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

Phototransformation in water

Link to relevant study record(s)

Reference

Endpoint:

phototransformation in water

Type of information:

experimental study

Adequacy of study:

key study

Study period:

2007-12-05 to 2008-08-22

Reliability:

1 (reliable without restriction)

Rationale for reliability incl. deficiencies:

guideline study

Study type:

direct photolysis

Qualifier:

according to guideline

Guideline:

OECD Guideline 316 (Phototransformation of Chemicals in Water - Direct Photolysis)

Version / remarks:

Draft version (August 2000)

Deviations:

no

GLP compliance:

yes

Remarks:

Ministerium für Umwelt und Naturschutz, Landwirtschaft und Verbraucherschutz, des Landes Nordrhein-Westfalen

Specific details on test material used for the study:

The test item is a lyophilised reaction product and therefore represents a mixture of various components. Therefore, five radio labelled representative “lead components” of the test substance were quantified by radioactivity and additionally analysed by LC-MS/MS.

Radiolabelling:

yes

Analytical method:

other: radio-HPLC to determine the single “lead components”, identification by MS/MS, liquid scintillation counting

Details on sampling:

- Sampling intervals for the parent/transformation products: 0, 1, 2, 3, 5 and 7 d
- Sampling method: aliquot of 50 µL was used for LSC-analysis, 1 mL was transferred into a HPLC-vial and analysed by radio-HPLC, for determination of test item sorbed to the glass walls of the test vessels: vessels were rinsed with 2 mL of acetonitriI/water mixture (3:7 v:v) containing 0.5% formic acid, ultrasonic bath treatment of vessels with solvent for 5 minutes, LSC and radio-HPLC without any further work up
- Sampling methods for the volatile compounds, if any: no gas trapping was applied during irradiation (as determined in the screening test)

Buffers:

- pH: 5, 7, 9
- Type and final molarity of buffer: MERCK ready to use buffers

Light source:

Xenon lamp

Light spectrum: wavelength in nm:

>= 290 - <= 800

Details on light source:

- Emission wavelength spectrum: 290 - 800 nm
- Filters used and their purpose: cut-off filters to ensure a wavelength between 290 nm and 800 nm
- Light intensity at sample and area irradiated: 700 W / m2, diameter: 21 cm, max. volume: 10 mL
- Relative light intensity based on intensity of sunlight: Spectrum as well as the spectral light intensity distribution of the Heraeus Suntes apparatus is comparable to that of daylight.
- Duration of light/darkness: 7 days contious light (corresponding to 30 days of natural summer sunlight, determined by chemical actinometry)

Details on test conditions:

TEST SYSTEM
- Type, material and volume of test apparatus/vessels: cylindric trays (diameter 21 mm, max. volume 10 ml)
- Details of traps for volatile, if any: vials were flushed by a stream of CO2-free synthetic air to trap volatile transformation products
- If no traps were used, type of test system: closed
- Indication of test material adsorbing to the walls of test apparatus: yes, adsorbed material was removable by rinsing the vessel walls with acetonitrile/water

TEST MEDIUM
- Volume used/treatment: 10 mL
- Preparation of test medium: test item first was dissolved in ethanol. The stock solution was pipetted into 10 mL buffer solutions
- Renewal of test solution: no
- Identity and concentration of co-solvent: ethanol
- Concentration of solubilising agent: test solution concentration: 1%

REPLICATION
- No. of replicates (dark): 3
- No. of replicates (irradiated): 3

Duration:

7 d

Temp.:

20 °C

Initial conc. measured:

58.9 other: % component 1

Reference substance:

no

Dark controls:

yes

Preliminary study:

- during irradiation for 48 hours no significant volatilisation of test substance occurred

% Degr.:

<= 10

Sampling time:

7 d

Test condition:

pH 5, 7 and 9

Remarks on result:

other: Exception: 3 samples at pH 9

Remarks on result:

not determinable

Transformation products:

yes

Remarks:

during irradiation for 48 hours no significant volatilisation of test substance occurred. These signals were detected in the dark controls, too, at pH 7 in concentrations comparable to those found in the irradiated solutions.

Details on results:

- Anomalies or problems encountered: test material adsorbed onto the walls of the glass vessels used for the irradiation experiment. The adsorbed material was removable by rinsing the vessel walls with acetonitrile/water.
- radioactive mass balance from the irradiated solutions is generally in the range of 90 to 110%
- distribution of dissolved and adsorbed radioactivity clearly depends on the pH of the solution. Solubility of the test item is known to be increased at acidic pH.
- At pH 9 the adsorbed radioactivity ranged from about 20 to 40% ITR, and one sample with about 80% of adsorbed radioactivity was found. This sample is classified as an outlier and was not considered for further evaluations.
- A number of minor unidentified signals (u.i.) occurred in the radio-HPLC which might be due to transformation products. However, with two exceptions, their amounts were always below 5% of the initially applied radioactivity.
- Transformation products detected exclusively in the rinsing solutions may be due to surface-catalysed reactions on the vessel walls, since no correlation to the irradiation period could be observed.
- Two transformation products were detected by radio-detection at day 7 with an amount of 9.3 % and 4.9% ITR as a maximum. Highest concentrations were detected at pH 5 lowest at pH 7. These signals were detected in the dark controls, too, at pH 7 in concentrations comparable to those found in the irradiated solutions. Both signals did not exceed the trigger of 10% in any sampling or of 5% in two consecutive samplings, respectively. At the same time the concentration of C12 PDA was reduced dramatically in the irradiated samples, suggesting in a first instance that the substances detected may be transformation products of C12 PDA.
- The identity of two transformation products could not be clarified.
- The transformation products determined in the test solutions did not follow a common trend. Except the fact that the concentrations at the 7d sampling are generally highest, the concentrations at other samplings vary. In addition both substances were detected in the dark controls, too, in the case of pH 7 even in the same concentration range.

Validity criteria fulfilled:

not specified

Conclusions:

No kinetics for direct phototransformation could be determined in a test for phototransformation of the test item in water. It is concluded that direct phototransformation over a period of 30 days of natural summer sunlight is an insignificant process for the test item within the environmentally relevant pH range of natural waters between pH 5 and 9.

Executive summary:

The test item was tested for direct photolysis according to a draft OECD guideline. The test item is a lyophilised reaction product. As a result, it represents a mixture of various components. To assess the test item’s susceptibility to photolysis, five radio labelled representative“lead components” of the test substance were quantified by radioactivity and additionally analysed by LC-MS/MS. For the mixture no substance specific absorption coefficient can be determined. Thus, neither a theoretical photolysis half life nor the quantum yield could be determined.

14C-radioactively labelled test item. was dissolved in buffered aqueous media of defined pH-values (pH 5, 7 or 9) and irradiated using a light source of spectral irradiation comparable to that of sunlight. Samples were irradiated for 7 days at 20°C in the SUNTEST device at continuous irradiation, corresponding to 30 days of natural summer sunlight as determined by chemical actinometry.The concentrations of the lead compounds of the test item were measured as a function of time. At days 0, 1, 2, 3, 5, and 7 the mass balance (14C) as well as the identity of five “lead components” of the test item and potential photolysis products were assayed using LSC, radio-HPLC and LC-MS/MS.

The test material adsorbed onto the walls of the glass vessels used for the irradiation experiment. The adsorbed material was removable by rinsing the vessel walls with acetonitrile/water. The 14C-recovery was always in the range of 90% to 110% ITR with the exception of three single samples in pH 9 where substance solubility has been shown to be limited, which may have caused determination errors. However, these deviations do not affect the overall result of the study. HPLC-method was used for determination of the lead components of the test item. In addition, eluent fractions from radio-HPLC containing radioactive peaks were sampled and subjected to the identification procedure by LC-MS/MS.
Until the 5 day sampling, the pattern of the five lead components expressed as relative peak area of the radio-HPLC was approximately constant in the irradiated samples as well as in the respective dark controls.This was confirmed by positive identification of the signals by LC-MS/MS. Minor signals (predominantly below 1% but never exceeding 3%) appeared in the radio-HPLC chromatogram which could not be attributed to the test item, but did not show a positive correlation to the irradiation interval applied either. At the 7 day sampling two additional peaks were detected by radio-detection with an amount of 9.3% and 4 .9% ITR as a maximum. Both substances were detected in the irradiated samples at each pH tested.The transformation rate seems to be highest at pH 5. Both substances did not exceed the trigger for identification work of 10 % in any sampling or of 5 % in two consecutive samplings, respectively. At the same time the concentration of C12 PDA decreased to almost 50 % of its starting concentration in the irradiated samples, initially suggesting that the substances detected may be
transformation products of lead component C12 PDA. In addition an increase of the double substituted substances (diGly) was found.

Masses of 345 (u.i.1) and 285 (u.i.2) for the transformation products could be determined by LC-MS/MS. However, this is inconsistent with regard to C12 PDA decrease, since the mass of C12 PDA is only 242.4 g/mol. Thus, the identity of the transformation products could not be clarified.
Based on the data obtained, no kinetics for direct phototransformation could be determined. It was concluded that direct phototransformation within a period of 30 days of natural summer sunlight is an insignificant process for the test item within the environmentally relevant pH range of natural waters between pH 5 and 9.

Description of key information

Direct phototransformation within a period of 30 days of natural summer sunlight is an insignificant process for the test item within the environmentally relevant pH range of natural waters between pH 5 and 9 (Draft OECD 316).

Additional information

One study is available testing the direct photolysis of Amines, N-C10-C16-alkyltrimethylenedi-, reaction products with chloroacetic acid according to a draft OECD guideline 316.

To assess the test item’s susceptibility to photolysis, five radio labelled representative “lead components” of the test substance were quantified by radioactivity and additionally analysed by LC-MS/MS. For the mixture no substance specific absorption coefficient can be determined. Thus, neither a theoretical photolysis half-life nor the quantum yield could be determined.

14C-radioactively labelled test item was dissolved in buffered aqueous media of defined pH-values (pH 5, 7 or 9) and irradiated using a light source of spectral irradiation comparable to that of sunlight. Samples were irradiated for 7 days at 20°C in the SUNTEST device at continuous irradiation, corresponding to 30 days of natural summer sunlight as determined by chemical actinometry. The concentrations of the lead compounds of the test item were measured as a function of time. At days 0, 1, 2, 3, 5, and 7 the mass balance(14C) as well as the identity of five “lead components” of the test item and potential photolysis products were assayed using LSC, radio-HPLC and LC-MS/MS.

The test material adsorbed onto the walls of the glass vessels used for the irradiation experiment. The adsorbed material was removable by rinsing the vessel walls with acetonitrile/water. The 14C-recovery was always in the range of 90% to 110% ITR ( % Initially applied Total Radioactivity) with the exception of three single samples in pH 9 where substance solubility has been shown to be limited, which may have caused determination errors. However, these deviations do not affect the overall result of the study. HPLC-method was used for determination of the lead components of the test item. In addition, eluent fractions from radio-HPLC containing radioactive peaks were sampled and subjected to the identification procedure by LC-MS/MS. Until the 5 day sampling, the pattern of the five lead components expressed as relative peak area of the radio-HPLC was approximately constant in the irradiated samples as well as in the respective dark controls. This was confirmed by positive identification of the signals by LC-MS/MS. Minor signals (predominantly below 1% but never exceeding 3%) appeared in the radio-HPLC chromatogram which could not be attributed to the test item, but did not show a positive correlation to the irradiation interval applied either. At the 7 day sampling two additional peaks were detected by radio-detection with an amount of 9.3% and 4 .9% ITR as a maximum. Both substances were detected in the irradiated samples at each pH tested. The transformation rate seems to be highest at pH 5. Both substances did not exceed the trigger for identification work of 10% in any sampling or of 5% in two consecutive samplings, respectively.At the same time the concentration of C12 PDA decreased to almost 50 % of its starting concentration in the irradiated samples, initially suggesting that the substances detected may be transformation products of lead component C12 PDA. In addition an increase of the double substituted substances (diGly) was found.

Masses of 345 (unidentified signal 1) and 285 (unidentified signal 2) for the transformation products could be determined by LC-MS/MS. However, this is inconsistent with regard to C12 PDA decrease, since the mass of C12 PDA is only 242.4 g/mol. Thus, the identity of the transformation products could not be clarified. Based on the data obtained, no kinetics for direct phototransformation could be determined. It was concluded that direct phototransformation within a period of 30 days of natural summer sunlight is an insignificant process for the test item within the environmentally relevant pH range of natural waters between pH 5 and 9.