Ziram

Ziram	Last updated: 20/03/2021
(Also known as: zirame; carbazinc; methyl zimate; zirthane; DADZ)

SUMMARY

Ziram is a fungicide that currently has approval for use in the EU. It has a low aqueous solubility, is quite volatile and has a plow potential for leaching to groundwater. It is not generally persistent in soil or water systems. Ziram is moderately toxic to mammals and is also considered to be mutagenic and a recognised irritant. It is highly toxic to birds, fish and aquatic invertebrates and moderately toxic to algae, honeybees and earthworms.

GENERAL INFORMATION

Description

A broad spectrum fungicide to control common fungal diseases. Also used as a bird and animal repellent.

Example pests controlled

Anthracnose; Scab; Bitter rot; Black spot; Downey mildew; Leaf blight; Peach leaf curl; Powdery mildew; Storage rot

Example applications

Almonds; Pecans; Cherries; Apples; Pears; Plums; Peaches; Grapes; Tomatoes; Blueberries; Nectarines

Efficacy & activity

Tested in field development trials which demonstrated efficacious activity.

Availability status

Current

Introduction & key dates

1960, USA

UK regulatory status

UK COPR regulatory status

Not approved

Date COPR inclusion expires

Not applicable

UK LERAP status

Not applicable

EC Regulation 1107/2009 (repealing 91/414)

EC Regulation 1107/2009 status

Approved

Dossier rapporteur/co-rapporteur

Italy/Malta

Date EC 1107/2009 inclusion expires

30/04/2021

EU Candidate for substitution (CfS)

Yes - two 'Persistent-Bioaccumulative-Toxic' criteria

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

Chemical structure

Isomerism

None

Chemical formula

C₆H₁₂N₂S₄Zn

Canonical SMILES

CN(C)C(=S)[S-].CN(C)C(=S)[S-].[Zn+2]

Isomeric SMILES

No data

International Chemical Identifier key (InChIKey)

FNLPVVKNKZFOCR-UHFFFAOYSA-N

International Chemical Identifier (InChI)

InChI=1S/2C3H7NS2.Zn/c2*1-4(2)3(5)6;/h2*1-2H3,(H,5,6);/q;;+2/p-2

2D structure diagram/image available?

Yes

General status

Pesticide type

Fungicide, Repellent

Substance group

Carbamate

Minimum active substance purity

950 g kg⁻¹

Known relevant impurities

EU dossier - arsenic 250mg kg⁻¹

Substance origin

Synthetic

Mode of action

Contact action with protective properties. Multi-site activity.

CAS RN

137-30-4

EC number

205-288-3

CIPAC number

US EPA chemical code

034805

PubChem CID

8722

Molecular mass

305.84

PIN (Preferred Identification Name)

zinc bis(dimethyldithiocarbamate)

IUPAC name

zinc bis(dimethyldithiocarbamate)

CAS name

(T-4)-bis(dimethylcarbamodithioato-kS,kS')zinc

Other status information

Relevant Environmental Water Quality Standards

Herbicide Resistance Classification (HRAC)

Not applicable

Herbicide Resistance Classification (WSSA)

Not applicable

Insecticide Resistance Classification (IRAC)

Not applicable

Fungicide Resistance Classification (FRAC)

Examples of recorded resistance

Physical state

White powder

Formulations

Property

Value

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

Thionic
Ziram Granuflo
Tricarbamix
Triscabol
Zirex
Carbazinc

Example products using this active

Unicrop
AgroCare
FCC
Bayer CropScience
Farmoplant

Formulation and application details

Available in a range of formulations including wettable powders, water dispersible granules and liquids.

ENVIRONMENTAL FATE

Property

Value

Source; quality score; and other information

Interpretation

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

0.967

Low

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

1010

Ethyl acetate

2300

Acetone

110

Methanol

900

Xylene

Melting point (°C)

251

Boiling point (°C)

Degradation point (°C)

Flashpoint (°C)

Not expected to self ignite; Not highly flammable

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

4.47 X 10⁰¹

Calculated

Log P

1.65

Low

Bulk density (g ml⁻¹)

1.71

Dissociation constant pKa) at 25 °C

Vapour pressure at 20 °C (mPa)

1.8 X 10^-02

Low volatility

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

2.3 X 10^-06

Non-volatile

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

Neutral solution: 251nm = 39989, 270nm = 31586
Acidic solution: Maxima below UV cut-off point
Basic solution: 251nm = 52739

Surface tension (mN m⁻¹)

73.0

at 16 °C

Degradation

Property

Value

Source; quality score; and other information

Interpretation

General biodegradability

Soil degradation (days) (aerobic)

DT₅₀ (typical)

1.62

Non-persistent

DT₅₀ (lab at 20 °C)

1.62

Non-persistent

DT₅₀ (field)

6.3

Non-persistent

DT₉₀ (lab at 20 °C)

2.8

Non-persistent

DT₉₀ (field)

DT₅₀ modelling endpoint

Note

EU 2018 dossier lab studies DT₅₀ range 0.5-5.2 days, DT₉₀ range 2.1-18.3 days, Soils=5; Other sources: DT₅₀ 30 days (DW4)

Dissipation rate RL₅₀ on plant matrix

Value

Note

Dissipation rate RL₅₀ on and in plant matrix

Value

9.9

Note

Apricot fruit, n=1

Aqueous photolysis DT₅₀ (days) at pH 7

Value

0.3

Fast

Note

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

Value

0.7

Non-persistent

Note

pH sensitive: DT₅₀ 10.4 minutes at pH 4, 6.3 days at pH 9, all at 25 °C

Water-sediment DT₅₀ (days)

0.25

Fast

Water phase only DT₅₀ (days)

0.25

Fast

Soil adsorption and mobility

Property

Value

Source; quality score; and other information

Interpretation

Linear

K_d

61.1

Non-mobile

K_oc

4570

Notes and range

EU 2018 dossier K_d range 7.1-108.7 mL g⁻¹, K_oc range 1093-10865 mL g⁻¹, Soils=5

Freundlich

K_f

109.5

Non-mobile

K_foc

8189

¹/_n

1.1

Notes and range

EU 2018 dossier K_f range 5.1-577 mL g⁻¹, K_foc range 775-34779 mL g⁻¹, ¹/_n range 0.86-1.34, Soils=5

pH sensitivity

Fate indices

Property

Value

Source; quality score; and other information

Interpretation

GUS leaching potential index

0.07

Calculated

Low leachability

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

Value

5.19 X 10^-03

Calculated

Note

Potential for particle bound transport index

Medium

Calculated

Potential for loss via drain flow

Non-mobile

Calculated

Key metabolites

Metabolite

Formation medium

Estimated maximum occurrence fraction

1107/2009 relevancy

thiram (Ref: ENT 987)

Soil

0.494

Major fraction, Relvant

1,1-dimethylurea

Soil

0.105

Major fraction, Relvant

Other known metabolites

Metabolite name and reference

Aliases

Formation medium / Rate

Estimated maximum occurrence fraction

Metabolising enzymes

N,N-dimethylthioformamide

Water (Photolysis)

dithiocarbamic acid

Animal

1,1-dimethylurea

Soil (Aerobic)

Dimethyldithiocarbamic acid

DDC

Water

0.750

N,N-dimethylformamide

Water (Photolysis)

ECOTOXICOLOGY

Property

Value

Source; quality score; and other information

Interpretation

Bio-concentration factor

BCF (l kg⁻¹)

470

Threshold for concern

CT₅₀ (days)

Not available

Mammals - Acute oral LD₅₀ (mg kg⁻¹)

267

Rat

Moderate

Mammals - Short term dietary NOEL

(mg kg⁻¹)

(ppm diet)

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

Birds - Acute LD₅₀ (mg kg⁻¹)

Colinus virginianus

High

Birds - Short term dietary (LC₅₀/LD₅₀)

> 5200 mg kg feed⁻¹

Anas platyrhynchos

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

Fish - Acute 96 hour LC₅₀ (mg l⁻¹)

0.355

Oncorhynchus mykiss

Moderate

Fish - Chronic 21 day NOEC (mg l⁻¹)

0.189

Lepomis macrochirus

Moderate

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

0.172

Daphnia magna

Moderate

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

0.01

Daphnia magna

Moderate

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

0.140

,i>Americamysis bahia

Moderate

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

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

0.242

Chironomus riparius emergence

Moderate

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

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

Non-target plants

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

0.094

Pseudokirchneriella subcapitata

Moderate

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

Honeybees (Apis spp.)

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

> 100

Apis mellifera,/i>

Low

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

> 105

Apis mellifera,/i>

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)

140

Eisenia foetida

Moderate

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

13.3

Eisenia foetida

Moderate

Other soil macro-organisms

Acute LC₅₀ (mg kg⁻¹)

Chronic NOEC (mg kg⁻¹)

Other arthropod (1)

LR₅₀ g ha⁻¹

% Effect

0.2

Reproduction [Dose: 6.08 kg ha⁻¹]
Aphidius rhopalosiphi adult

Other arthropod (2)

LR₅₀ g ha⁻¹

% Effect

45.8

Total effect [Dose: 2.28 kg ha⁻¹ x 4apps Field test]
Typhlodromus pyri

Soil micro-organisms

Nitrogen mineralisation: NOEC 40 kg WG 76% /ha
Carbon mineralisation: NOEC 40 kg WG 76% /ha

Mesocosm study data

NOEAEC mg l⁻¹

0.01

Aquatic arthropods and algae as the thiram metabolite

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)

267

Rat

Moderate

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

2000

Rat

Mammals - Inhalation LC₅₀ (mg l⁻¹)

0.06

Rat (whole body)

Other Mammal toxicity endpoints

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

0.006

Rat SF=100

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

0.08

Rat SF=100

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

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

0.015

Rat SF=200

Dermal penetration studies (%)

0.2-5.0

concentration dependent

Dangerous Substances Directive 76/464

List II

Exposure Routes

Public

Low risk to bystanders

Occupational

Acceptable risks for operators and other workers

MRLs

European

EU MRL pesticide database

Notes

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

No data found

Respiratory tract irritant

Skin irritant

Skin sensitiser

Eye irritant

Phototoxicant

General human health issues

IARC Group 3 carcinogen; USEPA - some evidence to suggest possible human carcinogen
Inhibits alcohol metabolism and may be goitrogenic
Mutagenic
Thyroid, liver & adrenal toxicant

Handling issues

Property

Value and interpretation

General

Not explosive but may form explosive dust-air mixtures
No oxidising properties
IMDG Transport Code is usually 6.1

CLP classification 2013

Health: H302, H317, H318, H330, H335, H373
Environment: H400, H410

EC Risk Classification

T+ - Very toxic: R26
Xn - Harmful: R22, R41, R43, R48/22
Xi - Irritant: R37
N - Dangerous for the environment: R50, R53

EC Safety Classification

S1/2, S22, S26, S28, S36/37/39, S45, S60, S61

WHO Classification

II (Moderately hazardous)

UN Number

Usually 2811

Waste disposal & packaging

Packaging Group II (medium danger)

TRANSLATIONS

Language

Name

English

ziram

French

zirame

German

Ziram

Danish

ziram

Italian

ziram

Spanish

ziram

Greek

ziram

Polish

ziram

Swedish

ziram

Hungarian

ziram

Dutch

ziram

Record last updated:	20/03/2021
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