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TOXICITY TO FISH

Short-term toxicity to fish

Most of the tests were conducted in the end of the 1980s. Since the concentrations were not analytically verified, the reliability of the results is limited. Hence, most of the tests were considered to be valid with restrictions.

The available data reveal an increasing toxicity with raising chain length. The only exception is stearylamine (C18) where only a summary test report is available which indicates a slight drop of toxicity.

The lowest, well documented 96h-LC50 reported for fish is0.11mg/l (nominal) for oleylamine (C18). In this study the short-term toxicity toPimephales promelaswas examined by Akzo Nobel (1995b) in the presence and absence of humic acid using a static water test system according to the OECD Guideline 203 (1984). Fish were exposed at about 21°C for 96 h in reconstituted freshwater (pH 7.7-8.3, oxygen content 9.0-8.3 mg/l). Since the test material was insoluble in water, stock dispersions (approx. 0.1 g/l) were freshly prepared by ultrasonic treatment before each test was started. During each dosing step, the stock solutions were stirred to prevent any inhomogeneity of the stock solutions. At the start of the tests, all test solutions were clear and homogeneous. Five test concentrations in the nominal concentration range between 0.05 and 0.49 mg/l were employed. As test substance Armeen OD with a purity of 94% was used. During all tests the test substance content decreased strongly showing a rather wide spread of the recovery rates. The test protocol explained this by the following factors:

-        Adsorption onto the walls of test vessels or – especially - on other surfaces (such like the surfaces of the test animals).

-        Reaction with organic materials (humic acid).

-        Humic acid might act as an emulsifier and hence is likely to influence the extraction process during the chemical analysis (HPLC).

-        An incomplete water removal during the analytical procedure causes disturbances of the chemical analysis.

However, based on nominal concentrations a 96 h-LC50 of 0.11 mg/l was derived from this study. When taking the results of the chemical analysis into account by using the mean recovery rate (about 51%) as the actual test concentration throughout the test, the 96 h-LC50 can be calculated as0.06 mg/l.

From this study it can also be concluded that humic acid clearly has an effect on bioavailability of oleylamine for fish. . As compared to the test results without humic acid, the addition of 10 mg/l humic acid resulted in an approximate 14-fold decrease the calculated LC50 based on nominal concentrations and about 20-fold based on analytically determined concentrations.

Additional acute fish tests (see Table 7.1.1.1-1) in natural river water (River Boehme) with a DOCof 6.3 mg/l and suspended matter of 16.7 mg/L (APAG, 2006a & b) were carried out. In river water the Primary alkyl amines which are cationic surfactants at pH relevant in the environment, are either dissolved in water or sorbed to dissolved and particulate matter. No sorption to glass ware occurs under these conditions which were confirmed by measurements. This ensures reliable as well as reproducible results. Ecotoxicity is mitigated due to sorption but this kind of tests at least ensures that all added test substance is present in the test system and available for the exposure of the organism in dissolved or sorbed form. Mitigation can be taken into account by a factor of 10 applied to the ecotoxicty result. For risk assessment purposes these ecotoxicity results can be compared with the total or bulk concentration in surface water.

 

 Long-term toxicity to fish

Long-term test results for fish are not available.

Testing of vertebrates should be avoided due to animal welfare reasons. Comparing the available data on acute toxicity for fish and invertebrates indicates that additional chronic tests using fish might not contribute additional information relevant for risk assessment for aquatic ecosystems.

TOXICITY TO AQUATIC INVERTEBRATES

Short-term toxicity to aquatic invertebrates

Regarding the acute toxicity data towardsDaphnia magna(table 3.2.2 and 3.2.8) a dependence on the chain length of primary fatty amines cannot be stated.

The lowest short-term result forDaphnia magnawas found for oleylamine (Akzo Nobel, 1995a). This study was conducted according to the OECD Guideline 202 (1984) in the presence or absence of humic acid with Armeen OD (purity 94%) as test substance. Daphnia were exposed to five test concentrations in the nominal concentration range between 0.006 and0.09mg/l in a static system for 48 h at a temperature of 19.1-19.7°C and a pH of 8.0-8.2.For the preparation of the stock dispersions (0.1 g/l) ultrasonic treatment was used and during each dosing step the stock solutions were stirred. At the start of the tests, all test solutions were clear and homogeneous. Again, during all tests the test substance content (measured at0 hand 48 h via HPLC) decreased strongly showing a wide spread of the recovery rates(test without humic acid: recovery 48-118%, mean value 81%; test with 10 mg/l humic acid: recovery 23-98%, mean value 56%; test with 20 mg/l humic acid: recovery 0-23%, mean value 7.4%).Due to this, no calculations based on measured concentrations were performed.

Based on nominal concentrations the 48h-EC50 values were calculated as 0.011 mg/l (without humic acid),0.43mg/l (10 mg/l humic acid) and0.56mg/l (20 mg/l humic acid). Compared to the test results without humic acid, the addition of 10 mg/l humic acid resulted in an approximate 40-fold higher EC50.

Additionally, studies using different species of invertebrates describing effects of pH, temperature and stage of insect development are reported for different primary fatty amines (table 7.1.1.2.1-1 and 7.1.1.2.1-3). An enhancement of toxicity of octylamine and decylamine on larval mortality ofElminius modestusat higher pH and lower temperature is described by Christie & Crisp (1966). Larvae ofCulex pipiensquinquefasciatus are more sensitive to primary fatty amines than pupae (Mulla 1967 a, b) andAedes aegypti(Cline 1972). Larvae and pupae ofAnophelessp. andAedessp. are of similar sensivity to oleylamine and coco alkyl amines (Mulla 1970).

Additional acute daphnia tests (see Table 7.1.1.2.1-1) in natural river water (River Boehme) with aDOCof 6.3 mg/l and suspended matter of 16.7 mg/L (APAG, 2006a & b) were carried out. In river water the Primary alkyl amines which are cationic surfactants at pH relevant in the environment, are either dissolved in water or sorbed to dissolved and particulate matter. No sorption to glass ware occurs under these conditions which were confirmed by measurements. This ensures reliable as well as reproducible results. Ecotoxicity is mitigated due to sorption but this kind of tests at least ensures that all added test substance is present in the test system and available for the exposure of the organism in dissolved or sorbed form. Mitigation can be taken into account by a factor of 10 applied to the ecotoxicty result. For risk assessment purposes these ecotoxicity results can be compared with the total or bulk concentration in surface water.

 

  Long-term toxicity to aquatic invertebrates

The chronic toxicity of coco alkyl amine (Armeen CD), tallow alkyl amine (Armeen TD) and oleylamine (Armeen OD) toDaphnia magnawas studied under comparable conditions by Noack (2002 a-c) using a semi-static test system according to the OECD Guideline 211 (Sept. 1998).Five test concentrations in the nominal concentration range between 0.013 and 0.5 mg/l were applied by diluting a stock dispersion (10 mg/l). Testsolutions were renewed three times per week. As dilution water natural river water of agricultural background (middle reach of the river“Böhme”, lowerSaxony) was used. This river has been chosen due to its properties representing typical conditions of a German medium sized river. The concentration of suspended matter measured in the river water was in a range of 11.2 to 32.8 mg/l (mean value 18.4 mg/l) for coco alkyl amine and tallow alkyl amine and in a range of 10.0 to 26.2 mg/l (mean value 17.4 mg/l) for oleylamine. The content of humic acid amounted to 11.8 mg/l in all tests. A pre-treatment of the test vessels was not performed.

The concentrations of the active ingredient were determined in the old and new test media once per week in the stock solution, the highest test concentration of 0.5 mg/l and the control via GC-analysis. All samples were taken and analyzed without filtration to include test item adsorbed on suspended matter. In all tests the test item concentration decreased at the end of the test and recovery rates varied strongly (see table 3.2.6). According to the test protocol the most probable reason for the decrease or incomplete recovery during the test was seen in adsorption on particulate matter and humic acids. The variation in the recovery rates were explained by small differences in the concentration of suspended matter. The results were therefore based on nominal concentrations representing the total exposure concentration (dissolved and adsorbed on humic acid / suspended matter).

Tab. 7.1.1.2.2-1:Daphnia magna repro test with natural river water-analytically verified concentrations of the highest test item concentration (0.5 mg/l) [mg/l]

 

Coco alkyl amine

Tallow alkyl amine

Oleylamine

Sample
No.

new media
(0 hours)

old media
(3 days)

recovery

new media
(0 hours)

old media
(3 days)

recovery

new media
(0 hours)

old media
(3 days)

recovery

1

0.4

< LOQ

40%

0.2

< LOQ

20%

0.14

0.11

25%

2

0.2

< LOQ

20%

0.2

< LOQ

20%

0.22

< LOQ

22%

3

< LOQ

0.2

20%

0.3

0.2

50%

0.28

0.24

52%

4

< LOQ

< LOQ

0%

0.4

0.2

60%

0.24

0.23

47%

 

 

 

mean 20%

 

 

mean 37.5%

 

 

mean 36.5%

           < LOQ    below limit of quantification

 

Referring to nominal concentrations a 21d-NOECrepro of 0.013 mg/l was derived forcoco alkyl amine, tallow alkyl amine and oleylamine. When considering the validity of these studies, the following factors should be taken into account: 

-        No measures were taken to prevent the loss of test substance by adsorption onto surface of the test vessels. Therefore, a quantification of the fraction lost by adsorption onto the glass ware is not possible.

-        Only the highest test concentration was analytically verified showing highly variable recovery rates. At concentrations around the NOEC even lower recovery rates have to be expected. Due to this, the exposure concentrations maintained during the studies are highly uncertain.

TOXICITY TO ALGAE

Tab. 7.1.1.3-1 and 7.1.2.1-1 summarize the most relevant toxicity test results for aquatic algae.

The lowest effect values (nominal) for aquatic algae have been found for coco alkyl amine (96h-EBC50 = 0.0008 mg/l, 96-NOEC = 0.0002 mg/l), hydrogenated tallow alkyl amine (96h-EBC50 = 0.012 mg/l, 96-NOEC = 0.008 mg/l) and tallow alkyl amine (96h-EBC50 = 0.007 mg/l, 96-NOEC = 0.002 mg/l). These studies were conducted according to the OECD Guideline 201 (1984) withScenedesmus subspicatusas test organism by Berol Nobel (1991c-e):

For the preparation of the stock solutions solubilizer were used. The test vessels were exposed to the test substance overnight to allow pre-adsorption onto the surface of the glassware. At the start of the tests the glassware was rinsed with the test solution to be tested and then refilled with the fresh test solution. Samples for measurement of growth were taken every 24 hours and the absorbance was determined with a photometer at 665 nm. The cell densities of the control cultures at initiation and at termination were measured by direct counting. As no analytical measurements were performed, test results were based on nominal concentrations.

The actual cell concentration in the control after 72 hours is not given in the test reports but an estimation can be made by plotting the absorbance against cell number of the 0 and 96 h control values and assuming that the calibration was linear up to the maximum absorbance used. This estimation leads to conclusion that in the studies with coco alkyl amine and hydrogenated tallow alkyl amine the increase of cell concentration in the control was to low (well below factor 16). For this reason and due to the missing analytical data at very low effect concentration levels, the test results of Berol Nobel (1991c-e) are regarded as not suitable for effects assessment purposes.

Other EC50-values reported for primary fatty amines are in the nominal concentration range between0.04mg/l (oleylamine, tested in synthetic medium) and0.46mg/l (oleylamine, tested in natural river water).

For coco alkyl amine (Armeen CD), tallow alkyl amine (Armeen TD) and oleylamine (Armeen OD) test results are available, which were determined in natural, unfiltered river water (Noack 2002 d-f). Studies were conducted according to the OECD Guideline 201 (1984) in a static test system (temperature approx. 23°C, pH approx. 8) withDesmodesmus subspicatus(Scenedesmus subspicatus) as test organism. A pre-treatment of test vessels was not performed. Again, water of the river “Böhme” was used as dilution water (see section 7.1.1.2.2-1, long term toxicity). Exposure concentrations were analytically verified at 0 and 72 h in the highest tested concentration using GC/MS-analysis. Again, due to variations in the content of suspended matter and the adsorbing properties of the test substances, decreasing test concentrations associated with strongly varying recovery rates were observed(coco alkyl amine: 0-120%, mean 60%; tallow alkyl amine: 73-23%, mean 48%; oleylamine: 72-0%, mean 36%). Test results were therefore based on nominal concentrations. Referring to nominal concentrations for coco alkyl amine a 72h-ERC50 of0.16mg/l (72h-NOEC of 0.06 mg/l), for tallow alkyl amine a 72h-ERC50 of0.39mg/l (72h-NOEC of 0.125 mg/l) and for oleylamine a 72h-ERC50 of0.46mg/l (72h-NOEC of0.15mg/l) was determined indicating a slight decrease of toxicity with raising chain length.

TOXICITY TO AQUATIC MICROORGANISM

A number of tests on inhibition of respiration according to OECD Guideline 209 was conducted. An overview of the results is presented in table 3.2.7.

 

Table:Respiration tests according to OECD 209 [mg/l]

Substance

EC10

EC20

EC50

EC80

Remarks

Reference

Coco

5.5

7.5

14

25

Suspended with ultra-turrax

Hoechst AG (1989b)

 

2.7

14.2

75.3

direct addition of TS

Hoechst AG (1992a)

Tallow

7

12

32

90

 

Hoechst AG (1989c)

Hydrog. tallow

 

214

490

>1000

direct addition of TS

Hoechst AG (1993b)

Octadecenyl

 

62.7

222.5

790

direct addition of TS

Hoechst AG (1992b)

 

The results of the respiration tests suggest that the toxicity of hydrogenated tallow amine and octadecenylamine to sewage sludge is much lower than that of coco and tallow amine. Regarding the test results with other organisms, similar toxicity of the compounds is expected. It can be assumed that the different results may be caused by different bioavailability of the test substances. As discussed earlier, bioavailability of the test substances is largely dependent on the method of preparation of the test medium, although there is no real explanation for the differences of individual tests. For the PNEC derivation, the lowest effect value found with coco amine as test substance are used.