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Environmental Analysis Section Revision Date:1/09/09 

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 Title: Determination of Atrazine, Bromacil, Cyanazine, Diuron, Hexazinone, Metribuzin, 

Norflurazon, Prometon, Prometryn, Simazine, Deethyl Atrazine (DEA), Deisopropyl 

Atrazine ( ACET), Diamino Chlorotraizine ( DACT), Tebuthiuron and the metabolites 

Tebuthiuron-104, Tebuthiuron-106, Tebuthiuron-107 and Tebuthiuron-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), Deisopropyl Atrazine ( ACET), and Diamino 

Chlorotraizine ( DACT) in well water and river 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 water. The chemicals are eluted with 5% 

ammonium hydroxide in methanol. The eluant is then filtered, concentrated, 

reconstituted in 1:3 methanol/water 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 (Meyer 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 equivalent 
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5.5 Solid phase extraction manifold accessories: vacuum source, vacuum chamber, 

vacuum controller, cartridge fittings (tube adapters) and connectors,sample 

delivery tubing with stainless steel weight, sample collection tubes and rack. 

5.6 Sample filtration apparatus 

5.7 Liquid Chromatograph equipped 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 (DEA) 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 (surrogate) CAS#139-40-2 

6.15 Desmethyl-Norflurzon 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, Burdick & Jackson or equivalent 

6.22 Water, MS grade, Burdick & 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% ammonium 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 ± 2mL 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 ± 2mL methanol and 45 ± 0.5 mL water with 

4.50 ± 0.25 mL 1 M ammonium formate and 0.5 ± 0.05 mL formic acid. 
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Environmental Analysis Section Revision Date:1/09/09 

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6.31 Solid phase extraction cartridges: Waters 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 (calibrated at 0.5mL with methanol) 

 6.35 Fiberglass filters, 1um x 47 mm. 

 6.36 LCMS Columns: 

Analytical column: Waters SymmetryShieldRP18 5 μm, 3.9 x 150 mm column 

(part # 186000108) or equivalent 

Guard column: Waters SymmetryShieldRP18 5 μm, 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/mL for all the triazines except propazine 

was obtained from the CDFA/CAC Standards Repository. 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, Tebuthuiron, metabolites and propazine 

standards. The combination working standard was diluted to the following 

concentrations: 0.025, 0.05, 0.1, 0.2, 0.5, and 1 μg/mL in 1:3 methanol/water for 

instrument calibration. 

7.2 Keep all standards in the designated refrigerator for storage. 

7.3 The expiration date of each standard is six months from the preparation date or 

 the expiration date of the stock standards which ever comes first. 

8. Sample Preservation and Storage: 

Store all samples waiting for extraction in a separate refrigerator (32-40 °F). 
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9. Test Sample Preparation: 

9.1 Background Preparation 

The Department of Pesticide Regulation (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 background 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 1st MCX cartridge reservoir with methanol 

and attach it to the solid phase extraction manifold. Stack the 2nd MCX 
California Department of Food and Agriculture EM 62.9 

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Environmental Analysis Section Revision Date:1/09/09 

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Sacramento, CA 95832 Page 5 of 26 

cartridge to the 1st MCX cartridge with fitting connector. Add methanol to 

2nd reservoir.) 

9.3.7 Condition the cartridges with 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 2nd cartridge and place weighted tube ends into water 

sample. 

9.3.9 Allow the sample to pass through 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 minutes. 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 flow 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 μm 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 the 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/methanol). Vortex for 30 seconds. 

Transfer the extract into two autosampler vials with inserts. Analyzed by 

APCI/LC/MS/MS. 

10. Instrument Calibration: 
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10.1 The calibration standard curve consists of a minimum of three levels. The lowest 

level must be at or below the corresponding reporting limits. 

10.2 The LCMS calibration curves were 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 RP18 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 spectrometer (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/MS 
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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 0.250 
California Department of Food and Agriculture EM 62.9 

Center for Analytical Chemistry Revision:2 

Environmental Analysis Section Revision Date:1/09/09 

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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 the 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 μg and processed through the entire method 

along with a blank. The standard deviation derived from the spiked sample 
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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 the standard deviation obtained from n replicate 

analyses. For the n=7 replicates used to determine the MDL, t=3.143. 

The results for the standard deviations 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 blank. 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 data from the method validation for each 

analyte. The upper and lower warning 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 matrix blank and a spiked matrix sample. 

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

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

12.5.4 The sample shall be diluted if results fall outside of the calibration curve. 
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13. Calculations:

Quantitation is based on an external standard (ESTD) calculation using either the peak 

area or height. The LCMS software used a linear curve fit, with all levels weighted 

equally. Alternatively, at the chemist’s discretion, concentrations may be calculated 

using the response factor for 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 surrogate. Add 0.1 μg of propazine to each sample and 

processed through the entire analytical method. This allows the extraction steps 

to be monitored. 

15.2 The segment durations in the mass spectrometer settings determine the 

retention time windows for each analyte. As the HPLC column performance may 

change over time because of irreversible contamination, phase stripping, etc., it 

may be necessary to adjust these windows 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 verified before each sequence, and adjusted 

as necessary. 

15.3 The original method “Determination of Atrazine, Bromacil, Cyanazine, Diuron, 

Hexazinone, Metribuzin, Norflurazon, Prometon, Prometryn, Simazine, Deethyl 

Atrazine, (DEA), Deisopropyl Atrazine (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 replaced 
California Department of Food and Agriculture EM 62.9 

Center for Analytical Chemistry Revision:2 

Environmental Analysis Section Revision Date:1/09/09 

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Sacramento, CA 95832 Page 11 of 26 

with a Supelco Visiprep TM24 manifold. The LCQ DECA installed with the 

Waters SymmetrySheid RP18 5 μm, 3.9 x 150 mm column is the only instrument 

being used at this time. MDL and method 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 501.5 
California Department of Food and Agriculture EM 62.9 

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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 0.05 
California Department of Food and Agriculture EM 62.9 

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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 0.085 
California Department of Food and Agriculture EM 62.9 

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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 0.05 
California Department of Food and Agriculture EM 62.9 

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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 0.05 
California Department of Food and Agriculture EM 62.9 

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 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: 70.2 

 

 

 
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 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: 59.4 
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 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: 69.3 

 
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 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: 63.3 
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 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: 57.4 
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 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: 76.3 

 

 
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 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: 68.8 
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 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: 79.3 

 
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 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: 72.5 
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 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 I
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 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