Download DICHLOFLUANID

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81933364
DICHLOFLUANID
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CHEMICAL IDENTITY
Common name
Dichlofluanid
Chemical name (IUPAC)
N-dichlorofluoromethylthio-N',N'-dimethyl-N-phenylsulfamide
Synonym(s)
Chemical class (when available/relevant)
CAS number
1085-98-9
EU number
214-118-7
Molecular formula
C9H11Cl2FN2O2S2
SO2 N(CH3)2
N
Molecular structure
S
Molecular weight (g.mol-1)
333.2
1
CCl2F
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EXISTING EVALUATIONS AND REGULATORY INFORMATION
Annex III EQS Dir. (2008/105/EC)
Not Included
Existing Substances Reg. (793/93/EC)
Not listed
Pesticides(91/414/EEC)
Not included in Annex I
Biocides (98/8/EC)
Included in Annex I (wood preservative)
Not included in Annex I (Masonry preservative), because this product
type was not supported by submission of a dossier.
Pending (film preservative, antifouling)
PBT substances
No
Substances of Very High Concern
(1907/2006/EC)
No
POPs (Stockholm convention)
No
Other relevant chemical regulation
(veterinary products, medicament, ...)
No
Endocrine disrupter
Available information / Not investigated
Dichlofluanid is used as a wood preservative in biocidal products (E.C., 2006).
The review report for the active substance Dichlofluanid (E.C., 2006) has concluded that:
“It may be expected that wood preservatives containing dichlofluanid will fulfill the requirements laid down in Article
10(1) and (2) of Directive 98/8/EC.
This conclusion is however subject to:
i. compliance with the particular requirements in the following sections of this assessment report,
ii. the implementation of the provisions of Article 5(1), and
iii. the common principles laid down in Annex VI to Directive 98/8/EC, for each wood preservative containing
dichlofluanid.
Furthermore, these conclusions were reached within the framework of the uses that were proposed and supported by
the applicant (see Appendix III). Extension of the use pattern beyond those described will require an evaluation at
Member State level in order to establish whether the proposed extensions of use will satisfy the requirements of Article
5(1) and of the common principles laid down in Annex VI of Directive 98/8/EC.”
Dichlofluanid is also under assessment for the product types 07 (Film preservatives) and 21 (antifouling).
The substance has been subjected to a non-inclusion directive for product type 10 (Masonry preservatives),
because the applicant did not support this use by submission of a dossier.
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PROPOSED QUALITY STANDARDS (QS) to be defined later –on hold
3.1 ENVIRONMENTAL QUALITY STANDARD (EQS)
QS for -- is the “critical QS” for derivation of an Environmental Quality Standard
Value
Comments
Proposed AA-EQS for [matrix] [unit]
Corresponding AA-EQS in [water] [µg.L-1]
Critical QS is QS--.
See section 7
Proposed MAC-EQS for [freshwater] [µg.L-1]
Proposed MAC-EQS for [marine waters] [µg.L-1]
See section 7.1
Stakeholder’s comment (Lanxess): As dichlofluanid rapidly degrades in the environment to other, compounds which
are less toxic to the environment, the derivation of an environmental Quality standard (EQS) and consequent proposal
of dichlofluanid to the list of priority substances under the WFD is regarded as not appropriate.
3.2 SPECIFIC QUALITY STANDARD (QS)
Protection objective*
Unit
Value
Pelagic community (freshwater)
[µg.l-1]
Pelagic community (marine waters)
[µg.l-1]
Benthic community (freshwater)
[µg.kg-1 dw]
Benthic community (marine)
[µg.kg-1
Comments
See section 7.1
e.g. EqP,
see section 7.1
dw]
[µg.kg-1biota ww]
Predators (secondary poisoning)
[µg.l-1]
(freshwaters)
(marine waters)
See section 7.2
[µg.kg-1biota ww]
Human health via consumption of fishery
products
[µg.l-1]
Human health via consumption of water
[µg.l-1]
(freshwaters)
(marine waters)
See section 7.3
Please note that as recommended in the Technical Guidance for deriving EQS (drat version), “EQSs […] are not reported for ‘transitional and
marine waters’, but either for freshwater or marine waters”. If justified by substance properties or data available, QS for the different protection
objectives are given independently for transitional waters or coastal and territorial waters.
*
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MAJOR USES AND ENVIRONMENTAL EMISSIONS
4.1 USES AND QUANTITIES
Dichlofluanid is used as an active substance included in biocidal products.
Dichlofluanid has been evaluated for its use in wood preservation (product-type 8) up to Hazard Class 3 (i.e.
wood which is not covered and not in contact with ground, but exposed to weather or frequent wetting). It is
applied in solvent-based product formulations either in primers or incorporated in low binder-containing
paints (e.g. glazes). Products can be used for:
- the pre-treatment of timber (dipping and automated enclosed spraying by industrial/professional users);
- the protective treatment of wood in situ by brush application (both professional and amateur users).
Dichlofluanid is not recommended for treatment of wood inside housing areas (with the exception of window
frames and external doors, which will usually be treated on or before installation) or for spraying manually in
open systems (E.C., 2006).
Dichlofluanid is also under assessment for the product types 07 (Film preservatives) and 21 (antifouling).
The substance has been subjected to a non-inclusion directive for product type 10 (Masonry preservatives),
because the applicant did not support this use by submission of a dossier.
No information available on quantities produced or used.
4.2 ESTIMATED ENVIRONMENTAL EMISSIONS
No information available on environmental emissions.
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ENVIRONMENTAL BEHAVIOUR
5.1 ENVIRONMENTAL DISTRIBUTION
Dichlofluanid
Master reference
Water solubility (mg.l-1)
1.58 at 20 °C at pH 4. Solubility in water is
dependent of pH in the range of pH 4 to pH 9.
Volatilisation
Given the vapour pressure and Henry constant reported below,
dichlofluanid is not likely to volatilise.
E.C., 2006
Vapour pressure (Pa)
2.15 10-5 at 20 °C ; 5.37 10-5 at 25 °C
E.C., 2006
Henry's Law constant
(Pa.m3.mol-1)
4.5 10-3
E.C., 2006
Adsorption
The value of 1344 is used for derivation of quality standards.
Organic carbon – water
partition coefficient (KOC)
KOC = 1344
Log KOC = 3.13
Sediment – water partition
coefficient(Ksusp-water)
169
Bioaccumulation
E.C., 2006
Calculated from KOC
The BCF value 72 on fish is used for derivation of quality standards.
Octanol-water partition
coefficient (Log Kow)
log KOW = 3.5. Coefficient independent of
temperature (10 to 30 °C), respectively pH (range 4
to 9).
E.C., 2006
BCF (measured)
Dichlofluanid is unlikely to bioaccumulate.
BCF for Lepomis macrochirus is 72 +/- 14
E.C., 2006
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Relevant metabolite of dichlofluanid : DMSA
Master reference
-1
E.C., 2006
Water solubility (mg.l )
1300 at 20 °C
Volatilisation
DMSA is not likely to volatilise.
Vapour pressure (Pa)
2.5 10-4 at 20 °C
4.9 10-4 at 25 °C
E.C., 2006
Henry's Law constant (Pa.m3.mol3.8 10-5
1
)
Adsorption
E.C., 2006
DMSA is not likely to adsorb onto solid particles
Organic carbon – water partition
coefficient (KOC)
KOC = 53
Log KOC = 1.72
Suspended matter – water
partition coefficient(Ksusp-water)
2.2
E.C., 2006
Calculated from KOC
DMSA is not likely to bioaccumulate given the low log K OW
Bioaccumulation
Octanol-water partition
coefficient (Log Kow)
At 20 °C: KOW = 39; log KOW = 1.59
E.C., 2006
BCF (measured)
DMSA is unlikely to bioaccumulate.
E.C., 2006
5.2 ABIOTIC AND BIOTIC DEGRADATIONS
Dichlofluanid
Master reference
Hydrolysis
Dichlofluanid hydrolyses rapidly to DMSA (N,N-dimethyl-N’phenylsulfamide) at neutral pH.
DT50 dichlofluanid (20°C) = 25.6 h (1)
E.C., 2006
Photolysis
Due to its lack of UV absorbance at the wavelengths present in
sunlight, dichlofluanid is not degradable by direct
photodegradation in aqueous solution.
E.C., 2006
Biodegradation
In water, dichlofluanid is not readily biodegradable (9% after 28 days,
41% after 140 days).
In water/sediment systems, dichlofluanid was rapidly degraded in two
aerobic aquatic systems with DT50 values of 1.2 and 3 h.
Dichlofluanid does not constitute a lasting potential to contaminate
surface water or sediment.
E.C., 2006
(1) At
pH 9, the hydrolytic degradation was so rapid that at room temperature, even when the analysis was conducted
immediately, no dichlofluanid could be detected. At pH 7: DT50 (20°C) = 25.6 h, DT50 (30°C) = 5.4 h and DT50 (22°C,
extrapolated) = 18.8 h. At pH 4: DT50 (30°C) = 6.9 d, DT50 (40°C) = 2.8 d and DT50 (22°C, extrapolated) = 15.3 d.
Half lifess for DMSA in water/sediment are longer than for Dichlofluanid, however, it is not likely to be found in soil,
groundwater and surface water above acceptable values as it degrades further to the metabolite N,N-dimethylsulfamide.
N,N-dimethylsulfamide does not cause itself concerns. It can however react with ozone during a standard drinking
water preparation process (ozonisation) forming nitrosamine (NDMA), which is harmful to health.
Stakeholder’s comment (Lanxess): This reaction between N,N-dimethylsulfamide and ozone came into discussion in
the framework of plant protection uses of Tolylfluanid. Dichlofluanid was however not on the market for plant
protection purposes, solely for the limited biocidal uses (PT8, PT 7 and PT 21). These uses are not
comparable to plant protection uses.
Dichlofluanid is still under evaluation in PT 7 and PT 21. The stakeholder would like to refer also to
information on Tolylfluanid prepared by Finland. Finland proposed to evaluate the need for deriving an EQS
for the main degradation product of tolylfluanid, N,N-DMS, at a later stage, after evaluation of PT 7 and PT
21, e.g. within the Chemical Monitoring and Emerging Pollutants Sub Group or as part of priority setting
schemes within MS.
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Relevant metabolite of dichlofluanid : DMSA
Hydrolysis
Photolysis
Biodegradation
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Master reference
No hydrolysis of DMSA is detectable at pH 4, 7 and 9 at 22°C.
DT50 DMSA (20°C) > 1 year
E.C., 2006
No information available
In aerobic water/sediment systems, dichlofluanid was very rapidly
degraded to DMSA which stayed mainly in the water phase. No
further metabolite approaching or exceeding the 10 % mark within the
incubation time.
E.C., 2006
E.C., 2006
AQUATIC ENVIRONMENTAL CONCENTRATIONS
6.1 ESTIMATED CONCENTRATIONS
Compartment
Predicted environmental
concentration (PEC)
Master reference
0.39
Daginnus et al., 2009(1)
Freshwater
Marine waters (coastal and/or transitional)
No data available
Sediment
No data available
Biota (freshwater)
No data available
Biota (marine)
No data available
Biota (marine predators)
No data available
(1)
data originated from EU modelling-based prioritisation results.
6.2 MEASURED CONCENTRATIONS
Stakeholder’s comment (Lanxess): It is expected that all measured concentrations of dichlofluanid in the environment
will be below Limit of Detection, because the substance hydrolyses rapidly under environmentally relevant pH values in
the aquatic compartment and also in soil.
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Compartment
Measured environmental
concentration (MEC)
Master reference
cf. table above
James et al., 2009(1)
Freshwater
Marine waters (coastal and/or transitional)
WWTP effluent
No data available
cf. table above
Sediment
No data (0)
James et al., 2009(1)
No data (0)
No data (0)
Biota
James et al., 2009(1)
No data (0)
Biota (marine predators)
(1)
No data available
data originated from EU monitoring data collection.
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EFFECTS AND QUALITY STANDARDS
Dichlofluanid is extremely toxic to aquatic organisms, although it metabolises rapidly in DMSA, which is a low toxicity
molecule.
Stakeholder’s comment (Lanxess): The metabolite DMSA is less toxic than Dichlofluanid and degrades further to
N,N-dimethylsulfamide, a substance which does not fulfil the PBT criteria and does itself not present an unacceptable
risk to the environment. N,N-dimethylsulfamide came into discussion through plant protection uses of tolylfluanid,
which is chemically related to dichlofluanid. Only in the limited situations, when surface water containing N,NDimethylsulfamide is extracted for production of drinking water and during processing ozone is applied Nnitrosodimethylamine (NDMA) can occur.
7.1 ACUTE AND CHRONIC AQUATIC ECOTOXICITY
All (eco)toxicological data reported below are extracted from EU Draft Assessment Report (E.C., 2006) and were
therefore considered reliable at an EU level.
ACUTE EFFECTS
Algae &
aquatic plants
(mg.l-1)
Freshwater
Master reference
Dichlofluanid
Scenedesmus subspicatus / 72 h
ErC50 = 15
No data available
Marine
Dichlofluanid
Daphnia magna / 48h
EC50 = 0.42
E.C., 2006
DMSA
Daphnia magna / 48h
EC0 ≥ 95.6
E.C., 2006
Freshwater
Invertebrates
(mg.l-1)
No data available
Marine
No data available
Sediment
Freshwater
Fish
(mg.l-1)
E.C., 2006
Dichlofluanid
Oncorhynchus mykiss / 96 h
LC50 = 0.01
Marine
No data available
Sediment
No data available
No data available
Other taxonomic groups
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E.C., 2006
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CHRONIC EFFECTS
Algae &
aquatic plants
(mg.l-1)
Master reference
Dichlofluanid
Freshwater
DMSA
Marine
Dichlofluanid
Freshwater
Invertebrates
(mg.l-1)
Scenedesmus subspicatus / 96 h
NOErC = 1
Scenedesmus subspicatus / 72 h
NOErC > 97.7
No data available
Daphnia magna / 21d
NOEC repro, weight, length = 2.65 10-3
E.C., 2006
E.C., 2006
E.C., 2006
No data available
No data available
Marine
DMSA
Sediment
Dichlofluanid
Freshwater
Fish
(mg.l-1)
DMSA
Chironomus riparius / 28d
EC5 development = 9.7
Oncorhynchus mykiss / 21d
NOEC = 4.55 10-3
Pimephales promelas / 33d
NOEC weight, length = 4.07 10-3
Oncorhynchus mykiss / 21d
NOEC weight, length = 10
Marine
No data available
Sediment
No data available
E.C., 2006
E.C., 2006
E.C., 2006
E.C., 2006
No data available
Other taxonomic groups
Assessment
factor
Tentative QS
Oncorhynchus mykiss / 96 h
LC50 = 0.01 mg/l
100
0.1 µg/l
1 000
0.01 µg/l
10
0.26 µg/l
AA-QSmarine water, eco
Daphnia magna / 21d
NOEC = 2.6 10-3 mg/l
100
0.026 µg/l
AA-QSfreshwater, sed.
-
To be defined
To be defined
AA-QSmarine water, sed.
-
To be defined
To be defined
Tentative QSwater
Relevant study for derivation of QS
MACfreshwater, eco
MACmarine water, eco
AA-QSfreshwater, eco
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7.2 SECONDARY POISONING
Secondary poisoning of top predators
Master reference
Mammalian oral toxicity
Dog / Oral route carcinogenicity / 2 y / no effect reported
NOAEL : 25 mg.kg-1bw.d-1
NOEC : 100 mg.kg-1feed ww (CF= 40)
E.C., 2006
Avian oral toxicity
Colinus virginianus & Anas platyrhynchos / Oral / Subacute / 5
d
LC 50 : > 5000 mg.kg-1feed ww
E.C., 2006
Tentative QSbiota
Relevant study for derivation of QS
Biota
NOEC : 100 mg.kg-1feed ww
Assessment
factor
Tentative QS
90(1)
11 111 µg.kg-1biota ww
corresponding to
154 µg.L-1 (freshw.)
154 µg.L-1 (saltw.)
(1)
proposal made for the purpose of this dossier, according to REACH guidance on information requirements and chemical safety assessment
(ECHA, 2008)
7.3 HUMAN HEALTH
Stakeholder’s comment (Lanxess): The rapid hydrolysis of dichlofluanid in the aquatic environment leads to the
conclusion that human health via consumption of fishery products is not at risk. Further more BCF is low. Depuration
time (DT50) is 0.25 days (edible) and 0.24 d for the whole fish. DMSA and N,N-dimetyhlsulfamide are also expected to
not bioaccumulate.
Human health via consumption of fishery products
Master reference
Mammalian oral toxicity
Dog / Oral route carcinogenicity / 2 y / no effect reported
NOAEL = 25 mg.kg-1bw.d-1
CMR
Dichlofluanid is not classified for any carcinogenic, mutagenic
or reprotoxic properties
Tentative QSbiota, hh
Relevant study for derivation
of QSbiota, hh
Human health
NOAEL= 25 mg.kg-1bw.d-1
AF
100(1)
unknown
in WHO, 1983
E.C., 2008
Threshold
level
Tentative QSbiota, hh
0.3(1)
mg.kg-1bw.d-1
18.3 µg.kg-1biota ww
corresponding to
0.142µg.L-1 (freshw.)
0.142µg.L-1 (saltw.)
(1) No information is available concerning the study. The source of information is WHO (WHO, 1983) but there is no information on administered
doses and endpoints for the derivation of this ADI. Confidence in this study is therefore very low.
Human health via consumption of drinking water
Master reference
Existing drinking water
standard(s)
Directive 98/83/EC
0.1 µg.L-1 (preferred regulatory standard)
Any guideline
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BIBLIOGRAPHY, SOURCES AND SUPPORTIVE INFORMATION
Daginnus K., Gottardo S., Mostrag-Szlichtyng A., Wilkinson H., Whitehouse P., Paya-Pérez a. and Zaldívar
J.-M. (2009). A modelling approach for the prioritisation of chemicals under the Water Framework Directive.
Ispra, Italy, European Commission, Joint Research Centre, Institute for Health and Consumer Protection.:
48.
E.C. (2006). Assessment Report - Dichlofluanid, PT 8. Directive 98/8/EC concerning the placing of biocidal
products on the market. Inclusion of active substances in Annex I to Directive 98/8/EC.
E.C. (2008). Regulation (EC) No 1272/2008 of the European Parliament and of the Council of 16 December
2008 on classification, labelling and packaging of substances and mixtures, amending and repealing
Directives 67/548/EEC and 1999/45/EC, and amending Regulation (EC) No 1907/2006 (Text with EEA
relevance). Official Journal of the European Union. L353: 1355.
ECHA (2008). Guidance on information requirements and chemical safety assessment Chapter R.10:
Characterisation of dose [concentration]-response for environment. Guidance for the implementation of
REACH. Helsinki, European Chemicals Agency.
James A., Bonnomet V., Morin A. and Fribourg-Blanc B. (2009). Implementation of requirements on Priority
substances
within
the
Context
of
the
Water
Framework
Directive.
Contract
N°
07010401/2008/508122/ADA/D2. Prioritisation process: Monitoring-based ranking., INERIS / IOW: 58.
WHO (1983). Pesticide Residues In Food. Sponsored jointly by FAO and WHO. Evaluations 1983. Data and
recommendations of the joint meeting of the FAO Panel of Experts on Pesticide Residues in Food and the
Environment and the WHO Expert Group on Pesticide Residues, Geneva, 5 - 14 December 1983., World
Health Organisation.
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