Operating Parameters

Model: Finnigan Model DECA ion trap MS Ion Source Type: Atmospheric pressure Ionization (APCI) Source Polarity: Positive APCI Vaporizer Temp: 450 °C Capillary Temperature: 220 °C Sheath Gas flow rate: 80 (arb) Auxiliary Gas flow: 10 (arb) Mode of operation: MS/MSCalifornia Department of Food and Agriculture EM 62.9 Center for Analytical Chemistry Revision:2 Environmental Analysis Section Revision Date:1/09/09 3292 Meadowview Road Original Date: 7/21/1999 Sacramento, CA 95832 Page 7 of 26



### Compound Name Retention Time (min.) Molecular Weight Mass Range Product Ions

DACT 3.29 145.55 60-200 110 ACET 7.41 173.6 55-200 132,146 Teb-108 7.72 157.23 60-240 158 DEA 8.99 187.63 60-200 146 Teb-106 8.68 200.26 55-220 158, 184 Teb-107 9.19 172.26 50-200 89 Teb-104 9.25 214.28 55-250 172, 215 Hexazinone 10.79 252.32 80-275 171 Tebuthiuron 11.26 228.31 100-250 172 Cyanazine 11.29 240.70 75-275 214,216,241 Metribuzin 11.86 214.29 70-235 186,187 Simazine 12.20 201.66 65-225 124,132,174 Bromacil 12.30 261.1 100-280 205,207 Prometon 13.75 225.3 70-250 142,184 Atrazine 16.10 215.69 70-235 174,176 Norflurazon 17.41 303.7 100-350 284 Desmethyl Norflurazon 16.55 289.65 75-350 248,270,288

Diuron 18.45 233.10 60-250 72 Propazine 19.57 229.7 70-250 188,190 Prometryn 20.66 241.37 75-275 200 Note: The column conditions, temperature, mobile phase, etc. may slightly shift retention time.

11.1.3 Operating parameter Compound Name Segment / Scan # Segment Time 

### Parent Mass (m/z) Isolation Width (m/z) Normalized Collision Energy(%) Activation Q

DACT 1 5.0 147 5.0 40.0 0.400 ACET 2 / 1 3.1 175 5.0 40.0 0.300 Teb-108 2 / 2 158 3.0 30.0 0.250 DEA 3 / 1 1.50 189 5.0 30.0 0.300 Teb-106 3 / 2 201 3.0 32.0 0.250 Teb-107 3 / 3 172 3.0 35.0 0.250California Department of Food and Agriculture EM 62.9 Center for Analytical Chemistry Revision:2 Environmental Analysis Section Revision Date:1/09/09 3292 Meadowview Road Original Date: 7/21/1999 Sacramento, CA 95832 Page 8 of 26



### Teb-104 3 / 4 215 3.0 30.0 0.250 Hexazinone 4 / 1 1.70 253 5.0 37.0 0.300 Cyanazine 4 / 2 242 5.0 37.0 0.300 Compound Name Segment / Scan # Segment Time 

### Parent Mass (m/z) Isolation Width (m/z) Normalized Collision Energy(%) Activation Q

Metribuzin 4 / 3 215 5.0 34.0 0.300 Tebuthiuron 4 / 4 229 3.0 35.0 0.250 Simazine 5 / 1 1.0 203 5.0 40.0 0.300 Bromacil 5 / 2 262 5.0 34.0 0.350 Metribuzin 5 / 3 215 3.0 34.0 0.300 Tebuthiuron 5 / 4 229 3.0 35.0 0.250 Simazine 6 / 1 0.80 203 5.0 40.0 0.300 Bromacil 6 / 2 262 5.0 34.0 0.350 Prometon 6 / 3 226 3.0 38.5 0.300 Prometon 7 / 1 2.20 226 3.0 38.5 0.300 Atrazine 7 / 2 217 5.0 36.0 0.300 Atrazine 8 / 1 1.99 217 5.0 36.0 0.300 Norflurazon 8 / 2 305 5.0 39.0 0.300 Desmethyl Norflurazon 

### 8 / 3 290 4.0 45.0 0.250

Diuron 9 / 1 0.81 235 5.0 35.0 0.240 Norflurazon 9 / 2 305 5.0 39.0 0.300 Diuron 9 / 3 235 5.0 0.0 0.240 Diuron 10 / 1 1.20 235 5.0 35.0 0.240 Diuron 10 / 2 235 5.0 0.0 0.240 Propazine 10 / 3 231 5.0 40.0 0.300 Prometryn 11 / 1 3.20 242 3.0 37.5 0.300 Propazine 11 / 2 231 5.0 40.0 0.300

12. Quality Control :

12.1 Method Detection Limits (MDL)

Method Detection Limit (MDL) refers to t he lowest concentration of the analyte that a method can detect reliably. To determine the MDL, 7 surface water/well water samples are spiked at 0.100 μ g and processed through the entire method along with a blank. The standard deviation derived from the spiked sampleCalifornia Department of Food and Agriculture EM 62.9 Center for Analytical Chemistry Revision:2 Environmental Analysis Section Revision Date:1/09/09 3292 Meadowview Road Original Date: 7/21/1999 Sacramento, CA 95832 Page 9 of 26



### recoveries was used to calculate the MDL for each analyte using the following equation:

MDL = tS

Where t is the Student t test value for the 99% confidence level with n-1 degrees of freedom and S denotes t he standard deviation obtai ned from n replicate analyses. For the n=7 replicates used to determine the MDL, t=3.143.

The results for the standard devia tions and MDL are in Appendix 1.

12.2 Reporting Limit (RL)

Reporting limit (RL) refers to a level at which reliable quantitative results may be obtained. The MDL is used as a guide to determine the RL. The RL is chosen in a range 1-5 times the MDL, as per client agreement. The reporting limit for this method is 0.05 ppb.

12.3 Method Validation

The method validation consisted of five sample sets. Each set included four levels of fortification and a method bl ank. All spikes and method blanks were processed through the entire analytical method. Spike levels and recoveries for the triazines are shown in Appendix 2. 12.4 Control Charts and Limits

Control charts were generated using the dat a from the method validation for each analyte. The upper and lower warni ng and control limits are set at ± 2 and 3 standard deviations of the % recovery, respectively, shown in Appendix 2.

12.5 Acceptance Criteria

12.5.1 Each set of samples will have a matr ix blank and a spiked matrix sample.

12.5.2 The retention time should be within ± 2 per cent of t hat of the standards.

12.5.3 The recoveries of the matrix sp ikes shall be within the control limits.

12.5.4 The sample shall be diluted if resu lts fall outside of the calibration curve.California Department of Food and Agriculture EM 62.9 Center for Analytical Chemistry Revision:2 Environmental Analysis Section Revision Date:1/09/09 3292 Meadowview Road Original Date: 7/21/1999 Sacramento, CA 95832 Page 10 of 26



### 13. Calculations:

Quantitation is based on an external standard ( ESTD) calculation using either the peak area or height. The LCMS software used a lin ear curve fit, with all levels weighted equally. Alternatively, at the chemist’s discretion, concentrations may be calculated using the response factor fo r the standard whose value is < 30% to the level in the sample.

ppb = (sample peak area or ht) x (std conc) x (std vol. Injected 

### ) x (final vol of sample)(1000 μL/mL) (std.peak area or ht) x (sample vol injected) x (sample wt (g)



### 14. Reporting Procedure:

Sample results are reported out according to the client’s analytical laboratory specification sheets.

15. Discussion and References:

15.1 Propazine is used as a su rrogate. Add 0.1 μg of pr opazine to each sample and processed through the entire analytical met hod. This allows the extraction steps to be monitored.

15.2 The segment durations in the mass spectrometer sett ings determine the retention time windows for each analyte. As the HPLC column performance may change over time because of irreversible co ntamination, phase stripping, etc., it may be necessary to adjust these windo ws before beginning a sequence for the observed retention times of the analytes. Installation of a new guard column or analytical column may also necessitate adjustments of window times. These retention time windows should be veri fied before each sequence, and adjusted as necessary.

15.3 The original method “ Determination of Atrazine, Bromacil, Cyanazine, Diuron, Hexazinone, Metribuzin, Norflurazon, Pr ometon, Prometryn, Simazine, Deethyl Atrazine, (DEA), Deisopropyl Atrazi ne (ACET), and Diamino Chorotriazine (DACT) in Well Water and River Water By Liquid Chromatography-Atmospheric Pressure Chemical Ionization Mass Spectrometry” has been updated to reflect what is currently being used. The in house vacuum manifold has been replacedCalifornia Department of Food and Agriculture EM 62.9 Center for Analytical Chemistry Revision:2 Environmental Analysis Section Revision Date:1/09/09 3292 Meadowview Road Original Date: 7/21/1999 Sacramento, CA 95832 Page 11 of 26



### with a Supelco Visiprep TM24 manifold. The LCQ DECA installed with the Waters SymmetrySheid RP 18 

### 5 μm, 3.9 x 150 mm column is the only instrument being used at this time. MDL and me thod validation data for desmethy norflurazon in well water has been added. Hexazinone mdl and validation data was also updated.

15.4 References:

15.41 SOP # EM 501.4

15.42 SOP # EM 501.5California Department of Food and Agriculture EM 62.9 Center for Analytical Chemistry Revision:2 Environmental Analysis Section Revision Date:1/09/09 3292 Meadowview Road Original Date: 7/21/1999 Sacramento, CA 95832 Page 12 of 26



### Appendix 1

The Determination of Method Detection Limit (MDL) and Reporting Limit (RL) in Well Water

Results: Well Water 

### Spk\Analyte DACT ACET DEA Bromacil Cyanazine Diuron

0.1ppb 0.079 0.083 0.080 0.104 0.086 0.086 0.1ppb spk 2 0.083 0.092 0.088 0.085 0.086 0.108 0.1ppb spk 3 0.079 0.088 0.079 0.095 0.088 0.088 0.1ppb spk 4 0.084 0.091 0.082 0.101 0.087 0.068 0.1ppb spk 5 0.081 0.093 0.088 0.092 0.083 0.081 0.1ppb spk 6 0.081 0.084 0.081 0.095 0.084 0.091 0.1ppb spk 7 0.080 0.086 0.085 0.101 0.084 0.069 SD 0.002 0.0040 0.00372 0.00655 0.00200 0.0137
MDL 0.0063 0.013 0.0110 0.020 0.0063 0.043 RL 0.05 0.05 0.05 0.05 0.05 0.05



### Results: Well water 

### Spk\Analyte Hexazinone Metribuzin Simazine Prometon Atrazine Norflurazon

0.1ppb spk 1 0.082 0.074 0.077 0.077 0.075 0.089 0.1ppb spk 2 0.080 0.086 0.084 0.082 0.087 0.091 0.1ppb spk 3 0.083 0.077 0.073 0.071 0.073 0.090 0.1ppb spk 4 0.086 0.082 0.080 0.076 0.079 0.088 0.1ppb spk 5 0.087 0.083 0.082 0.081 0.082 0.085 0.1ppb spk 6 0.081 0.081 0.083 0.077 0.082 0.088 0.1ppb spk 7 0.083 0.082 0.085 0.081 0.083 0.089 SD 0.0078 0.0040 0.0043 0.0038 0.0048 0.0019
MDL 0.025 0.0125 0.0135 0.012 0.015 0.0063 RL 0.05 0.05 0.05 0.05 0.05 0.05California Department of Food and Agriculture EM 62.9 Center for Analytical Chemistry Revision:2 Environmental Analysis Section Revision Date:1/09/09 3292 Meadowview Road Original Date: 7/21/1999 Sacramento, CA 95832 Page 13 of 26



### Appendix 1: Continue

The Determination of Method Detection Limit (MDL) and Reporting Limit (RL) in Well Water

Results: Well water



### Spk\Analyte Desmethyl Norflurazon Prometryn Tebuthiuron Metabolite 104 Metabolite 106 Metabolite 107 Metabolite 108

0.1ppb spk 1 0.093 0.077 0. 093 0.101 0.098 0.085 0.081 0.1ppb spk 2 0.089 0.084 0. 090 0.110 0.101 0.093 0.085 0.1ppb spk 3 0.097 0.077 0. 095 0.116 0.107 0.093 0.101 0.1ppb spk 4 0.093 0.074 0. 100 0.138 0.102 0.102 0.101 0.1ppb spk 5 0.099 0.083 0. 088 0.103 0.096 0.094 0.082 0.1ppb spk 6 0.100 0.084 0. 089 0.099 0.090 0.092 0.081 0.1ppb spk 7 0.0102 0.084 0. 098 0.115 0.100 0.112 0.099 SD 0.005 0.0043 0.0046 0.0134 0.0053 0.0087 0.0098
MDL 0.015 0.0135 0.014 0.042 0.017 0.027 0.031
RL 0.05 0.05 0.05 0.05 0.05 0.05 0.05



### The Determination of Method Detection Limit (MDL) and Reporting Limit (RL) in Surface Water

Results: Surface Water 

### Spk\Analyte DACT ACET DEA Bromacil Cyanazine Diuron

0.1ppb 0.075 0.088 0.082 0.077 0.082 0.077 0.1ppb spk 2 0.077 0.096 0.090 0.102 0.095 0.087 0.1ppb spk 3 0.075 0.086 0.088 0.095 0.088 0.085California Department of Food and Agriculture EM 62.9 Center for Analytical Chemistry Revision:2 Environmental Analysis Section Revision Date:1/09/09 3292 Meadowview Road Original Date: 7/21/1999 Sacramento, CA 95832 Page 14 of 26

0.1ppb spk 4 0.087 0.086 0.083 0.100 0.083 0.097 0.1ppb spk 5 0.087 0.090 0.088 0.099 0.087 0.093 0.1ppb spk 6 0.082 0.107 0.089 0.108 0.087 0.094 0.1ppb spk 7 0.081 0.109 0.089 0.097 0.087 0.088 SD 0.005 0.010 0.003 0.010 0.0040 0.007 MDL 0.016 0.030 0.010 0.031 0.013 0.022 RL 0.05 0.05 0.05 0.05 0.05 0.05California Department of Food and Agriculture EM 62.9 Center for Analytical Chemistry Revision:2 Environmental Analysis Section Revision Date:1/09/09 3292 Meadowview Road Original Date: 7/21/1999 Sacramento, CA 95832 Page 15 of 26



### Appendix 1: Continue

The Determination of Method Detection Limit (MDL) and Reporting Limit (RL) in Surface Water Result Surface Water Spk\Analyte Hexazinone Metribuzin Simazine Prometon Atrazine Norflurazon

0.1ppb spk 1 0.110 0.076 0.077 0.076 0.075 0.083 0.1ppb spk 2 0.094 0.080 0.085 0.087 0.081 0.093 0.1ppb spk 3 0.102 0.081 0.080 0.083 0.078 0.092 0.1ppb spk 4 0.099 0.085 0.081 0.083 0.082 0.096 0.1ppb spk 5 0.122 0.088 0.089 0.088 0.087 0.101 0.1ppb spk 6 0.122 0.097 0.092 0.087 0.084 0.095 0.1ppb spk 7 0.125 0.097 0.093 0.091 0.088 0.102 SD 0.013 0.008 0.0042 0.005 0.005 0.006
MDL 0.040 0.025 0.013 0.016 0.016 0.019
RL 0.05 0.05 0.05 0.05 0.05 0.05



### The Determination of Method Detection Limit (MDL) and Reporting Limit (RL) in Surface Water

Results: Surface Water 

### Spk\Analyte Prometryn

0.1ppb spk 1 0.077 0.1ppb spk 2 0.088 0.1ppb spk 3 0.083 0.1ppb spk 4 0.088 0.1ppb spk 5 0.089 0.1ppb spk 6 0.084 0.1ppb spk 7 0.090 SD 0.005
MDL 0.016
RL 0.05California Department of Food and Agriculture EM 62.9 Center for Analytical Chemistry Revision:2 Environmental Analysis Section Revision Date:1/09/09 3292 Meadowview Road Original Date: 7/21/1999 Sacramento, CA 95832 Page 16 of 26



### Appendix 2

Method Validation Data in Well Water

Results: Well Water



### Analyte Spike ppb Recovery Set 1 (%) set 2 set 3 set 4 set 5 %

DACT 0.1 97.0 80.5 70. 0 82.0 90.0 Mean: 90.9 0.5 120 88.1 97.6 81.0 84.8 SD: 13.0
2.0 119.3 88.8 83.4 74.6 87.5 UCL: 130.
6.0 103.5 105.3 91.7 84.7 88.5 UWL: 117.
LWL: 64.8 LCL: 51.7

ACET 0.1 96.0 84.5 84.5 100.0 102.0 Mean: 92.2 0.5 100.3 83.8 94.8 82.6 80.0 SD: 9.34 2.0 114.6 86.6 90.0 83.8 98.4 UCL: 120 6.0 98.6 100.0 99.2 81.7 83.4 UWL: 111
LWL: 73.6 LCL: 64.2

DEA 0.1 86.0 75.5 79.0 88.0 87.0 Mean: 86.8 0.5 92.3 79.8 98.2 79.6 75.0 SD: 7.65 2.0 96.8 77.8 88.8 85.2 96.6 UCL: 110 6.0 87.3 94.8 99.5 85.0 84.0 UWL: 102
LWL: 71.5 LCL: 63.9

Bromacil 0.1 87.5 93.0 101 94.0 110.0 Mean: 98.3 0.5 99.5 104.1 106.0 89.2 87.2 SD: 9.39 2.0 99.2 108.7 97.8 91.0 99.2 UCL: 127 6.0 88.8 125.4 100.5 93.3 91.3 UWL: 117
LWL: 79.6 LCL: 70.2California Department of Food and Agriculture EM 62.9 Center for Analytical Chemistry Revision:2 Environmental Analysis Section Revision Date:1/09/09 3292 Meadowview Road Original Date: 7/21/1999 Sacramento, CA 95832 Page 17 of 26



### Results: Well Water



### Analyte Spike ppb Recovery Set 1 (%) set 2 set 3 set 4 set 5 %

Cyanazine 0.1 82.0 79. 0 82.0 87.0 86.0 Mean: 86.0 0.5 89.5 85.0 90.6 77.2 77.2 SD: 4.73 2.0 89.9 83.7 86.8 83.0 93.0 UCL: 100 6.0 89.0 90.0 92.5 87.5 88.2 UWL: 95.4
LWL: 76.5 LCL: 71.8

Diuron 0.1 83.5 79.0 80.0 85.0 84.0 Mean: 88.3 0.5 81.7 75.5 100.8 83.0 89.6 SD: 9.59 2.0 78.1 72.3 99.4 93.8 103.8 UCL: 117
6.0 90.3 89.5 97.7 96.2 103.7 UWL: 108
LWL: 69.2 LCL: 59.6

Hexazinone 0.1 73.0 71.0 64.0 74.0 74.0 Mean: 95.0 0.5 84.6 74.3 81.2 67.4 69.4 SD: 5.49 2.0 91.2 79.2 83.6 76.4 81.6 UCL: 111
6.0 94.2 86.4 88.3 82.5 80.2 UWL: 106
LWL: 84.0 LCL: 78.5

Metribuzin 0.1 79.0 72.5 82.0 89.5 82.0 Mean: 81.1 0.5 77.3 69.3 95.4 79.2 71.6 SD: 7.25 2.0 83.9 72.4 79.8 80.0 89.8 UCL: 103
6.0 79.7 86.8 94.5 76.7 81.3 UWL: 95.6
LWL: 66.6 LCL: 59.4California Department of Food and Agriculture EM 62.9 Center for Analytical Chemistry Revision:2 Environmental Analysis Section Revision Date:1/09/09 3292 Meadowview Road Original Date: 7/21/1999 Sacramento, CA 95832 Page 18 of 26



### Results: Well Water



### Analyte Spike ppb Recovery Set 1 (%) set 2 set 3 set 4 set 5 %

Simazlne 0.1 85.5 70.5 74.0 86.0 84.0 Mean: 82.9 0.5 94.3 73.3 91.4 74.4 72.0 SD: 9.21 2.0 100.6 72.8 82.2 76.2 90.4 UCL: 110
6.0 89.0 91.8 95.5 75.3 77.8 UWL: 101
LWL: 64.4 LCL: 55.2

Prometon 0.1 75.0 72.5 63.0 73.0 76.0 Mean: 80.6 0.5 85.8 75.3 88.6 71.2 69.8 SD: 8.90 2.0 95.6 79.4 82.2 79.0 90.2 UCL: 107
6.0 84.6 91.7 95.8 80.7 82.0 UWL: 98.4
LWL: 62.8 LCL: 53.9

Atrazine 0.1 77.0 71.5 74.0 86.0 78.0 Mean: 79.5 0.5 80.6 70.3 90.2 76.2 69.4 SD: 7.12 2.0 84.9 71.0 79.8 79.0 88.4 UCL: 101
6.0 76.3 86.7 95.5 77.3 78.0 UWL: 93.8
LWL: 65.3 LCL: 58.1

Norflurazon 0.1 89.0 78.0 82.0 91.0 88.0 Mean: 90.3 0.5 97.5 78.9 99.8 80.0 84.6 SD: 7.01 2.0 99.0 87.2 96.8 87.0 96.0 UCL: 111
6.0 96.8 94.5 98.2 90.8 91.2 UWL: 104
LWL: 76.3 LCL: 69.3California Department of Food and Agriculture EM 62.9 Center for Analytical Chemistry Revision:2 Environmental Analysis Section Revision Date:1/09/09 3292 Meadowview Road Original Date: 7/21/1999 Sacramento, CA 95832 Page 19 of 26



### Results: Well Water



### Analyte Spike ppb Recovery Set 1 (%) set 2 set 3 set 4 set 5 %

Desmethyl Norflurazon 0.1 101.2 111 99.0 88.0 107 Mean: 100 0.5 96.2 105.8 110 85.8 98.8 SD: 6.80 2.0 103.3 97.9 103.6 89.5 103 UCL: 121
5.0 101.4 99.2 106.8 97.4 97.3 UWL: 114
LWL: 86.5 LCL: 79.7

Propazine 0.1 84.3 79.0 85.0 95.5 87.0 Mean: 83.4 0.5 83.3 75.5 100.0 83.0 80.0 SD: 7.02 2.0 83.8 72.3 79.5 78.5 88.0 UCL: 104
6.0 78.3 89.5 91.5 75.5 78.0 UWL: 97.4
LWL: 69.3 LCL: 62.3

Prometryn 0.1 82.5 74.0 73.0 87.0 85.0 Mean: 83.0 0.5 86.3 74.6 91.2 76.6 70.4 SD: 7.13 2.0 93.1 75.5 85.0 80.4 90.0 UCL: 104
6.0 86.8 91.0 93.8 82.8 81.0 UWL: 97.3
LWL: 68.7 LCL: 61.6



### Validation of Tebuthiuron and its metabolites were added at a later date

Results: Well Water



### Analyte Spike ppb Recovery Set 1 (%) set 2 set 3 set 4 %

Tebuthiuron 0.1 97.0 90. 0 91.0 89.0 Mean: 96.6 0.5 103 98.6 89.6 89.8 SD: 11.1 2.0 108 89.0 107 82.5 UCL: 130
6.0 96.2 129 95.7 90.5 UWL: 119
LWL: 74.4 LCL: 63.3California Department of Food and Agriculture EM 62.9 Center for Analytical Chemistry Revision:2 Environmental Analysis Section Revision Date:1/09/09 3292 Meadowview Road Original Date: 7/21/1999 Sacramento, CA 95832 Page 20 of 26



### Validation of Tebuthiuron and it ’s metabolites in well water was added at a later date

Results: Well Water



### Analyte Spike ppb Recovery Set 1 (%) set 2 set 3 set 4 %

Tebuthiuron 104 0.1 134 120 86.0 115 Mean: 98.1 0.5 94.8 102 95.0 91.8 SD: 13.9 2.0 104 91.5 94.0 86.5 UCL: 140
6.0 88.5 93.3 83.5 89.2 UWL: 126
LWL: 70.2 LCL: 56.3



### Analyte Spike ppb Recovery Set 1 (%) set 2 set 3 set 4 %

Tebuthiuron 106 0.1 96.0 101 106 87.0 Mean: 94.6 0.5 102 95.2 84.0 92.4 SD: 8.06 2.0 104 97.0 101 69.5 UCL: 119
6.0 88.0 89.3 84.7 88.5 UWL: 111
LWL: 78.4 LCL: 70.4

Analyte Spike ppb Recovery Set 1 (%) set 2 set 3 set 4 %

Tebuthiuron 107 0.1 99.0 86.0 118 87.0 Mean: 91.9 0.5 108 84.4 91.8 92.4 SD: 11.4 2.0 99.5 83.5 102 69.5 UCL: 126
6.0 91.6 84.5 84.5 88.5 UWL: 115
LWL: 69.0 LCL: 57.6

Analyte Spike ppb Recovery Set 1 (%) set 2 set 3 set 4 %

Tebuthiuron 108 0.1 81.0 80. 0 73.0 72.0 Mean: 84.1 0.5 96.6 83.4 81.4 89.6 SD: 8.91 2.0 107 81.0 93.0 81.0 UCL: 111
6.0 87.8 78.5 78.7 82.2 UWL: 102
LWL: 66.3 LCL: 57.4California Department of Food and Agriculture EM 62.9 Center for Analytical Chemistry Revision:2 Environmental Analysis Section Revision Date:1/09/09 3292 Meadowview Road Original Date: 7/21/1999 Sacramento, CA 95832 Page 21 of 26



### Method Validation Data in Surface Water

Results: Surface Water



### Analyte Spike ppb Recovery Set 1 (%) set 2 set 3 set 4 set 5 %

DACT 0.1 84.0 80.0 80.8 96.8 82.0 Mean: 84.5 0.5 87.6 87.4 81.0 97.8 84.8 SD: 5.37 2.0 83.0 83.4 77.0 90.0 80.3 UCL: 101 6.0 85.3 82.7 79.0 82.0 84.7 UWL: 95.2
LWL: 73.7 LCL: 68.4

ACET 0.1 107.0 110.0 110.0 147.0 97.0 Mean: 103 0.5 93.8 104.0 95.0 97.4 81.6 SD: 12.3 2.0 95.6 106.0 95.4 104.0 103.0 CL: 140 6.0 102.0 105.0 99.8 103.0 101.0 UWL: 127
LWL: 78.3 LCL: 66.0

DEA 0.1 93.0 87.0 88.0 83.0 81.0 Mean: 93.7 0.5 104.0 98.6 90.2 95.0 86.4 SD: 7.3 2.0 95.4 100.0 88.4 99.6 86.2 UCL: 116 6.0 103.0 107.0 94.2 95.3 98.8 UWL: 108
LWL: 79.2 LCL: 71.9

Bromacil 0.1 101.0 89.0 101.0 91.0 89.0 Mean: 97.5 0.5 107.0 110.0 88.2 101.0 92.4 SD: 7.1 2.0 84.0 106.0 98.0 100.0 96.6 UCL: 119 6.0 102.0 106.0 94.0 96.7 96.8 UWL: 112
LWL: 83.3 LCL: 76.3California Department of Food and Agriculture EM 62.9 Center for Analytical Chemistry Revision:2 Environmental Analysis Section Revision Date:1/09/09 3292 Meadowview Road Original Date: 7/21/1999 Sacramento, CA 95832 Page 22 of 26



### Results: Surface Water



### Analyte Spike ppb Recovery Set 1 (%) set 2 set 3 set 4 set 5 %

Cyanazine 0.1 102.0 88.0 94.0 83.0 88.0 Mean: 107. 0.5 95.4 106.0 90.4 95.8 79.8 SD: 18.2 2.0 115.0 131.0 128.0 128.0 107.0 UCL: 162
6.0 109.0 136.0 128.0 134.0 107.0 UWL: 144
LWL: 70.8 LCL: 52.6

Diuron 0.1 102.0 93.0 72. 0 81.0 98.0 Mean: 92.2 0.5 96.2 110.0 76.0 102.0 86.4 SD: 9.8 2.0 100.0 90.4 87.2 93.4 85.8 UCL: 122
6.0 89.5 89.3 95.0 109.0 88.3 UWL: 112
LWL: 72.5 LCL: 62.7

Hexazinone 0.1 117.0 105.0 98.0 93.0 87.0 Mean: 94.7 0.5 104.0 99.8 86.4 97.6 76.8 SD: 8.9 2.0 96.8 98.4 94.8 86.8 82.2 UCL: 121
6.0 96.3 99.3 94.2 90.2 90.0 UWL: 112
LWL: 77.0 LCL: 68.1

Metribuzin 0.1 93.0 87.0 92.0 75.0 79.8 Mean: 89.2 0.5 92.2 103.0 80.2 87.6 79.6 SD: 6.78 2.0 85.2 95.8 95.2 90.4 90.0 UCL: 110
6.0 90.8 98.2 89.3 90.0 88.9 UWL: 103
LWL: 75.6 LCL: 68.8California Department of Food and Agriculture EM 62.9 Center for Analytical Chemistry Revision:2 Environmental Analysis Section Revision Date:1/09/09 3292 Meadowview Road Original Date: 7/21/1999 Sacramento, CA 95832 Page 23 of 26



### Results: Surface Water



### Analyte Spike ppb Recovery Set 1 (%) set 2 set 3 set 4 set 5 %

Simazlne 0.1 93.0 85.0 82.0 80.0 75.0 Mean: 87.0 0.5 93.2 99.2 78.8 89.8 78.8 SD: 6.88
2.0 86.6 91.2 82.8 91.2 78.8 UCL: 107.6
6.0 94.4 98.0 85.3 85.8 90.2 UWL: 100.7
LWL: 73.2 LCL: 66.3

Prometon 0.1 86.0 80.0 76.0 78.0 79.0 Mean: 86.5 0.5 92.8 96.2 80.6 89.4 81.6 SD: 6.36 2.0 86.4 91.4 82.0 89.0 80.4 UCL: 106
6.0 92.5 96.5 89.5 92.0 91.3 UWL: 99.2
LWL: 73.8 LCL: 67.5

Atrazine 0.1 88.0 82.0 78.0 78.0 76.0 Mean: 85.5 0.5 92.4 97.2 83.4 86.2 72.2 SD: 6.33 2.0 83.8 92.8 84.6 86.4 84.8 UCL: 104
6.0 90.0 94.7 88.7 85.3 85.2 UWL: 98.1
LWL: 72.8 LCL: 66.5

Norflurazon 0.1 98.0 92.0 88.0 86.0 89.0 Mean: 96.0 0.5 104.0 106.0 89.6 95.3 90.6 SD: 5.59 2.0 96.8 101.0 96.0 95.2 101.0 UCL: 113
6.0 95.8 103.0 96.7 101.0 95.8 UWL: 107
LWL: 84.9 LCL: 79.3California Department of Food and Agriculture EM 62.9 Center for Analytical Chemistry Revision:2 Environmental Analysis Section Revision Date:1/09/09 3292 Meadowview Road Original Date: 7/21/1999 Sacramento, CA 95832 Page 24 of 26



### Results: Surface Water



### Analyte Spike ppb Recovery Set 1 (%) set 2 set 3 set 4 set 5 %

Propazine 0.1 98.0 90.5 78.5 84.0 79.0 Mean: 89.8 0.5 110.0 105.0 86.5 97.5 81.5 SD: 8.65 2.0 90.0 93.0 81.5 86.5 77.5 CL: 116
6.0 96.5 93.0 89.5 90.0 88.5 UWL: 107
LWL: 72.5 LCL: 63.9

Prometryn 0.1 92.0 90.0 95.0 86.0 86.0 Mean: 91.9 0.5 96.6 102.0 83.2 89.2 80.0 SD: 6.46 2.0 88.0 98.0 93.0 93.6 83.4 UCL: 111
6.0 97.3 106.0 93.8 93.2 91.2 UWL: 105
LWL: 78.9 LCL: 72.5California Department of Food and Agriculture EM 62.9 Center for Analytical Chemistry Revision:2 Environmental Analysis Section Revision Date:1/09/09 3292 Meadowview Road Original Date: 7/21/1999 Sacramento, CA 95832 Page 25 of 26



### Updated By: Original signed by: 8/26/2010

________________________ _____________ Jean Hsu Date Environmental Scientist

Updated By: Original signed by: 8/26/2010

________________________ _____________ Jane White Date Environmental Scientist

Updated By: Original signed by: 8/26/2010

________________________ _____________ Paul Lee Date Staff Environmental Scientist

Approved By :

Original signed by: 8/26/2010

_______________________ __ ____________ Steve Siegel Date Sr. Environmental Scientist

Approved By:

Original signed by: 8/26/2010

_______________________ __ ____________ Elaine Wong Date Environmental Program Manager ICalifornia Department of Food and Agriculture EM 62.9 Center for Analytical Chemistry Revision:2 Environmental Analysis Section Revision Date:1/09/09 3292 Meadowview Road Original Date: 7/21/1999 Sacramento, CA 95832 Page 26 of 26



### Revision Log: Date What was revised? Why? 9/10/07 Add data for Desmethyl Norflurazon in well water 1/09/09 Add data for Tebuthiuron and metabolites in well water