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Registration Dossier
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EC number: 233-046-7 | CAS number: 10025-87-3
Toxicological Summary
Administrative data
Workers - Hazard via inhalation route
Systemic effects
Long term exposure
- Hazard assessment conclusion:
- no hazard identified
Acute/short term exposure
- Hazard assessment conclusion:
- no hazard identified
DNEL related information
Local effects
Long term exposure
- Hazard assessment conclusion:
- high hazard (no threshold derived)
- Most sensitive endpoint:
- irritation (respiratory tract)
Acute/short term exposure
- Hazard assessment conclusion:
- high hazard (no threshold derived)
- Most sensitive endpoint:
- irritation (respiratory tract)
DNEL related information
Workers - Hazard via dermal route
Systemic effects
Long term exposure
- Hazard assessment conclusion:
- no hazard identified
Acute/short term exposure
- Hazard assessment conclusion:
- no hazard identified
DNEL related information
Local effects
Long term exposure
- Hazard assessment conclusion:
- high hazard (no threshold derived)
- Most sensitive endpoint:
- skin irritation/corrosion
Acute/short term exposure
- Hazard assessment conclusion:
- high hazard (no threshold derived)
- Most sensitive endpoint:
- skin irritation/corrosion
Workers - Hazard for the eyes
Local effects
- Hazard assessment conclusion:
- high hazard (no threshold derived)
Additional information - workers
Hazard conclusion (worker)
I. Introduction:
Classification
Harmonized Classification - Annex VI of Regulation (EC) (No 1272/2008 (CLP Regulation)
Acute Tox.4*, H302; Skin Corr. 1A, H314; Acute Tox.2*, H330; STOT RE1, H372
Known occupational exposure limit(s):
SCOEL: 8-hour TWA 0.01 ppm (0.064 mg/m³); STEL 0.02 ppm (0.13 mg/m³)
TRGS 900: 0.02 ppm (= 0.13 mg/m³); exceeding factor: 1
MAK: 0.02 ppm (= 0.13 mg/m³); exceeding factor: 1
Other national OELs are in the range of 0.1 to 0.2 ppm (= 0.6 to 1.2 mg/m³) Limit values - Eight hours and 0.1 to 0.8 ppm (= 0.6 to 4 mg/m³) Limit value – Short term.
GESTIS International Limit Values Database: http://limitvalue.ifa.dguv.de
Hazard conclusion (worker)
II: Hazard conclusion - worker (systemic and local effects):
Route of exposure |
Local effect |
Systemic effect |
Inhalation (long term) |
high hazard band ** |
No hazard identified * |
Inhalation (short term) |
high hazard band ** |
No hazard identified * |
Dermal (long term) |
high hazard band |
No hazard identified * |
Dermal (short term) |
high hazard band |
No hazard identified * |
Hazard for eyes |
high hazard band |
|
* "In water, phosphoryl trichloride hydrolyzes to phosphoric acid and hydrochloric acid with t1/2 < 10 seconds (Riess, 2002): POCl3 + 3 H2O → H3PO4 + 3 HCl" (OECD SIDS for phosphoryl trichloride, 2004).
** Known occupational exposure limits (TRGS900/MAK)
According to ECHA Guidance Document R.8; Appendix R 8-13 (Version 2.1, November 2012) a national Occupational Exposure Limit (OEL) can be used in place of a DNEL under certain circumstances.
In the German Technische Regel für Gefahrstoffe (TRGS, Technical Rule for Hazardous Substances) 900 established by the German Federal Institute for Occupational Safety and Health (BAuA) the legally binding OEL for phosphoryl trichloride is 0.02 ppm (= 0.13 mg/m³) with an exceeding factor of 1 (Peak limitation); (TRGS900, 2016).
The OEL for phosphoryl trichloride in the TRGS 900 is based on a comprehensive opinion of the MAK Commission (MAK 2006; Senate Commission for the Investigation of Health Hazards of Chemical Compounds in the Work Area).
The rationale for the revised MAK value in the MAK value documentations - Supplement 2016 (translated from German language) is as follows:
"The critical effect of phosphoryl trichloride is the local irritation.
MAK value. There are no new data on the scientific justification of a MAK value for phosphoryl trichloride. Therefore, the comparison with the potency of phosphorus trichloride is also used for the MAK value of phosphoryl trichloride. This time, the differences in the hydrolysis rate and the associated dangers of deeper penetration into the airways (Rationale 1984) and the varying LC50 values (Supplement 2006) are not based on the differences in sensory irritation in probands and in rats. For this purpose, the results published by a Russian working group are used, However, the concentration data of this working group are presumably too low, so that only the relation between the potency of both phosphorus compounds and not the absolute values can be used for this consideration" (MAK, 2016).
SCOEL: According to the SCOEL recommendation from the scientific committee on occupational exposure limits for phosphoryl trichloride is for a 8-hour TWA: 0.01 ppm (0.064 mg/m³) and for STEL 0.02 ppm (0.13 mg/m³) (SCOEL/REC/181 Phosphoryl trichloride, Adopted 23 September 2015).
III. Systemic effects (worker)
Systemic inhalation exposure (worker)
"In water, phosphoryl trichloride hydrolyzes to phosphoric acid and hydrochloric acid with t1/2 < 10 seconds (Riess, 2002): POCl3 + 3 H2O → H3PO4 + 3 HCl" (OECD SIDS for phosphoryl trichloride, 2004).
The neutralization products of phosphoric acid and hydrochloric acid (phosphate and chloride) are naturally occurring substances in the body and at physiological concentrations no hazard is identified with respect to short-term and/or long-term system inhalation exposure.
Systemic dermal exposure (worker)
"In water, phosphoryl trichloride hydrolyzes to phosphoric acid and hydrochloric acid with t1/2 < 10 seconds (Riess, 2002): POCl3 + 3 H2O → H3PO4 + 3 HCl" (OECD SIDS for phosphoryl trichloride, 2004).
The neutralization products of phosphoric acid and hydrochloric acid (phosphate and chloride) are naturally occurring substances in the body and at physiological concentrations no hazard is identified with respect to short-term and/or long-term system dermal exposure.
The hydrolysis products are ions with high water solubility. A penetration of the hydrolysis products through the skin barrier is not expected and therefore no toxicologically relevant bioavailability is assumed.
Reproductive Toxicity – systemic effects (worker)
"Studies with phosphoryl trichloride concerning effects on fertility and development were not available and there were also no data on fertility effects for the hydrolysis products phosphoric acid and hydrochloric acid. Because phosphoryl trichloride as well as its hydrolysis products is a toxicant acting at the portal-of-entry, and because it is unlikely to reach the reproductive organs or the embryo/fetus, toxicity to reproduction or developmental toxicity in mammals are not likely to occur following exposure to phosphoryl trichloride by any route. Studies with PCl3 did not show respective effects. The other product of hydrolysis and subsequent partial neutralisation of phophorus trichloride, mono sodium phosphite, gave also no indication of a carcinogenic potential after long term oral exposure" (OECD SIDS for phosphoryl trichloride, 2004).
Therefore a separate OEL for reproductive toxicity (fertility and development) is not necessary. This is in line with the recent MAK value documentation that concludes, that there is no reason to fear damage to the embryo or fetus when the MAK value is observed (so called pregnancy group C).
Overall, "[p]hosphoryl trichloride is hydrolyzed in seconds or minutes in water or moist air. Studies on metabolism and toxicokinetics of the parent compound are not feasible. Distribution in the body is limited due to hydrolysis. Phosphoryl trichloride is a toxicant acting at the portal-of-entry. It is unlikely to reach organs distant from the portal of entry. Therefore, systemic toxicity not related to the effects of irritation is not expected by any route. The products of hydrolysis, hydrochloric acid and phosphoric acid, also act at the portal of entry” (OECD SIDS for phosphoryl trichloride, 2004).
IV. Local effects (worker)
Irritation/corrosion
Phosphoryl trichloride was found to cause corrosive effects in a skin irritation study (Imlay, 1977). Similar effects are reported in studies by Birch (1978) and Molodkina (1973). A study summary (Pauluhn, 1984) reports corrosive effects within 60 second of the dermal application of 100 µl phosphoryl trichloride.
According to Annex VI of Regulation (EC) 1272/2008 phosphoryl trichloride is harmonized classified for causing severe skin burns and eye damage (Skin Corr. 1A, H314).
Sensitization
No studies with phosphoryl trichloride (CAS no. 10025-87-3) are available for skin sensitization. The data requirement is waived due to the harmonized classification of phosphoryl trichloride as Skin Corr. 1A, H314 and the severity of the skin reactions seen in an acute dermal toxicity study and a dermal irritation study. Dermal exposure to phosphoryl trichloride will be dominated by local irritation and skin sensitisation is considered to be unlikely.
Conclusion on local effects:
"Phosphoryl trichloride reacts with water, forming hydrochloric acid and phosphoric acid. Due to this hydrolytic reaction, phosphoryl trichloride is corrosive to the skin, eyes and respiratory tract.
Studies with phosphoryl trichloride concerning sensitising properties are not available. The hydrolysis product hydrochloric acid gave no indication for a sensitising potential in humans and experimental animals. Data on phosphoric acid, the second hydrolysis product, are not available, but no specific effects are expected due to its structure" (OECD SIDS for phosphoryl trichloride, 2004).
For local effects the derivation of a long-term DNEL for dermal and inhalation toxicity is not appropriate due to the skin irritation/corrosion.
Based on the harmonized classification Skin Corr. 1A, H314 phosphoryl trichloride should be allocated to the high hazard band with respect to short-term and/or long-term local inhalation and dermal exposure and hazard to the eyes.
Additional remark:
Based on the evaluation of the MAK Commission (MAK 2016; Senate Commission for the Investigation of Health Hazards of Chemical Compounds in the Work Area) and published in the List of MAK and BAT Values 2016: Maximum Concentrations and Biological Tolerance Values at the Workplace a MAK value for inhalation toxicity of 0.02 ml/m³ (ppm) = 0.13 mg/m³ is stated (MAK, 2016).
Exceeding factor for short-term exposure is 1.
Overall, the allocation of phosphoryl trichloride to the high hazard band is justified for local inhalation and dermal effects and hazard to the eyes.
References:
MAK (2016). Kreis P, Bartsch R, van Thriel C, Brüning T, Hartwig A and MAK Commission 2016. Phosphorylchlorid [MAK Value Documentation in German language, 2016]. The MAK Collection for Occupational Health and Safety. 1:252–255.
SCOEL/REC/181 Phosphoryl trichloride, Adopted 23 September 2015
OECD SIDS (2004). Phosphoryl trichloride (CAS no. 10025-87-3); http://www.inchem.org/documents/sids/sids/10025873.pdf
General Population - Hazard via inhalation route
Systemic effects
Long term exposure
- Hazard assessment conclusion:
- no hazard identified
Acute/short term exposure
- Hazard assessment conclusion:
- no hazard identified
DNEL related information
Local effects
Long term exposure
- Hazard assessment conclusion:
- high hazard (no threshold derived)
- Most sensitive endpoint:
- irritation (respiratory tract)
Acute/short term exposure
- Hazard assessment conclusion:
- high hazard (no threshold derived)
- Most sensitive endpoint:
- irritation (respiratory tract)
DNEL related information
General Population - Hazard via dermal route
Systemic effects
Long term exposure
- Hazard assessment conclusion:
- no hazard identified
Acute/short term exposure
- Hazard assessment conclusion:
- no hazard identified
DNEL related information
Local effects
Long term exposure
- Hazard assessment conclusion:
- high hazard (no threshold derived)
- Most sensitive endpoint:
- skin irritation/corrosion
Acute/short term exposure
- Hazard assessment conclusion:
- high hazard (no threshold derived)
- Most sensitive endpoint:
- skin irritation/corrosion
General Population - Hazard via oral route
Systemic effects
Long term exposure
- Hazard assessment conclusion:
- no hazard identified
Acute/short term exposure
- Hazard assessment conclusion:
- no hazard identified
DNEL related information
General Population - Hazard for the eyes
Local effects
- Hazard assessment conclusion:
- high hazard (no threshold derived)
Additional information - General Population
Hazard conclusion (general population)
I: Hazard conclusion – general population (systemic and local effects):
Route of exposure |
Local effect |
Systemic effect |
Inhalation (long term) |
high hazard band |
No hazard identified * |
Inhalation (short term) |
high hazard band |
No hazard identified * |
Dermal (long term) |
high hazard band |
No hazard identified * |
Dermal (short term) |
high hazard band |
No hazard identified * |
Oral (long term) |
- |
No hazard identified * |
Oral (short term) |
- |
No hazard identified * |
Hazard for eyes |
high hazard band | |
* "In water, phosphoryl trichloride hydrolyzes to phosphoric acid and hydrochloric acid with t1/2 < 10 seconds (Riess, 2002): POCl3 + 3 H2O → H3PO4 + 3 HCl" (OECD SIDS for phosphoryl trichloride, 2004).
II. Systemic effects (general population)
Systemic oral and inhalation exposure (general population)
"In water, phosphoryl trichloride hydrolyzes to phosphoric acid and hydrochloric acid with t1/2 < 10 seconds (Riess, 2002): POCl3 + 3 H2O → H3PO4 + 3 HCl" (OECD SIDS for phosphoryl trichloride, 2004).
The neutralization products of phosphoric acid and hydrochloric acid (phosphate and chloride) are naturally occurring substances in the body and at physiological concentrations no hazard is identified with respect to short-term and/or long-term system inhalation exposure.
Systemic dermal exposure (general population)
"In water, phosphoryl trichloride hydrolyzes to phosphoric acid and hydrochloric acid with t1/2 < 10 seconds (Riess, 2002): POCl3 + 3 H2O → H3PO4 + 3 HCl" (OECD SIDS for phosphoryl trichloride, 2004).
The neutralization products of phosphoric acid and hydrochloric acid (phosphate and chloride) are naturally occurring substances in the body and at physiological concentrations no hazard is identified with respect to short-term and/or long-term system dermal exposure.
The hydrolysis products are ions with high water solubility. A penetration of the hydrolysis products through the skin barrier is not expected and therefore no toxicologically relevant bioavailability is assumed.
Reproductive Toxicity – systemic effects (general population)
"Studies with phosphoryl trichloride concerning effects on fertility and development were not available and there were also no data on fertility effects for the hydrolysis products phosphoric acid and hydrochloric acid. Because phosphoryl trichloride as well as its hydrolysis products is a toxicant acting at the portal-of-entry, and because it is unlikely to reach the reproductive organs or the embryo/fetus, toxicity to reproduction or developmental toxicity in mammals are not likely to occur following exposure to phosphoryl trichloride by any route. Studies with PCl3 did not show respective effects. The other product of hydrolysis and subsequent partial neutralisation of phophorus trichloride, mono sodium phosphite, gave also no indication of a carcinogenic potential after long term oral exposure" (OECD SIDS for phosphoryl trichloride, 2004).
Overall, "[p]hosphoryl trichloride is hydrolyzed in seconds or minutes in water or moist air.
Studies on metabolism and toxicokinetics of the parent compound are not feasible. Distribution in the body is limited due to hydrolysis. Phosphoryl trichloride is a toxicant acting at the portal-of-entry. It is unlikely to reach organs distant from the portal of entry. Therefore, systemic toxicity not related to the effects of irritation is not expected by any route. The products of hydrolysis, hydrochloric acid and phosphoric acid, also act at the portal of entry” (OECD SIDS for phosphoryl trichloride, 2004).
III. Local effects (general population)
Irritation/corrosion
Phosphoryl trichloride was found to cause corrosive effects in a skin irritation study (Imlay, 1977). Similar effects are reported in studies by Birch (1978) and Molodkina (1973). A study summary (Pauluhn, 1984) reports corrosive effects within 60 second of the dermal application of 100 µl phosphoryl trichloride.
According to Annex VI of Regulation (EC) 1272/2008 phosphoryl trichloride is harmonized classified for causing severe skin burns and eye damage (Skin Corr. 1A, H314).
Sensitization
No studies with phosphoryl trichloride (CAS no. 10025-87-3) are available for skin sensitization. The data requirement is waived due to the harmonized classification of phosphoryl trichloride as Skin Corr. 1A, H314 and the severity of the skin reactions seen in an acute dermal toxicity study and a dermal irritation study. Dermal exposure to phosphoryl trichloride will be dominated by local irritation and skin sensitisation is considered to be unlikely.
Conclusion on local effects:
"Phosphoryl trichloride reacts with water, forming hydrochloric acid and phosphoric acid. Due to this hydrolytic reaction, phosphoryl trichloride is corrosive to the skin, eyes and respiratory tract. Studies with phosphoryl trichloride concerning sensitising properties are not available. The hydrolysis product hydrochloric acid gave no indication for a sensitising potential in humans and experimental animals. Data on phosphoric acid, the second hydrolysis product, are not available, but no specific effects are expected due to its structure" (OECD SIDS for phosphoryl trichloride, 2004).
For local effects the derivation of a long-term DNEL for dermal and inhalation toxicity is not appropriate due to the skin irritation/corrosion.
Based on the harmonized classification Skin Corr. 1A, H314 phosphoryl trichloride should be allocated to the high hazard band with respect to short-term and/or long-term local inhalation and dermal exposure and hazard to the eyes.
Overall, the allocation of phosphoryl trichloride to the high hazard band is justified for local inhalation and dermal effects and hazard to the eyes.
References:
OECD SIDS (2004). Phosphoryl trichloride (CAS no. 10025-87-3); http://www.inchem.org/documents/sids/sids/10025873.pdf
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