Environmental risk limits for dodine

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Environmental risk limits for dodine

Letter report 601716007/2008 C.E. Smit | M. van der Veen

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RIVM Letter report 601716007/2008

Environmental risk limits for dodine

Marijn van der Veen Els Smit

Contact:

Marijn van der Veen

Expertise Centre for Substances marijn.van.der.veen@rivm.nl

This investigation has been performed by order and for the account of Directorate-General for

Environmental Protection, Directorate for Soil, Water and Rural Area (BWL), within the framework of the project "Standard setting for other relevant substances within the WFD".

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Parts of this publication may be reproduced, provided acknowledgement is given to the 'National Institute for Public Health and the Environment', along with the title and year of publication.

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Rapport in het kort

Environmental risk limits for dodine

Dit rapport geeft milieurisicogrenzen voor het fungicide dodine in water en sediment.

Milieurisicogrenzen zijn de technisch-wetenschappelijke advieswaarden voor de uiteindelijke

milieukwaliteitsnormen in Nederland. De milieurisicogrenzen zijn afgeleid volgens de methodiek die is voorgeschreven in de Europese Kaderrichtlijn Water. Hierbij is gebruikgemaakt van de beoordeling in het kader van de Europese toelating van gewasbeschermingsmiddelen (Richtlijn 91/414/EEG), aangevuld met gegevens uit de openbare literatuur.

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1 Introduction

1.1 Background and scope of the report

In this report, environmental risk limits (ERLs) for surface water and sediment are derived for the fungicide dodine. The derivation is performed within the framework of the project ‘Standard setting for other relevant substances within the WFD’, which is closely related to the project ‘International and national environmental quality standards for substances in the Netherlands’ (INS). Dodine is part of a series of 25 pesticides that appeared to have a high environmental impact in the evaluation of the policy document on sustainable crop protection (‘Tussenevaluatie van de nota Duurzame Gewasbescherming’; MNP, 2006) and/or were selected by the Water Boards (‘Unie van Waterschappen’; project ‘Schone Bronnen’; http://www.schonebronnen.nl/).

The following ERLs are considered:

• Maximum Permissible Concentration (MPC) – the concentration protecting aquatic ecosystems and humans from effects due to long-term exposure

• Maximum Acceptable Concentration (MACeco) – the concentration protecting aquatic ecosystems

from effects due to short-term exposure or concentration peaks.

• Serious Risk Concentration (SRCeco) – the concentration at which possibly serious ecotoxicological

effects are to be expected.

More specific, the following ERLs can be derived depending on the availability of data and characteristics of the compound:

MPCeco, water MPC for freshwater based on ecotoxicological data (direct exposure)

MPCsp, water MPC for freshwater based on secondary poisoning

MPChh food, water MPC for fresh and marine water based on human consumption of fishery products

MPCdw, water MPC for surface waters intended for the abstraction of drinking water

MACeco, water MAC for freshwater based on ecotoxicological data (direct exposure)

SRCeco, water SRC for freshwater based on ecotoxicological data (direct exposure)

MPCeco, marine MPC for marine water based on ecotoxicological data (direct exposure)

MPCsp, marine MPC for marine water based on secondary poisoning

MACeco, marine MAC for marine water based on ecotoxicological data (direct exposure)

1.2 Status of the results

The results presented in this report have been discussed by the members of the scientific advisory group for the INS-project (WK-INS). It should be noted that the Environmental Risk Limits (ERLs) in this report are scientifically derived values, based on (eco)toxicological, fate and physico-chemical data. They serve as advisory values for the Dutch Steering Committee for Substances, which is appointed to set the Environmental Quality Standards (EQSs). ERLs should thus be considered as proposed values that do not have any official status.

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2 Methods

The methodology for the derivation of ERLs is described in detail by Van Vlaardingen and Verbruggen (2007), further referred to as the ‘INS-Guidance’. This guidance is in accordance with the guidance of the Fraunhofer Institute (FHI; Lepper, 2005).

The process of ERL-derivation contains the following steps: data collection, data evaluation and selection, and derivation of the ERLs on the basis of the selected data.

2.1 Data collection

In accordance with the WFD, data of existing evaluations were used as a starting point. For dodine, the evaluation report prepared within the framework of EU Directive 91/414/EC (Draft Assessment Report, DAR) was consulted (EC, 2005; further referred to as DAR). An on-line literature search was performed on TOXLINE (literature from 1985 to 2001) and Current Contents (literature from 1997 to 2007). In addition to this, all potentially relevant references in the RIVM e-tox base and EPA’s ECOTOX database were checked.

2.2 Data evaluation and selection

For substance identification, physico-chemical properties and environmental behaviour, information from the List of Endpoints of the DAR was used. When needed, additional information was included according to the methods as described in Section 2.1 of the INS-Guidance. Information on human toxicological threshold limits and classification was also primarily taken from the DAR.

Ecotoxicity studies (including bird and mammal studies) were screened for relevant endpoints (i.e. those endpoints that have consequences at the population level of the test species). All ecotoxicity and bioaccumulation tests were then thoroughly evaluated with respect to the validity (scientific reliability) of the study. A detailed description of the evaluation procedure is given in the INS-Guidance (see Section 2.2.2 and 2.3.2). In short, the following reliability indices were assigned:

- Ri 1: Reliable without restriction

’Studies or data … generated according to generally valid and/or internationally accepted testing guidelines (preferably performed according to GLP) or in which the test parameters documented are based on a specific (national) testing guideline … or in which all parameters described are closely related/comparable to a guideline method.’

- Ri 2: Reliable with restrictions

’Studies or data … (mostly not performed according to GLP), in which the test parameters

documented do not totally comply with the specific testing guideline, but are sufficient to accept the data or in which investigations are described which cannot be subsumed under a testing guideline, but which are nevertheless well documented and scientifically acceptable.’

- Ri 3: Not reliable

’Studies or data … in which there are interferences between the measuring system and the test substance or in which organisms/test systems were used which are not relevant in relation to the exposure (e.g., unphysiologic pathways of application) or which were carried out or generated

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according to a method which is not acceptable, the documentation of which is not sufficient for an assessment and which is not convincing for an expert judgment.’

- Ri 4: Not assignable

’Studies or data … which do not give sufficient experimental details and which are only listed in short abstracts or secondary literature (books, reviews, etc.).’

All available studies were summarised in data-tables, that are included as Annexes to this report. These tables contain information on species characteristics, test conditions and endpoints. Explanatory notes are included with respect to the assignment of the reliability indices.

With respect to the DAR, it was chosen not to re-evaluate the underlying studies. In principle, the endpoints that were accepted in the DAR were also accepted for ERL-derivation with Ri 2, except in cases where the reported information was too poor to decide on the reliability or when there was reasonable doubt on the validity of the tests. This applies especially to DARs prepared in the early 1990s, which do not always meet the current standards of evaluation and reporting.

In some cases, the characteristics of a compound (i.e. fast hydrolysis, strong sorption, low water solubility) put special demands on the way toxicity tests are performed. This implies that in some cases endpoints were not considered reliable, although the test was performed and documented according to accepted guidelines. If specific choices were made for assigning reliability indices, these are outlined in Section 3.3 of this report.

Endpoints with Ri 1 or 2 are accepted as valid, but this does not automatically mean that the endpoint is selected for the derivation of ERLs. The validity scores are assigned on the basis of scientific

reliability, but valid endpoints may not be relevant for the purpose of ERL-derivation (e.g. due to inappropriate exposure times or test conditions that are not relevant for the Dutch situation).

After data collection and validation, toxicity data were combined into an aggregated data table with one effect value per species according to Section 2.2.6 of the INS-Guidance. When for a species several effect data were available, the geometric mean of multiple values for the same endpoint was calculated where possible. Subsequently, when several endpoints were available for one species, the lowest of these endpoints (per species) is reported in the aggregated data table.

2.3 Derivation of ERLs

For a detailed description of the procedure for derivation of the ERLs, reference is made to the INS-Guidance. With respect to the selection of the final MPCwater, an additional comment should be made:

2.3.1 Drinking water

The INS-Guidance includes the MPC for surface waters intended for the abstraction of drinking water (MPCdw, water) as one of the MPCs from which the lowest value should be selected as the general

MPCwater (see INS-Guidance, Section 3.1.6 and 3.1.7). According to the proposal for the daughter

directive Priority Substances, however, the derivation of the AA-EQS (= MPC) should be based on direct exposure, secondary poisoning, and human exposure due to the consumption of fish. Drinking water was not included in the proposal and is thus not guiding for the general MPC value. The exact way of implementation of the MPCdw, water in the Netherlands is at present under discussion within the

framework of the “AMvB Kwaliteitseisen en Monitoring Water”. No policy decision has been taken yet, and the MPCdw, water is therefore presented as a separate value in this report. The MPCwater, is thus

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(MPCsp, water) or human consumption of fishery products (MPChh food, water); derivation of the latter two

depends on the characteristics of the compound.

Related to this, is the inclusion of water treatment for the derivation of the MPCdw, water. According to

the INS-Guidance (see Section 3.1.7), a substance specific removal efficiency related to simple water treatment should be derived in case the MPCdw, water is lower than the other MPCs. For pesticides, there

is no agreement as yet on how the removal fraction should be calculated, and water treatment is therefore not taken into account. In case no A1 value is set in Directive 75/440/EEC, the MPCdw, water is

set to the general Drinking Water Standard of 0.1 µg/L for organic pesticides as specified in Directive 98/83/EC.

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3 Derivation of environmental risk limits for dodine

3.1 Substance identification, physico-chemical properties, fate and human

toxicology

3.1.1 Identity

NH2

C CH₃CO₂

CH₃(CH₂)₁₁NH NH2

Figure 1. Structural formula of dodine. Table 1. Identification of dodine.

Parameter Name or number Source

Common/trivial/other name dodine, doguadine, dodine acetate Tomlin, 2003;

EC, 2006

Chemical name 1-dodecylguanidinium acetate (IUPAC)

dodecylguanidine monoacetate

Tomlin, 2003; EC, 2006

CAS number 2439-10-3 EC, 2006

EC number 219-459-5 EC, 2006

SMILES code CCCCCCCCCCCCNC(N)=N(H)(H)OC(=O)C

free base: CCCCCCCCCCCCNC(N)=[N+](H)(H)

Use class Fungicide EC, 2006

Mode of action multisite inhibitor acting mainly on the fungus membranes

EC, 2006

Authorised in NL Yes

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3.1.2 Physico-chemical properties

Physico-chemical properties of dodine are summarised in Table 2.

Table 2. Physico-chemical properties of dodine.

Parameter Unit Value Remark Reference

Molecular weight [g/mol] 287.4 EC, 2006

227.4 free base

Water solubility [mg/L] 870 pH 4.9, 20 ºC EC, 2006

930 pH 6.9, 20 °C

790 pH 9.1, 20 °C

pKa [-] -

log KOW 0.96 shake flask EC, 2006

4.31 Calculated for the free-base Biobyte, 2006

log KOC [-] 6.6 Arithmeic mean EC, 2006

Vapour pressure [Pa] <5.49 x 10-6 Calculated EC, 2006

Melting point [°C] 133.2 EC, 2006

Boiling point [°C] n.a. Decomposition prior to

boiling

EC, 2006

Henry’s law constant [Pa.m3/mol] < 1.7 x 10-3 20 °C EC, 2006

n.a. = not applicable.

In view of the characteristics of dodine, being a surfactant with a dodecyl-group, it is hardly possible to experimentally derive the log Kow. The log Kow of 0.96 as given in the DAR is considered

unrealistically low in view of the structural formula of dodine. The estimated log Kow of 4.31 for the

free base is considered to be more relevant, and is used as a worst case for risk assessment.

3.1.3 Behaviour in the environment

Table 3. Selected environmental properties of dodine.

Hydrolysis half-life DT50 [d] 576 pH 5, 25 °C (extrapolated) EC, 2006

Photolysis half-life DT50 [d] 12.6 28 d under natural light at 40 °N EC, 2006

Readily biodegradable No EC, 2006

Biodegradation in water/ sediment systems

DT50 [d] 0.71 whole system, 20 °C EC, 2006

Relevant metabolites guanidine photometabolite EC, 2006

3.1.4 Bioconcentration and biomagnification

An overview of the bioaccumulation data for dodine is given in Table 4.

Table 4. Overview of bioaccumulation data for dodine.

BCF (fish) [L/kg] 919 calculated with log Kow 4.31 Veith et al., 1979

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3.1.5 Human toxicological threshold limits and carcinogenicity

The following R-phrases related to human toxicology are proposed in the DAR: R22, R23, R38, R41. According to ESIS, dodine is assigned R22, R36/38 (http://ecb.jrc.it/esis/; date of search 17 March 2008). Dodine is not classified as being carcinogenic.

An ADI of 0.1 mg/kgbw/d is proposed in the DAR, based on a 1-year dog study with NOAEL values of

10 mg/kgbw/d with a safety factor of 100.

3.2 Trigger values

This section reports on the trigger values for ERLwater derivation (as demanded in WFD framework).

Table 5. Dodine: collected properties for comparison to MPC triggers.

Parameter Value Unit Method/Source Derived at section

Log Kp,susp-water 5.6 [-] KOC × fOC,susp1 KOC: 3.1.2

BCF 919 [L/kg] 3.1.4

BMF 1 [kg/kg] 3.1.4

Log KOW 4.2 [-] 3.1.2

R-phrases R22,R23,R36/38, R41, R50/R53 [-] 3.1.5

A1 value 1.0 [µg/L] Total pesticides

DW Standard 0.1 [µg/L] General value for organic pesticides

1_f

OC,susp = 0.1 kgOC/kgsolid(EC, 2003).

o dodine has a log Kp, susp-water ≥ 3; derivation of MPCsediment is triggered.

o dodine has a log Kp, susp-water ≥ 3; expression of the MPCwater as MPCsusp, water is required.

o dodine has a BCF ≥ 100 L/kg; assessment of secondary poisoning is triggered.

o dodine has an R22 classification and the log Kow is ≥ 3; the MPCwater for human health via food

(fish) consumption (MPChh food, water) need to be derived.

o For dodine, no specific A1 value or Drinking Water Standard is available from Council Directives 75/440, EEC and 98/83/EC, respectively. Therefore, the general Drinking Water Standard for organic pesticides applies.

3.3 Toxicity data and derivation of ERLs for water

3.3.1 MPC

eco, water

and MPC

eco, marine

An overview of the selected toxicity data for dodine is given in Table 6 for freshwater, marine toxicity data are given in Table 7. Detailed toxicity data for dodine are tabulated in Appendix 1.

With respect to the selection of data for derivation of the MPC, the following should be noted: Dodine shows a fast decline of concentrations in water over time. Therefore, studies in which the concentrations were not measured were assigned Ri 3. Studies in which concentrations were measured, were only assigned Ri 2 when the endpoint could be based on time weighted average concentrations. Otherwise, Ri 3 was assigned.

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Table 6. Dodine: selected freshwater toxicity data for ERL derivation.

Chronica Acutea

Taxonomic group NOEC/EC10 (µg/L) Taxonomic group L(E)C50 (µg/L)

Algae 4.8b Algae 6.9d

Crustacea 4.4 Crustacea 30e

Pisces 99c Pisces 700

Pisces 840

Pisces 598

a._{For detailed information see Appendix 1.}

b._{Preferred endpoint growth rate for Pseudokirchneriella subcapitata} c._{Most sensitive endpoint for Pimephales promelas, parameter growth} d._{Preferred endpoint growth rate for Pseudokirchneriella subcapitata.}

e._{Geometric mean of 18 and 49 µg/L, parameter mortality/immobility for Daphnia magna}

Table 7. Dodine: selected marine toxicity data for ERL derivation.

Chronica Acutea

Taxonomic group NOEC/EC10 (µg/L) Taxonomic group L(E)C50 (µg/L)

Crustacea 390

Pisces 3700

a_{For detailed information see Appendix 1.}

3.3.1.1 Treatment of fresh- and saltwater toxicity data

ERLs for freshwater and marine waters should be derived separately. For pesticides, data can only be combined if it is possible to determine with high probability that marine organisms are not more sensitive than freshwater organisms (Lepper, 2005). For dodine, there are not sufficient marine toxicity data (acute base set not complete; no chronic data) and ERLs for the marine compartment cannot be derived.

3.3.1.2 Mesocosm and field studies

An outdoor mesocosm study was performed with the product Dodine 400 SC. An evaluation of the study is included in Appendix 4. From this study, a NOEC of 6 µg as/L was derived, based on the absence of effects at this treatment level. Because dodine concentrations in water show a fast decline with time (DT50 0.83 days), the study does not allow for the assessment of effects due to chronic

exposure. It will, however, be considered for the derivation of the MAC. 3.3.1.3 Derivation of MPCeco, water and MPCeco, marine

The base-set for freshwater toxicity data is complete. Chronic NOECs are available for algae, crustaceans, and fish. An assessment factor of 10 is applied to the lowest NOEC of 4.4 µg/L for crustacea. The MPCeco, water is 0.44 µg/L.

For the marine environment, only acute data are available. The base-set is not complete because data for algae are missing. The MPCeco, marine cannot be derived.

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3.3.2 MPC

sp, water

and MPC

sp, marine

In view of the log Kow ≥ 3, derivation of the MPCsp, water and MPCsp, marine is triggered. The available

toxicity data for mammals and birds are presented in Appendix 2. In Table 8, the MPCoral is derived

applying the appropriate assessment factors to the data. No default assessment factors are available for a 56-days mammal and a 6-weeks bird test, a factor of 300 is used as a worst case.

Table 8. Dodine: derivation of the MPCoral, min.

Species Exposure time NOAEC LC50 AForal MPCoral

[mg/kgdiet] [mg/kgdiet] dog 1 y 400 30 13.33 mouse 56 d 625 300 2.08 mouse 56 d 625 300 2.08 mouse 91 d 600 90 6.67 mouse 91 d 600 90 6.67 mouse 78 w 200 30 6.67 rat 28 d 200 300 0.67 rat 28 d 200 300 0.67 rat 90 d 200 90 2.22 rat 90 d 200 90 2.22 rat 2 y 400 30 13.33 rat 2 gen 200 30 6.67 rat 2 gen 200 30 6.67 Mallard duck 5 d 325 3000 0.11 Mallard duck 6 w 750 300 2.50 Mallard duck 20+11+2 w 200 30 6.67

The lowest MPCoral, duck for Mallard ducks is 0.11 mg/kgdiet, based on a short-term toxicity study. There

are, however, also long-term data available, which according to the INS-Guidance prevail over the short-term study. The MPCoral, duck for Mallard ducks based on the long-term test is 6.67 mg/kgdiet.

A similar reasoning leads to a MPCoral, mouse of 6.67 mg/kgdiet for mice, and MPCoral, rat of 6.67 mg/kgdiet

for rat. The overall lowest MPCoral, min is thus 6.67 mg/kgdiet.

The MPCsp, water is derived as MPCoral, min / (BCF × BMF) = 6.67 / (919 × 1) = 7.3 × 10-3 mg/L = 7.3

µg/L.

Because toxicity data for marine predators are generally not available, the MPCoral, min as derived above is used as a representative for the marine environment also. To account for the longer food chains in the marine environment, an additional biomagnification step is introduced (BMF2). This

factor is the same as given in Table 4. The MPCsp, marine is derived as MPCoral, min / (BCF × BMF1 ×

BMF2) = 6.67 / (919 × 1 × 1) = 7.3 × 10-3 mg/L = 7.3 µg/L.

3.3.3 MPC

hh food, water

Derivation of MPChh food,water for dodine is triggered (Table 5). The MPChh food is calculated from the

ADI (0.1 mg/kgbw/d), a body weight of 70 kg and a daily fish consumption of 115 g, as MPC hh food =

0.1 x 0.1 x 70/0.115 = 6.1 mg/kg.

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3.3.4 MPC

dw, water

The Drinking Water Standard is 0.1 µg/L, the MPCdw, water is 0.1 µg/L.

3.3.5 Selection of the MPC

water

and MPC

marine

The lowest value of the routes included (see Section 2.3.1) is the ecotoxicological MPCeco, water. The

MPCwater = 0.44 µg/L..

No MPCmarine can be selected due to the absence of data.

3.3.5.1 MPCsusp, water

Because the log Kp, susp-water ≥ 3 (Table 5), the final MPCwater has to be recalculated in an MPCsusp, water,

which refers to the concentration in suspended matter. The MPCsusp, water is calculated according to:

MPCsusp, water = MPCwater, total / (Csusp, Dutch standard × 10-6 + ( 1/ Kp,susp-water,Dutch standard)), with MPCwater, total

being the above derived MPCwater in mg/L and Csusp, Dutch standard is 30 mg/L.

For this calculation, Kp,susp-water,Dutch standard is calculated as KOC x fOC,susp,Dutch standard. This is not the same

as the European standard fOC,susp which is used in the table with trigger values. With a log KOC of 6.6

(Koc 3981072 L/kg) an fOC,susp,Dutch standard of 0.1176, the Kp,susp-water,Dutch standard is calculated to be 468361

L/kg.

The MPCsusp, water is 0.44 x 10-3 / (30 × 10-6 + (1 / 468361)) = 14 mg/kgdw.

3.3.6 MAC

eco

3.3.6.1 MACeco, water

The MACeco is based on the acute toxicity data. The compound has a potential to bioaccumulate; the

mode of action is most likely non-specific, but there is a high interspecies variation. Therefore, an assessment factor of 1000 should be applied. The lowest EC50 is 6.9 µg/L, leading to a MACeco, water of

6.9/1000 = 6.9 ng/L. This value is below the MPCeco, water of 0.44 µg /L, and since it is not realistic to

assume that acute effects on species occur below a level that is deemed to be protective for chronic exposure, the MACeco, water is initially set to 0.44 µg/L.

A NOEC of 6 µg as/L was derived from an outdoor mesocosm study, based on initial concentrations (see Appendix 3). From a comparison of mesocosm studies with the insecticides chlorpyrifos and lambda-cyhalothrin, it can be concluded that an assessment factor of 3 may be necessary to cover variation at the level of the NOEAEC1 in case one reliable study is available (De Jong et al., 2008, based on Brock et al., 2006). Lepper (2005) argues that the scope of protection of an environmental quality standard under the WFD is broader than that of the “acceptable concentration” under Directive 91/414. It should be considered that the quality standard must be protective for all types of surface waters and communities that are addressed by the respective standard. Mesocosm studies performed in the context of 91/414 are normally focused on agricultural ditches that can be characterised as

eutrophic shallow water bodies. Environmental quality standards under the WFD, however, must assure protection also for water bodies that significantly differ from this paradigm (Lepper, 2005). In addition, dodine is a fungicide, which may affect several taxonomic groups. It is therefore in principle

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proposed to use an assessment factor of 3 on the NOEC instead of on the NOEAEC. The MACmesocosm

is 2.0 µg/L.

Since the most sensitive group from the acute dataset is also represented in the mesocosm, the MACeco, water is set to 2.0 µg/L.

3.3.6.2 MACeco, marine

Since the marine base set is not complete, it is not possible to derive the MACeco, marine

3.3.7 SRC

eco, water

Three chronic NOECs are available for algae, Daphnia and fish. In this case, the SRCeco, water is set to

the geometric mean of the aggregated chronic toxicity values (see Table 6), which is 13 µg/L.

3.4 Toxicity data and derivation of ERLs for sediment

3.4.1 Sediment toxicity data

There are no sediment toxicity data available.

3.4.2 Derivation of MPC

sediment

Because there are no sediment toxicity data, the MPCsediment needs to be derived by applying the

equilibrium partitioning method on the MPCeco,water of 0.44 µg/L

First, the MPCsediment is calculated using TGD default values, and subsequently this MPCsediment is

recalculated to Dutch standard sediment.

1000

water eco, susp ww EqP, TGD, sediment,

=

!

"

MPC

RHO

K

MPC

susp water with Ksusp-water:

solid

1000

p

solid

water

air

susp susp susp water air susp water susp

RHO

K

F

K

F

K

"

=

!

"

+

!

Using Kp,susp = 398107 L/kg (log Kp, susp = 5.6), Fairsusp = 0, Fwatersusp = 0.9, Fsolidsusp = 0.1, RHOsusp =

1150 kg/m3, Fsolidsusp = 0.1, RHOsolid = 2500 kg/m3, the Ksusp-water is calculated as 99528, and the

MPCsediment, TGD, EqP, ww as 38 mg/kgww.

This value is converted to dry weight and subsequently to Dutch standard sediment using the following equations: ww EqP, TGD, sediment, susp susp dw EqP, TGD, sediment,

solid

RHO

MPC

F

RHO

MPC

!

=

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dw EqP, TGD sediment, TGD susp, sediment standard Dutch dw EqP, sediment, standard Dutch

MPC

Foc

MPC

=

!

With FocDutch standard sediment = 0.0588 and Focsusp,TGD = 0.1, the MPCDutch standard sediment, EqP, dw =

103 mg/kgdw.

3.4.3 Derivation of SRC

eco, sediment

Since no valid sediment toxicity data are available, the SRCeco, sediment is calculated using the

(unrounded) SRCeco, water and the partitioning method, analogous to the calculation of the MPCsediment.

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4 Conclusions

In this report, the risk limits Maximum Permissible Concentration (MPC), Maximum Acceptable Concentration for ecosystems (MACeco), and Serious Risk Concentration for ecosystems (SRCeco) are

derived for dodine in water and sediment. No risk limits were derived for the marine compartment because data were not available.

The ERLs that were obtained are summarised in the table below. The MPC value that was set for this compound until now, is also presented in this table for comparison reasons. It should be noted that this is an indicative MPC (‘ad-hoc MTR’), derived using a different methodology and based on limited data.

Table 9. Derived MPC, MACeco, and SRC values for dodine.

ERL Unit MPC MACeco SRC

Water, olda µg/L 5.1 × 10-3

Water, newb µg/L 0.44 2.0 13

Water, suspended matter mg/kgdw 14 - -

Drinking waterb µg/L 0.1c - -

Sediment µg/kgdw 1.0 x 105 - 3.0 x 106

Marine µg/L n.d.d n.d.d -

Marine, suspended matter mg/kgdw n.d.d n.d.d -

Marine sediment mg/kgdw n.d.d - -

a _{indicative MPC (‘ad-hoc MTR’), source: Helpdesk Water}

http://www.helpdeskwater.nl/emissiebeheer/normen_voor_het/zoeksysteem_normen/

b _{The MPC}

dw, water is reported as a separate value from the other MPCwater values (MPCeco, water, MPCsp, water or

MPChh food, water). From these other MPC water values (thus excluding the MPCdw, water) the lowest one is selected as

the ‘overall’ MPCwater.

c _{provisional value pending the decision on implementation of the MPC}

dw, water (see Section 2.3.1) d _{n.d. = not derived due to lack of data}

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EC. 2003. Technical Guidance Document in support of Commission Directive 93/67/EEC on Risk Assessment for new notified substances, Commission Regulation (EC) No 1488/94 on Risk Assessment for existing substances and Directive 98/9/EC of the European Parliament and of the Council concerning the placing of biocidal products on the market. Part II. Ispra, Italy: European Chemicals Bureau, Institute for Health and Consumer Protection. Report no. EUR 20418 EN/2. Lepper P. 2005. Manual on the Methodological Framework to Derive Environmental Quality Standards

for Priority Substances in accordance with Article 16 of the Water Framework Directive (2000/60/EC). 15 September 2005 (unveröffentlicht) ed. Schmallenberg, Germany: Fraunhofer-Institute Molecular Biology and Applied Ecology.

MNP. 2006. Tussenevaluatie van de nota Duurzame gewasbescherming. Bilthoven, The Netherlands: Milieu- en Natuurplanbureau. MNP-publicatienummer: 500126001.

Tomlin CDS. 2003. e-Pesticide Manual 2002-2003 (Twelfth edition) Version 2.2. British Crop Protection Council.

Van Vlaardingen PLA, Verbruggen EMJ. 2007. Guidance for the derivation of environmental risk limits within the framework of the project 'International and National Environmental Quality Standards for Substances in the Netherlands' (INS). Bilthoven, The Netherlands: National Institute for Public Health and the Environment (RIVM). Report no. 601501031. 117 pp.

Veith GD, Defoe DL, Bergstedt BV. 1979. Measuring and estimating the bioconcentration factor of chemicals in fish. J Fish Res Board Can 36: 1040-1048.

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R IV M R ep or t 6 01 71 60 07

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1. 1. A cu te t ox ic it y of d od in e to f re sh w at er o rg an is m s. S p ec ie s A T es t T es t P u ri ty T es t p H T H ar d n es s E xp . C ri te ri o n T es t V al u e R i N o te s R ef er en ce p ro p er ti es ty p e C o m p o u n d w at er C aC O 3 ti m e en d p o in t [% ] [° C ] [m g/ L] [m g/ L] hn er ie lla s ub ca pi ta ta Y S do di n e 94 dw 25 12 0 h gr ow th r at e E C 50 0. 01 10 0 3 1, 2 E C , 2 00 6 (H ob er g, 1 99 3) hn er ie lla s ub ca pi ta ta Y S do di n e 94 dw 25 12 0 h ce ll de ns ity E C 50 0. 00 09 5 3 1, 2 E C , 2 00 6 (H ob er g, 1 99 3) hn er ie lla s ub ca pi ta ta Y S do di n e 99 24 12 0 h gr ow th r at e E C 50 0. 00 91 0 3 1, 3, 5 E C , 2 00 6 (H ob er g, 1 99 5) hn er ie lla s ub ca pi ta ta Y S do di n e 99 24 12 0 h ce ll de ns ity E C 50 0. 00 25 0 3 1, 3, 5 E C , 2 00 6 (H ob er g, 1 99 5) hn er ie lla s ub ca pi ta ta Y S 40 0 S C 40 23 72 h gr ow th r at e E C 50 0. 00 69 0 2 4 E C , 2 00 6 (M ig ch ie ls en , 2 00 4) hn er ie lla s ub ca pi ta ta Y S 40 0 S C 40 23 72 h bi om as s E C 50 0. 00 56 0 2 4 E C , 2 00 6 (M ig ch ie ls en , 2 00 4) a gn a < 24 h F do di n e 94 48 h im m o bi lit y E C 50 0. 01 8 2 5 E C , 2 00 6 (P ut t, 19 92 ) a gn a < 24 h R do di n e 95 48 h im m o bi lit y E C 50 0. 05 3 3 5 E C , 2 00 6 (C al ey , 1 98 9) a gn a < 24 h Y S do di n e 98 48 h im m o bi lit y E C 50 0. 14 6 3 6 E C , 2 00 6 (M ig ch ie ls en , 2 00 2) a gn a < 24 h Y R 40 0 S C 40 48 h im m o bi lit y E C 50 0. 04 9 2 E C , 2 00 6 (M ig ch ie ls en , 2 00 4) a gn a < 24 h N S do di n e am 26 h m or ta lit y E C 50 0. 05 8 3 7 F re ar a nd B oy d, 1 96 7 fa sc ia tu s m at ur e N ? S do di n e 97 .6 7. 1 15 44 96 h m or ta lit y LC 50 1. 10 0 3 7 M ay er a nd E lle rs ie ck , 1 98 6 a lu di na m al le at a N S do di n e dt w 22 48 h m or ta lit y LC 50 2. 70 4 8, 9 N is hi uc hi a nd Y os hi d a, 1 97 2 b is e xu st us N S do di n e dt w 22 48 h m or ta lit y LC 50 2. 30 4 8, 9 N is hi uc hi a nd Y os hi d a, 1 97 2 ta N S do di n e dt w 22 48 h m or ta lit y LC 50 2. 40 4 8, 9 N is hi uc hi a nd Y os hi d a, 1 97 2 pi ra li be rt in a N S do di n e dt w 22 48 h m or ta lit y LC 50 2. 00 4 8, 9 N is hi uc hi a nd Y os hi d a, 1 97 2 af fin is Ju ve ni le N S do di n e 95 24 h m or ta lit y LC 50 0. 93 0 3 7 H ou rd ak is e t a l., 1 99 5 af fin is M at ur e N S do di n e 95 24 h m or ta lit y LC 50 2. 99 0 3 7 H ou rd ak is e t a l., 1 99 5 ac ro ch iru s m at ur e Y R do di n e 95 .3 22 96 h m or ta lit y LC 50 0. 70 0 2 4 E C , 2 00 6 (C al ey e t al ., 1 99 0 b) ch us m yk is s m at ur e Y R do di n e 95 .3 14 96 h m or ta lit y LC 50 0. 84 0 2 4 E C , 2 00 6 (C al ey e t al ., 1 99 0 a) et er om or ph a m at ur e N S M el pr ex 6 5 65 8. 1 20 20 96 h m or ta lit y LC 50 0. 92 3 7 T oo by e t a l., 1 97 5 ar pi o 2. 3c m 0 .3 3 g Y R do di n e 99 dw 8 21 36 7 96 h m or ta lit y LC 50 0. 59 8 2 5 M ig h ie ls en , 2 00 5 ar pi o Y 40 0 S C 40 am 7. 7 18 0 96 h m or ta lit y LC 50 1. 40 0 3 10 M ig h ie ls en , 2 00 7 l g ro w th n ot e xp on en tia l a nd ir re g ul ar 6 se di m en t ad de d; c on ce nt ra tio n du ri ng te st n ot g iv en o in t b as ed o n in iti a l m ea su re d; s tr on g de cl in e 7 st at ic , c on ce nt ra tio ns n o t m ea su re d v al ue fr om 1 5-d ay s te st 8 ar tic le in J ap an es e; o rig in al r es u lt as T Lm o in t r ec al cu la te d ba se d on m ea su re d co nc en tr at io ns 9 pu rit y un kn ow n al e nd po in t b as ed o n m ea su re d co nc en tr at io ns 10 se di m en t ad de d; c on ce nt ra tio ns d ec lin e to < 5 0% a ft er 2 4 h

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R IV M L et te r re po rt 6 01 71 60 07 C h ro n ic t ox ic it y of d od in e to f re sh w at er o rg an is m s. S p ec ie s A T es t T es t P u ri ty T es t p H T H ar d n es s E xp . C ri te ri o n T es t V al u e R i N o te s R ef er en ce p ro p er ti es ty p e C o m p o u n d w at er C aC O 3 ti m e en d p o in t [% ] [° C ] [m g/ L] [m g/ L] ie lla s ub ca pi ta ta Y S do di n e 94 dw 12 0 h N O E C gr ow th r at e 0. 00 60 0 3 1, 2 E C , 2 00 6 (H ob er g, 1 99 3) ie lla s ub ca pi ta ta Y S do di n e 94 dw 12 0 h N O E C ce ll de ns ity 0. 00 00 8 2 3 1, 2 E C , 2 00 6 (H ob er g, 1 99 3) ie lla s ub ca pi ta ta Y S do di n e 99 12 0 h N O E C gr ow th r at e 0. 00 04 2 3 1, 3, 4 E C , 2 00 6 (H ob er g, 1 99 5) ie lla s ub ca pi ta ta Y S do di n e 99 12 0 h N O E C ce ll de ns ity 0. 00 00 5 9 3 1, 3, 4 E C , 2 00 6 (H ob er g, 1 99 5) ie lla s ub ca pi ta ta Y S 40 0 S C 40 72 h N O E C gr ow th r at e 0. 00 48 2 4 E C , 2 00 6 (M ig ch ie ls en , 2 00 4) a < 24 h Y F do di n e 99 tw 20 21 d re pr od uc tio n N O E C 0. 00 44 2 4 E C , 2 00 6 (P ut t 19 95 ) a < 24 h Y F do di n e 99 tw 20 21 d im m o bi lit y E C 50 0. 03 00 2 4 E C , 2 00 6 (P ut t 19 95 ) om e la s eg gs Y F do di n e 97 tw 25 5 d ha tc hi ng > 0, 4 2 4 E C , 2 00 6 (S ou sa , 19 95 ) om e la s eg gs Y F do di n e 97 tw 25 35 d m or ta lit y N O E C 0. 20 0 2 4 E C , 2 00 6 (S ou sa , 19 95 ) om e la s eg gs Y F do di n e 97 tw 25 35 d gr ow th N O E C 0. 09 9 2 4 E C , 2 00 6 (S ou sa , 19 95 ) w th n ot e xp on en tia l a nd ir re g ul ar as ed o n in iti a l m ea su re d; s tr on g de cl in e ue fr om 1 5-d ay s te st nd po in t b as ed o n m ea su re d co nc en tr at io ns

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te r re po rt 6 01 71 60 07 23 1. 3. A cu te t ox ic it y of d od in e to m ar in e or ga n is m s. S p ec ie s A T es t T es t P u ri ty T es t p H T H ar d n es s E xp . C ri te ri o n T es t V al u e R i N o te s R ef er en ce p ro p er ti es ty p e C o m p o u n d w at er C aC O 3 ti m e en d p o in t [% ] [° C ] [m g/ L] [m g/ L] ba h ia < 24 h Y F do di n e 94 nw 25 32 96 h m or ta lit y LC 50 0. 39 0 2 1 E C , 2 00 6 (B et te nc ou rt , 1 99 2) v irg in ic a ju ve ni le Y F do di n e nw 31 96 h sh el l g ro w th E C 50 0. 09 8 3 1, 2 E C , 2 00 6 (D io n ne , 1 9 92 ) v irg in ic a ju ve ni le Y F do di n e nw 31 96 h m or ta lit y LC 50 > 0 .1 20 3 1, 2 E C , 2 00 6 (D io n ne , 1 9 92 ) v ar ie ga te s m at ur e Y F do di n e 94 nw 22 96 h m or ta lit y LC 50 3. 70 0 2 1 E C , 2 00 6 (B et te nc ou rt , 1 99 2) al e nd po in t b as ed o n m ea su re d co nc en tr at io ns nc e b et w ee n c on tr ol a nd s ol ve nt c on tr ol ; s ol ve n t c on tr ol d oe s no t m ee t v al id ity c rit er ia

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R IV M L et te r re po rt 6 01 71 60 07

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T ox ic it y of d od in e to b ir d s an d m am m al s. S pe ci es P ur ity A pp lic at io n E xp . C rit er io n T es t N O A E L N O A E C LC 50 R i N ot es R ef er en ce pr op er tie s ro ut e tim e en dp o in t D ie t D ie t (a ge , s ex ) [% ] [m g/ kgbw /d ] [m g/ kgdi et ] [m g/ kgdi et ] il 20 g , 1 1 d ay s ol d 95 .3 di et 5 d LC 50 m or ta lit y > 9 76 > 5 20 0 2 E C , 2 00 6 (H ak in 1 9 90 a) 8 da ys , 1 00 g 95 .3 di et 5 d LC 50 m or ta lit y 28 0 32 5 2 E C , 2 00 6 (H ak in 1 9 90 b) il 49 w ee ks , 2 20 -3 00 g 94 di et 6 w N O E C m or ta lit y ! 1 35 ! 1 50 0 2 4 E C , 2 00 6 (P ed er se n & M u m pe r 19 93 a 11 0 w ee ks , 1 00 0-1 40 0 g 94 di et 6 w N O E C m or ta lit y 50 75 0 2 4 E C , 2 00 6 (P ed er se n 19 93 b il 20 w ee ks , 1 50 -2 50 g 94 di et 24 + 13 + 2 w N O E C re pr od uc tio n ! 9 5 ! 1 00 0 2 4 E C , 2 00 6 (P ed er se n 19 94 a 24 w ee ks , 1 20 0 g 94 di et 20 + 11 + 2 w N O E C re pr od uc tio n 20 20 0 2 4 E C , 2 00 6 (P ed er se n 19 94 b 6-9 kg , 7 m on th s 94 ca ps ul es 6 w N O A E L 1. 25 3 1, 2 E C , 2 00 6 (S m ith 1 9 94 ) 6 m on th s, 6 -9 k g 99 ca ps ul es 1 y N O A E L bo dy w ei g ht 10 40 0 2 3 E C , 2 00 6 (T ru tte r 19 96 ) 4 w ee ks , 1 8-21 g, M al e 95 di et 56 d N O A E L bo dy w ei g ht 10 9. 4 62 5 2 4 E C , 2 00 6 (M ul he rn e t al ., 19 88 ) 4 w ee ks , 1 8-21 g, f em a le 95 di et 56 d N O A E L bo dy w ei g ht 15 0. 4 62 5 2 4 E C , 2 00 6 (M ul he rn e t al ., 19 88 ) 28 d , 2 3 .2 -3 0. 1g , m a le 94 di et 91 d N O A E L bo dy w ei g ht 94 60 0 2 4 E C , 2 00 6 (K an ga s 19 94 ) 28 d , 1 7 .3 -2 3. 9g , f em a le 94 di et 91 d N O A E L bo dy w ei g ht 11 6 60 0 2 4 E C , 2 00 6 (K an ga s 19 94 ) 98 .6 di et 78 w N O A E L bo dy w ei g ht 29 -3 6 20 0 2 4 E C , 2 00 6 (W ill ia m s, 1 99 8) 28 d , 1 8 2-22 8g , m al e 94 di et 28 d N O A E L bo dy w ei g ht < 4 7 < 5 00 3 2, 4 E C , 2 00 6 (B at h am 1 9 94 b) 28 d ,1 3 1-17 3g , f em a le 94 di et 28 d N O A E L bo dy w ei g ht < 5 0 < 5 00 3 2, 4 E C , 2 00 6 (B at h am 1 9 94 b) 5 w ee ks , m al e 99 di et 28 d N O A E L fo od u pt ak e 17 .7 20 0 2 2, 4 E C , 2 00 6 (D an ge 1 99 7) 5 w ee ks , f em a le 99 di et 28 d N O A E L fo od u pt ak e 19 .2 20 0 2 2, 4 E C , 2 00 6 (D an ge 1 99 7) 3, 5 w , 3 5-50 g, m a le 95 di et 90 d N O A E L bo dy w ei g ht 14 .1 20 0 2 4 E C , 2 00 6 (L in a et a l., 1 98 4) 3, 5 w , 3 5-50 g, fe m al e 95 di et 90 d N O A E L bo dy w ei g ht 14 .9 20 0 2 4 E C , 2 00 6 (L in a et a l., 1 98 4) 98 .6 di et 2 y N O A E L bo dy w ei g ht 20 -2 6. 5 40 0 2 4 E C , 2 00 6 (D an ge , 19 98 ) 98 .6 di et 2 ge n N O A E L bo dy w ei g ht 13 .1 4 20 0 2 4, 5 E C , 2 00 6 (H en w oo d, 1 99 6) 98 .6 di et 2 ge n N O A E L re pr od uc tio n 52 .6 ! 8 00 2 4 E C , 2 00 6 (H en w oo d, 1 99 6) 98 .6 di et 2 ge n N O A E L pu p de ve lo pm e nt 13 .1 4 20 0 2 4 E C , 2 00 6 (H en w oo d, 1 99 6) a d ju st ed d ur in g s tu dy in 2 g ro up s e-fin d in g E C c al cu la te d w ith d ef au lt co nv er si on fa ct or A C b as ed o n d ie ta ry c on ce nt ra tio ns u se d in t es t na l t ox ic ity

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F oe ke m a E M , L ew is W E, H o orn sm a n G , Va n he t G ro en ew o ud H , V a n d er V lie s E M . 20 07 . D et er m in at io n o f th e bi ol og ic al e ff ec ts a n d fa te o f D od in e 4 0 0C S in o u td oo r po nd s. D en H e ld er, T h e N et he rl a nd s: I M AR ES. R e po rt n o. C 1 11 /0 7, 8 7 pp . (w ith An ne xe s). D a ta p ro vi d ed b y A gri ph ar SA, Be lg iu m . Po p u la ti o n ; C o m m u n ity ph yt op la nk to n; z o op la nk to n; p e rip hy to n; g as tro po ds ; c ru st ac ea ns ; in se ct s; m ac ro ph yt es o d ou td o or m es os os m ro p er ti e s ca . 2 20 0 L, n a tu ra l s ed im en t c a. 1 0 cm o n D od in e 4 00 SC ( 38 4-31 5 g as /L ) r eg im e 3, 6 , 16 , 4 1 an d 1 0 9 " g as /L ; tw o ap pl ic at io ns w ith 5 -d in te rv al ; ca lc u la te d in iti al , b as ed o n m e as ur ed D o di ne in d os in g so lu tio ns Y; s ta rt in g at 1 h p os t-ap pl ic at io n u nt il 28 d re [ °C ] 14 -2 2 ; > 1 7 as f ro m o n e w ee k af te r 2 n d a p pl ic at io n 8. 5-9. 5; t re at m e nt e ff ec t at 4 1 a nd 1 0 9 " g as /L [m g C aC O3 /L ] ti m e 63 d N O EC o in t ph yt op la nk to n, z o op la nk to n a s/ L ] 6 Y OEC D ; SE T AC ; C LA SSI C 1 oo r m es oc os m s tu dy w as p er fo rm ed w it h th e fu ng ic id e D od in e 40 0 S C in c om pl ia nc e w it h G L P . T he p re se nt e va lu at io n of th e st ud y is b as ed o n th e or ig in al s tu dy r ep or t. te m . G la ss -f ib re t an ks (∅ 1 90 -2 00 c m ; 1 10 c m d ee p) . M es oc os m s se t-up in A pr il 2 00 7 w it h se di m en t (c a. 1 0 cm ; 3 .3 % O M ) an d w at er ( 86 -9 0 cm ) fr om L ak e M ar ke rm ee r. l o rg an is m s w er e in tr od uc ed ( sn ai ls , 3 0 B it hy ni a te nt ac ul at a an d 20 L ym ne a st ag na li s; c ru st ac ea ns , 5 0 A se ll us a qu at ic us a nd 6 0 G am m ar us s p. ; m ac ro ph yt es , c a. 4 g w w t na de ns is a nd 1 1 g w w t M yr io ph yl um s pi ca tu m ) an d w at er w as r e-ci rc ul at ed f or 3 7 da ys p ri or to a pp li ca ti on . M es oc os m s w er e tr ea te d tw ic e (2 4 an d 29 M ay ; i nt er va l 5 d ) in e 40 0 S C , n om in al a pp li ca ti on r at es 3 , 7 , 1 8, 4 5 an d 11 0 µ g as /L a pp li ed e ve nl y on th e su rf ac e. I nt er na l ci rc ul at io n (1 00 L /h ) th ro ug ho ut th e st ud y. R ep li ca te p on ds f or ts , t hr ee c on tr ol p on ds . l s am pl in g. T re at m en t s ol ut io ns a na ly se d. W at er s am pl es ta ke n 1, 3 , 2 4 h af te r ea ch a pp li ca ti on , 5 d a ft er 1 st a pp li ca ti on ( be fo re 2 nd ), a nd o n da ys 1 0 an d 28 a ft er 1 st io n (5 a nd 2 3 af te r 2 nd ). S ed im en t s am pl es o n da ys 5 ( be fo re 2 nd a pp li ca ti on ), 1 0 an d 63 . A na ly si s by L C /M S -M S , L O Q 0 .1 µ g/ L w at er , 0 .0 1 m g/ kg w w t s ed im en t. l s am pl in g. Z oo pl an kt on , p hy to pl an kt on , p er ip hy to n, e m er ge d in se ct s (f lo at in g tr ap s) , ( m ac ro -) in ve rt eb ra te s w er e sa m pl ed b ef or e an d un ti l 6 3 da ys a ft er tr ea tm en t. yt e bi om as s w as d et er m in ed a t t he e nd o f th e st ud y. tm en t a nd s ta ti st ic s. H al f-li fe o f te st c om po un d w it h fi rs t-or de r ki ne ti cs . D if fe re nc es b et w ee n co nt ro ls a nd tr ea tm en ts a na ly se d by A N O V A w it h B on fe rr on i p os t-te st . d at a tr an sf or m ed lo g( n+ 0. 1) . M ul ti va ri at e st at is ti cs ( P R C ) on z oo pl an kt on , f yt op la nk to n, m ac ro -i nv er te br at es a nd w at er q ua li ty p ar am et er s w it h C A N O C O . D at a m at io n (e it he r lo g( n+ 0. 1) , l og o r sq ua re r oo t) . S ig ni fi ca nc e of P R C a na ly se d by M on te -C ar lo p er m ut at io n.

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R IV M L et te r re po rt 6 01 71 60 07 na ly si s. C al cu la te d av er ag e no m in al c on ce nt ra ti on b as ed o n ac tu al a m ou nt in d os in g so lu ti on s w as 3 , 6 , 1 6, 4 1 an d 10 9 µ g as /L . A ct ua l c on ce nt ra ti on s in r ep li ca te p os t-ap pl ic at io n w er e 55 -2 88 % a nd 4 3-14 3% o f no m in al a ft er 1 st a nd 2 nd a pp li ca ti on , r es pe ct iv el y. O ve ra ll a ve ra ge c on ce nt ra ti on s 1, 3 a nd 2 4 h af te r bo th a pp li ca ti on s th e ta bl e be lo w . C on ce nt ra ti on s ju st b ef or e th e 2 nd a pp li ca ti on w er e < 1 µ g as /L , e xc ep t fo r th e hi gh es t t re at m en t le ve l. C al cu la te d av er ag e D T50 w as 0 .8 3 da ys . T he re i s e of a cc um ul at io n of t he c om po un d in th e w at er c ol um n. C al cu la te d no m in al c on ce nt ra ti on s w er e us ed to e xp re ss e nd po in ts . 1 h o u r p o st a p p li c ati o n 1 3 h p o st ap p lic ati o n 1 24 h p o st a p p li ca ti o n 1 [! g a s/ L ] [% o f n o m in al ] [! g a s/ L ] [% o f n o m in al ] [! g a s/ L ] [% o f n o m in al ] 3 10 0 4* 14 9 1 32 8 13 6 6 99 3 48 19 12 0 16 10 0 9 55 42 10 2 35 86 17 42 11 7 10 7 87 79 51 47 m e as ur em en ts a ft er 1 st a nd 2 n d a p pl ic at io n ue t o sa m pl e co nt am in at io n a fte r 1 st a pp lic a tio n, re co ve ry a ft er 2 n d a p pl ic at io n is 1 13 % o f n om in al m ic al p ar am et er s. S ig ni fi ca nt e ff ec ts o n D O , p H a nd tu rb id it y at 2 x 4 1 an d 2 x 10 9 µ g as /L , p ar tl y ex pl ai ne d as s ec on da ry e ff ec ts d ue to c ha ng es in p ri m ar y pr od uc ti on . ys te m . N o si gn if ic an t e ff ec t w er e ob se rv ed o n bi om as s an d co m m un it y st ru ct ur e of p er ip hy to n, n or o n m ac ro ph yt es . T he P R C -a na ly si s sh ow ed a s ig ni fi ca nt e ff ec t o n n, p hy to pl an kt on , m ac ro -i nv er te br at es a nd w at er q ua li ty p ar am et er s at 2 x 4 1 an d 2 x 10 9 µ g as /L . S ig ni fi ca nt e ff ec ts p er t re at m en t le ve l ar e su m m ar is ed in th e ta bl e m ar y of e ff ec ts in m es oc os m s tu dy G ro u p Sp e ci e s/ ta x o n Si g n ifi c an t eff ec t o n d ay N o te s 4 11 18 25 32 39 46 53 60 ph yt op la nk to n Sc en ed es m us s p. ↑ ef fe ct n ot p re se n t a t 2 x 6 a n d 2 x 16 " g as /L zo op la nk to n F ili n ia lo ng is et a ↑ ↑ lo w n u m be rs /a bs e nt in c on tro l a s fro m d ay 1 8 ph yt op la nk to n un id en tif ie d m ic ro -a lg a e ↓ lo w n u m be rs /a bs e nt in c on tro l a s fro m d ay 1 8 F ili n ia lo ng is et a ↑ lo w n u m be rs /a bs e nt in c on tro l a s fro m d ay 1 8 zo op la nk to n Ke ra te lla q ua dr at a ↓ in cre as e at 2 x 1 6 " g as /L ; n o ef fe ct a t 2 x 4 1 an d 2 x 1 09 " g a s/ L un id en tif ie d m ic ro -a lg a e ↓ lo w n u m be rs /a bs e nt in c on tro l a s fro m d ay 1 8 C ru ci g en ia s p. ↑ ↑ lo w n u m be rs /a bs e nt in c on tro l ph yt op la nk to n M yc ro cy st is a eru gi no sa ↑ ↑ lo w n u m be rs /a bs e nt in c on tro l F ili n ia lo ng is et a ↑ ↑ lo w n u m be rs /a bs e nt in c on tro l a s fro m d ay 1 8 Ke ra te lla q ua dr at a ↑ no e ff ec t at 2 x 4 1 an d 2 x 1 09 " g a s/ L zo op la nk to n Po ly ar th a sp . ↓

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te r re po rt 6 01 71 60 07 27 m ar y of e ff ec ts in m es oc os m s tu dy ( co nt .) G ro u p Sp e ci e s/ ta x o n Si g n ifi c an t eff ec t o n d ay N o te s 4 11 18 25 32 39 46 53 60 D O in cre as e on d ay 3 2; n .s . at n ex t s am pl in g (d ay 3 5) in d ic at iv e of e n ha nc e d p ri m ary p ro d uc tio n pH in cre as e on d ay 3 2, 3 5; n .s . at n ex t s a m p lin g (d ay 3 9) in d ic at iv e of e n ha nc e d p ri m ary p ro d uc tio n w at er q ua lit y tu rb id ity in cre as e on d ay 4 -6 ,1 4, 18 ; n .s . a t n ex t s a m pl in g (d ay 2 1) in d ic at iv e of e n ha nc e d p ri m ary p ro d uc tio n ch lo ro p hy ll a in cre as e on d ay 5 ,6 ,1 4; n .s . a t n ex t s a m pl in g (d ay 1 8) un id en tif ie d m ic ro -a lg a e ↑ lo w n u m be rs /a bs e nt in c on tro l a ft er da y 18 An kri st o de sm us a n g us tu s ↑ lo w n u m be rs /a bs e nt in c on tro l Sc en ed es m us s p. ↑ ↑ C ru ci g en ia s p. ↑ lo w n u m be rs /a bs e nt in c on tro l An ky ra a nc or a ↓ M yc ro cy st is a eru gi no sa ↑ lo w n u m be rs /a bs e nt in c on tro l ph yt op la nk to n fla ge lla te s < 3 " m ↓ ↓ D ap hn ia lo ng is pi n a ↓ F ili n ia lo ng is et a ↑ ↑ ↑ lo w n u m be rs /a bs e nt in c on tro l a s fro m d ay 1 8 zo op la nk to n Po ly ar th a sp . ↓ D O in cre as e on d ay 7 ,1 4 ,4 9; d ec re as e o n da y 28 ,3 2 ,3 5; n .s . at n ex t sa m pl in g (d ay 3 9) in d ic at iv e of e n ha nc e d p ri m ary p ro d uc tio n pH in cre as e on d ay 1 1; d ec re as e o n d ay 2 8-46 ; n. s. a t n ex t s a m p lin g (d a y 49 ) in d ic at iv e of e n ha nc e d p ri m ary p ro d uc tio n w at er q ua lit y tu rb id ity in cre as e on d ay 4 -6 ,1 4-21 ; n .s . a t n ex t s a m pl in g (d ay 2 5) in d ic at iv e of e n ha nc e d p ri m ary p ro d uc tio n ch lo ro p hy ll a in cre as e on d ay 1 1, 1 8; n .s . at n ex t s a m p lin g (d ay 2 5) un id en tif ie d m ic ro -a lg a e ↑ ↑ lo w n u m be rs /a bs e nt in c on tro l a ft er da y 18 An kri st o de sm us a n g us tu s ↑ ↑ ↑ lo w n u m be rs /a bs e nt in c on tro l Sc en ed es m us s p. ↑ C ru ci g en ia s p. ↑ lo w n u m be rs /a bs e nt in c on tro l An ky ra a nc or a ↓ ↓ ↓ ↓ M yc ro cy st is a eru gi no sa ↑ lo w n u m be rs /a bs e nt in c on tro l fla ge lla te s < 3 " m ↓ ph yt op la nk to n fla ge lla te s 3-10 " m ↑ ↑ Bo sm in a sp . ↓ ↓ D ap hn ia lo ng is pi n a ↓ ↓ ↓ ↓ ↓ ↓ ↓ C eri od ap hn ia s p. ↓ ↓ ↓ Si m oc e ph al us v et ul us ↓ zo op la nk to n F ili n ia lo ng is et a ↓ ↑ ↑ lo w n u m be rs /a bs e nt in c on tro l a s fro m d ay 1 8 As el lu s a qu at ic us no e ff ec t un til d ay 3 3; s ig n ifi ca nt in cre as e o n da y 61 cu m ul a tiv e n um b ers o n tr ap s da y 0-3 3 an d da y 61 G am m aru s sp . tre n d to w ard s de cr ea se u nt il d ay 3 3; s ig ni fic an t de cre as e on d ay 6 1 cu m ul a tiv e n um b ers o n tr ap s da y 0-3 3 an d da y 61 m ac ro -i nv ert eb ra te s Pro cl a di us c h ore us si gn ifi ca nt in cr ea se to w ar ds s tu dy e nd rs c on cl ud e th at e ff ec ts a t t re at m en t l ev el s 2 x 3, 2 x 6 a nd 2 x 1 6 µ g as /L c an b e cl as si fi ed a s C la ss 2 : s li gh t e ff ec ts , s ho rt -t er m a nd /o r qu an ti ta ti ve ly r es tr ic te d re sp on se o f ew s en si ti ve e nd po in ts a nd o nl y ob se rv ed a t i nd iv id ua l s am pl in gs ; e ff ec ts a t t re at m en t l ev el 2 x 4 1 µ g as /L a s C la ss 3 : c le ar r es po ns e of s en si ti ve e nd po in ts a t s om e nt s am pl in g da te s, to ta l re co ve ry w it hi n 8 w ee ks ; ef fe ct a t t re at m en t l ev el 2 x 1 09 µ g as /L a s C la ss 5 : c le ar r es po ns e of s en si ti ve e nd po in ts , t ot al r ec ov er y lo ng er th an 8 er l as t a pp li ca ti on .

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R IV M L et te r re po rt 6 01 71 60 07 o f th e sc ie n ti fi c re li ab il it y of t h e fi el d s tu d y a su it ab le ( se m i) fi el d st ud y e te st s ys te m r ep re se nt a r ea li st ic f re sh w at er c om m un it y? Y es . sc ri pt io n of th e ex pe ri m en ta l s et -u p ad eq ua te a nd u na m bi gu ou s? Y es . po su re r eg im e ad eq ua te ly d es cr ib ed ? Y es . O ve ra ll m ea n m ea su re d co nc en tr at io ns a ft er a pp li ca ti on a re in g oo d ag re em en t w it h ca lc ul at ed n om in al c on ce nt ra ti on s. T he re id en ce o f ac cu m ul at io n of th e co m po un d in th e w at er c ol um n be tw ee n ap pl ic at io ns a nd c al cu la te d no m in al c on ce nt ra ti on s ca n be u se d to e xp re ss th e en dp oi nt s. in ve st ig at ed e nd po in ts s en si ti ve a nd in a cc or da nc e w it h th e w or ki ng m ec ha ni sm o f th e co m po un d? Y es . A lg ae a nd c ru st ac ea ns a re m os t s en si ti ve in la bo ra to ry s tu di es , ta ti ve s of th es e gr ou ps a re p re se nt in th e m es oc os m s an d sh ow e ff ec ts . si bl e to e va lu at e th e ob se rv ed e ff ec ts s ta ti st ic al ly ? Y es . F ul l s ta ti st ic al a na ly se s ar e pr es en te d, in cl ud in g m ul ti -v ar ia te s ta ti st ic s r es ul t i n an o ve ra ll a ss es sm en t o f th e st ud y re li ab il it y. T he s tu dy is c on si de re d to b e re li ab le ( R i 1 ). o f th e en d p oi n t to b e u se d f or s ta n d ar d s et ti n g n Sc en ed es m us s p. o bs er ve d at 2 x 3 µ g as /L i s co ns id er ed n ot to b e re la te d to th e te st s ub st an ce , b ec au se it w as n ot o bs er ve d at th e tw o ne xt h ig he r tr ea tm en t l ev el s. T he th e ro ti fe r F il in ia lo ng is et a is o bs er ve d in a ll t re at m en ts . H ow ev er , p op ul at io n de ns it y of th is s pe ci es w as a lr ea dy d ec li ni ng a t t he ti m e of a pp li ca ti on , a nd th e ob se rv ed f ac t a d el ay ed d ec li ne , m os t p ro ba bl y du e to r ed uc ed p re da ti on . I n th e co nt ro l, to ta l n um be rs o f F . l on gi se ta o n da y 18 w er e 4, 4 a nd 0 a nd it w as a bs en t as f ro m d ay 2 5. as /L , n um be rs w er e 7 an d 46 o n da y 18 , a nd 4 a nd 2 o n da y 25 . A lt ho ug h si gn if ic an t, th e ef fe ct o n da y 25 is n ot c on si de re d cr uc ia l fo r cl as si fi ca ti on o f ef fe ct s. A t 2 x 6 im il ar r ea so ni ng a pp li es . T he d ec re as e on K er at el la q ua dr at a at 2 x 6 µ g as /L is c on si de re d no t t o be r el at ed to th e te st s ub st an ce , b ec au se a t t he s am e sa m pl in g da te a n o bs er ve d at 2 x 1 6 µ g as /L a nd n o ef fe ct s w er e se en a t 2 x 4 1 an d 2 x 10 9 µ g as /L . T he u ni de nt if ie d al ga e sp ec ie s sh ow s an e ff ec t a t 2 x 6 µ g as /L a nd h ig he r, th e er ve d at 2 x 4 1 an d 2 x 10 9 µ g as /L is m er el y a de la ye d de cl in e. C on si de ri ng th e ex te nt a nd d ur at io n of e ff ec ts a t t he r es pe ct iv e tr ea tm en ts , t re at m en t l ev el 2 x 6 µ g as /L d as th e N O E C . S in ce th er e is n o ev id en ce o f ac cu m ul at io n of r es id ue s, th e N O E C c an b e se t t o 6 µ g as /L . B ec au se d od in e co nc en tr at io ns s ho w a r el at iv el y fa st d ec li ne T50 0 .8 3 da ys ), th e st ud y do es n ot a ll ow f or t he a ss es sm en t o f ef fe ct s du e to c hr on ic e xp os ur e, it c an , h ow ev er , b e co ns id er ed f or th e de ri va ti on o f th e M A C .

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te r re po rt 6 01 71 60 07 29

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4. 1. T ox ic it y of d od in e to s ed im en t or ga n is m s. S pe ci es S ed im en t A T es t P ur ity pH o. m . C la y T E xp . C rit er io n T es t R es ul t R es ul t V al id ity N ot es R ef er en ce pr op er tie s ty pe co m po un d tim e en dp o in t te st w at er st d. s ed im en t (a ge , s ex ) [% ] [% ] [% ] [° C ] [m g/ L] [m g/ kg dw ] us r ip ar iu s la rv ae ,2 -3 d O E C D S do di n e 96 .2 2. 72 20 28 d N O E C em er ge nc e ! 3 .2 3 1, 2, 3 E C , 2 00 6 (D es m ar es -K oo pm an s, 2 00 2) N O E C de ve lo pm en t ! 3 .2 3 1, 2, 3 at er s pi ke d dp o in t b as ed o n n om in al in iti a l i n w at er p ha se , a ct ua l i n iti al 7 2-82 % a fte r 20 m in . E C D a rt ifi ci al s o il, 5 % p ea t ( 1. 6% O C ) w at er :s ed im en t 4 :1

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Appendix 6. References used in the appendices

EC. 2006. Dodine, Draft Assessment Report. Rapporteur Member State: Portugal.

Foekema EM, Lewis WE, Hoornsman G, Van het Groenewoud H, Van der Vlies EM. 2007. Determination of the biological effects and fate of Dodine 400CS in outdoor ponds. Den Helder, The Netherlands: IMARES North. Report no. C111/07. 88 pp. Data provided by Agriphar S.A.

Frear DEH, Boyd, JE. 1967. Use of Daphnia magna for the microbioassay of pesticides. I. Development of standardized techniques for rearing Daphnia and preparation of dosage-mortality curves for pesticides. J Econ Entomol 60: 1228-1236.

Hourdakis A, Machera K, Anagnostopoulos E. 1995. Dodine in contaminated wastewater biological treatment plant. Determination and toxicity in aquatic organisms. Fresenius Environ Bull 4: 679-84. Mayer FL Jr, Ellersieck MR. 1986. Manual of Acute Toxicity: Interpretation and Data Base for 410

Chemicals and 66 Species of Freshwater Animals. Washington DC, USA: US Dep Interior Fish Wildl Serv. 505 pp.

Migchielsen MHJ. 2007. 96-hour acute study in carp with Dodine 400 g/l SC in a water sediment system (static). Den Bosch, The Netherlands: NOTOX. Report no. 485964. 38 pp. Data provided by Agriphar S.A.

Migchielsen MHJ. 2005. 96-hour acute study in carp with dodine (semi-static). Den Bosch, The Netherlands: NOTOX. Report no. 431077. 42 pp. Data provided by Agriphar S.A.

Nishiuchi Y, Yoshida K. 1972. Toxicities of pesticides to some fresh water snails Bull Agric Chem Insp Stn 12: 86-92.

Tooby TE, Hursey PA, Alabaster JS. 1975. The acute toxicity of 102 pesticides and miscellaneous substances to fish. Chem Ind 21: 523-526.

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RIVM

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