Clopyralid

Clopyralid	Last updated: 12/01/2021
(Also known as: clopyralid-olamine; Dowco 290; clopyralid acid; 3,6-dichloropicolinic acid; DCP)

SUMMARY

A herbicide approved for use in the EU. It has a high aqueous solubility, is volatile and, based on its chemical properties, there is a high risk of it leaching to groundwater. It can be persistent in both soil and water systems depending upon conditions. It has a low mammalian toxicity and is not expected to bioaccumulate. It is an irritant. It is moderately toxic to birds, fish, aquatic invertebrates, honeybees and earthworms. It has a low toxicity to aquatic plants and algae.

GENERAL INFORMATION

Description

A herbicide for a post-emergence control of many broad-leaved weeds in a range of crops

Example pests controlled

Broadleaved weeds generally; Capeweed; Volunteer peas; Thistles; Prickly lettuce; Knapweed; Volunteer vetch; Cape ivy

Example applications

Cereals including wheat, barley, oats, triticale; Turf; Ornamentals; Non-cropped and fallow land; Industrial situations

Efficacy & activity

Research supports the effectiveness of clopyralid to control a wide range of broadleaved weeds

Availability status

Current

Introduction & key dates

1977, France

UK regulatory status

UK COPR regulatory status

Approved

Date COPR inclusion expires

30/04/2024

UK LERAP status

None

EC Regulation 1107/2009 (repealing 91/414)

EC Regulation 1107/2009 status

Approved

Dossier rapporteur/co-rapporteur

Finland/Poland

Date EC 1107/2009 inclusion expires

30/04/2021

EU Candidate for substitution (CfS)

Listed in EU database

Yes

Approved for use (✓) under EC 1107/2009 in the following EU Member States

ATAustria	BEBelgium	BGBulgaria	CYCyprus	CZCzech Republic	DEGermany	DKDenmark	EEEstonia	ELGreece
✓	✓	✓	✓	✓	✓	✓	✓	✓
ESSpain	FIFinland	FRFrance	HRCroatia	HUHungary	IEIreland	ITItaly	LTLithuania	LULuxembourg
✓	✓	✓	✓	✓	✓	✓	✓	✓
LVLatvia	MTMalta	NLNetherlands	PLPoland	PTPortugal	RORomania	SESweden	SISlovenia	SKSlovakia
✓		✓	✓	✓	✓	✓	✓	✓

Also used in

Australia, USA

Chemical structure

Isomerism

Chemical formula

C₆H₃Cl₂NO₂

Canonical SMILES

C1=CC(=NC(=C1Cl)C(=O)O)Cl

Isomeric SMILES

No data

International Chemical Identifier key (InChIKey)

HUBANNPOLNYSAD-UHFFFAOYSA-N

International Chemical Identifier (InChI)

InChI=1S/C6H3Cl2NO2/c7-3-1-2-4(8)9-5(3)6(10)11/h1-2H,(H,10,11)

2D structure diagram/image available?

Yes

General status

Pesticide type

Herbicide

Substance group

Pyridine compound

Minimum active substance purity

950 g kg⁻¹

Known relevant impurities

EU dossier - None declared

Substance origin

Synthetic

Mode of action

Selective, systemic, absorbed through leaves and roots. Synthetic auxin.

CAS RN

1702-17-6

EC number

216-935-4

CIPAC number

455

US EPA chemical code

117401

PubChem CID

15553

Molecular mass

192.0

PIN (Preferred Identification Name)

3,6-dichloropyridine-2-carboxylic acid

IUPAC name

3,6-dichloropyridine-2-carboxylic acid

CAS name

3,6-dichloro-2-pyridinecarboxylic acid

Other status information

PAN Listed as Highly Hazardous Chemical; Potential groundwater contaminant

Relevant Environmental Water Quality Standards

Herbicide Resistance Classification (HRAC)

Herbicide Resistance Classification (WSSA)

Insecticide Resistance Classification (IRAC)

Not applicable

Fungicide Resistance Classification (FRAC)

Not applicable

Examples of recorded resistance

Physical state

Cream to white coloured crystals

Related substances & organisms

2,4-D

MCPA

diflufenican

florasulam

picloram

triclopyr

Formulations

Property

Value

Example manufacturers & suppliers of products using this active now or historically

Esteem
Galera
Grazon 90
Stinger
Lontrel
Dowco 290

Example products using this active

AgriGuard
Dow AgroSciences
Teliton

Formulation and application details

Usually supplied as a soluble concentrate, wettable powder or emulsifiable concentrate

ENVIRONMENTAL FATE

Property

Value

Source; quality score; and other information

Interpretation

Solubility - In water at 20 °C (mg l⁻¹)

7850

High

Solubility - In organic solvents at 20 °C (mg l⁻¹)

250000

Acetone

102000

Ethyl acetate

4600

Xylene

6000

n-Hexane

Melting point (°C)

149.6

Boiling point (°C)

Decomposes before boiling

Degradation point (°C)

164

Flashpoint (°C)

Not expected to self ignite; Not highly flammable

Octanol-water partition coefficient at pH 7, 20 °C

2.34 X 10^-03

Calculated

Log P

-2.63

Low

Bulk density (g ml⁻¹)

1.76

Dissociation constant pKa) at 25 °C

2.01

Strong acid

Vapour pressure at 20 °C (mPa)

1.36 X 10^-09

Low volatility

Henry's law constant at 25 °C (Pa m³ mol⁻¹)

1.80 X 10^-11

Non-volatile

Maximum UV-vis absorption L mol⁻¹ cm⁻¹

Neutral solution: Maxima at 220nm, 280nm : 22100nm, 9200nm & 4790nm
Acidic solution: Maxima at 202nm, 225nm, 281nm : 16200nm, 8890nm & 3800nm
Basic solution: Maxima at 220nm, 279nm : 9300nm, 5030nm

Surface tension (mN m⁻¹)

71.5

at 20 °C

Degradation

Property

Value

Source; quality score; and other information

Interpretation

General biodegradability

Not readily biodegradable

Soil degradation (days) (aerobic)

DT₅₀ (typical)

23.2

Non-persistent

DT₅₀ (lab at 20 °C)

23.2

Non-persistent

DT₅₀ (field)

8.2

Non-persistent

DT₉₀ (lab at 20 °C)

82.6

Moderately persistent

DT₉₀ (field)

49.5

DT₅₀ modelling endpoint

23.7

representative of field studies

Note

EU 2017 dossier lab studies DT₅₀ range 4.9-64.6 days, DT₉₀ range 16.2-214.6 days, Soils=10; field studies DT₅₀ range 2.0-13.5 days, DT₉₀ range 12.1-78.7 days; Other sources: DT₅₀ 40 days (R3)

Dissipation rate RL₅₀ on plant matrix

Value

Note

Dissipation rate RL₅₀ on and in plant matrix

Value

5.4

Note

Published literature RL₅₀ range 4.3-6.7 days, 3 field crops, various matrices, n=3

Aqueous photolysis DT₅₀ (days) at pH 7

Value

271

Stable

Note

Not significant degradation route

Aqueous hydrolysis DT₅₀ (days) at 20 °C and pH 7

Value

Stable

Note

Stable pH 4 to pH 9, 50 °C

Water-sediment DT₅₀ (days)

Water phase only DT₅₀ (days)

148

Stable

Soil adsorption and mobility

Property

Value

Source; quality score; and other information

Interpretation

Linear

K_d

0.071

Very mobile

K_oc

5.0

Notes and range

EU dossier K_d range 0.032-0.151, K_oc range 3.43-7.34 mL g⁻¹, Soils=5

Freundlich

K_f

K_foc

¹/_n

Notes and range

pH sensitivity

Limited evidence of decreasing adsorption with increasing pH

Fate indices

Property

Value

Source; quality score; and other information

Interpretation

GUS leaching potential index

3.02

Calculated

High leachability

SCI-GROW groundwater index (μg l⁻¹) for a 1 kg ha⁻¹ or 1 l ha⁻¹ application rate

Value

4.30 X 10^-02

Calculated

Note

Potential for particle bound transport index

Low

Calculated

Potential for loss via drain flow

Very mobile

Calculated

ECOTOXICOLOGY

Property

Value

Source; quality score; and other information

Interpretation

Bio-concentration factor

BCF (l kg⁻¹)

Lepomis macrochirus

Low potential

CT₅₀ (days)

0.1

Mammals - Acute oral LD₅₀ (mg kg⁻¹)

> 5000

Rat

Low

Mammals - Short term dietary NOEL

(mg kg⁻¹)

> 15

Rat 2 year

High

(ppm diet)

> 150

Mammals - Chronic 21d NOAEL (mg kg⁻¹ bw d⁻¹)

> 1500

Unknown species Reproductive NOAEL

Low

Birds - Acute LD₅₀ (mg kg⁻¹)

1465

Anas platyrhynchos

Moderate

Birds - Short term dietary (LC₅₀/LD₅₀)

> 1033 mg kg bw⁻¹ day⁻¹

Colinus virginianus

Birds - Chronic 21d NOEL (mg kg⁻¹ bw d⁻¹)

118

Anas platyrhynchos NOEC

Moderate

Fish - Acute 96 hour LC₅₀ (mg l⁻¹)

> 99.9

Oncorhynchus mykiss

Moderate

Fish - Chronic 21 day NOEC (mg l⁻¹)

10.8

Pimephales promelas

Low

Aquatic invertebrates - Acute 48 hour EC₅₀ (mg l⁻¹)

> 99

Daphnia magna

Moderate

Aquatic invertebrates - Chronic 21 day NOEC (mg l⁻¹)

Daphnia magna

Low

Aquatic crustaceans - Acute 96 hour LC₅₀ (mg l⁻¹)

Sediment dwelling organisms - Acute 96 hour LC₅₀ (mg l⁻¹)

Sediment dwelling organisms - Chronic 28 day NOEC, static, water (mg l⁻¹)

50.0

Chironomus riparius

Low

Sediment dwelling organisms - Chronic 28 day NOEC, sediment (mg kg⁻¹)

Aquatic plants - Acute 7 day EC₅₀, biomass (mg l⁻¹)

Lemna gibba

Low

Non-target plants

Algae - Acute 72 hour EC₅₀, growth (mg l⁻¹)

30.5

Raphidocelis subcapitata

Low

Algae - Chronic 96 hour NOEC, growth (mg l⁻¹)

Unknown species

Low

Honeybees (Apis spp.)

Contact acute LD₅₀ (worst case from 24, 48 and 72 hour values - μg bee⁻¹)

> 98.1

Apis mellifera

Moderate

Oral acute LD₅₀ (worst case from 24, 48 and 72 hour values - μg bee⁻¹)

> 100

Apis mellifera

Low

Unknown mode acute LD₅₀ (worst case from 24, 48 and 72 hour values - μg bee⁻¹)

Bumblebees (Bombus spp.)

Contact acute LD₅₀ (worst case from 24, 48 and 72 hour values - μg bee⁻¹)

Oral acute LD₅₀ (worst case from 24, 48 and 72 hour values - μg bee⁻¹)

Mason bees (Osmia spp.)

Contact acute LD₅₀ (worst case from 24, 48 and 72 hour values - μg bee⁻¹)

Oral acute LD₅₀ (worst case from 24, 48 and 72 hour values - μg bee⁻¹)

Other pollinators (1)

Acute LD₅₀ (worst case from 24, 48 and 72 hour values - μg insect⁻¹)

Mode of exposure

Other pollinators (2)

Acute LD₅₀ (worst case from 24, 48 and 72 hour values - μg insect⁻¹)

Mode of exposure

Earthworms - Acute 14 day LC₅₀ (mg kg⁻¹)

> 1000

Eisenia foetida

Low

Earthworms - Chronic NOEC, reproduction (mg kg⁻¹)

>= 1.97

Eisenia foetida

Moderate

Other soil macro-organisms

Acute LC₅₀ (mg kg⁻¹)

Chronic NOEC (mg kg⁻¹)

Other arthropod (1)

LR₅₀ g ha⁻¹

2000

as mL/ha
Aphidius rhopalosiphi

% Effect

0 / 90

Mortality / Fecundity [Dose: 0.2 kg ha⁻¹]
Aphidius rhopalosiphi adult

Other arthropod (2)

LR₅₀ g ha⁻¹

2000

as mL/ha
Typhlodromus pyri

% Effect

5.9 / 27.7

Mortality / Fecundity [Dose: 0.2 kg ha⁻¹]
Typhlodromus pyri protonymph

Soil micro-organisms

Nitrogen mineralisation: No significant adverse effect
Carbon mineralisation: No significant adverse effect

Dose: 5 x field rate

Mesocosm study data

NOEAEC mg l⁻¹

HUMAN HEALTH AND PROTECTION

General

Property

Value

Source; quality score; and other information

Interpretation

Threshold of Toxicological Concern (Cramer Class)

High (class III)

Mammals - Acute oral LD₅₀ (mg kg⁻¹)

> 5000

Rat

Low

Mammals - Dermal LD₅₀ (mg kg⁻¹ body weight)

5000

Rat

Mammals - Inhalation LC₅₀ (mg l⁻¹)

> 1.0

Rat (nose only)

Other Mammal toxicity endpoints

ADI - Acceptable Daily Intake (mg kg⁻¹ bw day⁻¹)

0.15

Rat SF=100

ARfD - Acute Reference Dose (mg kg⁻¹ bw day⁻¹)

None allocated

AAOEL - Acute Acceptable Operator Exposure Level (mg kg⁻¹ bw day⁻¹)

AOEL - Acceptable Operator Exposure Level - Systemic (mg kg⁻¹ bw day⁻¹)

1.00

Dermal penetration studies (%)

25-75

concentration dependent

Dangerous Substances Directive 76/464

Exposure Routes

Public

Minimal risk of dietary exposure

Occupational

Risk of exposure acceptable under label recommendations for use for personal protection clothing and equipment

European MRLs

EU MRL pesticide database

Drinking Water Standards

Drinking Water MAC (μg l⁻¹)

Health issues

Specific human health issues

Carcinogen

Genotoxic

Endocrine disruptor

; ; ; ;

Reproduction / development effects

Acetyl cholinesterase inhibitor

Neurotoxicant

Respiratory tract irritant

Skin irritant

Skin sensitiser

No data found

Eye irritant

Phototoxicant

No data found

General human health issues

Possible liver and kidney toxicant

Handling issues

Property

Value and interpretation

General

Prevent release of dust
Not explosive or oxidising

CLP classification 2013

Health: H318

EC Risk Classification

Xn - Harmful: R41

EC Safety Classification

S2, S26, S39

WHO Classification

III (Slightly hazardous)

UN Number

Usually 3077

Waste disposal & packaging

Packaging Group III (minor danger)

TRANSLATIONS

Language

Name

English

clopyralid

French

clopyralid

German

Clopyralid

Danish

clopyralid

Italian

clopiralid

Spanish

clopiralida

Greek

clopyralid

Polish

chlopyralid

Swedish

klopyralid

Hungarian

klopiralid

Dutch

clopyralid

Record last updated:	12/01/2021
Contact:	aeru@herts.ac.uk
Please cite as:	Lewis, K.A., Tzilivakis, J., Warner, D. and Green, A. (2016) An international database for pesticide risk assessments and management. Human and Ecological Risk Assessment: An International Journal, 22(4), 1050-1064. DOI: 10.1080/10807039.2015.1133242