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176 Shekarriz and L. Allen: Nanoporous Gold Electrocatalysis for Ethylene Monitoring
tassium permanganate scrubber for 35 s, a total of
1.083 min cycle. This process continued for over 100 min
and a data point was taken after each cycle. By injecting a
10,000 ppm gas sample into the container, the initial concentration
was brought up to approximately 1 ppm and
was allowed to be scrubbed out while monitoring this process
with the sensor. This is evident in the slope of the two
curves. While the time constant for the electrocatalytic
scrubbing was linked to Equation (3), the potassium permanganate
scrubber time constant, which is approximately
34 min, was related to the ratio of container volume
(4 L) to the flow rate of air directed through the scrubber
during each cycle (200 ml min –1 for 35 s). Clearly, the
electrocatalytic depletion rate is roughly 10 % of that for
potassium permanganate scrubber, which is 100 %.
Application in Apple and Pear Chamber Measurements
Tests were performed with various apples and pears kept in
RA and CA chambers. These tests were carried out in collaboration
with Dr. Jinhe Bai at the Oregon State University
Experiment Station in Hood River, Oregon and Dr. Jim Mattheis
at USDA-ARS in Wenatchee, Washington. For testing
of pears, 18 different RA chambers were each filled with 10
pears. The air from each chamber was recirculated through
our sensor while a small sample was simultaneously run
through a GC. The data was then plotted for comparison as
shown in Fig. 9. The very low ethylene producing pears
were treated with 1-methylcyclopropene, which is an ethylene
blocker. The agreement is quite good even at very
low concentrations of significantly smaller than 0.5 ppm.
Another set of tests were performed for measuring the
rate of ethylene production, which appears to be an important
parameter for postharvest fruit quality characterization.
By measuring the rate of ethylene production for
various apples, one can determine the physiological maturity
of fruit. This “real-time” information permits the
grower to make instant decisions regarding timing the
harvest as well as deciding on whether or not the fruit is
storable or needs to be sold quickly. In these experiments,
after placing a single apple in a sealed jar, the jar was connected
to the sensor to measure the rate of ethylene build
up inside the jar. Fig. 10 shows the results of our measurements
for two different types of ‘Fuji’ apples, namely, organic
vs. conventional. The results produce a very unambiguous
measure of the ethylene production rate in each
case, by simply using the slope of the curve at any point
as a measure of the ethylene production rate.
Conclusions
In this paper, a new electrocatalytic sensor was presented
where both sensitivity and response time was shown to be
significantly better than standard diffusion-type electrochemical
sensors. The oxidation reaction of the ethylene
molecules on the surface of the nanoporous catalyst was
shown to take place quite efficiently, typically between 0.1
and 0.2 µmol h –1 cm –2 . This high reactivity yields response
time of better than 10 s and a sensitivity that provides the capability
to measure ethylene down to 10 ppb using the current
electrocatalyst configuration. Future developments
could potentially provide even higher sensitivity and possibly
better response times than those reported in this paper.
The linearity of the sensor response provides a simple calibration
operation that only requires a single point calibration
at the expected range of measurement. The utility and
use of this device was shown for monitoring ethylene levels
during pear storage, monitoring scrubbing of ethylene in
storage, and for determining the ethylene production rate of
apples (or other fruit) as needed for quality control in postharvest
processes.
Acknowledgements
Financial contribution was made by the Small Business
Innovation Research program of the US Department of
Agriculture under two grants: 2004-33610-14425 and
2005-33610-16464. Financial assistance was also provided
by the Washington Tree Fruit Research Commission,
and the Pacific Northwest National Laboratory (PNNL).
The author would like to acknowledge the technical support
from Dr. Larry Pederson from PNNL and Dr. Jinhe
Bai from OSU Experiment Station for their support in this
project. The authors would also like to thank Dr. Michael
Blanke from the University of Bonn and Dr. Ralph Gäbler
from Invivo, GmbH for their constructive comments and
for testing the beta prototypes.
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Received March 18, 2008 / Accepted June 19, 2008
Addresses of authors: Reza Shekarriz and W. Lloyd Allen, Fluid
Analytics, Inc., 17488 Mardee Ave., Lake Oswego, OR 97035,
USA, e-mail: reza@fluid-analytics.com.
Europ.J.Hort.Sci. 4/2008