1. Green Assessment for Analytical Methods
Julee Driver*, Douglas Raynie
SDSU Chemistry and Biochemistry

2. Why does green matter? Energy consumption Environment Health Safety
Life
Energy consumption
Safety
Environment
Health
Why do we care if something is green? Could hurt our environment – sustainability – hurt future generations. Could harm us – toxicity. Petroleum as an energy source is limited in quantity – need to conserve. Some products/methods/processes are greener than others and often there are alternatives available should one wish to operate in a greener manner.

3. Opportunities for greenness
Solvents, Reagents
Equipment, Instrumentation
Sample prep.
Analysis
Take sample – sample type and amount; Analysis – sample prep time, analysis time.

4. Non-green consequences
Solvents, reagents
Toxicity, Bioaccumulation, Persistence
Reactivity, Flammability, Waste
Equipment, instrumentation
Safety
Energy
Sample prep.
Waste
Analysis

5. 12 principles of green chemistry
1. Prevent waste.
2. Maximize atom economy.
3. Design less hazardous chemical synthesis.
4. Design safer chemicals.
5. Use safer solvents and reaction conditions.
6. Design for energy efficiency.
7. Use renewable feedstocks.
8. Reduce use of derivatives.
9. Use catalysts.
10. Design for degradation.
11. Analyze in real time.
12. Minimize potential for accidents.

6. Green assessment criteria
Environmental hazard
Greenhouse gas chemical
Ozone depletion
Ozone generation
Persistent, bioaccumulative
Health hazard
Toxicity
Carcinogenicity
Irritant
Safety hazard
Flammability
Corrosivity
Reactivity
Waste Properties
Air, land, water emissions
Waste amount
Energy Efficiency
Solvent evaporation
Instrumentation use

7. Other assessments ‘Greenness Profile’ Developed by
ACS Green Chemistry Institute in collaboration with 25 environmental method experts
Profile was published and applied to methods in NEMI database
Criteria evaluated:
PBT
Hazard
Corrosive
Waste amount
PBT – meant included in EPT TRI PBT list; hazard meant included in EPT TRI listed chemical, RCRA D,K,P,U; corrosive by pH; Waste amount greater than 50 grams.

8. Other assessments – ‘Greenness profile’
Criterion score:
Green
Less green
Criterion
How to decide?
PBT
Is chemical listed on EPA’s TRI PBT?
Hazard
Is chemical listed on EPA’s TRI1 or RCRA subpart D (F, P, or U)?
Corrosive
Is pH during analysis < 2 or > 12?
Waste Amount
Is the waste > 50 g?
‘Quantitative’ value assigned to each criteria = ‘Green’ or ‘less green’; For each, if yes then assignment is ‘less green’, if no then assignment is ‘green’; Basically pass or fail.

9. Other assessments - ‘Greenness Profile’
Profile symbol
PBT
Hazard
Corrosive
Waste

11. Other assessments – ‘Green index value’
* Developed by Rich Gurney, Simmons College

12. Assessment comparison
12 Principles of Green Chemistry
GCI – NEMI
GIV
Dolphin
This assessment
Waste X
Toxicity
Environmental persistence
Accident potential
Energy efficiency
Renewable feedstocks

13. Greenness assessment for analytical methods
Goals for new assessment:
User friendly
Have a clear and simple evaluation process
Increase the range of discrimination possible
Of methods in NEMI database, 2/3 fail waste. If nearly all fail, is the evaluation effective?
Possible to differentiate between how badly one fails?
Include energy use as a criteria
Develop assessment which can be applied to any chemical process

14. Greenness assessment criteria
Flammability
Health hazard
Reactivity
4. Use and generate substances that possess little or no toxicity to human health and the environment
Specific hazard
NFPA Hazard Symbol

15. Green assessment – health criteria
NFPA score
0 = most green = minimal or slight toxicity
Recognized innocuous, minor irritation possible
2 = less green = moderate toxicity
Intense or continued exposure could cause temp. incapacitation or residual injury
4 = least green = serious toxicity
Serious temp. or residual injury on short term exposure or a known or suspected human carcinogen
Since NFPA ratings are a guide for much of our analysis, I’ll give an example of the meaning of their ratings; health is the blue quadrant; give an example – say cyclohexane has a ‘4’ health rating because…

16. Green assessment – scoring criteria
1 =
2 =
3 =

17. Green assessment – health hazard
1 =
2 =
3 =
Slightly toxic, slight irritant; NFPA health hazard score is 0 or 1.
Moderately toxic; could cause temporary incapacitation; NFPA = 2.
Serious injury on short term exposure; known or suspected small animal carcinogen; NFPA = 3 or 4.

18. Green assessment – safety hazard
1 =
2 =
3 =
Based on NFPA flammability, reactivity, special hazard ratings

19. Green assessment – environmental hazard
1 =
2 =
3 =
Based on use or generation of:
Greenhouse gas generators
Ozone generators
Ozone depleters
Persistance
Bioaccumulation

20. Green assessment – waste properties
1 =
2 =
3 =
Based on ratio of waste to sample size
Type of waste also considered

21. Green assessment – energy
1 =
2 =
3 =
Wet chemistry method.
Instrumental method such as GC, HPLC; extensive solvent evaporation required.
Instrumental method such as ICP-MS; or AA.

22. Green assessment - profile
Health
Environmental
Energy
Waste F
Safety

23. Aknowledgements Paul T. Jackson, PhD Associate professor
St. Olaf College, Northfield MN
Jennifer Young, PhD
Senior program manager
ACS Green Chemistry Institute