Activated carbon.
Granular activated carbon is still the most
common medium used for adsorptive "chemical"
filtration. Carbon selects for molecules
with a higher affinity for the carbon than
they have for water. Though its action is
generally described as "chemical"
filtration, adsorptive filtration is actually
a physical process, not a chemical one. There
are no ion exchanges or chemical bonding
between the adsorbed molecules and the surfaces
of the carbon pore spaces that adsorb them.
Activated carbon adsorbs
dissolved organic molecules. These include natural byproducts of the
partial decomposition of plant and animal
materials, such as organic acids (humic acid,
fulvic acid, etc.), phenols and polyphenols,
proteins and carbohydrates, hormones and
many medications. The more soluble an organic
molecule is, however, the less adsorbable
it is likely to be. Though many of these
dissolved substances remain in the water
precisely because they are resistant to microbial
breakdown, the bacteria that colonize carbon
surfaces will consume some of the organics
sorbed to the carbon surfaces. Organic molecules
trapped in carbon pores are still available
to nitrifying bacteria also, as long as there
are sufficient local supplies of oxygen.
Fresh activated carbon will also adsorb a
wide variety of noxious molecules that originate
outside the aquarium: insecticides, volatile
chemicals like dry-cleaning fluids, PCBs
in your tapwater, dyes (including some used
for medications), perfumes, etc. Granular
activated carbon will also adsorb some things
you might not consider so undesirable: EDTA
and other chelating agents, heavy metals
etc. Chemist Shawn Keslar experimented and
found that in the first 100 hours, carbon
adsorbed over 60% of the iron and almost
50% of the manganese added to water. His
report to the Aquatic-Plants Digest is archived
at theKrib.com.
Some kinds of granular activated carbon are
sold in packages as "pre-washed."
This is not a genuine convenience, because
you are buying water at an activated-carbon
price. What percentage by weight of a "pre-washed"
carbon is represented by water? Is it as
acceptable as a "water-added" packaged
ham, or is it more like the frozen-food industry,
where selling packaged ice as product is
considered disreputable?
The best articles describing activated charcoal
were written by Tim Hovanec, for Aquarium Fish, May 1993 and again in June 1998. (There
was a further recap in the June 2000 issue.)
Though none of this matter was archived at
the Aquarium Fish website, you can find condensed versions
of his two carbon articles among Hovanec's
library at the Marineland website. Those versions don't reprint Hovanec's
useful table of what substances activated
carbon adsorbs well, moderately, only fairly,
or not at all: the table is reproduced at
the Discus-L mailing-list site. Hovanec's assessment of carbon's adsorption
of complexed copper and ferric iron is only
"fair." I can't square these two
assessments, but I feel that no one currently
arguing about adsorption of desirable trace
elements seems to have looked at this table.
North Dakota State U Extension Service offers
a series of easily-understood papers "Treatment systems for household water
supplies" one of which give basic information on activated
carbon filtration. The paper stresses that
activated carbon is most effective in adsorbing
organic contaminants with fairly large molecules
that get trapped in the pores: pesticides,
aromatic hydrocarbons, industrial solvents,
PCBs. They emphasize that activated carbon
does not remove microbes, sodium, nitates, fluoride,
nor hardness, nor lead and other heavy metals.
"Generally, the least soluble organic
molecules are most strongly adsorbed. Often
the smaller organic molecules are held the
tightest, because they fit into the smaller
pores." Adsorption of many organic molecules
is stronger at lower temperatures (your aquarium,
rather than your water heater) and at lower
pH, the paper points out.
AmQuel. AmQuel
binds free ammonia in the water,
part of the nitrification
"cycle." I mention it here because its action is
really an aspect of chemical filtration.
Phosphate and "Heavy Metal" adsorbers. Products like Phos-Guard and Phos-Zorb package
granules of aluminum oxide in a nylon pillow
that you pre-soak and then place in your
filter, where they adsorb phosphates. They
don't work overnight, but they offer an excellent
way to achieve low levels of phosphates,
which encourage algae. They have certain
drawbacks, though, so you can't just pack
a pillow into your filter canister and forget
it: when bacterial biofilm coats their surfaces,
bacteria may scavenge the adsorbed phosphate
and make it available to algae once again.
A periodic overnight soak in a bleach
solution (followed by de-chlorination) will
keep the phosphate-adsorbing granules from
bio-fouling in this way.
Laterite. Certain components of your mixed substrate
will also pull phosphates out of the water.
Cations associated with colloidal clay will
attract the negatively-charged phosphates,
according to Diana Walstad. Thus baked or
unbaked laterite in your substrate mix is in effect an aspect of your adsorptive,
or "chemical" filtration.
PolyFilters. PolyFilters adsorb and absorb a wide range
of contaminants, including dissolved organic
substances. They have been made since 1976
only by Poly-Bio-Marine Inc. Their website
at www.poly-bio-marine.com is a model of accessible scientific clarity.
PolyFilter is one of the few aquarium products
that scarcely needs to be marketed with hype.
It's single drawback is that it's more expensive
than activated charcoal. Since the white
spun polyester pad turns dark mahogany brown
from organics it has sorbed, you can see
when it's time to replace the pad. Polyfilter
also selectively sorbs toxic ammonia at levels
above 0.1 mg/L but doesn't adsorb the harmless
ionized form, ammonium, which is used by
plants. It adsorbs phosphates and some nitrates
(in freshwater, though not if you were using
it in saltwater).
Zeolites. Zeolites have varied industrial careers
as sorbents, ion-exchangers and catalysts.
"Zeolite is a generic name for a group
of hydrous silicates in which the bases are
alumina and the alkalis and alkaline earths,
generally characterized by swelling up and
fusing to a glass or enamel under the blowpipe;
commonly found in the cavities of igneous
rocks,"
says the Oxford English Dictionary. Zeolites also contain a surprising amount
of trapped water. "'Zeolite' means 'the
stone that boils'," geologist Ken Deffeyes
told John McPhee in Basin and Range (1981). "If you take one small zeolite
crystal, of scarcely more than a pinhead's
diameter, and heat it until the water has
come out, the crystal will have an internal
surface area equivalent to a bedspread."
The expanded zeolite's open framework, full
of channels and fissures, works as a molecular
sieve. Some zeolites have a fibrous and wooly
structure, others are plated like mica flakes.
Because of their variable porous structure,
zeolites have significant cation exchange
capacities (precisely quantified by the pros
as "CEC" but "lots" "some"
and "few" have to do for me). You'll
find interesting technical information on
the zeolites at http://webmineral.com, and at FishDoc you'll find more specific information on
using zeolite in aquaria
to bind temporary
pulses of ammonia.
Geologists have broken down naturally-occuring
zeolites by the variations in their molecules
and structure into 48 minerals, but zeolites
are artificially produced, too. All the zeolites
adsorb ions and molecules, that is they bind
them to their enormous surfaces. They contain
large numbers of molecular sites occupied
by cations, often sodium (Na+), which they
are ready to exchange for an ion in the water
that has a more powerful positive charge,
calcium (Ca++), for example. When a zeolite
exchanges two sodium ions for a calcium ion,
the water is being softened, but total dissolved
solids (TDS) are not being reduced. Zeolites
will bind ammonium (NH4) but they have less effect on un-ionized
ammonia (NH3), so you can see that the higher your pH
is-- and proportionally the more NH3 you have-- the less useful zeolites are
going to be for you. In saltwater, zeolites
don't work at all.
Taking advantage of the differential in a
particular zeolite's affinity for one molecule
over another, industries use selected zeolites
to separate out many kinds of chemicals;
buried beds of zeolite can adsorb the radioactive
elements in an underground plume spreading
from a nuclear waste site. That same clinoptilolite
you may use in the aquarium for some temporary
ammonia sequestering is also the strongest
adsorber of strontium and cesium in radioactive
wastes! Or zeolites can be made part of the
grit in poultry feed to adsorb toxins and
improve the animals' health. You can control
the desirable properties of zeolites best
by containing some in a bag in the filter
system rather than by incorporating it permanently
in the substrate.
The cation exchange capacity ("CEC")
of a particular zeolite can become exhausted.
The adsorption of ions by zeolites is reversible,
a fact that gives rise to worries and some
confusion. Though some strongly charged ions
in the water can "bump" some others,
you can't very effectively recharge zeolites,
except in concentrated brines or with powerful
acids or alkalis.
One common species of zeolite is clinoptilolite which has a high affinity for ammonia and
other positively-charged ions. It can even
adsorb some sodium from the water. Clinoptilolites
have a microscopic sheeted structure with
ringlike channels through the sheets, like
restacked deli slices of swiss cheese. The
resulting openings and channels act as ion-exchange
sites and also as molecular sieves that permit
movement, entrapment and adsoption of relatively
large molecules like ammonia, and even carbonates
and nitrates. Most clinoptilolites exchange
sodium ions, which limits their usefulness
in water softening, as far as aquaria are
concerned. But "potassium clinoptilolite,"
or Clinoptilolite-K, has unrealized aquarium
potential, it would seem. Have a look:
run a search on "clinoptilolite-K"
at http://www.google.com. In ion-exchange, the released potassium
ion would be taken up by plants as fertilizer,
and the resulting growth spurt should even
help reduce phosphate levels. GSA Resources
(see their informative website at www.gsaresources.com) is a corporate leader in developing applications
for zeolites as ion-exchange media and filtration
employed in aquaculture and water treatment
facilities. Besides their more usual sodium
clino, they market a Clinoptilolite-K they
call "Cabsorb," ZK406H. They sell
samples in quantities that would permit some
aquarium experimentation.
One zeolite is packaged for the aquarium
market under the name Ammo-Chips. Since zeolite
adsorbs ammonium, it is often added to the
filter media (about a teaspoon per 20 gallons
will do) in order to reduce an expected "pulse"
of ammonia when new fish are added to the
tank. As the chemical filtration capacity
of the zeolite quickly diminishes during
the first few days, biofiltration takes up
the increased ammonia resources. The result,
if you do this right, eliminates even a small
ammonia "spike." If zeolite were
used continuously, however, it would be competing
with aquarium plants for the ammonia, though
ammonia ions adsorbed to zeolites in a filter
are still available to nitrifying bacteria.
One drawback is, you'll be exporting those
bacteria when you renew the filter media.
Another drawback is, that as nitrifying bacteria
using the zeolite as a substrate oxidize
ammonium to nitrite, they rob the molecule
of its positive charge, and the zeolite may
release nitrite or nitrate anions into the
water.
Ion-exchange resins are another part of the chemical filtration
arsenal. The phenomenon of ion-exchange was
first recognized in the 19th century when
certain clay minerals were found to remove
potassium and ammonium ions from water, with
the release of an equivalent number of calcium
ions.
Most of the adsorptive "chemical"
filtration media mentioned up to now don't
actually chemically modify the water; ion-exchange
processes do. The Brits call the kinds I've
been talking about "adsorptive"
filtration rather than "chemical"
filtration.
There are several kinds of synthetic adsorbents
in bead form or woven pads available at your
LFS. Any of them are more expensive than
activated carbon, but some can be regenerated
and reused, which helps amortize the initial
cost. Generally they are white or cream-colored
when new and show you when they're exhausted
by discoloring to dark brown. Some can be
regenerated in a strong solution of household
hyperchlorite bleach. Other less do-able
recharging techniques would involve steeping
in caustic alkali or strong acid solutions.
Perhaps you can spend your energy and your
cash more effectively than in attempting
to re-use any chemical filtration medium.
In ion exchange, ions of the same net charge
are exchanged, a free ion in the water taking
the place of an equivalent ion bound to a
solid, such as a zeolite as I was just explaining,
or to a bead of artificial resin.
Resins in bead form contained in a nylon
flow-through pillow are sometimes used to
exchange calcium and magnesium ions for sodium
ions, thus softening the water. This is great
for doing the laundry but never a real improvement
in aquarium water, especially since two positively-charged
sodium ions (Na+) have to be released for every Ca++ or Mg++ ion taken out of the water. Those Na ions
are more stressful than the ions responsible
for hardness, so you're really not ahead
of the game. Resins that are said to be partly
rechargeable in a salty brine, according
to the manufacturer's instructions, are giving
off sodium ions, which makes them undesirable
for the freshwater aquarium, in my opinion.
However, if potassium chloride is substituted
for sodium chloride (common salt) in recharging
such resins, which seems to be acceptable
procedure, then a K+ ion will be released instead of a Na+, and the plants will benefit. Apparently
it doesn't matter which cation is used.
De-ionizing resins. Don't confuse ion-exchange resins with de-ionizing
resins that extract ions from the water,
exchanging them for H+ ions and lowering
the total dissolved solids (TDS). These desirable
kinds of ion-exchange resins you can use
in the aquarium are termed acid/base resins.
They take up calcium and magnesium, releasing
a proton (H+) in exchange. One is marketed
for the hobby as Tapwater Purifier.
De-ionized water ("DI Water"). Wastewater managers can get water of great
purity, with ions and organics
at the parts-per-billion
level, by using a cation
exchanger in series
with an anion exchanger.
First the cation
exchange resin replaces
all positively-charged
ions with hydrogen ions,
then the anion exchanger
replaces negatively-charged
ions with hydroxide
(OH). The two freed ions
combine to form
molecules of water. A final
run through activated
carbon removes big organic
molecules with
approximately neutral charges.
In industrial
use, the resins are re-charged
with sulfuric
acid and sodium hydroxide.
Peat filtration. Peat filtration is one way to use humic
substances released by peat-- but also by
leaf litter, coconut shells, Osmunda fiber,
used green teabags, even bogwood-- to achieve
some softening and to chelate various substances.
Rather than repeat this material here, I
suggest you check it out in the "Softening" page.