Amines, N-C12-18-alkyltrimethylenedi-, reaction products with chloroacetic acid, sodium salts

Adsorption / desorption

Link to relevant study record(s)

Reference

Endpoint:

adsorption / desorption: screening

Type of information:

read-across from supporting substance (structural analogue or surrogate)

Adequacy of study:

key study

Study period:

2017-02-20 to 2017-05-15

Reliability:

1 (reliable without restriction)

Rationale for reliability incl. deficiencies:

guideline study

Justification for type of information:

REPORTING FORMAT FOR THE ANALOGUE APPROACH
See for justification of read across chapter 13

Reason / purpose for cross-reference:

read-across source

Qualifier:

according to guideline

Guideline:

OECD Guideline 106 (Adsorption - Desorption Using a Batch Equilibrium Method)

Version / remarks:

Samples were centrifuged < 3000 g because glass vessels had to be used. Higher centrifugation forces could have been destructive to these vials.
For the adsorption isotherms, the use of a concentration range in the order of two magnitudes was not feasible. With regard to the limit of quantification, relativelyhigh test item concentrations were required when using a soil solution ratio of 1 g soil to 100 mL of aqueous phase. The non-linearity of the adsorption is already observed at the concentration range used, as can be seen by the 1/n values.
Limited stability of the test item in 0.01 M CaCl2 solution was observed, which is presumably related to the chemical structure of the test item and the formation of metal complexes with Ca2+. Therefore, adaptions of the test system were necessary and demineralized water was used as aqueous medium.

These deviations are considered to have no impact on the quality and the integrity of the study.

Deviations:

yes

Remarks:

see above at "Version / remarks"

Qualifier:

according to guideline

Guideline:

other: Council Regulation (EC) No. 440/2008, Method C.18 (2008)

GLP compliance:

yes (incl. QA statement)

Type of method:

batch equilibrium method

Media:

soil

Radiolabelling:

no

Test temperature:

Nominal: 20 ± 2 °C

Analytical monitoring:

yes

Details on sampling:

Medium: CaCl2-solutionwas used during Tier 1. Deionised water was used to prepare the CaCl2 solution (0.01 M).
Deionised water was used during Tier 2 and Tier 3.

Soil / Solution ratio: 1:100

Agitation: By horizontal shaker. Frequency was adjusted to avoid sedimentation of soil particles during treatment.

Test temperature: 20 +/- 2 °C
 
Test Procedure:

Test vessels: Disposable glass bottles (120 mL)
Concentration for adsorption / desorption experiments: Tier 2: 7.00 mg/L; Tier 3: 3.00 mg/L, 16.5 mg/L, 23.5 mg/L, 30.0 mg/L

Stock solutions: Stock solutions of Sodium oleylamphopolycarboxyglycinate were prepared in HPLC water and stored at room temperature.


Preparation

Preparation of the Soil samples (conditioning):
The soils were weighed into the test vessels and an appropriate volume of 0.01 M CaCl2 solution or test medium was added. After agitation overnight (12 h minimum), the samples were used for adsorption experiments.

Preparation of the samples for adsorption experiments:
The soil samples were conditioned as described above. 0.1 volume-% of the stock solutions, related to the volume of the
aqueous phase in the soil suspensions was added in order to adjust the test concentrations. Afterwards, the samples were agitated.

Preparation of the samples for desorption experiments:
Test vessels from the adsorption experiments were used for this purpose. After completion of the adsorption experiments the test vessels were centrifuged, weighed and the supernatant was replaced by fresh test medium. Then the test vessels were agitated again to investigate the desorption behavior of the test item.

Preparation of samples for analysis:
The soil suspensions were centrifuged at 3000 rpm (2504 g) after agitation to separate the phases, followed by analysing the concentration of the main component of Sodium oleylamphopolycarboxyglycinate in aqueous phase by LC-MS/MS. For analysis of the soil, the aqueous phase was decanted and the soil was extracted. Extracts were also analysed by LC-MS/MS.

Replicates: All samples were prepared in duplicate.

Controls:
CaCl2 solution or test medium was conditioned as described above, followed by separation of the aqueous phase by centrifugation. Then the aqueous phase was fortified acc. to the concentrations used for the test item samples to verify the stability of the test item in the aqueous phase under test conditions. The samples were agitated as long as the test item sample with the longest agitation period.
Additional control replicates were prepared during Tier 1 without conditioning the CaCl2 solution prior to spiking. Samples without conditioning were prepared for comparison of the test item stability with and without soil-conditioning (e.g. different ionic environment and pH value).

Replicates: Duplicates

Blank:
Blank samples were prepared for all soils as described for the test item samples but without fortification with the test item. The samples were agitated as long as the samples with the longest agitation period.

Replicates: Duplicates (Tier 1), single (Tier 2 and Tier 3)

Sample Preparation:

Dilution medium: 2-Propanol / matrix-conditioned demineralized water (50:50)

Standards:
Stock solutions of 10 g/L of the test item in HPLC water were prepared and were diluted to calibration standards.
Tier 1: 8 calibration standards in the range of 50 to 1000 µg/L were prepared using methanol : HPLC water (50 : 50).
Tier 2 and Tier 3: 8 calibration standards in the range of 50 to 1000 µg/L were prepared using dilution medium.

Aqueous phase:
Samples were centrifuged at 3000 rpm (2504 g) for 5 min. An aliquot of each aqueous sample was stabilized by dilution with 2-propanol or methanol during Tier 1 (factor 2). Samples were diluted to calibration range with dilution medium, if necessary.

Test vessel adsorption
After sampling of the aqueous phase, the test vessels were emptied and rinsed with 0.01 M CaCl2. 2-Propanol was used for extraction of the test item from the test vessel. Therefore, the vessel was shaken by hand for 1 min, ultrasound was used for 5 min and the vessel was shaken 20 min on a shaker. 0.01 M CaCl2 was used if dilution factor 2 was needed, dilution medium for further dilutions to calibration range, if necessary.

Soil extraction:
After decantation of the aqueous phase, the soil was used for extraction. The wet soil was extracted by using an accelerated solvent extractor (ASE) and was weighed into a solvent extractor cell (approx. 1 g dry weight). To each sample, 2 g magnesium chloride hexahydrate and 4 g silica gel were added and homogenised carefully with the soil. Then, the samples were extracted with 2-propanol : HPLC water (50 : 50). For parameters of the extraction method see below. Extracts were transferred quantitatively into a 100 mL measuring flask and filled up with 2-propanol : HPLC water (50 : 50). Aliquots were diluted with 2-propanol : HPLC water (50 : 50) to calibration range.

Parameters of the extraction method:
Preheat: 1 min
Heat: 6 min
Static: 10 min
Flush: 50 % (v/v)
Purge: 90 sec
Cycles: 3
Pressure: 1500 psi
Temperature: 125 °C
Solvent: 2-propanol : HPLC water (50 : 50)

Samples for method validation:
Samples were prepared as described above (‘soil samples (conditioning)’). The aqueous phases were decanted and spiked with test item at 1 x LOQ level. Blank samples were prepared accordingly but without spiking with test item. Samples were diluted with 2-propanol by a factor 2.

Sample storage: All samples were stored at room temperature prior and after analysis.

Matrix no.:

#1

Matrix type:

loamy sand

% Clay:

8.5

% Silt:

11.3

% Sand:

80.2

% Org. carbon:

1.47

pH:

5.4

CEC:

7.6 meq/100 g soil d.w.

Matrix no.:

#2

Matrix type:

clay loam

% Clay:

25.2

% Silt:

42.3

% Sand:

32.6

% Org. carbon:

1.74

pH:

7.4

CEC:

22 meq/100 g soil d.w.

Matrix no.:

#3

Matrix type:

loamy sand

% Clay:

10.2

% Silt:

31.1

% Sand:

58.7

% Org. carbon:

0.916

pH:

7.3

CEC:

10 meq/100 g soil d.w.

Matrix no.:

#4

Matrix type:

other: Dystric Cambisol

% Clay:

17

% Silt:

36.8

% Sand:

46.4

% Org. carbon:

3.01

pH:

5.5

CEC:

16.6 meq/100 g soil d.w.

Matrix no.:

#5

Matrix type:

Luvisol

% Clay:

20.3

% Silt:

75.7

% Sand:

4.1

% Org. carbon:

1.31

pH:

6.8

CEC:

17.3 meq/100 g soil d.w.

Details on matrix:

Relevant Characteristics of Soils for Adsorption / Desorption

Soil Parameter LUFA 2.2 LUFA 2.4 LUFA 5M Eurosoil 3 Eurosoil 4
Soil type (LUFA Soils) 1) Loamy sand Clayey loam Loamy sand
FAO soil unit (Eurosoils) 2) Dystric Cambisol Orthic Luvizol
pH (0.01 M CaCl2) 5.4 3) 7.4 3) 7.3 3) 5.5 5) 6.8 5)
Organic Carbon [%] 1.47 4) 1.74 4) 0.916 4) 3.01 5) 1.31 5)
Clay (< 0.002 mm) [%] 8.5 4) 25.2 4) 10.2 4) 17.0 2) 20.3 2)
Silt (0.002-0.063 mm) [%] 11.3 4) 42.3 4) 31.1 4) 36.8 2) 75.7 2)
Sand (0.063-2 mm) [%] 80.2 4) 32.6 4) 58.7 4) 46.4 2) 4.1 2)
Cation exchange capacity [mval/100 g] 7.6 4) 22 4) 10 4) 16.6 2) 17.3 2)
1) according to German DIN
2) data taken from Gawlik and Muntau, Eurosoils II Laboratory and Reference Materials for Soil-related Studies, Environment Institute 1999
3) data obtained from LUFA Speyer, analysis data sheet from 2016-03-15
4) determined externally at AGROLAB GMBH (non-GLP)
5) values taken from soil certificates

Origin of soils:
Landwirtschaftliche Untersuchungs- und Forschungsanstalt LUFA Speyer, Obere Langgasse 40, 67346 Speyer, Germany

European Commission, Joint Research Centre, Institute for Reference Materials and Measurements IRMM Retieseweg, B-2440 Geel, Belgium


Storage at test facility: Room temperature, in closed containers


Date of receipt:
LUFA 2.2 (batch: F2.24016): 2016-10-24
LUFA 2.4 (batch: F2.44116): 2016-10-24
LUFA 5M (batch: F5M5015): 2016-12-17
Eurosoil 3 (IRMM-443-3 batch: 102): 2016-09-27
Eurosoil 4 (IRMM-443-4 batch: 27): 2017-03-09

Expiry date:
According to test facility standard operation procedure, the expiry date was set to five years after receipt of the soils.
LUFA 2.2 (batch: F2.24016): 2021-10-24
LUFA 2.4 (batch: F2.44116): 2021-10-24
LUFA 5M (batch: F5M5015): 2021-12-17
Eurosoil 3 (IRMM-443-3 batch: 102): 2021-09-27
Eurosoil 4 (IRMM-443-4 batch: 27): 2022-03-09

Characterization date:
LUFA soils were characterized in relation to their organic carbon content and cation exchange capacity externally at Agrolab GmbH.
LUFA 2.2 (batch: F2.24016): 2017-02-13
LUFA 2.4 (batch: F2.44116): 2017-02-13
LUFA 5M (batch: F5M5015): 2017-02-13

Key result

Sample No.:

#1

Phase system:

soil-water

Type:

other: Koc

Value:

63 732 L/kg

Temp.:

20 °C

pH:

6.7

Matrix:

LUFA 2.2

% Org. carbon:

1.47

Remarks on result:

other: Koc at 7 mg/L

Remarks:

Concentration in water at equilibrium: 290 ug/L

Sample No.:

#1

Phase system:

soil-water

Type:

other: Koc Fads

Remarks:

From Freundlich isotherm

Value:

56 689 L/kg

Temp.:

20 °C

pH:

6.7

Matrix:

LUFA 2.2

% Org. carbon:

1.47

Key result

Sample No.:

#2

Phase system:

soil-water

Type:

other: Koc

Value:

98 867 L/kg

Temp.:

20 °C

pH:

8.4

Matrix:

LUFA 2.4

% Org. carbon:

1.74

Remarks on result:

other: Koc at 7 mg/L

Remarks:

concentration in water at equilibrium: 166 ug/L

Sample No.:

#2

Phase system:

soil-water

Type:

other: Koc fads

Remarks:

from Freundlich isotherm

Value:

68 742 L/kg

Temp.:

20 °C

pH:

8.4

Matrix:

LUFA 2.4

% Org. carbon:

1.74

Key result

Sample No.:

#3

Phase system:

soil-water

Type:

other: Koc at 7 mg/L

Value:

20 765 L/kg

Temp.:

20 °C

pH:

8.8

Matrix:

LUFA 5M

% Org. carbon:

0.916

Remarks on result:

other: Concentration in water at equilibrium 1015 ug/L

Sample No.:

#3

Phase system:

soil-water

Type:

other: Koc Fads

Remarks:

Freundlich isotherm Koc

Value:

19 464 L/kg

Temp.:

20 °C

pH:

8.8

Matrix:

LUFA 5M

% Org. carbon:

0.916

Key result

Sample No.:

#4

Phase system:

soil-water

Type:

other: Koc at 7 mg/L

Value:

31 279 L/kg

Temp.:

20 °C

pH:

7

Matrix:

Eurosoil 3

% Org. carbon:

3.01

Remarks on result:

other: Concentration in water at equilibrium 276 ug/L

Sample No.:

#4

Phase system:

soil-water

Type:

other: Koc Fads

Remarks:

Freundlich isotherm Koc

Value:

20 925 L/kg

Temp.:

20 °C

pH:

7

Matrix:

Eurosoil 3

% Org. carbon:

3.01

Key result

Sample No.:

#5

Phase system:

soil-water

Type:

other: Koc at 7 mg/L

Value:

203 597 L/kg

Temp.:

20 °C

pH:

7.9

Matrix:

Eurosoil 4

% Org. carbon:

1.31

Remarks on result:

other: Concentration in water at equilibrium 261 ug/L

Sample No.:

#5

Phase system:

soil-water

Type:

other: Koc Fads

Remarks:

Freundlich isotherm Koc

Value:

150 645 L/kg

Temp.:

20 °C

pH:

7.9

Matrix:

Eurosoil 4

% Org. carbon:

1.31

Concentration of test substance at end of adsorption equilibration period:

24 hours equilibrium time with 7 mg/L starting concentration with a soil/solution ratio of 1/100:
Soil #1: LUFA 2.2: 290 µg/L
Soil #2: LUFA 2.4: 166 µg/L
Soil #3: LUFA 5M: 1015 µg/L
Soil #4: Eurosoil 3: 276 µg/L
Soil #5: Eurosoil 4: 261 µg/L

Temperature: The temperature was in the range of 20 ± 2 °C during the course of the studie.

Dry Weights: The dry weight of each solid matrix was determined.

 

Soil Dry Weights Mean values (n = 3)

	Soil type
	LUFA 2.2	LUFA 2.4	LUFA 5M	Eurosoil 3	Eurosoil 4
soil dry weight [%]	92.8	92.9	93.2	97.7	96.9

 pH Values:

The pH values of the aqueous media of the test systems were measured before and after equilibration with the corresponding soils and after addition of the test item in the highest test item concentration. Results are shown in the following table.

 

 pH Values of the Aqueous Media Soil / solution ratio 1:100

	Soil type
	LUFA 2.2	LUFA 2.4		LUFA 5M	Eurosoil 3		Eurosoil 4
demineralized water	7.1		7.1	7.1	7.8	7.8
after soil contact	7.2	8.5		8.4	6.9		7.1
after addition of the test item	6.7	8.4		8.8	7.0		7.9

 Results of Tier 1:

DuringTier 1 experiments have been conducted to find the optimal matrix / solution ratio and the time to reach equilibrium for each matrix. Therefore, the amount adsorbed at equilibrium was determined. In addition, test item stability was demonstrated by measuring test item control samples with conditioned CaCl₂ solution but without soil and test item control samples without conditioning with soil during the experiments. The mass balance was evaluated.

 

Adsorption Experiments using 0.01 M CaCl₂

Experiments have been conducted in LUFA soils 2.2 and 2.4 using a soil / solution ratio of 1:100. Samples were taken after 4, 24 and 48 hours and the aqueous phase was analysed.

Adsorption of ≥ 94% was already observed after 4 h. In addition, solubility was visually determined in aqueous solutions. The solubility is high in demineralized water (demin.) but when CaCl₂ 0.01 M is used, precipitation occurred (visually confirmed). The test item can be redissolved if the pH value is increased. If the solution in demin. is acidified, precipitation is observed as well. Based on these observations, sodium hydroxide was added to the test item control samples at the end of the experiment to demonstrate that the low recovery observed was caused by precipitation of the test item. Addition of sodium hydroxide and thereby increase of the pH value led to a recovery improvement from 73% to 90% for LUFA 2.2. The solubility of the test substance in the test system is therefore considered to be dependent on pH and the calcium cations in the aqueous solution. In addition, un-conditioned 0.01 M CaCl₂ was used for additional test item control samples. The results observed were comparable. Recovery rates of 58% and 51% were obtained prior to adding sodium hydroxide.

 Tier 1:Adsorption Experiments LUFA 2.2 1:100
Applied test item concentration: 10000 µg/L, n=2

Sampling point     [h]	Adsorption       [%]	Recovery rate of un-conditioned control pH = 6.4 [%]	Recovery rate of un-conditioned control after addition of NaOH [%]	Recovery rate of conditioned control pH = 6.5 [%]	Recovery rate of conditioned control after addition of NaOH [%]
0	-	99	-	86	-
4	94	-	-	-	-
24	96	-	-	-	-
48	96	58	85	73	90

-                 not determined

 

Tier 1:Adsorption Experiments LUFA 2.4 1:100
Applied test item concentration: 10000 µg/L, n=2

Sampling point     [h]	Adsorption       [%]	Recovery rate of un-conditioned control pH = 6.4 [%]	Recovery rate of un-conditioned control after addition of NaOH [%]	Recovery rate of conditioned control pH = 7.5 [%]	Recovery rate of conditioned control after addition of NaOH [%]
0	-	97	-	90	-
4	98	-	-	-	-
24	> 98^1)	-	-	-	-
48	> 98^1)	51	106	92	87

1)               measured concentration of aqueous phase was lower than the lowest calibration level

-                 not determined

The lower recovery in CaCl₂ solution (conditioned and un-conditioned) can be presumably attributed to the calcium binding to the chelating part of the molecule and consequently precipitation of the test item calcium complex.

By increasing the pH, calcium is replaced by sodium and the sodium complex is apparently better soluble. Since the precipitation of the test item is also expected to occur in the test vessels with soil, this would result in an overestimation of the fraction sorbed.

 

Test Item Stability in the Aqueous Phase and Test Vessel Adsorption

Since CaCl₂ should be added to the test medium to mimic environmental conditions, stability of test item control samples was additionally investigated in 0.001 M CaCl₂ solution and 0.01 M NaCl solution.

Sodium was used instead of calcium since the solubility of the sodium complex is apparently higher than the calcium complex. Solubility/ stability was compared in 0.01 M CaCl₂solution, 0.001 M CaCl₂solution, 0.01 M NaCl solution and also demineralized water.

 

Tier 1:Stability in Test Item Control Samples of LUFA 2.2 – 1 mg/L

Soil / solution ratio 1:100, test item concentration 1 mg/L, n=2

Matrix	pH after addition of test item	Sampling point [h]	Recovery rate^1) [%]
0.01 M CaCl2(un-conditioned)	7.4	0	85
		4	70
		24	47
0.01 M CaCl2conditioned	7.0	0	105
		4	50
		24	32
0.001 M CaCl2(un-conditioned)	6.8	0	102
		4	73
		24	59
0.001 M CaCl2conditioned	7.2	0	84
		4	80
		24	61
0.01 M NaCl (un-conditioned)	-	0	66
		4	76
		24	35
0.01 M NaCl conditioned	7.3	0	64
		4	91
		24	69
demin. (un-conditioned)	7.8	0	99
		4	70
		24	87
demin. conditioned	7.8	0	89
		4	85
		24	68

1)         recovery from nominal concentration at 0h, recovery rate from initially measured concentration at 4 h and 24 h

2)         one replicate shown, second replicate not taken into account

-          not determined

 Tier 1:Stability in Test Item Control Samples of LUFA 2.2 – 10 mg/L

Soil / solution ratio 1:100, test item concentration 10 mg/L, n=2

Matrix	pH after addition of test item	Sampling point [h]	Recovery rate^1) [%]
0.01 M CaCl2(un-conditioned)	7.1	0	86
		4	43
		24	30
0.01 M CaCl2conditioned	7.1	0	108
		4	40
		24	26
0.001 M CaCl2(un-conditioned)	-	0	123
		4	74
		24	51
0.001 M CaCl2conditioned	-	0	130
		4	74
		24	53
0.01 M NaCl (un-conditioned)	-	0	110
		4	86
		24	69
0.01 M NaCl conditioned	-	0	118
		4	95
		24	78
demin. (un-conditioned)	8.1	0	105
		4	80
		24	75
demin. conditioned	7.9	0	98
		4	91
		24	80

1)     recovery from nominal concentration at 0 h, recovery rate from initially measured concentration at 4 h and 24 h

-       not determined

 

After 24 h, the test vessels of the 10 mg/L samples of conditioned matrices were rinsed with sodium hydroxide solution to redissolve the precipitated substance from test vessel walls. The recovery rates to the nominal concentration were 3% and 6% for samples in 0.001 M CaCl₂ solution and 0.01 M NaCl solution, respectively and 9% and 24% for samples in demin. and 0.01 M CaCl₂ solution, respectively (not shown in the tables). These results demonstrated that the highest amount of test item could be rinsed from test vessel walls in 0.01 M CaCl₂ solution.

Compared to samples in 0.01 M CaCl₂ solution, the test item control samples in 0.001 M CaCl₂ solution showed a slightly better recovery rate but the recovery was still only approx. 50% after 24 h. Samples in NaCl or demin. showed higher stabilities (less precipitation) after 24 h. Therefore, additional adsorption experiments were conducted with these test media.

 

Test vessel adsorption has been evaluated in these preliminary experiments and was observed to be 9% for test item control samples in demin. As test vessel adsorption is higher in control samples than in test item replicates (due to absence of soil and the higher adsorption to soil than to the test vessel) and as the mass balance is 90% in test item replicates (see below), the test vessel adsorption is considered to be negligible and was not further taken into account in Tier 2 and Tier 3.

 

Adsorption Experiments using 0.01 M NaCl and Demin:

Additional adsorption experiments were performed with 0.01 M NaCl solution and demin. as test medium. Test item control samples were observed to be stable in demin. for a duration of the experiment of 29 h , whereas the recovery rate of samples in 0.01 M NaCl was lower.

 

Tier 1:Adsorption Experiments LUFA 2.2 – 0.01 M NaCl + Demin.
soil / solution ratio: 1:100, applied test item concentration: 7000 µg/L, n=2

Matrix	Sampling point   [h]	Adsorption   [%]	Recovery rate test item control [%]
demin.	0	-	123
	4	90	-
	24	96	70
	28^1)/ 29^2)	84	128
0.01 M NaCl	0	-	135
	4	90	-
	24	95	51

-                 not determined

1)               adsorption sample

2)               test item control sample

 

With regard to these results and the higher stability of the test item control sample, demineralized water was used as test medium for Tier 2 and Tier 3.

 

 

 

Mass Balance:

The soil extraction efficiency was evaluated with LUFA 2.2 and 2.4 soils using a soil solution ratio of 1:40. This ratio was chosen for the determination of the soil extraction efficiency for practical reasons.

Smaller centrifuge tubes could be used at this soil solution ratio which facilitated the transfer of the soil pellet after centrifugation.

The test item was extractable from soil using accelerated solvent extraction (ASE). Based on the observed total substance recovery (mass balance) of 90% it is considered justified to use the indirect method as basis for the calculation of the equilibrium adsorption constants.

 

Tier 1:Mass Balance
soil / solution ratio 1:40, applied test item concentration: 7000 µg/L, n=2

Matrix	Sampling point [h]	Recovery rate from aqueous phase [%]	Recovery rate from solid phase [%]	Mass balance^1) [%]
LUFA 2.2	24	9	81	90
LUFA 2.4	24	6	84	90

1)          Sum of aqueous and solid phase

Tier 2–Adsorption Kinetics:

The adsorption kinetics was evaluated using a nominal test item concentration of 7.00 mg/L. A soil / solution ratio of 1:100 was used for each soil. After spiking, samples of the aqueous phase were measured at defined sampling points. In addition, test item control samples were analysed at each sampling point. The following table shows the amount of test item measured in the aqueous phase and based on this value the calculated amount adsorbed to the solid matrix (indirect method). The percentage of adsorption and recovery rate for the test item control are given after 24 h (adsorption equilibrium) and this sampling was used to calculate the distribution coefficients K_d and the corresponding organic carbon normalized distribution coefficients K_OC.

 Measured Amounts in Aqueous Phase, Calculated Amount for Solid Matrices, Percent of Adsorption and Distribution Coefficients K_d and K_OC

Applied test item concentration: 7000 µg/L, n = 2
equilibration time: 24 h

Soil type	msoil [g]	Vaq [mL]	m^adsaq(eq) [µg]	m^adss(eq) [µg]	Kd [mL/g]	KOC [mL/g]	Adsorption [%]	Recovery Control [%]^1)
LUFA 2.2	0.928	100	29.0	252	937	63732	90	90
LUFA 2.4	0.929	100	16.6	265	1720	98867	94	90
LUFA 5M	0.932	100	101	180	190	20765	64	86
Eurosoil 3	0.977	100	27.6	254	942	31279	90	81
Eurosoil 4	0.969	100	10.5	271	2667	203597	96	79

m_soil          = used amount of soil (dry weight)

V_aq            = used volume of aqueous phase

m^ads_aq        = amount of a.i. in the aqueous phase at equilibrium

m^ads_s          = amount of a.i. in the soil at equilibrium

1)              = recovery from initially measured (0 h) concentration after 24 h

Tier 3– Desorption Kinetics:

The desorption kinetics of the test item was evaluated during 24 h, using the soils of the adsorption kinetics test (after 24 h adsorption).The table below shows the 24 h desorption coefficient K_des. Since the desorption coefficient is for certain soils higher than the adsorption coefficient K_d, the test item adsorption is considered to be not completely reversible.

Percent of Desorption and Desorption Coefficient K_des 

Applied test item concentration: 7000 µg/L, n = 2

Soil Type	msoil[g]	Vaq[mL]	m^desaq(eq) [µg]	m^adss(eq) [µg]	Kdes[mL/g]	Desorption [%]
LUFA 2.2	0.928	100	12.4	252	2087	5
LUFA 2.4	0.929	100	15.1	265	1785	6
LUFA 5M	0.932	100	42.8	180	344	24
Eurosoil 3	0.977	100	14.8	254	1647	6
Eurosoil 4	0.969	100	12.5	271	2132	5

m_soil          = used amount of soil (dry weight)

V_aq            = used volume of aqueous phase

m^des_aq        = amount a.i. measured in the aqueous phase after desorption step

(without entrained water)

m^ads_s          = amount of a.i. adsorbed to soil at equilibrium

Tier 3– Adsorption Isotherms:

The adsorption isotherm was determined with additional concentrations of 3.00 mg/L, 16.5 mg/L, 23.5 mg/L and 30.0 mg/L after adsorption for 24 h. Deviating from the guideline, no concentration range in the order of two magnitudes was feasible. With regard to the limit of quantification, relatively high test item concentrations were required and applied to approx.1 g soil dry weight. The non-linearity of the adsorption is already observed at the concentration range used. This is demonstrated by the 1/n values (especially for LUFA 5M with 1/n = 0.69).

The table below shows the Freundlich adsorption coefficient K_d and the organic carbon normalized Freundlich adsorption coefficient K^OC_F.

 

Freundlich AdsorptionIsotherms

Applied test item concentrations: 3500, 7000, 16500, 23500, 30000 µg/L

Soil Type	msoil[g]	Vaq[mL]	r^2	1/n	K^adsF	K^OCF
LUFA 2.2	0.928	100	0.993	0.94	833	56689
LUFA 2.4	0.929	100	0.946	0.91	1196	68742
LUFA 5M	0.932	100	0.955	0.69	178	19464
Eurosoil 3	0.977	100	0.969	0.85	630	20925
Eurosoil 4	0.969	100	0.926	0.93	1973	150645

m_soil    = used amount of soil (dry weight) [g]

V_aq      = used volume of aqueous phase

n         = regression constant

%OC   = percentage of organic carbon content in the soil

K^ads_F    = Freundlich adsorption coefficient [µg^1-1/n(mL)^1/ng^-1]

K^OC_F     = Freundlich adsorption coefficient normalized to content of organic carbon [µg^1-1/n(mL)^1/ng^-1]

Tier 3– Desorption Isotherms:

The desorption isotherm was determined after adsorption for 24 h and desorption for 24 h. The non-linearity of the desorption is observed at the concentration range used.The table below summarizes the Freundlich desorption isotherm characteristics.

 

Freundlich Desorption Isotherms

Applied test item concentrations: 3500, 7000, 16500, 23500, 30000 µg/L

Soil Type	msoil[g]	r^2	1/n	K^desF
LUFA 2.2	0.928	0.953	1.42	5148
LUFA 2.4	0.929	0.974	1.24	3508
LUFA 5M	0.932	0.983	0.62	232
Eurosoil 3	0.977	0.960	0.91	1289
Eurosoil 4	0.969	0.950	1.22	3312

m_soil=      used amount of soil (dry weight) [g]

n      =      regression constant

K^des_F =      Freundlich desorption coefficient [µg^1-1/n(mL)^1/ng^-1]

Control Samples:

The test item stability was confirmed by measurement of two test item control replicates during each adsorption experiment. The table below shows the recovery rate for control samples. The recovery is related to the initially measured concentration at 0 h (recovery rates for samples at 0 h are related to the nominal applied concentration). The test item is considered to be stable in the test system, if demineralized water is used as test medium.

 

Recovery Rates [%] of the Control Samples

ConcentrationTier 2– Adsorption kinetics:7000 µg/L

ConcentrationTier 3– Adsorption isotherm: 3500 µg/L

	LUFA 2.2	LUFA 2.4	LUFA 5M	Eurosoil 3	Eurosoil 4
Tier 2- adsorption kinetics 0 h	83	96	96	110	102
Tier 2- adsorption kinetics 2 h	93	84	93	46^1)	48^1)
Tier 2- adsorption kinetics 4 h	94	96	91	92	89
Tier 2- adsorption kinetics 6 h	79	103	81	90	84
Tier 2- adsorption kinetics 24 h	90	90	86	81	79
Tier 3- adsorption isotherm 0 h	97	95	92	95	81
Tier 3- adsorption isotherm 24 h	90	89	101	83	114

1)    = value not plausible, presumably related to sampling error

 

Validity criteria fulfilled:

yes

Conclusions:

Valid Guideline study performed under GLP conditions

Executive summary:

The adsorption / desorption behavior of the test item Sodiumoleylamphopolycarboxyglycinate (batch no.1297986) was investigatedin five different soils accordingto OECD guideline 106 and EC C.18 from 2017-02-20 to 2017-05-15 at Noack Laboratorien GmbH, 31157 Sarstedt, Germany. Distribution coefficients K_d and organic carbon normalized distribution coefficients K_OC were determined with a single concentration. The desorption behavior / reversibility of the adsorption from the soils and the degree of adsorption and desorption as a function of the test item loading level (Freundlich adsorption and desorption isotherms) in the aqueous phase were investigated.

 

Experiments have been conducted in LUFA soils 2.2 and 2.4 using a soil / solution ratio of 1:100 during Tier 1. The solubility is high in demineralized water (demin.) but when CaCl₂ 0.01 M was used, precipitation occurred. The lower solubility in CaCl₂ solution (soil-conditioned and un-conditioned) is presumably attributed to the calcium binding to the chelating part of the molecule. Since the test item concentration could not be lowered because of the relatively high limit of quantification, solubility / stability was also proven in 0.001 M CaCl₂ solution, 0.01 M NaCl solution and demineralized water. With regard to the results of these experiments and the stability of the test item control samples (samples in soil-conditioned test medium without soil, spiked with the test item), demineralized water was used as test medium for Tier 2 and Tier 3. The mass balance was 90% in LUFA 2.2 and LUFA 2.4 and therefore the indirect method is considered acceptable for deriving the equilibrium constants throughout the study.

Experiments for adsorption and desorption kinetics were conducted with a soil / solution ratio of 1:100 and a nominal test item concentration of 7.00 mg/L. The adsorption equilibrium was reached after 24 hours. For investigations concerning the Freundlich adsorption and desorption isotherms, additional concentrations of 3.00 mg/L, 16.5 mg/L, 23.5 mg/L and 30.0 mg/L have been applied. The test substance concentrations used, did not cover a concentrationrange in the order of two magnitudes. With regard to the limit of quantification, relatively high test item concentrations were required with a soil solution ratio of 1 g soil to 100 mL of aqueous phase. The non-linearity of the adsorption is already observed at the concentration range used.

The table presents the observed distribution coefficients K_d and their corresponding organic carbon normalized distribution coefficients K_OC. Furthermore, the mobility of the test item in the investigated matrices was classified according to McCallet al.(1980). Additionally, the desorption coefficient K_des, the organic carbon normalized Freundlich adsorption coefficient K^OC_F as well asthe Freundlich desorption coefficient K^des_F are presented in the summarizing table.

Summarized Endpoints

Mobility according to Mc Call et al.(1980): K_OC 0 – 50 very high, K_OC 50 – 150 high, K_OC 150 – 500 medium, K_OC 500 – 2000 low, K_OC 2000 – 5000 slight, K_OC > 5000 immobile; based on results of Tier 2
K_d and K_oc were determined during Tier 2

K_des, K^OC_F and K^des_F were determined duringTier 3

	ca.i.^1) [µg/L]	Kd[mL/g]	KOC[mL/g]	Kdes[mL/g]	K^OCF[µg^1-1/n(mL)^1/ng^-1]	1/n	K^desF[µg^1-1/n(mL)^1/ng^-1]	Mobility according to McCallet al.
Soil type	Soil /solution ratio 1:100
LUFA 2.2	290	937	63732	2087	56689	0.94	5148	immobile
LUFA 2.4	166	1720	98867	1785	68742	0.91	3508	immobile
LUFA 5M	1015	190	20765	344	19464	0.69	232	immobile
Eurosoil 3	276	942	31279	1647	20925	0.85	1289	immobile
Eurosoil 4	261	2667	203597	2132	150645	0.93	3312	immobile

1)    = concentration of the active ingredient in the aqueous phase at equilibrium (Tier 2)

n    = regression constant (Freundlich adsorption isotherm)

 

The test item adsorbs strongly to all tested soils with K_oc values > 5000. The desorption was determined to be not completely reversible. The adsorption does not show a linear correlation to the applied concentration (Freundlich adsorption isotherm). The 1/n values obtained from the isotherms demonstrate the non-linearity.

Description of key information

The adsorption/desorption behaviour of Amines, N-C12 -18 -alkytrimethylenedi-, reaction products with chloroacetic acid, sodium salts (or Sodium cocoamphopolycarboxyglycinate) was not evaluated in a standard OECD 106 tests. Instead the available adsorption / desorption test with Sodium oleylamphopolycarboxyglycinate is read across to Amines, N-C12 -18 -alkytrimethylenedi-, reaction products with chloroacetic acid, sodium salts. This read across is considered to be justified as the sorption to the sodium oleyl amphopolycarboxy glycinate to soil is higher than the adsorption of the sodium coco amphopolycarboxy glycinate. This will lead to worst-case predicted soil and sediment concentrations in the sodium cocoamphopolycarboxy glycinate risk assessment.

In the adsorption/desorption test with Sodium oleylamphopolycarboxyglycinate investigated in five different soils according to OECD guideline 106.

Freundlich adsorption and desorption isotherms using 5 different test concentrations were determined for each of the 5 soils. In addition distribution coefficients Kd and organic carbon normalized distribution coefficients KOC were determined at 7 mg/L. The mean Koc of Sodium oleylamphopolycarboxyglycinate for the 5 soils is 83648 L/kg

Key value for chemical safety assessment

Koc at 20 °C:

83 648

Additional information

The adsorption/desorption behaviour of Amines, N-C12 -18 -alkytrimethylenedi-, reaction products with chloroacetic acid (or cocoamphopolycarboxyglycinate) was not evaluated in a standard OECD 106 tests. Instead the available adsorption / desorption test with Sodium oleylamphopolycarboxyglycinate is read across to Amines, N-C12 -18 -alkytrimethylenedi-, reaction products with chloroacetic acid. This read across is considered to be justified as the sorption to the oleyl amphopolycarboxy glycinate to soil is higher than the adsorption of the coco amphopolycarboxy glycinate. This will lead to worst-case predicted soil, sediment and sludge concentrations in the cocoamphopolycarboxy glycinate risk assessment.

The adsorption / desorption behavior of Sodiumoleylamphopolycarboxyglycinate was investigated in five different soils according to OECD guideline 106.

Freundlich adsorption and desorption isotherms using 5 different test concentrations were determined for each of the 5 soils. In addition distribution coefficients K_d and organic carbon normalized distribution coefficients K_OC were determined with a single concentration.

 

During Tier 1 the soil solution ratio, the equilibration time, sorption to the test vessel and test substance stability were evaluated using LUFA soils 2.2 and 2.4. The solubility of the test item is high in demineralized water (demin.) but when CaCl₂0.01 M was used, precipitation occurred. The lower solubility in CaCl₂ solution (soil-conditioned and un-conditioned) is presumably attributed to the calcium binding to the chelating part of the molecule. In relation to the detection limit and limited solubility of the test item in test media the test concentration in Tier 1 and 2 was 7 mg/L. Solubility and stability of the test item was shown in 0.001 M CaCl₂solution, 0.01 M NaCl solution and demineralized water. The Tier 1 results showed that equilibrium was reached with 24 hours, that a soil solution ratio of 1:100 is needed and that there is a mass balance of 90% in LUFA 2.2 and LUFA 2.4 and that therefore the indirect method (back calculation of the concentration sorbed based on the observed concentration in the aqueous phase assuming 100% mass balance) is considered acceptable for deriving the equilibrium constants throughout the study.

In Tier 2 the adsorption coefficients Kd and Koc were determined for each of the 5 soils.

For Tier 3, measurement of the Freundlich adsorption and desorption isotherms, additional concentrations of 3.00 mg/L, 16.5 mg/L, 23.5 mg/L and 30.0 mg/L were introduced. The test substance concentrations used, did not cover a concentrationrange in the order of two magnitudes. With regard to the limit of quantification, relatively high test item concentrations were required with a soil solution ratio of 1 g soil to 100 mL of aqueous phase. The non-linearity of the adsorption is already observed at the concentration range used.

K_d and K_oc for 5 soils were determined during Tier 2 at 7 mg/L

K_des,K^OC_F and K^des_F were determined duringTier 3

	ca.i.^1) [µg/L]	Kd[mL/g]	KOC[mL/g]	Kdes[mL/g]	K^OCF[µg^1-1/n(mL)^1/ng^-1]	1/n	K^desF[µg^1-1/n(mL)^1/ng^-1]	Mobility according to McCallet al.
Soil type	Soil /solution ratio 1:100
LUFA 2.2	290	937	63732	2087	56689	0.94	5148	immobile
LUFA 2.4	166	1720	98867	1785	68742	0.91	3508	immobile
LUFA 5M	1015	190	20765	344	19464	0.69	232	immobile
Eurosoil 3	276	942	31279	1647	20925	0.85	1289	immobile
Eurosoil 4	261	2667	203597	2132	150645	0.93	3312	immobile

1)    = concentration of the active ingredient in the aqueous phase at equilibrium (Tier 2)

n    = regression constant (Freundlich adsorption isotherm)

 

The test item adsorbs strongly to all tested soils withK_ocvalues > 5000. The desorption was determined to be not completely reversible. The adsorption does not show a linear correlation to the applied concentration (Freundlich adsorption isotherm). The 1/n values obtained from the isotherms demonstrate the non-linearity.