Nicaraguan Campesino Coffee Roasted Under Different Conditions and Analyzed Using Gas
Chromatography and Principal Component Analysis
                   By Spencer Ubben,* Susan C. Jackels,* and Charles F. Jackels**
                  *Chemistry Department, Seattle University, Seattle, Washington
                                                         **Computing and Software Systems and Science and Technology Programs, University of Washington Bothell, Bothell, Washington
RESULTS
As heating element power levels decreased, the time of roast increased with 60% and 70% having been affected the greatest.
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Figure 2.  Temperature versus Time plots for coffee roasted with various percents of heating element power.
Figure 3. Key aroma components with characteristics and origin from roasting (3)(5).
Figure 4. Relative change in Peak Area % as a function of roast level for key aroma components.
Figure 5. Roasted coffee training set loadings of PC 1 versus GC retention time in seconds.
The largest increase of nitrogen-containing heterocyclic compounds such as pyridine was found in the 60% roast as seen on figure 4.  The increasing concentration levels seen in pyridine, 2-Furanmethanol, 2-Furanmethanol, acetate and decreasing concentration of 2-Furancarboxaldehyde, 5-methyl- and 2-Propanone, 1-(acetyloxy)- are confirmed with three decreasing peaks anti correlated with two increasing peaks as seen on figure 5.                                                     
ABSTRACT
          The overall research goal is to develop an analytical method based on gas chromatography of roasted coffee aroma in order to correlate aroma components with quality, origin and distinctiveness of various coffees.  In this initial phase of the research, we took one coffee, Nicaraguan Campesino green coffee, and roasted it varying the roast power from 100% to 60% in order to create roasted samples of different character (mild to dark roast).  The ground, roasted coffee was head-space sampled by solid phase micro-extraction and the aroma components separated and detected by GC-FID.  Principal component analysis was applied to the data sets, resulting in four components responsible for over 80% of the variation.  PC1 (67.3% of variance) differentiated the 60% roast from the other roasts and identified 6 GC peaks as responsible for the variation.  GC-MS was used to identify the compounds in the peaks.  In conclusion, GC analysis of roasted coffee aroma can differentiate coffees of different roast conditions.
INTRODUCTION
      With coffee prices reaching the lowest inflation-adjusted prices in 100 years in 2001, the impact remains considerable among the poverty-stricken coffee producers in developing countries (1). Nicaragua, the second poorest country in the Western hemisphere, has lost roughly 122,000 jobs to the crisis and has had a notable impact on family farms (2). One solution to the crisis is to support family farms with development programs.  Cooperative groups of farmers are working toward organic and fair-trade certifications and are using inexpensive methods to farm and produce better coffee for specialty markets in developed countries.
          Coffee farmers will benefit from feed back on the characteristics and quality of their coffee. Traditional coffee tasting is expensive, subjective and difficult to obtain.  Therefore, we are interested in developing an analytical method based on gas chromatography of roasted coffee aroma.
Figure 1. Gas Chromatogram of aroma compounds in roasted Campesino coffee.
          Over 1000 volatile chemicals have been identified in brewed coffee as contributing to the smell and taste.  Gas chromatography can separate the compounds for further analysis. The volatile chemicals in extracts from roasted coffee beans were analyzed by gas chromatography in a recent study by Moon, et al, who found that furfural derivatives and furanones were yielded in relatively high concentrations under mild roasting conditions and then decreased at higher roasting intensities (3).
SPME (solid phase micro extraction) has been applied to the study of coffee brew aroma as a simple, rapid, solvent-free, and inexpensive method (4).  Of the available fibers for SPME, such as polydimethylsiloxane
METHODS
-Campesino coffee from Nicaragua purchased from Café Campesino, Inc., Americus, Georgia.
-250 grams of green coffee was roasted in a Hottop Coffee Roaster with the % power level remaining constant at 60, 70, 80, 90, 100 or Auto setting.
-After roasting, the coffee was stored in a sealed container at room temperature to allow the roast to develop for two days.
-Coffee was then ground to a fine powder at setting 5 in a Rancillo Rocky grinder.
-3.5 grams were placed in a 35 mL headspace vial and maintained in the oven at 60 degrees for 30 minutes and then sampled for 5 minutes with a SPME
( DVB/CAR/PDMS).
-SPME was placed in the GC injection port and the sample was run. Injection was in the splitless mode, initial temperature 40 o C; temperature ramp rate: 3 oC per minute to 190 o C. Temperature held at 190 for 10 min. Temperature ramp rate: 15 o C per minute 190 to 250 o C.  Total run time was 66 minutes.
-Data was scaled normalized and aligned using “COW” (Tomasi C., van den Berg F., and Andersson C., 2004).
- PCA was performed with PLS Toolbox 5.5/MATLAB.
CONCLUSIONS
          The results indicated that it is possible to classify the aroma profile of roasted coffee by roast level.  With longer roasts such as 60% and 70% bringing about the largest decrease in concentration levels of the sweet, bread-like and caramellic furans and largest increase of pleasant-burnt/smoky nitrogen-containing heterocyclic compound such as pyridines, pyrazines and pyrroles (3).
           This knowledge can be applied to future research aimed at coffee quality improvement.  Results from this and future research may lead to new, inexpensive techniques that can be utilized and applied by impoverished coffee farmers in Nicaragua and other poverty-stricken countries impacted by the coffee crisis.
LITERATURE CITED
1.  Oxfam International. 2003. Mugged:  Poverty in your Coffee Cup.  Oxford, U.K.: Oxfam Publishing Nov. 2003. 58P.
2.  International Coffee Organization. 2003.  Impact of the coffee crisis on poverty in producing countries.  London:  International Coffee Organization.  International Coffee Council document 89-5. 10 p. Available:  http://www.ico.org/documents/icc89-5r1e.pdf.
3.  Moon, J. K.; Shibamoto, T. Role of Roasting Conditions in the Profile of Volatile Flavor Chemicals Formed from Coffee Beans. J. Agric. Food Chem. 2009, 57, 5823-5831.
4.  Lopez-Galilea, I.; Fournier, N.; Cid, C.; Guichard, E. Changes in Headspace Volatile Concetrations of Coffee Brews Caused by the Roasting Process and the Brewing Procedure. J. Agric. Food Chem. 2006, 54, 8560-8566.
5. Gonzalez-Rios O., et al.  Impact of “ecological” post-harvest processing on coffee aroma: II. Roasted coffee. Journal of Food Composition and Analysis. 2007, 20, 297-307.
Background Image from Flickr: http://flickr.com/photos/tonx/145685020/
STATEMENT OF PURPOSE
The purpose is to use the coffee aroma profile of freshly roasted coffee to develop a method involving gas chromatographic separation and subsequent PCA.  Our goal is to characterize and differentiate the aroma components under a range of roast conditions for a single coffee.
(PDMS), divinylbenzeze(DVB), or carboxen (CAR), a SPME fiber with all three adsorbents coated on it works best for adsorbing coffee aroma (4).
       In order to classify and make use of hundreds of different brewed coffee compounds, principal component analysis (PCA) was used. Principal component analysis has been used in the past for analysis and classification of a multitude of compounds.  In a recent study which used PCA to differentiate coffee brew samples, it was found that conventional and torrefacto roasted coffee brews were successfully classified by use of PCA (4).
        This study was conducted in order to characterize coffee by use of PCA on aroma profiles of coffee that had been roasted under varying levels of roast power.  Aroma was sampled over freshly ground coffee.  If PCA is successful in differentiating one coffee roast from another based solely on the gas chromatography data, then it may be possible to apply the same technique to differentiate coffees from different regions as well as various growing conditions. 
Figure 6. Roasted coffee scores of training set verses validation set.
Note: 60% coffee roasts were successfully differentiated from other roasts using previously constructed training set.  Data from a different technician, SPME fiber, coffee batch and 6 months later were able to be  classified using the training set, thus demonstrating robustness of method.
Figure 7.  Roasted coffee scores for PC1 versus PC 2.
- Principle component 1 is responsible for 67.45% of the variance in the roasted coffee samples while PC 2 has a very little impact at only 9.47%.  As seen in figure 7 the 60% roasts are classifiable by PCA .  70% roasts are also brought out but not to the degree of 60% roast.
ACKNOWLEDGEMENTS
The authors would like to thank their respective institutions, Seattle University and University of Washington Bothell, for the resources needed to accomplish this project.
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