In preparation for OSIRIS-REx and other future sample return missions concerned with analyzing organics, we conducted an Organic Contamination Baseline Study for JSC Curation Labsoratories in FY12. For FY12 testing, organic baseline study focused only on molecular organic contamination in JSC curation gloveboxes: presumably future collections (i.e. Lunar, Mars, asteroid missions) would use isolation containment systems over only cleanrooms for primary sample storage. This decision was made due to limit historical data on curation gloveboxes, limited IR&D funds and Genesis routinely monitors organics in their ISO class 4 cleanrooms

Calaway, Michael J.

NASA Technical Reports Server

Michael J. Calaway 
Jacobs Technology (ESCG) 
Astromaterials Acquisition and Curation Office 
NASA Johnson Space Center 
 
CAPTEM MEETING 
March 24, 2013 
1 
https://ntrs.nasa.gov/search.jsp?R=20130011274 2019-08-31T00:19:58+00:00Z
2 
In preparation for OSIRIS-REx and other future sample return missions concerned with 
analyzing organics, we conducted an Organic Contamination Baseline Study for JSC 
Curation Laboratories in FY12: 
Compiled a history of JSC Curation collections involving organic laboratory testing 
from Apollo program to present (over 40 years):  
Apollo Program and the Lunar Receiving Laboratory 
Lunar interim curation laboratory and the construction of B31N 
Xylan contamination in Lunar lab and lessons learned 
ALH84001 and the Organic Contamination Review Group – Bada committee 
Genesis Mission and Prospects of Mars Sample Return (1990s) 
Organic Contamination Results in Gloveboxes from 1998 to 2001 and the Dixon Report 
Genesis Testing – a Decade of Detailed Organic Testing in an ISO Class 4 Cleanroom 
For FY12 testing, organic baseline study focused only on molecular organic 
contamination in JSC curation gloveboxes:  presumably future collections (i.e. Lunar, 
Mars, asteroid missions) would use isolation containment systems over only 
cleanrooms for primary sample storage.  This decision was made due to limit 
historical data on curation gloveboxes, limited IR&D funds and Genesis routinely 
monitors organics in their ISO class 4 cleanrooms. 
2012 Organic Contamination Baseline Study 
Advanced curation glovebox (ACG) and an Apollo 11 Lunar processing glovebox (LPG) 
were chosen for molecular organic contamination testing .  The test plan was to clean 
each glovebox with curatorial technical support procedure (TSP) 23: Ultra-Pure Water 
(UPW) ONLY cleaning.  Afterwards, the following tests would be done: 
Liquid particle counts on UPW rinse water from cleaning 
SEM particle identification from UPW rinse filters from cleaning 
TD-GC-MS analysis by Vertical Silicon Wafer Exposure 
TD-GC-MS analysis by Surface Silicon Wafer Exposure 
TD-GC-MS analysis by Absorbent Tube Exposure 
NVR/FT-IR Analysis by Methylene Chloride Surface Exposure (ACG ONLY) 
GC-MS analysis by Methylene Chloride Surface Exposure (ACG ONLY) 
Three measurement constraints:   
1) Test the difference between a working glovebox (LPG) after being cleaned 
compared to a cleaned glovebox (ACG) without samples, tools, and supplies.     
2) Test current cleaning procedures and the difference of cleaning a glovebox in-situ 
in the laboratory versus relocating a glovebox to preclean for cleaning. 
3) The methylene chloride surface exposure was only done in the ACG due to the 
remote possibility of contaminating lunar samples. 
2012 Organic Contamination Glovebox Testing 
3 
Possible Known Organic Material Sources: 
  
Teflon – bags, jars, and fittings 
Nylon – tool bags 
Viton – gaskets 
Polycarbonate – window 
Neoprene – gloves 
Silicone – heat sealer 
Note: Lunar sample processing/handling 
during testing and use of the heat 
sealer on Teflon bags. 
Lunar Processing Glovebox (LPG)  
4 
LPG located inside the ISO Class 6 
cleanroom environment 
Advanced Curation Glovebox (ACG) 
ACG located inside the ISO Class 5 
cleanroom environment 
Possible Known Organic Material Sources: 
  
Viton – gaskets 
Hypalon – gloves 
 
Note: Testing with minimal disturbance.  
No sample processing or tool use 
during testing. 
 
Advanced Curation Glovebox TSP 23 Cleaning 
UPW Particle Count per 10 ml 
Particle 
Size (µm) 
Genesis 
Before 
Control Rinse 1 Rinse 2 Rinse 3 
Final 
Rinse 
Genesis 
After 
Control 
MIL-STD 
Level 50 
1 27 331.33 104526.33 4412.00 13289.75 45 
3 1 14.00 21167.00 533.33 1806.75 3 
5 1 5.67 6503.33 159.00 707.75 0 5.3 
10 1 1.67 492.33 19.00 26.75 0 
25 0 0.33 4.33 0.33 0.50 0 0.34 
50 0 0.00 0.00 0.00 0.25 0 
100 0 0.00 0.00 0.00 0.25 0 
150 0 0.00 0.00 0.00 0.25 0 
Note: all counts are averages of measurements. 
Lunar Glovebox TSP 23 Cleaning 
UPW Particle Count per 10 ml 
Particle 
Size 
(µm) 
Genesis 
Before 
Control 
Lunar 
UPW 
Baseline Rinse 1 Rinse 2 
Final 
Rinse 
Genesis 
After 
Control 
MIL-STD 
Level 50 
1 2 886.40 3622.67 2005.33 1246.60 4 
3 0 54.80 749.67 394.33 128.80 0 
5 0 15.20 340.33 185.67 40.20 0 5.3 
10 0 1.60 101.33 47.00 6.20 0 
25 0 0.00 22.00 0.67 0.60 0 0.34 
50 0 0.00 19.33 0.00 0.40 0 
100 0 0.00 18.67 0.00 0.40 0 
150 0 0.00 17.00 0.00 0.40 0 
Note: all counts are averages of measurements. 5 
SEM Particle Analysis from Glovebox TSP 23 Cleaning 
392 particles were surveyed with over 450 spot analyses  
with a low angled backscatter electron (LABe) detector on a JEOL JSM-7600F FE-SEM 
6 
Metals
29%
Organics
36%
Geologic
Material
35%
Lunar Apollo 11 Processing Glovebox
0.8 µm Filter
Metals
19%
Organics
57% Geologic
Material
24%
Advanced Curation Glovebox
0.8 µm Filter
Hydrocarbons
Control 
Wafer 
(ng/cm²)
Vertical 
Exposure 
(ng/cm²)
Surface 
Exposure 
(ng/cm²)
Low boilers C7-C10 * * 0.2
Medium boilers >C10-C20 * 1.8 2.5
High boilers >C20 * 0.1 0.2
Sum >= C7 * 1.9 2.9
Identified Compounds
Diethylformamide * * *
Diethylacetamide * * *
Alkyl amine * * *
2-Butoxyethyl acetate * * *
Octafluoropentanal(m/z:51,69,100,131,151,181,200,231,281) * * *
2-Cyclohexen-1-one, 3,5,5-trimethyl- * 0.3 0.3
Dibutylformamide * 0.2 0.2
Cyclo(Me2SiO)6 * 0.2 0.2
2,6-di-tert-Butylquinone * * *
Cyclo(Me2SiO)7 * * *
Cyclo(Me2SiO)8 * * 0.1
Cyclo(Me2SiO)9 * 0.2 0.3
Dibutyl phthalate * * 0.1
Cyclo(Me2SiO)10 * 0.1 0.2
Siloxane * 0.1 0.1
* Recording Limit = < 0.1 ng/cm²
Lunar Curation Glovebox
7 
TD-GC-MS Analysis Vertical and Surface Silicon Wafer Exposure 
TD-GC-MS conducted by Air Liquide Electronics Balazs Nanoanalysis , Fremont, CA  
 Lunar Glovebox TD-GC-MS Results 
 
Identified Chemicals above reporting limit:  
 
2-Cyclohexen-1-one, 3,5,5-trimethyl- (Isophorone):  solvent used in printing 
inks, paints, lacquers, adhesives, copolymers, coatings, finishings and 
pesticides.  Also used as a chemical intermediate:  ingredient in wood 
preservatives and floor sealants. 
 
Dibutylformamide (DBF): additive or reducing agent used in manufacturing of 
polymers, rubbers, medicines, herbicides, flame retardants in fabrics, solvents, 
inks, and photo paper. 
 
Dibutyl phthalate (DBP): plasticizer is found in adhesives, solvents and inks. 
 
Cyclo(Me2SiO)6 
Cyclo(Me2SiO)8 
Cyclo(Me2SiO)9 
Cyclo(Me2SiO)10 
Siloxane – mainly found in silicone adhesives, etc. 
 
Note: silicones are most likely from heat sealer 
8 
Hydrocarbons
Control 
Wafer 
(ng/cm²)
Vertical 
Exposure 
(ng/cm²)
Surface 
Exposure 
(ng/cm²)
Low boilers C7-C10 * 0.4 0.4
Medium boilers >C10-C20 * 7.1 9.6
High boilers >C20 * 1.1 1.8
Sum >= C7 * 8.6 11.8
Identified Compounds
Dibutylamine * * *
N-Formylpiperidine * * 0.1
2-(2-Butoxyethoxy)ethanol * 0.6 1
Caprolactam * 0.2 0.6
Tripropylene glycol * * *
Dibutylformamide * * 0.1
N,N-Dibutylacetamide * * *
Texanol * * *
Dimethyl phthalate * * *
Diisopropyl adipate * * *
2,6-di-butyl-2,5-cyclohexadiene-1,4-dione * * *
2,6-di(t-butyl)-4-hydroxy-4-methyl-2,5-cyclohexadien-1-one * * *
Cyclo(Me2SiO)7 * * *
Diethyl phthalate * 0.2 0.3
TXIB * 0.3 0.3
Piperidine, 1,1'-carbonylbis- * * *
Cyclo(Me2SiO)8 * 0.3 0.5
Tri(2-chloroethyl) phosphate * 0.2 0.2
Benzenesulfonamide, N-butyl- + 3,5-di-tert-Butyl-4-hydroxybenzaldehyde * * *
Benzenesulfonamide, N-butyl- * * *
Isopropyl Myristate * * *
Diisobutyl phthalate * 0.1 0.1
Cyclo(Me2SiO)9 * * 0.1
Dibutyl phthalate * 0.5 0.6
C17-C22 Hydrocarbon * * 0.1
* Recording Limit = < 0.1 ng/cm²
Advanced Curation Glovebox
9 
TD-GC-MS Analysis Vertical and Surface Silicon Wafer Exposure 
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Advanced Curation Glovebox TD-GC-MS Results 
 
Identified Chemicals above reporting limit:  
 
N-Formylpiperidine – solvents  
2-(2-Butoxyethoxy)ethanol – solvents/paints 
Caprolactam – Nylon-6 
Dibutylformamide (DBF) – rubber/polymer additive 
Diethyl phthalate (DEP) – plasticizer  
TXIB – plasticizer  
Tri(2-chloroethyl) phosphate – flame retardant in plastics  
Dibutyl phthalate (DBP) – plasticizer  
Diisobutyl phthalate (DIBP) – plasticizer  
Cyclo(Me2SiO)8 – silicones  
Cyclo(Me2SiO)9 – silicones  
C17-C22 Hydrocarbon 
10 
Hydrocarbons
Control 
Blank 
(ng/L)
TD-GC-MS 
Results 
(ng/L) Hydrocarbons
Control 
Blank 
(ng/L)
TD-GC-MS 
Results 
(ng/L)
Low boilers C7-C10 * 1.2 Low boilers C7-C10 * 0.6
Medium boilers >C10-C20 * 3.8 Medium boilers >C10-C20 * 18.8
High boilers >C20 * * High boilers >C20 * 0.1
Sum >= C7 * 5 Sum >= C7 * 19.5
Identified Organic Compounds Identified Organic Compounds
Cyclo(Me2SiO)3 * * Methyl methacrylate * *
Ethylbenzene * * Cyclo(Me2SiO)3 * *
m,p-Xylene * * Cyclo(Me2SiO)4 * *
o-Xylene * * Limonene * *
Cyclo(Me2SiO)4 * 0.2 C3 benzene * *
Cyclo(Me2SiO)5 * * C10-C14 Hydrocarbon * 0.2
Methylnaphthalene * * C16-C20 hydrocarbon * 16.8
Chlorodecane * 0.3
C12-C16 Hydrocarbons * 0.3
Lunar Curation Glovebox
* Reporting Limit = < 0.1 ng/L
Advanced Curation Glovebox
* Reporting Limit = < 0.1 ng/L
11 
TD-GC-MS Analysis Adsorbent Stainless Steel Tube Exposure 
TD-GC-MS conducted by Air Liquide Electronics Balazs Nanoanalysis , Fremont, CA  
Organics in air results provides a better understanding 
of the organic cleanliness of the gaseous nitrogen 
environment and sometimes provides a better Volatile 
Organic Compound (VOC) load.   
 
Hydrocarbon load in the LCG is much lower when 
compared with the ACG.  This difference is unknown.  
However, the hydrocarbon load in the advanced 
curation glovebox could be indicative of unclean piping 
infrastructure in B31 compared to nitrogen piping 
infrastructure in B31N.    
 
LCG has 0.2 ng/L of Cyclo(Me2SiO)4 ; silicone 
outgassing 
 
LCG has 0.3 ng/L of chlorodecane which is a plasticizer 
indicative of outgassing rubber.  
 
Cyclo(Me2SiO)4 and chlorodecane: possibly heat sealer 
with silicone rubber strip. 
TD-GC-MS Analysis Adsorbent Results 
12 
ISO-AMC Class TVOC  
Concentration  
(ng/m3) 
0 109 
– 1  108 
– 2  107 
– 3  106 
– 4  105 
– 5  104 
– 6  1000 
– 7  100 
– 8  10 
– 9  1 
– 10  0.1 
– 11  0.01 
– 12 0.001 
ISO-AMC air cleanliness class 
ISO 14644-8 
LCG hydrocarbons = 5000 ng/m3 
ISO-AMC =  – 5   (104 ng/m3) 
ACG hydrocarbons = 19500 ng/m3 
ISO-AMC = – 4 (105 ng/m3) 
No significant infrared absorption bands 
 
C-H stretching absorption bands (2958, 2927, and 2856 cm-1) 
Carbonyl stretching absorption band (1732 cm-1) 
Aromatic ring mode absorption bands (1600 and 1580 cm-1) 
C-H bending absorption band (1461 cm-1) 
C-H umbrella mode absorption band (1379 cm-1) 
C-C-O stretching absorption band (1287 cm cm-1) 
O-C-C stretching absorption band (1126 cm-¹) 
C-H in-plane bending absorption band (742 cm cm-1), which is typical for a 
dialkyl phthalate (e.g. diheptyl or dioctyl phthalate).   
  
These results show the presence of aromatic hydrocarbons.  The carbonyl can be 
interpreted as indicative of some organometallic complexes.   However, the 
interpretation of the presence of Dialkyl phthalate is a common group of chemical 
associated with plasticizers mainly in the manufacturing of PVC.  This 
interpretation of the results matches closely with the GC-MS analysis.   
Surface Methylene Chloride Exposure NVR/FT-IR Results 
13 
NVR/FT-IR conducted by Air Liquide Electronics Balazs Nanoanalysis , Fremont, CA  
Surface Methylene Chloride Exposure: GC-MS Results 
 
2-Chloro-Ethanol, Phosphate (3:1) or TCEP – C9H15O6P 
 TCEP is commonly used as a reducing agent in biochemistry and in detergents.  Also 
widely used as a flame retardant and manufacturing of PVC vinyl, electronics, 
adhesives, upholstery, carpeting, rubber, plastics, paints, and varnishes.   
 
+N-Butylbenzenesulphonamide or NBBS – C10H15NO2S 
 NBBS is widely used as a plasticizer in industrial chemicals and drugs.  NBBS also has 
antifungal properties and commonly used on agricultural fields for over 30 years.   
 
Bis(2-Ethylhexyl) Phthalate (DOP) or DEHP – C24H38O4 
 DEHP is a common plasticizer in many plastics manufacturing and most common in 
the outgassing of PVC type materials.  DEHP is widely found in the environment and 
municipal water supplies in low levels from manufacturing of PVC.      
 
+1, 2-Benzenedicarboxylic Acid, Dinonyl Ester or DNP – C26H42O4 
 DNP is commonly used as an additive to impart flexibility in PVC resins and as an 
additive in lubricating oils.  DNP has also been used in the manufacturing of 
thermoplastics, rubbers, paints and adhesives.   
14 
GC-MS conducted by Air Liquide Electronics Balazs Nanoanalysis , Fremont, CA  
SUMMARY 
Hydrocarbons, plasticizers, silicones, and rubbers are found in JSC cleanrooms and 
gloveboxes. 
It is difficult to trace specific sources given that these additives are used in many 
different types of manufacturing.   
In some cases, it is unclear if some of these detected organics are from inside the lab 
or from the background environment (e.g. common plasticizers released into the 
Houston air and not filtered through the ULPA). 
In some cases, it is unclear if some of these detected organics are from human 
interaction inside the lab (e.g. soaps, perfumes, nail polish). 
If more of an organic free environment is determined a requirement for future 
sample return missions, more can be done on choosing better materials as well as 
modifying current handling and cleaning procedures. 
Final written report (NASA STI) will have detailed information on the history of 
mitigating organic contamination and recommendation for the future of curation 
involving organic contamination (pending end of FY13). 
Secured 2nd year FY13 funding to conduct focused organic cleaning studies to reduce 
organic contamination found by the baseline study, update current procedures, and 
research industry’s state-of-the-art cleaning technologies. 
15 


Organic Contamination Baseline Study: In NASA JSC Astromaterials Curation Laboratories. Summary Report

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