Forest Herbicide Residues in Surface Water and Plants in the Tribal Territory of the

Lower Klamath River Watershed of California

P. Wofford, K.S. Goh, D. Jones, H. CasjensDepartment of Pesticide Regulation

H. Feng, J. Hsu, D. Tran, J. Medina, J. White, Center for Analytical Chemistry

California Department Food & Agriculture

December 9, 2002Klamath

Outline

Introduction Objectives Sampling Methods

– Water sampling– Plant sampling– Fish tissue sampling

Results and Discussion

Introduction

U.S. EPA grant Herbicide exposure concerns Yurok Environmental Monitoring Work Group

Yurok Environmental Monitoring Work Group

Tribal members and staff County Department of Agriculture personnel Timber company personnel CIBA personnel Department of Pesticide Regulation personnel

&

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&

&

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(/10 1

"!96"!169

Requa

Klamath

Klamath Glen

JohnsonsPecwan

Weitchpec

Patricks Point

Trinidad

Major roads

Waterways

County lines

Yurok Ancestral Territory

Hoopa Valley Reservation

Yurok Reservation

State owned

National Park Service

U. S. Bureau of Land Management

U.S. Forest Service

Private Ownership

N0 2 4 Miles

Del Norte County

Humbolt County

Study Area

Herbicides Monitored

Atrazine 2,4-D Glyphosate Triclopyr

Objectives

WATER Monitor aerial herbicide application drift into

waterways Monitor herbicide runoff during rainfall events

PLANTS Monitor aerial herbicide application drift Measure rate of herbicide dissipation on plants

at application sites

Water Sampling Methods

Grab sample ISCO® autosampler Minimum Detection Limits:

– Atrazine = 0.05 ppb– 2,4-D and triclopyr = 0.10 ppb– Glyphosate = 2.00 ppb

Water Quality Parameters:– Temperature, pH, dissolved oxygen, and electrical

conductivity

Drift During Application

Monitored waterways which ran through application area

Five aerial applications monitored Sampled during entire application

$

$

$

(/101

Site F

Site G

Site E

Highways

River and Creeks

$

Aerial Applications

Sampling Sites

N

1 0 1 Miles

Site G13 acres

glyphosate1100 ft away

Site E40 acrestriclopyr

In boundary

Site F105 acrestriclopyr

1700 ft away

Fall 1999

$

$

(/101

Site I

Site J

1 0 1 2 Miles

N

Sampling Sites

Aerial Applications

$

River and Creeks

Highways

Site I245 acres

triclopyr, 2,4-D200 ft away

Site J230 acres

triclopyr, 2,4-D400 ft away

Spring 2000

Aerial Application Monitoring - Site I

0

0.2

0.4

0.6

0.8

1

1.2

8:26 8:28 8:30 8:32 8:34 9:26 10:26 11.26

Time of day

Con

cen

trat

ion

(p

pb

) 2,4-D

Triclopyr

Rainfall Event Monitoring

12 sites monitored Both ground and aerial

applications monitored

$

$

$

$

"!169

(/101

Site B

Site C

Hunt

er C

reek

Blue Creek

Pec

wan

Cre

ek

Wils

on C

reek

Site A

Bear CreekT

erw

er C

reek

Site D

Pacific O

cean

Klamath R

iver Del Norte County

Humboldt County

Highways

Aerial Applications

Ground Applications

River and Creeks

$ Sampling Site

N

Site Aground9 acresatrazine

82 ft away

Site Bground36 acres

atrazine, triclopyr2500 ft away

Site Cground25 acresatrazine

2500 ft awaySite Daerial

360 acres2,4-D, atrazine2 miles away

Spring 1999

$

$

$

(/101

Site F

Site G

Site E

Highways

River and Creeks

$

Aerial Applications

Sampling Sites

N

1 0 1 Miles

Site G13 acres

glyphosate1100 ft away

Site E40 acrestriclopyr

In boundary

Site F105 acrestriclopyr

1700 ft away

Fall 1999

Aerial Application Rain runoff - Site E

0

0.1

0.2

0.3

0.4

0.5

11:40 12:40 13:40 14:40 15:40 16:40 17:40 18:40

Time of day

Con

cen

trat

ion

(p

pb

) Triclopyr

$

$

$

$

$

"!169

(/101

Site M

Site J

Site L

Site K

Site H

Del Norte County

Humboldt County

N

Highways

Aerial Applications

Ground Applications

River and Creeks

$ Sampling Site

1 0 1 2 Miles

Site Hground36 acres

atrazine, triclopyr500 ft away

Site Jaerial

230 acres2,4-D, triclopyr

400 ft awaySite Kground80 acresatrazine

1300 ft awaySite Laerial

20 acres2,4-D, triclopyr

200 ft awaySite M

aerial100 acres

2,3-D, triclopyr1600 ft away

Spring 2000

Aerial Application Rain runoff - Site L

0

0.1

0.2

0.3

0.4

0.5

13:22 14:22 15:22 16:22 17:22 18:22 19:22 20:22Time of day

Con

cen

trat

ion

(p

pb

) 2,4-D

Triclopyr

Plant Sampling Methods

Only triclopyr and 2,4-D were monitored Composite samples

Plants Selected For Monitoring

Beargrass (Xerophyllum tenax) - leaves Huckleberry (Vaccinium ovatum) - berries Maidenhair fern (Adiantum pedatum) - stems Manzanita (Arctostaphyllos spp.) - berries Oregon grape (Berberis nevosa) - roots Tanoak (Lithocarpus densiflorus) - acorn Willow (Salix spp.) - shoots Yarrow (Achillea milleforlium) - stems and leaves

beargrass

huckleberry

manzanita

Oregon grape

tanoak acorns

yarrow

Minimum Detection Limits for 2,4-D and triclopyr on monitored plants

Beargrass = 0.05 ppm Huckleberry = 0.05 ppm Maidenhair fern = 0.05 ppm Manzanita = 0.03 ppm Oregon grape = 0.05 ppm (estimated) Tanoak = 0.05 ppm Yarrow = 0.10 ppm

Off-site Movement During Application

Four applications monitored Sampling sites on downwind side of application Sampled beargrass, yarrow, and huckleberry

Site P225

acresbeargrass

Site Q35 acres

Beargrass huckleberry

Site S25 acresyarrow

Site V25 acresbeargrass

Number

of

Average Concentration (ppm)

Site Distance (ft) Samples triclopyr 2,4-D

P 121 1 ND ND

210 1 ND ND

Q 185 - 215 6 ND ND

220 - 240 6 ND ND250 - 285 6 ND ND

S 20 - 23 3 0.11 0.10

100 - 150 4 ND ND

V 0 3 0.56 0.41

30 - 41 3 0.14 0.10

50 - 90 3 ND ND

Dissipation sampling

Five application areas monitored Sampled beargrass, huckleberry, manzanita,

and yarrow

$

$

$

$

$

(/101

Klamath River

Hunte

r Cre

ek

Terw

er C

reek

Site N

Site O

Site R

West Fo

r k

Blue C

reek

Site W

Site U

Pac ific O

cean

Del Norte County

Humboldt County

"!169

$

Bald Hills RoadJo

hnso

n Road

Hancorne Ranch Road

Tectah Creek

Met

tah

Cre

ek

Site THumboldt County

0.25 0 0.25 Miles

N

1 0 1 2 Miles

Application Sites

Rivers and Creeks

Highways

$ Sampling Sites

Site N25 acresbeargrass

Site O66 acresbeargrass

Site R116 acres

huckleberryyarrow

Site T45 acres

Manzanita

Site W40 acresbeargrass

Site NBeargrass

Days After Application

01 14 43 91 146 511

Co

nce

ntr

atio

n (

pp

m)

0.0

0.5

1.0

7.0

Triclopyr 2,4-D Non-Detect Value

Site OBeargrass

Days After Application

01 14 43 91 511

Co

nce

ntra

tion

(ppm

)

0.0

0.5

1.0

7.0

Triclopyr 2,4-D Non-Detect Value

Site RYarrow

Days After Application

01 916 32 65 157 372

Co

nce

ntr

atio

n (

pp

m)

0.0

1.0

2.0

3.0

4.0

5.0

6.0

7.0

Triclopyr 2,4-D Non-Detect Value

Site RHuckleberry

Days After Application

01 9 16 32 65

Con

cent

ratio

n (p

pm)

0.0

0.5

1.0

7.0

Triclopry 2,4-D Non-Detect Value

No berries available for sampling

Site TManzanita

Days After Application

01 916 32 65 157 372

Con

cent

ratio

n (

ppm

)

0.0

1.0

7.0

Triclopyr 2,4-D Non-Detect Value

Site WBeargrass

Days After Application

01 916 32 65 157 372

Con

cent

ratio

n (p

pm)

0.0

1.0

2.0

7.0

Triclopyr2,4-DNon-Detect Value

Fish Tissue Sampling with the Department of Fish and Game

Chemical analysis by the Department of Fish and Game

Sampled fish tissue and water in two creeks downstream from applications

Sampled:– sculpin (Cottus gulosus) in McGarvey Creek – steelhead trout (Oncorhynchus mykiss) in the West

Fork of Blue Creek

$

$

"!169

McGarvey Creek

sculpin samplewater sample

Pacific O

cean

Humboldt County

Del Norte County

West Fork Blue Creek

steelhead trout samplewater sample

Highways

River and Creeks

$ Sampling Sites

N

1 0 1 Miles

sculpin

Steelhead trout

Fish Tissue Results

Site Date Concentration (ppb)

triclopyr 3,5,6-trichloro-2-pyridinol

2,4-D 2,4-dichlorophenol

McGarvey Creek

4/13/01 ND1 ND2 ND3 ND4

5/1/01 ND ND ND ND

5/8/01 ND ND ND ND

West Fork Blue Creek

4/13/01 ND ND ND ND

5/1/01 ND ND ND ND

5/8/01 ND ND ND ND

Minimum report limit: 1 1 ppb, 2 5 ppb, 3 2 ppb , 5 5 ppb

Water Results

Site Date Concentration (ppb)

triclopyr 2,4-D

McGarvey Creek

4/13/01 ND ND

5/1/01 ND ND

5/8/01 ND ND

West Fork Blue Creek

4/13/01 ND ND

5/1/01 ND ND

5/8/01 ND ND

Minimum report limit: 0.10 ppb

Additional Sampling

Plant sampling in Hupa and Kaurk gathering areas– Beargrass, woodwardia fern, willow, tanoak acorns,

and huckleberry analyzed for triclopyr and 2,4-D

Plant sampling in area treated for spotted knapweed– Deerbrush and Oregon grape roots analyzed for

2,4-D

Additional Sampling (continued)

Two rain runoff sampling events following atrazine applications

Tanoak acorns and huckleberry sampled for 2,4-D and triclopyr

ACKNOWLEDGMENTS

Yurok Environmental Monitoring Work GroupLori Harder McKinnon, John Melvin, Ken Childs, Sr., Richard Myers,

Susan Burdick, Jene McCovey, Kevin McKernan, Marty Geslak,Ora Smith, LaVerne Glaze, Renee Stauffer, Holly Hensher, Ron

Johnson, Jennifer Kalt, Wendy George, Bessie Lee, and Chuck Striplen

County Department of AgricultureJohn Falkenstrom, Jeff Dolf

Glenn Anderson, Dave Cavyell

Simpson Timber CompanyBernard Bush, John Pricer, and Dale Miller

Center for Analytical ChemistryC. Cooper, L. Ortiz, R. Wichert, I. Aguilar,

T. Woreniecka, J. Echelberry, J. Temple and A. Vaques

Department of Pesticide RegulationPaul Gosselin, John Sanders, Kathy Brunetti, Carissa Gana,Jesse Ybarra, Roger Sava, Johanna Walters, and Nina Bacey

U.S. Environmental Protection AgencyNancy Frost and Annie Yates