Environmental Fate of Nitramines and Nitrosamines Released as - - PowerPoint PPT Presentation

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Environmental Fate of Nitramines and Nitrosamines Released as - - PowerPoint PPT Presentation

Dec 11, 2023 506 likes •664 views

Environmental Fate of Nitramines and Nitrosamines Released as Degradation Products from Post Combustion CO 2 -Capture Plants Lisbet Srensen, M.Sc. Odd Gunnar Brakstad, Astrid Hyldbakk, Kolbjrn Zahlsen, Eirik da Silva, Andy Booth SINTEF

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SINTEF Materials and Chemistry

Lisbet Sørensen, M.Sc.

Odd Gunnar Brakstad, Astrid Hyldbakk, Kolbjørn Zahlsen, Eirik da Silva, Andy Booth

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Environmental Fate of Nitramines and Nitrosamines Released as Degradation Products from Post Combustion CO2-Capture Plants

lisbet.sorensen@sintef.no

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SINTEF Materials and Chemistry

Amines Nitrosamines Nitramines Other degradation products

2 lisbet.sorensen@sintef.no

Dissolution into water droplets Deposition in terrestrial and aquatic environmental compartments Release from amine based PCCS plant Transport and transformation in the atmosphere

?

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SINTEF Materials and Chemistry

3 lisbet.sorensen@sintef.no

NDMA NDELA NMOR NPz DNPz

Nitramines

O N N O

N N O N N O O H N OH N O O N N N H

N N O

MEA-NO2 Pz-NO2 MNA DMNA

N N

+ O

  • O

NH N

+ O

  • O

O H NH N

+ O

  • O

O

  • N

+ O

N N H

MEA Piperazine

HN NH

Nitrosamines

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SINTEF Materials and Chemistry

4 lisbet.sorensen@sintef.no

Evaluating environmental fate and effects

Initial deposition site Transport mechanisms

  • leaching (rain)
  • natural waters (river)

Degradation in "final" or temporary matrices Yes/No - > Degradation rates

  • photodegradation
  • biodegradation

Assumptions: Atmospheric release - > wet deposition Toxicity

  • bioavailability
  • drinking water (human)
  • uptake in plants
  • uptake in organisms (including fish etc.)
  • uptake mechanisms
  • concentration levels

Risk assessment

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SINTEF Materials and Chemistry

5 lisbet.sorensen@sintef.no

Previous work – Photodegradation in natural sunlight

A theoretical and experimental study has looked at the photolytic degradability of nitramines and nitrosamines exposed to natural sunlight Degradation half-lives of nitrosamines were found to be in the range 6-12 minutes Nitramines showed no potential of photodegradation by sunlight

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SINTEF Materials and Chemistry

6 lisbet.sorensen@sintef.no

Previous work – Biodegradability in freshwater

Test of ready biodegradability (OECD) showed that only nitrosamines and nitramines with –OH groups had potential to biodegrade in natural freshwater (e.g. drinking water) Tests at low concentrations revealed a half-life of NDELA of ~30 days, regardless of initial concentration (1-100 µg/L).

Test solution 1 L Headspace

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SINTEF Materials and Chemistry

7 lisbet.sorensen@sintef.no

Selection of compounds for soil and biodegradation study

Biodegradable in freshwater, Polar Not biodegradable in freshwater, less polar Nitramines Nitrosamines

N N

+ O

  • O

N N O

O H N OH N O

O H NH N

+ O

  • O

NDMA DMNA MEA-NO2 NDELA

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SINTEF Materials and Chemistry

8 lisbet.sorensen@sintef.no

Chemical analysis of N-amines

Sample preparation is challenging – highly water soluble compounds – some have low boiling point or are otherwise sensitive to heat Implications:

  • preferrable to sample from the water phase in two-phase

systems (e.g. soil-water)

  • low LODs for analysis necessary

– avoid pre-concentration step – expected environmental concentrations are very low Analysis by LC –MS/MS QqQ

  • Direct injection of water sample
  • Deuterated ISTD for quantification

Ion source LOQ (ppb) DMNA ESI 1 MEA-NO2 APCI 0.1 NDMA APCI 1 NDELA APCI/ESI 1

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SINTEF Materials and Chemistry

9 lisbet.sorensen@sintef.no

Biodegradability under anoxic conditions

Clay as bacteria source 100 mL test units

  • wet clay
  • sterilized freshwater 1:4
  • nutrients
  • sterile control units included

Redox and pH measurements to ensure stabile conditions Pre-incubation of test units for 26 days prior to experiment start-up At experiment start-up, the chemical were spike in the samples at initial concentrations of 100 µg/L Sampling regime: 0, 7, 14, 21, 28 and 56 days

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SINTEF Materials and Chemistry

10 lisbet.sorensen@sintef.no

Biodegradability under anoxic conditions

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SINTEF Materials and Chemistry

11 lisbet.sorensen@sintef.no

Soil adsorption

Soil pH (in 0.01 M CaCl2) Organic carbon content % Soil texture Porosity (water content %) Eberg 6,1 4,5 Fat clay 30 Leistad 6,9 6,1 Loamy clay 29 Halsen 4,6 1,0 Loamy silt 6 Glava 4,5 2,5 Blue clay 24

Four soil types selected for testing according to OECD 106

Trondheim

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SINTEF Materials and Chemistry

12 lisbet.sorensen@sintef.no

Soil adsorption

The soil was air-dried and suspended in 0.01 M CaCl2 at a ratio of 1:5 The suspension was sterilized before spiking in the chemical The solution was shaken for 2-7 days Adsorption in %:

  • No adsorption to soil observed
  • If nitramines and nitrosamines are deposited in soil, wash out and further transport to

groundwater must be expected

  • Soil is not a final sink of N-amines

Eberg Halsen Glava Leistad NDMA < 10 < 10 < 10 < 10 NDELA < 10 < 10 < 10 < 10 DMNA < 10 < 10 < 10 < 10 MEA-NO2 < 10 < 10 < 10 < 10

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SINTEF Materials and Chemistry

13 lisbet.sorensen@sintef.no

Biodegradability in soil?

Non-sterilized soil-water samples - > depletion of some test compounds were observed Not explained by adsorption Depletion in % (48 hours):

  • May be attributed to biodegradation in soil
  • This appear to be a very rapid process
  • Needs further investigation

Eberg Halsen Glava Leistad NDMA < 10 < 10 < 10 < 10 NDELA 76 ± 2 < 10 < 10 < 10 DMNA 61 ± 4 < 10 48 ± 15 15 ± 2 MEA-NO2 96 ± 1 27 ± 4 < 10 37 ± 3

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SINTEF Materials and Chemistry

14 lisbet.sorensen@sintef.no

Summary

Given an atmospheric release of nitrosamines or nitramines, followed by wet deposition If deposited in freshwater:

  • Nitrosamines will degrade rapidly by photolysis
  • Nitramines are persistent to photodegradation
  • N-amines containing –OH groups will be susceptible to aerobic biodegradation and

relatively short half-lives have been observed for some compounds

  • The same trend is observed in anoxic environment
  • Less biodegradable nitramines may persist in the water and potentially accumulate

If deposited in a terrestric environment (soil):

  • Neiter nitrosamines nor nitramines will adsorb to and be bound in the soil
  • > If environmental conditions allow leaching to groundwater or surrounding lakes
  • r rivers, this is likely to occur
  • It could be that soil bacterial communities will degrade the N-amines (rapidly)
  • This hypothesis need further investigation
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SINTEF Materials and Chemistry

The SOLVfate funders: Gassnova Enel Mitsubishi Heavy Industries The team at: SINTEF Environmental Technology SINTEF CO2 Capture Technology SINTEF Biotechnology and Nanomedicine

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Acknowledgements