Amines, N-C10-16-alkyltrimethylenedi-, reaction products with chloroacetic acid

Adsorption / desorption

Link to relevant study record(s)

Reference

Reference 1

Endpoint:

adsorption / desorption: screening

Type of information:

experimental study

Adequacy of study:

other information

Study period:

2001-11-26 to 2001-12-03

Reliability:

3 (not reliable)

Rationale for reliability incl. deficiencies:

significant methodological deficiencies

Principles of method if other than guideline:

- Principle of test: Prior to the actual adsorption/desorption experiment, which should be performed according to OECD 106 (2000), a test was performed to check the suitability of Total Organic Carbon (TOC) measurement for the analysis of adsorption/desorption samples, as TOC measurement is the only available method of analysis for the test item. It was tested to what extent extractable soil organic matter would interfere with the determination of the test item concentration.
- Short description of test conditions: Two test soils with the high contents of organic matter (% organic matter: 5.2 and 4.0) were used. Four replicates of each soil were incubated with 0.01 M aqueous CaCI2 solution at a soil solution ratio of 2:5 (w/w) on a platform shaker at 20 ± 2°C for 24 hours. The supernatants were separated from the soils and two supernatants of each soil were spiked with the test item to final concentrations of 0.30 mg/L and 3.0 mg/L. Two supernatants were not spiked (blanks).
- Parameters analysed / observed: The spiked and the blank soils samples were analyzed by TOC measurement.

GLP compliance:

yes (incl. QA statement)

Remarks:

Inspectorate for Health Protection, Commodities and Veterinary Public Health, Ministry of Health, Welfare and Sport,

Type of method:

batch equilibrium method

Media:

soil

Radiolabelling:

no

Analytical monitoring:

yes

Remarks:

TOC measurement is the only available method of analysis for TEGO 2000

Remarks on result:

other:

Remarks:

No results can be derived due to the lack of a specific analytical method for the test substance.

Validity criteria fulfilled:

not applicable

Conclusions:

The adsorption/desorption screening test with the test item cannot be performed due to the lack of a specific analytical method for the test substance.

Executive summary:

The adsorption/desorption behaviour of the test item on five soils, encompassing a range of pH values, soil types (i.e.% sand, clay and silt) and % organic matter was to be investigated. Prior to the actual adsorption/desorption test, a test was performed to check the suitability of Total Organic Carbon (TOC) measurement for the analysis of adsorption/desorption samples, as TOC measurement is the only available method of analysis for Amines, N-C10-C16-alkyltrimethylenedi-, reaction products with chloroacetic acid. Four replicates of Cranfield 164 soil (% organic matter: 5.2) and Speyer 6S soil (% organic matter: 4.0) were incubated with 0.01 M aqueous CaCI2 solution at a soil solution ratio of 2:5 (w/w) on a platform shaker at 20 ± 2°C for 24 hours. Subsequently, the supernatants were separated from the soils and two supernatants of each soil were spiked with the test item to final concentrations of 0.30 mg/L and 3.0 mg/L. Two supernatants were not spiked (blanks). The spiked and the blank soil samples were analyzed by TOC measurement. The TOC contents of the spiked soil samples did not differ significantly from those of the blank soil samples, due to very high concentrations of organic matter extracted from the soils (30-40 mg/L). Therefore, it had to be concluded that the adsorption/desorption test cannot be performed using the TOC method of analysis. In other analytically supported studies, the TOC content was used as a measure for the test item content. For the adsorption/desorption study, this is not possible because soil-extractable organic matter hinders the TOC measurements. Development of another specific analytical method for the measurement of the test item concentrations in adsorption/desorption samples has not been possible. 

Reference 2

Endpoint:

adsorption / desorption: screening

Type of information:

experimental study

Adequacy of study:

key study

Study period:

2020-05-05 to 2020-10-29

Reliability:

1 (reliable without restriction)

Rationale for reliability incl. deficiencies:

guideline study

Qualifier:

according to guideline

Guideline:

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

Version / remarks:

2000

Qualifier:

according to guideline

Guideline:

EU Method C.18 (Adsorption / Desorption Using a Batch Equilibrium Method)

Version / remarks:

2008

GLP compliance:

yes (incl. QA statement)

Remarks:

Staatliches Gewerbeaufsichtsamt Hildesheim, Germany

Type of method:

batch equilibrium method

Media:

other: soil and sediment

Specific details on test material used for the study:

Each component of the test item surrogate was provided as standard substance. These standards were used for calibration and fortification of the matrix by weighing 10 mg each for a 10000 mg/L mixed standard solution. Additionally, 10 mg were weighed into one measuring flask per standard and one mixed standard solution was prepared by dilution. For Tier 3 10 mg each of the representative components
were weighed into one measuring flask to obtain mixed standard solutions used as surrogate for the biocidal product. For Tier 1 and 2 10 mg were weighed into one measuring flask per component.

Radiolabelling:

no

Test temperature:

20 - 21°C

Analytical monitoring:

yes

Details on sampling:

- Concentrations: Tier 1 and Tier 2: 320 µg component/L, Tier 3: 100, 320, 1000, 3200 and 10000 µg test item/L
- Sampling interval: Tier 2: 0 h, 4 h, 24 h, 29 h and 48 h, Tier 3: 48 h, Leine for Adsorption 24 h

Matrix no.:

#1

Matrix type:

other: silty sand

% Clay:

4.1

% Silt:

10.5

% Sand:

85.4

% Org. carbon:

0.718

pH:

4.9

CEC:

2.4 other: mval/100g

Matrix no.:

#2

Matrix type:

loamy sand

% Clay:

8.5

% Silt:

11.3

% Sand:

80.2

% Org. carbon:

1.47

pH:

5.4

CEC:

7.6 other: mval/100g

Matrix no.:

#3

Matrix type:

clay loam

% Clay:

23.3

% Silt:

28.6

% Sand:

38.1

% Org. carbon:

1.85

pH:

7.4

CEC:

22 other: mval/100g

Matrix no.:

#4

Matrix type:

other: sediment Giften

% Clay:

1.8

% Silt:

3.6

% Sand:

94.6

% Org. carbon:

0.17

pH:

7.6

CEC:

2 other: mval/100g

Matrix no.:

#5

Matrix type:

other: sediment Leine

% Clay:

16.7

% Silt:

55.6

% Sand:

27.7

% Org. carbon:

2.69

pH:

7.3

CEC:

19.4 other: mval/100g

Details on matrix:

#1: LUFA 2.1 (soil), batch no. F2.1 2817, Landwirtschaftliche Untersuchungs- und Forschungsanstalt LUFA Speyer, Germany
#2: LUFA 2.2 (soil), batch no. F2.2 4016, Landwirtschaftliche Untersuchungs- und Forschungsanstalt LUFA Speyer, Germany
#3: LUFA 2.4 (soil), batch no. F2.4 2617, Landwirtschaftliche Untersuchungs- und Forschungsanstalt LUFA Speyer, Germany
#4: Giften (sediment), Giften, Germany (52° 13‘ 0.542“ N; 9° 49‘ 44.36“ E)
#5: Leine (sediment), Schulenburg, Germany (52° 16‘ 48.25“ N; 9° 13‘ 29.60“ E)

Details on test conditions:

TEST CONDITIONS
- Buffer: 0.01 M CaCl2 (in ultrapure water)

TEST SYSTEM
- Type, size and further details on reaction vessel: 50 mL glass bottles
- Water filtered: not mentioned
- Amount of soil/sediment/sludge and water per treatment (if simulation test): 1 g and 50 mL water
- Soil/sediment/sludge-water ratio: 1:50
- Number of reaction vessels/concentration: 2
- Measuring equipment: The matrices were weighed into the test vessels and an appropriate volume of 0.01 M CaCl2-solution was added. After agitation overnight (12 h minimum), the samples were used for adsorption experiments. 0.1 volume-% of the spiking solutions, related to the volume of the aqueous phase in the matrix suspensions were added in order to adjust the test concentrations. Afterwards, the samples were agitated. The test vessels were centrifuged after completion of the adsorption experiments, weighed and the supernatant was replaced by fresh 0.01 M CaCl2-solution. Then, the test vessels were agitated again to investigate the desorption behavior of the test item. The matrix suspensions were centrifuged after agitation at 2000 rpm to separate the phases, followed by analysing the concentration of the analytes in aqueous phase by an appropriate analytical method. For analysis of the matrix, the aqueous phase was decanted and the matrix was extracted.
- Method of preparation of test solution: Stock solutions were prepared in acetonitrile / ultrapure water 50 / 50 + 1% trifluoro acetic acid. For Tier 3 10 mg each of the representative components
were weighed into one measuring flask to obtain mixed standard solutions used as surrogate for the biocidal product. An appropriate volume of these stock solutions, related to the volume of the aqueous phase in the matrix suspensions, were used for spiking.

Type:

Koc

Value:

> 5 281 - < 199 028 L/kg

Matrix:

#1

% Org. carbon:

0.718

Remarks on result:

other: components with lowest and highest Koc, respectively: N-C12-Gly and C14-PDA

Type:

Koc

Value:

> 14 884 - < 194 800 L/kg

Matrix:

#2

% Org. carbon:

1.47

Remarks on result:

other: components with lowest and highest Koc, respectively: N-C12-Gly and C14-PDA

Type:

Koc

Value:

> 20 680 - < 498 984 L/kg

Matrix:

#3

% Org. carbon:

1.85

Remarks on result:

other: components with lowest and highest Koc, respectively: N’-C12-diGly and C14-PDA

Type:

Koc

Value:

> 23 789 - < 645 133 L/kg

Matrix:

#4

% Org. carbon:

0.17

Remarks on result:

other: components with lowest and highest Koc, respectively: N-C12-Gly and C14-PDA

Type:

Koc

Value:

> 35 440 - < 280 977 L/kg

Matrix:

#5

% Org. carbon:

2.69

Remarks on result:

other: components with lowest and highest Koc, respectively: N-C12-Gly and C12-PDA

Transformation products:

not measured

Table 1: Overview on the Results of Tier 1

Parameter	Result
Determination of matrix / solution ratios with the aim to obtain at least an adsorption of > 20%	Adsorption > 20% with matrix / solution ratio 1:50
Adsorption to the test vessel	Control Samples: Adsorption observed Matrix samples: No significant adsorption observed
Time to reach adsorption equilibrium	48 h
Investigation of stability and parental mass balance	Substance was stable as test item control samples were stable Mass balance was partly below 90% due to formation of non-extractable residues

Table 2: Tier 2 - Adsorption Kinetics – N-C12-Gly, Equilibrium Time, Measured Amounts in Aqueous Phase and Matrix Extracts, Kd and Koc

Applied concentration, mixed components, nominal: 320 µg/L

n = 2, Vaq = 50 mL

Matrix	teq [h]	mmatrix [g]	madsaq [µg]	Ads [%]	OC [%]	Kd [ml/g]	KOC [ml/g]
LUFA 2.1	48	0.97	8.76	42	0.718	38	5281
LUFA 2.2	48	0.93	3.00	80	1.47	219	14884
LUFA 2.4	48	0.89	0.776	95	1.85	1048	56653
Giften	48	1.00	8.39	45	0.171	41	23789
Leine	24	1.00	0.738	95	2.69	953	35440

 

Table 3: Tier 2 - Adsorption Kinetics – C12-PDA - Equilibrium Time, Measured Amounts in Aqueous Phase and Matrix Extracts, Kd and Koc

Applied concentration, mixed components, nominal: 320 µg/L

n = 2, Vaq = 50 mL

Matrix	teq [h]	mmatrix [g]	madsaq [µg]	Ads [%]	OC [%]	Kd [ml/g]	Koc [ml/g]
LUFA 2.1	48	0.97	0.760	94	0.718	775	107931
LUFA 2.2	48	0.93	0.480	96	1.47	1313	89352
LUFA 2.4	48	0.89	0.0838	99	1.85	8133	439602
Giften	48	1.00	0.986	92	0.171	567	331713
Leine	24	1.00	0.0864	99	2.69	7558	280977

Table4: Tier 2 - Adsorption Kinetics – N’-C12-Gly- Equilibrium Time, Measured Amounts in Aqueous Phase and Matrix Extracts, Kd and Koc

Applied concentration, mixed components, nominal: 320 µg/L

n = 2, Vaq = 50 mL

Matrix	teq [h]	mmatrix [g]	madsaq [µg]	Ads [%]	OC [%]	Kd [ml/g]	Koc [ml/g]
LUFA 2.1	48	0.97	7.36	53	0.718	59	8200
LUFA 2.2	48	0.93	3.05	81	1.47	224	15251
LUFA 2.4	48	0.89	1.44	91	1.85	563	30409
Giften	48	1.00	7.16	55	0.171	60	35092
Leine	24	1.00	0.479	97	2.69	1704	63343

 

Table 5: Tier 2 - Adsorption Kinetics – N’-C12-diGly- Equilibrium Time, Measured Amounts in Aqueous Phase and Matrix Extracts, Kd and Koc

Applied concentration, mixed components, nominal: 320 µg/L

n = 2, Vaq = 50 mL

Matrix	teq [h]	mmatrix [g]	madsaq [µg]	Ads [%]	OC [%]	Kd [ml/g]	Koc [ml/g]
LUFA 2.1	48	0.97	2.21	86	0.718	318	44322
LUFA 2.2	48	0.93	0.852	95	1.47	946	64386
LUFA 2.4	48	0.89	2.03	87	1.85	383	20680
Giften	48	1.00	6.66	58	0.171	69	40235
Leine	24	1.00	0.214	99	2.69	4023	149537

Table 6: Tier 2 - Adsorption Kinetics – C14-PDA - Equilibrium Time, Measured Amounts in Aqueous Phase and Matrix Extracts, Kd and Koc

Applied concentration, mixed components, nominal: 320 µg/L

n = 2, Vaq = 50 mL

Matrix	teq [h]	mmatrix [g]	madsaq [µg]	Ads [%]	OC [%]	Kd [ml/g]	Koc [ml/g]
LUFA 2.1	48	0.97	0.494	97	0.718	1429	199028
LUFA 2.2	48	0.93	0.262	98	1.47	2864	194800
LUFA 2.4	48	0.89	0.0861	99	1.85	9231	498984
Giften	48	1.00	0.616	96	0.171	1103	645133
Leine	24	1.00	0.160	99	2.69	5099	189555

 

Table 7: Tier 2 - Adsorption Kinetics – N’-C14-Gly - Equilibrium Time, Measured Amounts in Aqueous Phase and Matrix Extracts, Kd and Koc

Applied concentration, mixed components, nominal: 320 µg/L

n = 2, Vaq = 50 mL

Matrix	teq [h]	mmatrix [g]	madsaq [µg]	Ads [%]	OC [%]	Kd [ml/g]	Koc [ml/g]
LUFA 2.1	48	0.97	2.26	86	0.718	315	43862
LUFA 2.2	48	0.93	0.579	96	1.47	1444	98214
LUFA 2.4	48	0.89	0.247	98	1.85	3615	195415
Giften	48	1.00	1.77	89	0.171	403	235816
Leine	24	1.00	0.229	99	2.69	3849	143087

Table 8: Tier 3 - Desorption Kinetics– Recovery in Aqueous Phase, Kdes and KdesOC values

Applied concentration, mixed components, nominal:320 µg/L

n = 2, Vaq ads = 50 mL, Vaq des = 50 mL

	N-C12-Gly				C-12-PDA
Matrix	tdes [h]	Des [%]	Kdes [ml/g]	KdesOC [ml/g]	tdes [h]	Des [%]	Kdes [ml/g]	KdesOC [ml/g]
LUFA 2.1	48	30	00.12	17	48	3	2.4	335
LUFA 2.2	48	3	1.1	76	48	1	2.8	188
LUFA 2.4	48	0	9.0	484	48	0	-363	-19614
Giften	48	39	000.084	49	48	7	00.58	341
Leine	48	2	1.9	69	48	0	-418	-15533
	N’-C12-Gly				N’-C12-diGly
LUFA 2.1	48	32	0.10	14	48	8	00.66	92
LUFA 2.2	48	10	0.39	26	48	3	1.5	102
LUFA 2.4	48	1	1.90	102	48	2	1.5	83
Giften	48	37	00.085	50	48	30	00.11	66
Leine	48	1	4.2	155	48	0	34	1244
	C14-PDA				N’-C14-Gly
LUFA 2.1	48	2	03.9	536	48	8	0.59	83
LUFA 2.2	48	0	14	949	48	1	3.00	203
LUFA 2.4	48	0	-444	-24027	48	1	11	591
Giften	48	5	0.99	577	48	9	0.44	259
Leine	48	0	-373	-13848	48	0	36	1339

tdes= time to reach desorption equilibrium, after 48 h adsorption

Des = desorption at desorption equilibrium

Vaq ads  = used volume of aqueous phase during adsorption

Vaq des  = used volume of aqueous phase during desorption

Validity criteria fulfilled:

not applicable

Description of key information

Koc = 58119 L/kg (geometric mean normalised of 5 soils, OECD guideline 106)

Additional information

The adsorption and desorption of Amines, N-C10-C16-alkyltrimethylenedi-, reaction products with chloroacetic acid was investigated according to OECD guideline 106. The study was performed using 14C-labelled representative lead components (C12 moiety) of the test substance. The average adsorption/desorption behaviour of the test substance was determined by measuring total 14C-radioactivity without differentiation of the single components of the test substance. Five soils with different content of organic carbon and clay were selected. The adsorption of the test substance onto each of the five soils was a rapid process: The results of the adsorption kinetics revealed that in most cases the adsorption equilibrium was reached already after 1 hour. Percentage of adsorbed 14C-radioactivity (mean values) were in the range of 85.8 % to 96.0 %. Calculated adsorption coefficients (KFads) were in the range of 853.3–2428.8.

The desorption experiments showed that the adsorption was only marginally reversible. Only 4.7–7.7 % of the adsorbed test substance were desorbed. Calculated desorption coefficients (KFdes) were in the range of 1350.2–3183.5. According to SSLRC mobility classification, Amines, N-C10-C16-alkyltrimethylenedi-, reaction products with chloroacetic acid can be classified as non-mobile (Koc > 4000 mL/g). From the Koc values for adsorption, the mean normalised Koc is calculated to be 58119 (geometric mean).

 

This result is supported by a further study performed according to OECD 106. In this study, the adsorption behavior of relevant representative components of Amines, N-C10-C16-alkyltrimethylenedi-, reaction products with chloroacetic acid was assessed. The representative compounds make up to > 95% of the UVCB substance. The adsorption / desorption behavior of the components was investigated in three different soils and two different sediments. Furthermore, investigations about the adsorption and desorption as a function of the test item loading level (Freundlich isotherms) in the aqueous phase were performed. The distribution coefficients Kd ranged from 38 mL/g to 9231 mL/g and the corresponding organic carbon normalized distribution coefficients Koc from 5281 mL/g to 645133 mL/g. The adsorption was determined to be not completely reversible. Concentrations of 100, 320, 1000, 3200 and 10000 µg test item/L were used for the determination of the Freundlich adsorption and desorption isotherms. The test item does not show a linear Freundlich adsorption and the adsorption was higher in lower concentrations.

 

To cover the range of different log Koc values determined for the substance components, the environmental exposure assessment was performed using two different approaches. In the first approach (Approach I) the lowest determined log Koc value was used to cover the lower boundary of the adsorption potential. In the second approach (Approach II) the highest determined log Koc was used in the fate estimation.