| In
Part One of this examination of carbon we looked at the ability
of granular activated carbon to remove yellowing compounds (gelbstoff)
from reef aquarium water. In this second installment we will
look at issues surrounding the use of carbon in the reef tank.
Passive
Use of Carbon
The traditional approach to carbon usage has been to place
it in a chamber into which water is forced directly through
the carbon. Delbeek (1990) writes, In a correctly designed
sump, all of the water is forced to flow through the carbon
chamber.
The
first challenge to this method of using carbon was expressed
by Julian Sprung in his Reef Notes column in Freshwater
and Marine Aquarium. He wrote, Placement of bags of
activated carbon in such a way that water flows around them,
but is not directly forced through them may be all that is
necessary to maintain the water free of yellowing compounds
(Sprung 1995). Mr. Sprung elaborated on the passive
approach to carbon filtering (Delbeek and Sprung 1994) stating
that, Through contact with the water flowing over the
carbon, and through diffusion, organics will be taken up with
less rapid depletion of trace elements than the prescribed
method. While many hobbyists have adopted this approach
to using carbon, no evidence has been presented to the hobby
that supports Mr. Sprungs two assertions regarding passive
use of carbon first, that it is effective in removing
color and second, that it is less likely to remove trace elements
from the water.
To
test Mr. Sprungs contentions, I set up two tanks with
carbon filters. The first the active tank
was set up using the arrangement outlined in part one
of this report. I placed 20 grams of Hydrocarbon 2, a lignite
carbon distributed by Two Little Fishies, in an acrylic tube
with water circulating from the test tank, through the tube
and back into the tank.
A
second tank the passive tank was
set up in a similar fashion, except that instead of placing
the 20 grams of carbon in a carbon chamber, it was placed
in a mesh bag. Additionally, instead of using a Powerhead
to pump water through the carbon chamber, it was mounted on
the side of the tank to circulate water in the tank so that
water flowed around the mesh bag much as it would were the
carbon bag placed in a sump.
Aged
reef tank water was prepared as outlined in part one, so that
the initial color of the water was 100 APHA units. Hourly
color measurements were taken until color was reduced to zero
in tank 1. Periodic measurements continued in tank two for
the next 168 hours.
| Figure
1 shows the results for the first 40 hours. The yellowing
compounds were virtually eliminated in tank 1 in approximately
five hours. Over the same period, nearly 70 percent of
the color remained in the passive tank. As the graph demonstrates,
color continued to decline for the next 24 hours, but
the rate of decline decreased and eventually stopped at
approximately 20 percent of the original color. Even after
seven days, the water had a yellow cast to it. Because
the same quantity of carbon eliminated the color in tank
1, it is unlikely that the carbon in tank 2 was exhausted.
To explain why the carbon ceased to function, we have
to turn to the mechanism by which carbon works. |
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Figure
1
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Carbon
removes color and other large organic molecules from water
through adsorption. Adsorption is the chemical bonding of
the target molecules to the carbon (Moe 1989). Carbon is most
effective when it is dry. It is most attractive
to these molecules at this stage. As Spotte (1992) explains,
Adsorption rate is a mass transfer process, limited
by factors that control diffusion...The greatest adsorption
rate takes place immediately after wetting because
the concentration gradient is steepest. Spotte, quoting
Morris and Weber (1964) writes, The quantity of dissolved
organics removed by activated carbon is not a linear function
with time...absorption involves the rapid formation of an
equalibrium interfacial concentration followed by slow diffusion.
(Spotte 1970) In other words, carbon is most effective when
first put in the tank and gradually becomes less effective
as it does its job. Carbon, whether used actively or passively,
is most useful at the start of its use. Extended use of carbon
suffers from diminishing returns. Passive use of carbon works
to some degree, but will not eliminate yellowing compounds.
It is no replacement for active flow-through use
of carbon.
Removal
of trace elements by GAC
Mr. Sprungs second assertion about the potential depletion
of trace elements by carbon has been repeated many times since
his original column. John Tullock is the latest to join the
fearful chorus by writing, Others, including the noted
Norwegian aquarist Alf Nilsen, have stated a suspicion that
continual use of activated carbon can lead to stony coral
bleaching if replenishment of trace elements such as iodine
is not done on a regular basis (Tullock 1997). Iodine
is a minor element, not a trace element, and when added to
seawater it quickly becomes predominantly iodide. Because
of the excessive dosing fueled by such hand wringing, iodide
probably accumulates as often as it is depleted in reef tanks.
Like
many aspects of the hobby, this folklore has never been evaluated.
To determine the accuracy of this claim, I removed approximately
5 gallons (20 liters) of water from my 300-gallon (1100 liters)
reef tank and added potassium iodide from ESV until the water
measured 0.1 milligram per liter (mg/L) of iodine/iodide as
measured by the Seachem test kit. The purpose of increasing
the iodide concentration to this level was to exaggerate the
iodide gradient and make the detection of adsorption more
likely.
The
water was divided between two tanks. I placed 20 grams of
Hydrocarbon 2 in one tank in the acrylic tube as before. In
the second tank, the carbon was placed in a mesh bag. Both
tanks were run for 48 hours and then the iodide concentration
was measured. The Seachem test kit permits up to six side-by-side
measurements, so both tanks were measured simultaneously with
two replications. Measurements were taken at full strength
and with a 5:1 dilution to counteract the difficulty of interpreting
the color at the high end of the scale. After 48 hours, the
passive tank had a slightly higher concentration of iodide
as indicated by a slightly darker color at the 5:1 dilution.
The color difference, however, was only detectable by directly
comparing the colors, suggesting a minimal difference in concentration.
Passive
use of carbon, however, involves the continuous use of carbon,
so at 48 hours, the carbon in the active tank
was removed, while the carbon in the passive tank remained.
The two tanks operated for another 24 hours, at which time
iodide levels were once again measured. At 72 hours, the levels
of iodide as indicated by the test color were indistinguishable.
The conclusion I came to was that the use of carbon has minimal
impact on iodide concentrations and that passive use of carbon
has no lesser affect on iodide levels than active use.
How
much carbon should you use?
The conscientious hobbyist seeking guidance on the use of
carbon will find that the entire body of hobbyist literature
over the past 10 years on the use of carbon has been based
on a single recommendation. In 1988, Thiel recommended 3 to
3.5 pints (1.5 quarts) of carbon per 50 gallons, without explaining
the basis for his recommendation. Moe (1989) cited Thiel on
the question of quantity of carbon, but inexplicably presented
the recommendation as 34 ounces without stating whether this
was the volume or weight of the carbon. In 1990, Delbeek also
cited Thiel, but came up with a recommendation of 36 ounces.
Delbeek and Sprung (1995) again repeated the recommendation.
None
of the references that refer to the original recommendation
makes it clear whether they are talking about the volume of
carbon or the weight. Three pints converts to six cups or
48 ounces in volumetric terms, so the 34 to 36 ounce recommendations
seem low if they are simply converting the original Thiel
recommendation.
Converting
the original volume of 3 pints into weight is more problematic.
The weight of a given volume of carbon depends on the density
of the carbon. Three pints of one of the bituminous-based
carbons I tested weighed a little over 17 ounces. The same
volume of the top performing lignite-based carbon weighed
nearly 30 ounces. The coconut carbon fell between these two
extremes.
Delbeek
and Sprung also refer to the Wilkens and Birkholz (1988) recommendation
of 500 grams per 100 liters, stating that this amount of carbon
is roughly equivalent (to the Thiel recommendation).
The 500 gram recommendation works out to be about 31 ounces,
so it would appear that recommendations since Moe have been
based on the weight of carbon. Because Albert Thiel is a strong
advocate of coconut carbon, his suggestion of 3 to 3.5 pints
of carbon implies a weight of approximately 20 to 25 ounces
of carbon, considerably less than the other authors advocate.
A
hobbyist following the recommendations of Hovanec (1993) to
use bituminous-based carbon and Delbeek and Sprung (1994)
to use 36 ounces of carbon could find him- or herself dealing
with three-quarters of a gallon of carbon for a 50-gallon
reef tank. In one of the more understated observations in
their book, Delbeek and Sprung (1994, page 113) write, although
this recommendation does seem excessive, one could use it
as an upper figure and work downwards. Indeed.
To
put a recommendation of 3 pints of carbon per 50 gallons into
perspective, when the city of Cincinnati began testing the
use of carbon, they installed carbon columns of only 28 inches
to treat drinking water flowing through the water treatment
system at 2 gallons per minute per square foot (gpm/sqft),
treating nearly a million gallons of water a day (McCreary
and Snoeyink 1977). Perhaps a review of the 10-year-old recommendation
is long overdue.
Spotte
(1992) recommends 1 gram of carbon per liter, one fifth that
suggested by hobby authors. Even the author of the much quoted
10-year-old recommendation has rethought the use of carbon.
Albert Thiel now advocates 3 level tablespoons per 50 gallons,
about one-thirtieth of his original recommendation (http://www.netpets.org/fish/reference/freshref/carbmeth.html).
To
better understand the impact of quantity on the removal of
yellowing compounds, I ran three different tanks using 60
grams, 30grams and 15 grams of carbon. This is equivalent
to 96, 48 and 24 ounces respectively for a 50-gallon tank.
I used bituminous carbon from ESV for the test.
| As
the graph in Figure 2 demonstrates, the quantity of carbon
used had an impact on the rate at which color was removed,
but not to the degree one might think. The largest quantity
of carbon removed the most color, but it took four times
the weight of carbon to remove twice the color. The smallest
quantity of carbon removed 50 units of color in seven
hours, far more than is necessary for the average tank.
This suggests that the most efficient use of carbon is
to use the least amount of carbon necessary. |
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Figure 2
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As the graph in Figure 2 demonstrates, the quantity of carbon
used had an impact on the rate at which color was removed,
but not to the degree one might think. The largest quantity
of carbon removed the most color, but it took four times the
weight of carbon to remove twice the color. The smallest quantity
of carbon removed 50 units of color in seven hours, far more
than is necessary for the average tank. This suggests that
the most efficient use of carbon is to use the least amount
of carbon necessary.
Thiels
current recommendation of 3 tablespoons per 50 gallons is
probably all that is necessary to keep a reef tank free of
color. Thiel also recommends using carbon for 12 hours a week
and then removing it. This too is prudent advice. A healthy
tank, particularly one with an adequate foam fractionator,
should not need much more than this duration of carbon usage.
Unfortunately,
Thiel does not mention circulation rates through the carbon.
As I mentioned in Part One, the typical pOver filter for carbon
use moves water past the carbon at a much faster rate than
research recommends. A popular canister filter for carbon
use has a flow rate of 250 gallons per hour. Evidence suggests
that adsorption rates decline when water moves past the carbon
faster than 65 milliliters per minute, roughly one gallon
per hour. Spotte recommends that no more than one tank volume
be circulated through the carbon per day. Using Thiels
12-hour guideline combined with Spottes one tank volume
suggestion, translates into a flow rate of about 4 gallons
per hour for a 50-gallon tank. Clearly, using a pOver filter
for carbon is not the best approach.
Conclusion
Granular activated carbon is a valuable tool for the reef
hobbyist. It can play a significant role in maintaining a
healthy tank. The hobbys traditional approach to the
use of carbon, however, has been misguided. Optimum use of
carbon requires only periodic use. Slow circulation of water
through small amounts of carbon will remove significant amounts
of color. Passive use of carbon, as well as circulation through
high-volume pOver filters should be avoided.
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