Registration Dossier

Administrative data

Hazard for aquatic organisms

Freshwater

Hazard assessment conclusion:
PNEC aqua (freshwater)
PNEC value:
0.19 µg/L
Assessment factor:
2
Extrapolation method:
sensitivity distribution

Marine water

Hazard assessment conclusion:
PNEC aqua (marine water)
PNEC value:
1.14 µg/L
Assessment factor:
2
Extrapolation method:
sensitivity distribution

STP

Hazard assessment conclusion:
PNEC STP
PNEC value:
20 µg/L
Assessment factor:
10
Extrapolation method:
assessment factor

Sediment (freshwater)

Hazard assessment conclusion:
PNEC sediment (freshwater)
PNEC value:
1.8 mg/kg sediment dw
Assessment factor:
1
Extrapolation method:
equilibrium partitioning method

Sediment (marine water)

Hazard assessment conclusion:
PNEC sediment (marine water)
PNEC value:
0.64 mg/kg sediment dw
Assessment factor:
1
Extrapolation method:
equilibrium partitioning method

Hazard for air

Air

Hazard assessment conclusion:
no hazard identified

Hazard for terrestrial organisms

Soil

Hazard assessment conclusion:
PNEC soil
PNEC value:
0.9 mg/kg soil dw
Extrapolation method:
sensitivity distribution

Hazard for predators

Secondary poisoning

Hazard assessment conclusion:
PNEC oral
PNEC value:
0.16 mg/kg food
Assessment factor:
10

Additional information

A basic assumption made in this hazard assessment and throughout the CSRs on cadmium and cadmium compounds, (in accordance to the same assumption made in the EU RA process), is that the causative factor for ecotoxicity of these substances is the Cd++ion. As a consequence, for the setting of PNEC's for these substances, the generic PNEC as derived for the Cd++ ion is used, and is always referring to the Cd ion concentration.

However, Cd-substances can differ significantly in their solubility, i.e. their capacity to release cadmium ions into (environmental) solution. That effect is checked eventually in the transformation/dissolution tests and may result in different environmental hazard and, consequently, different classification for aquatic effect.

The detailed deriviation of the PNEC's for the Cd-ion for the several environmental compartments can be found back in CSR for e.g. Cd metal (November 2010). Hereunder, a brief summary of the derivation of the different PNEC values is given:

In the EU RA, it was concluded that the conditions for using a statistical extrapolation method to derive the PNEC for Cd in freshwater were met. Accordingly, this approach is also used for the present analysis. All chronic data mentioned in table below are used in a species sensitivity distribution (SSD), and the PNEC is derived based on the HC5 concentration.

The HC5 calculated out of this SSD is 0.38 µg Cd/l. according to the EU risk assessment, an AF of 2 was used. This leads to a PNEC of 0.19 µg Cd/L.

organism

medium

H

endpoint

NOEC (µg/L)

reference

Salmo gairdneri

aerated well water; T 10; O27.5; pH 8-8.6

375-390

mortality

12

Lowe-Jinde and Niimi, 1984

Salmo gairdneri

no geometric mean calculation: different test medium

synthetic water (ISO 1977); T 25; pH 8.3

100

median survival time

4

 

(no geomean)

Dave et al., 1981

Oncorhynchus kisutch

sand filtered Lake Superior Water; continuous flow; DO 10.3; Al 41; Ac 3; pH 7.6

45

biomass

1.3

Eaton et al., 1978

Salvelinus fontinalis

sand filtered Lake Superior Water; continuous flow; DO 10.3; Al 41; Ac 3; pH 7.6

45

biomass

1.1

 

Eaton et al., 1978

Salvelinus fontinalisgeometric mean calculation: same test medium, same endpoint (biomass)

sterilised Lake Superior water; pH 7-8; Al 38-46; Ac 1-10; DO 4-12; T 9-15

42-47

total weight of young /female of the 2nd generation

0.9 geomean =1.0

Benoit et al, 1976

Salvelinus fontinalis

reconstituted soft water: T 14-; DO 9.3-11.4 mg/L; Cd(BG) <0.2 µg/L; pH 6.3-7.6; H 20

20

survival

8

Jop et al., 1995

Salvelinus fontinalisgeometric mean calculation: similar test medium, same endpoint (survival)

river water: T 14-; DO 8.7-12.2 mg/L; Cd(BG) <4 µg/L; pH 6.6-7.4; H 16-28

16-28

survival

62 geomean =22

Jop et al., 1995

Salmo salar

municipal water charcoal filtered and UV sterilised; BC 0.13 µg Cd/L; pH 6.5-7.3; T 5-10; DO 11.1-12.5; Al 14-17

19-28

total biomass

0.47

 

Rombough and Garside, 1982

Catostomus commersoni

Esox lucius

Salvelinus namaycush

Salmo trutta (late eyed eggs)

sand filtered Lake Superior Water; continuous flow; DO 10.3; Al 41; Ac 3; pH 7.6

45

standing crop (biomass)

biomass

4.2

4.2

4.4

1.1

Eaton et al., 1978

Jordanella floridae

untreatedwater; T 25; DO 8.3; Al 42; Ac 2.4; pH 7.1-7.8

44

reproduction

4.1

Spehar, 1976

Brachydanio rerio

synthetic water (changed ISO); T 24; DO >80%; pH 7.2

100

reproduction

1

Bresch., 1982

Oryzias latipes

no geometric mean calculation: different test medium

tap water; continuous flow; T 20

200

100

mortality and

abn. behaviour

6

3

 

 

Canton and Slooff, 1982

Xenopus laevis

tap water; continuous flow; T 20

170

inhibition of larvae development

9

Canton and Slooff, 1982

Pimephaless promelasgeometric mean calculation: same test medium, same endpoint (reproduction)

pond water diluted with carbon filtered demineralised tap water; DO 6.5-6.6; pH 7.6-7.7; Al 145-161; Ac 8-12; T 16-27

201-204

reproduction (pond fish)

reproduction (laboratory fry)

13

 

14geomean =13.5

Pickering and Gast, 1972

Daphnia magna

 

50 µm filtered and sterilisedwater; pH 8.1; T 20; H 224

224

intrinsic rate of natural increase

3.2

Van Leeuwen et al., 1985

Daphnia magna

no geometric mean calculation: different endpoints

NPR synthetic water; pH 8.4; T 20

200

mortality

1

 

 

Van Leeuwen et al., 1985

Daphnia magna

different medium

synthetic water; T 25; pH 8; DO 69%

11

reproduction

0.6

 

 

Kühn et al., 1989

Daphnia magna

Synthetic water; Al 65; T 25

90

reproduction

2

Winner, 1988

D. magna:

geometric mean calculation: similar medium, same endpoint)

well water: T 20±2°C; DO 4.9-7.9; Cd(BG) 0.08; pH 7.9

103

reproduction

0.16geomean =0.6

Chapman et al., 1980

 

well water: T 20±2°C; DO 4.9-7.9; Cd(BG) 0.08; pH 8.2

209

reproduction

0.21

Chapman et al., 1980t

Daphnia magna

 

unchlorinated, carbon filtered well water, aerated to saturation; Al 230; pH 8; DO >5; T 23; Cd < 0.01 µg Cd/L

240

reproductive impairment

2.5

Elnabarawy et al., 1986

Daphnia magna

no geometric mean calculation: different medium

aerated well water; DO >70%; pH 8; T 22; Al 250

300

reproduction

0.8

Knowles and McKee, 1987

Daphnia magna

culture medium; pH8.4; T 20

150

biomass production/female

2.5

Bodar et al., 1988a

Daphnia magna

no geometric mean calculation: different medium

20 µm cloth filteredwater; pH 7.7; Al 42.3; DO 9; T 18

45.3

weight/animal

 

1

Biesinger and Christensen, 1972

Daphnia pulex

 

Whatman N° 1 filteredwater; pH 7.7; Al 42.4; Cd < 1µg L-1

65

longevity

1

Bertram and Hart, 1979

Daphnia pulex

unchlorinated, carbon filtered well water, aerated to saturation; Al 230; pH 8; DO >5; T 23; Cd < 0.01 µg Cd/L

240

reproductive impairment

7.5

Elnabarawy et al., 1986

Aplexa hypnorum: immature

Lake Superiorwater; DO 7.5; T 24

 

growth

4.41

Holcombe et al., 1984

Physa integra

untreated Lake Superior water; pH 7.1-7.7; T 15; DO 10-11; Al 40-44; Ac 1.9-3

44-48

mortality

8.3

Spehar et al., 1978

Daphnia galeata mendotae

10 µm filtered Lake Michigan water; T 18.5

120

number of individuals

2

Marshall, 1978

Ceriodaphnia reticulata

unfiltered river water; static; Ac 2-4.2; Al 41-65; pH 7.2-7.8

55-79

reproduction

3.4

Spehar and Carlson, 1984

Ceriodaphnia reticulata

no geometric mean calculation: different medium

unchlorinated, carbon filtered well water, aerated to saturation; Al 230; pH 8; DO >5; T 23; Cd < 0.01 µg/L

240

reproductive impairment

0.25

Elnabarawy et al., 1986

Ceriodaphnia dubia

 no geometric mean calculation: different medium, different endpoint

Synthetic water; Al 65; T 25

90

mortality

1.5

Winner, 1988

Ceriodaphnia dubia

reconstituted soft water: T 14-; DO 9.3-11.4 mg/L; Cd(BG) <0.2 µg/L; pH 6.3-7.6; H 20

20

reproduction

10

Jop et al., 1995

Ceriodaphnia dubiageometric mean calculation: similar medium, same endpoint (reproduction)

river water: T 14-; DO 8.7-12.2 mg/L; Cd(BG) <4 µg/L; pH 6.6-7.4; H 16-28

16-28

reproduction

11geomean =10.5

Jop et al., 1995

Hyalella azteca

well water: T 23; pH 7.8

280

Survival

0.51

Ingersoll and Kemble, 2000

Chironomus tentans

well water: T 23; pH 7.8

280

weight

5.8

Ingersoll and Kemble, 2000

Selenastrum capricornutum

modified ISO 6341 medium; 0.2 µm filtered; T 20.3-25.6; pH 7.7-10.4

49

cell number

2.4

LISEC, 1998a

Coelastrum proboscideum

AM; T 31; pH 5.3;

32

biomass

6.3

Müller and Payer 1979

Asterionella formosa

AM; pH 8

121

growth rate

0.85

Conway and Williams 1979

Chlamydomonas reinhardii

AM; pH 6.7; T 20

42

steady state cell number

7.5

Lawrence et al. 1989

Scenedesmus quadricauda

AM; pH 7

 

biomass (OD)

31

Bringmann and Kühn, 1980

Lemna paucicostata

no geometric mean calculation: different medium

AM; T 25

pH>6

pH 5.1

pH 5.1

 

120

120

700

number of fronds

 

5

10

10

Nasu and Kugimoto, 1981

T = temperature (°C); H = hardness (as mg CaCO3/L); DO = dissolved oxygen (mg O2/L); Al = alkalinity (mg CaCO3/L); Ac = acidity (mg CaCO3/L); AM, artificial medium.

 

The marine cadmium database largely fulfils the species and taxonomic requirements for input chronic toxicity data as explained in the RIP R. 10 guidance (at least 10 species NOECs and 8 taxonomic groups). Indeed, 48 species mean NOECs based on 62 NOEC values, coming from 39 families and from 9 taxonomic groups covering three trophic levels were found to fulfil the relevancy and reliability requirements as explained by Klimisch et al. 1997. The marine Cd database includes 1 micro- and 1 macro-algae species, 4 annelid species, 11 crustacean species, 7 echinoderm species, 13 mollusc species, 3 nematod species, 2 cnidarian species, 1 ascidian species and 6 fish species.

Following endpoints were selected for the use in SSD for the derivation of marine PNEC for Cd.

 

Cadmium aquatic marine database (chronic toxicity data)

Taxonomic group

Species name

Family

Geomean NOECaddvalue

(µg Cddiss/L)

Reliability

Micro-Algae (1)

-         Chaetoceros compressum

Chaetocerotacae

18.3

2

Macro-Algae (1)

-         Ulva pertusa

Ulvaceae

63

2

Annelids

(4)

 Capitella capitata

Ctenodrilus serratus

Neanthes arenaceadontata

Ophryotrocha diadema

Capitellidae

Ctenodrilidae

Nereididae

Dorvilleidae

126.5

320.9

126.5

100

2

2

2

2

Cnidarians

(2)

 Eirene viridula

Campanularia flexuosa

Eirenidae

Campanulariidae

100

87.7

2

2

Crustaceans

(11)

Artemia franciscana

Artemia parthenogenetica

Artemia persimilis

Artemia salina

Balanus Amphitrite

Elminius modestus

Mysidopsis bahia

Paragraspus quadridentatus

Penaeus monodon

Tigriopus brevicornis

Moina monogolica

Artemiidae

Artemiidae

Artemiidae

Artemiidae

Balanidae

Archaeobalanidae

Mysidae

Grapsidae

Penaeidae

Harpacticidae

Moiniidae

39.3

106.1

99.5

56.7

5

316

2.2

105

33.3

36.7

1.8

2

2

2

2

2

2

2

2

2

2

1

Echinoderms (7)

Arbacia lixula

Asterias amurensis

Echinometra mathaei

Lytechinus pictus

Paracentrotus lividus

Sphaerechinus granularis

Strongylocentrotus droebachiensis

Arbaciidae

Asteriidae

Echinometridae

Toxopneustidae

Echinidae

Toxopneustidae

Strongylocentrotidae

357

10000

10

4.2

35.5

623

12.5

2

2

2

2

2

2

2

Molluscs

(13)

Crassostrea cucullata

Crassostrea gigas

Crassostrea margaritacea

Haliotis rubra

Ilyanassa obsolete

Isognomon californicum

Meretrix lusoria

Mya arenaria

Mytilus edulis

Mytilus galloprovincialis

Perna viridis

Ruditapes decussatus

Tresus nuttalli

Ostreidae

Ostreidae

Ostreidae

Haliotidae

Nassariidae

Isognomonidae

Veneridae

Myidae

Mytilidae

Mytilidae

Mytilidae

Veneridae

Mactridae

7.1

13

12.6

520

112.4

0.3

33.3

50

480

119.8

345.8

265

42

2

2

2

2

2

2

2

2

2

2 and 1

2 and 1

2

2

Nematods

(3)

Monhystera disjuncta

Monhysteramicrophthalma

Pellioditis marina

Monhysteridae

Monhysteridae

Rhabditidae

3333

1000

25000

2

2

2

Ascidians (1)

Ciona intestinalis

Ascidiaceae

430.5

1 and 2

Fish

(6)

Atherinops affinis

Epinephelus coioides

Lates calcarifer

Menidia menidia

Mugil cephalus

Pseudopleuronectes americanus

Atherinidae

Serranidae

Centropomidae

Atherinidae

Mugilidae

Pleuronectidae

10

33.3

794

259.8

20

283.7

1

2

2

2

2

2

TOTAL:

10 Tax. gps

 

48 species

 

39 families

 

48 species mean NOECs

 

The 5thpercentile value of the SSD (the HC5), set at 50% confidence value, using the lognormal distribution (ETX 2.0) function, results in a value of 2.28 µg Cd/L.This value is taken forward for the PNEC derivation. Using an AF of 2 leads to a PNEC of 1.14 µg Cd/L.

The assessment of the freshwaterPNECsediment for cadmium identified only two long-term ecotoxicity studies from the scientific literature. However, both the “Added” EqP (using partitioning coefficients and a robust aquatic toxicity database from the Cd RAR) and AF (using the lowest NOEC from a field colonization study) approaches produced consistent derivations for the freshwater benthic compartment. The resulting value is considered protective for EU freshwater ecosystems: freshwater PNECadd, sedimentof 1.80 mg/kg d. w. (equivalent to 0.40 mg/kg w. w.). It is emphasized that this is an added PNEC, i. e. natural background needs to be taken into account when characterising the risk from monitored data.

The assessment of the marine PNECsediment for cadmium identified only two long-term ecotoxicity studies from the scientific literature. However, an “Added” EqP (using partitioning coefficients and a robust aquatic toxicity database) approach provided a reliable derivation for the marine benthic compartment. The resulting value is considered protective for EU marine ecosystems: marine PNECsediment, addedof 0.64 mg/kg d. w. (equivalent to 0.14 mg/kg w. w.). It is emphasised that this is an added PNEC, i. e. natural Bg needs to be taken into account when characterising the risk from monitored data.

The PNEC soil is set based on the lowest observed HC5 derived by statistical extrapolation from the microflora data, i. e.2.3 µg Cd/kg d. w. In the Cd RA, an AF 1 or 2 was considered. The current analysis rather suggests using an AF 1 on the HC5 to derive the PNEC. It is noted that the PNECsoilbased on secondary poisoning is 0.9 µg Cd/g dwwhich is below the proposed value. The latter value is therefore proposed and used for PNECsoil in this assessment. This is in accordance with the approach followed in the Cd RA (ECB 2007).

The EU risk assessment discussed available data for Cd toxicity to micro-organisms.There were 2 high quality studies available, both performed according to OECD protocol (OECD 209) for testing effect on sludge respiration, showing similar NOEC values when Cd was expressed as the dissolved fraction. The LOEC values observed on the dissolved Cd fraction were high as compared to LOEC values for aquatic species. This suggested low sensitivity of bacteria to Cd was confirmed by results on bacterial cultures of Pseudomonas putida, Zoogloea ramigera and Escherichia coli, which also showed LOECs in the 1mg/l range (RA Cd/Cd0 table 3.2.32.) / The PNEC for STP was derived in the EU risk assessment by applying an assessment factor of 10 on the lowest observed NOEC (200 µg Cd/l) which yielded a PNECSTPof 20 µg Cd/l. The same PNEC is used for the present exercise.

The EU risk assessment on cadmium identified 4 good quality feeding studies on birds and 5 studies on mammals. According to the RA, the PNEC oral secondary poisoning is derived from the lowest NOEC on Mallard ducks (1.6 mg Cd/kg diet; White et al 1978).The PNEC oral can be calculated applying an assessment factor of 10 on this long-term feeding study,i. e. 0.16mg Cd/kg diet.

Conclusion on classification

CdZnS is specifically exempted from classification under DSD 67/548/EEC. The reason for this non-classification is the insolubility of the substance.

For CLP, data were generated to check this existing classification against the CLP rules. To this end, transformation/dissolution (T/D) tests were performed on the CdZnS, and reference was made towards newly generated T/D and ecotoxicity data obtained on another sparingly soluble Cd-compound, i.e. CdTe. By comparing T/D data between CdZnS and CdTe, and referring to aquatic effect levels observed for CdTe, the aquatic hazard of the CdZnS could be assessed as follows:

Acute aquatic classification

Standard ecotoxicity testing on CdTe revealed a lowest EC50 value of 1.14 mg CdTe/L observed for Daphnia magna (resulting in no acute classification of CdTe). T/D testing on CdTe demonstrated the sparingly soluble character of this substance (3.2% of Cd solubilised after 7days in pH 6 medium, which is maximising Cd-solubilisation in the relevant pH range 6 -8.5). The solubility of Cd from CdZnS was however even much lower than the solubility of Cd in CdTe: after 7 days only 0.06 % of the Cd was solubilised from CdZnS at pH 6. Considering a) the lowest EC50 value of CdTe of 1.14mg/l, and b) the 50x lower solubility of Cd in CdZnS, as compared to CdTe, it is concluded that also CdZnS is not classified for acute aquatic effect.

Chronic aquatic classification

Standard ecotoxicity testing on CdTe revealed a lowest NOEC value of 0.2 mg CdTe/L observed for Daphnia magna,resulting in classification as

"chronic3" of CdTe - in this respect it is noted that Cadmium compounds are considered as being "equivalent to rapidly degradable" based on their rapid removal from the water column, see section 4.6.). T/D testing on CdTe demonstrated the sparingly soluble character of this substance (3.8% of Cd solubilised after 28 days in pH 6 medium, which is maximising Cd-solubilisation in the relevant pH range 6 -8.5). From T/D tests, it was shown that the solubility of Cd from CdZnS was however even much lower than the solubility of Cd in CdTe: after 28 days only 0.23 % of the Cd was solubilised from CdZnS at pH 6. Considering a) the lowest NOEC value of CdTe of 0.2mg/l, and b) the fact that >16 x less Cd solubilizes from the CdZnS as compared to CdTe (in other words, 16x more CdZnS loading (~=0.2 x 16 ~= 3.3 mg/l - would be needed to reach the lowest NOEC value), it is concluded that CdZnS is not classified for chronic aquatic effect.

This analysis confirms the non-classification of CdZnS for aquatic effects under CLP.