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Determining Environmental
Assessment Levels (EALs) for
amines and degradation by-products
-
And the poetic assertions of Donald Rumsfeld
Rick Gould and David Howard
Environment Agency
September 2023
The known and unknown
2
“There are known knowns,
These are the things we know we know.
We also know there are known unknowns.
That is to say, we know there are some things
we do not know.
But there are also unknown unknowns.
The ones we don’t know we don’t know.”
What we know
3
• More than one type of
carbon-capture plant
• Amine-based solvent-
capture most common
• Emissions of amines and
degradation by-products
• Nitramines and
nitrosamines
• Varying degrees of
toxicity
• Need to assess and
reduce risks
Over a decade of global research
4
Amine degradation by-products
5
1. Reactions believed to occur predominantly in the atmosphere
2. CERC ADMS-Amines Module
Known unknowns
6
• Regulatory – relatively new process, permitting beginning
• Environmental assessment levels (EALs) unavailable for
most amines and by-products
• Currently only EALs for ethanolamine (MEA) and N-
Nitrosodimethylamine (NDMA)
• Little or no toxicity data for many compounds
• Industrial reluctance to sharing data on amine-based
solvents
• Commercial confidentiality - proprietary solvents
• Need for environmental-risk factors
• Environmental Assessment Levels (EALs for modelling)
• Measurement methods
Regulatory loop
7
Target chemicals for EALs
8
Primary
amines
Secondary
amines
Tertiary
amines
Nitramines Nitrosamines
Team: Ricardo, UKHSA, Environment Agency, plus CCSA, other stakeholders
Five-step process
9
Step 1
Collating the original list of chemicals
• Harmonised/notified
classifications
• Structural alerts
• Mutagenic,
carcinogenic, skin
sensitisation
Step 2
Collating hazard data
Step 5
Overall ranking
Step 4
Scoring - toxicological reviews
Step 3
Scoring chemicals according to hazard
• 40 substances
• Included intermediaries and breakdown
products
Collate the list of chemicals
Harmonised classifications
(for relevant hazard codes relating
to inhalation)
Group 1 16 chemicals
Notified classifications
(for relevant hazard codes relating
to inhalation)
Group 2 14 chemicals
No classifications / no database
entry (ECHA)
Group 3 10 chemicals
ECHA: The European Chemicals Agency
Hazard criteria
11
Eye
irritation
Acute
inhalation
Sensitising
Skin, respiratory
Organ
toxicity
(Acute)
CMR
Carcinogenic,
mutagenic,
reproductive
Organ
toxicity
(Chronic)
Data and methodologies
12
Databases • Agency for Toxic Substances and
Disease Registry (ATSDR)
• Organisation for Economic Co-
operation and Development
(OECD) Chemicals Database
• European Chemicals Agency
(ECHA)
• OECD
Methodologies • Cramer Classification (Low,
Medium, High)
• Simplified Molecular-Input Line-
Entry System (SMILES)
• ECHA Read Across Assessment
Framework (RAAF)
Tools Toxtree – Open Source software for
structural alerts
Toxtree
13
Source: https://toxtree.sourceforge.net/
Toxic hazard
estimation by a
decision-tree
approach
The fifteen compounds
14
Primary amines
2-amino-2-methyl-propanol
Secondary amines
Dimethylamine
Diethylamine
Piperazine
Diethanolamine
Morpholine
Tertiary amines
2-(diethylamino)ethanol
N-Methyldiethanolamine
Nitramines
N-nitrodiethanolamine
Diethylnitramine
Dimethylnitramine
N-nitromorpholine
2-methyl-2-(nitroamino)-1-propanol
Nitrosamines
N-nitrosopiperazine
N-nitrosomorpholine
From data to EALs
15
Sufficient data for EALs
Primary amines
2-amino-2-methyl-propanol
Secondary amines
Dimethylamine
Diethylamine
Piperazine
Diethanolamine
Morpholine
Tertiary amines
2-(diethylamino)ethanol
Nitrosamines
N-nitrosomorpholine
Insufficient or no data for EALs
Nitramines
N-Methyldiethanolamine
N-nitrodiethanolamine
Diethylnitramine
Dimethylnitramine
N-nitromorpholine
2-methyl-2-(nitroamino)-1-propanol
Nitrosamines
N-nitrosopiperazine
ECHA Read Across Assessment Framework
16
Read-across methods
17
Physical
Analogues:
e.g. NDMA
Chemical
Toxicity
Structural Patterns
Properties Categories
Analytical
data
Next steps
18
• Finalise report and dossiers/EALs
• Includes guidance on the read-across
methodology
• Operators and 3rd parties to be able to develop their
own EALs
• Robust and reproducible
• Consultation this autumn
• Publication of EALs
• Target – by end of March 2024
Contact
19
• Rick Gould
richard.gould@environment-agency.gov.uk

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16.30 Environmental Assessment Levels in relation to Carbon Capture and Storage.pdf

  • 1. Determining Environmental Assessment Levels (EALs) for amines and degradation by-products - And the poetic assertions of Donald Rumsfeld Rick Gould and David Howard Environment Agency September 2023
  • 2. The known and unknown 2 “There are known knowns, These are the things we know we know. We also know there are known unknowns. That is to say, we know there are some things we do not know. But there are also unknown unknowns. The ones we don’t know we don’t know.”
  • 3. What we know 3 • More than one type of carbon-capture plant • Amine-based solvent- capture most common • Emissions of amines and degradation by-products • Nitramines and nitrosamines • Varying degrees of toxicity • Need to assess and reduce risks
  • 4. Over a decade of global research 4
  • 5. Amine degradation by-products 5 1. Reactions believed to occur predominantly in the atmosphere 2. CERC ADMS-Amines Module
  • 6. Known unknowns 6 • Regulatory – relatively new process, permitting beginning • Environmental assessment levels (EALs) unavailable for most amines and by-products • Currently only EALs for ethanolamine (MEA) and N- Nitrosodimethylamine (NDMA) • Little or no toxicity data for many compounds • Industrial reluctance to sharing data on amine-based solvents • Commercial confidentiality - proprietary solvents • Need for environmental-risk factors • Environmental Assessment Levels (EALs for modelling) • Measurement methods
  • 8. Target chemicals for EALs 8 Primary amines Secondary amines Tertiary amines Nitramines Nitrosamines Team: Ricardo, UKHSA, Environment Agency, plus CCSA, other stakeholders
  • 9. Five-step process 9 Step 1 Collating the original list of chemicals • Harmonised/notified classifications • Structural alerts • Mutagenic, carcinogenic, skin sensitisation Step 2 Collating hazard data Step 5 Overall ranking Step 4 Scoring - toxicological reviews Step 3 Scoring chemicals according to hazard
  • 10. • 40 substances • Included intermediaries and breakdown products Collate the list of chemicals Harmonised classifications (for relevant hazard codes relating to inhalation) Group 1 16 chemicals Notified classifications (for relevant hazard codes relating to inhalation) Group 2 14 chemicals No classifications / no database entry (ECHA) Group 3 10 chemicals ECHA: The European Chemicals Agency
  • 12. Data and methodologies 12 Databases • Agency for Toxic Substances and Disease Registry (ATSDR) • Organisation for Economic Co- operation and Development (OECD) Chemicals Database • European Chemicals Agency (ECHA) • OECD Methodologies • Cramer Classification (Low, Medium, High) • Simplified Molecular-Input Line- Entry System (SMILES) • ECHA Read Across Assessment Framework (RAAF) Tools Toxtree – Open Source software for structural alerts
  • 14. The fifteen compounds 14 Primary amines 2-amino-2-methyl-propanol Secondary amines Dimethylamine Diethylamine Piperazine Diethanolamine Morpholine Tertiary amines 2-(diethylamino)ethanol N-Methyldiethanolamine Nitramines N-nitrodiethanolamine Diethylnitramine Dimethylnitramine N-nitromorpholine 2-methyl-2-(nitroamino)-1-propanol Nitrosamines N-nitrosopiperazine N-nitrosomorpholine
  • 15. From data to EALs 15 Sufficient data for EALs Primary amines 2-amino-2-methyl-propanol Secondary amines Dimethylamine Diethylamine Piperazine Diethanolamine Morpholine Tertiary amines 2-(diethylamino)ethanol Nitrosamines N-nitrosomorpholine Insufficient or no data for EALs Nitramines N-Methyldiethanolamine N-nitrodiethanolamine Diethylnitramine Dimethylnitramine N-nitromorpholine 2-methyl-2-(nitroamino)-1-propanol Nitrosamines N-nitrosopiperazine
  • 16. ECHA Read Across Assessment Framework 16
  • 18. Next steps 18 • Finalise report and dossiers/EALs • Includes guidance on the read-across methodology • Operators and 3rd parties to be able to develop their own EALs • Robust and reproducible • Consultation this autumn • Publication of EALs • Target – by end of March 2024