PERCHLORATE IN MARINE BIOTA AND BY-PRODUCTS
G. J. Harvey, ASC/ENVR USAF WPAFB OH Gregory.harvey@wpafb.af.mil, (937)255-3276; J.O’Lear and R. Godfrey, ManTech
ABSTRACT
Kelp and oily fish such as menhaden are routinely
harvested on industrial scales on North American
continental shelves. This harvested kelp and fish
have found many agricultural, nutritional, and
industrial uses. Just as iodine can accumulate in
kelp, perchlorate can bioaccumulate in terrestrial,
fresh water, and marine plants. Previous studies
have also shown that perchlorate can accumulate
in marine fish meal fertilizer products.
Commercially available kelp fertilizer, kelp food
supplements, alginates, fishmeal, fish emulsions,
fish by-products, and seabird guano from diverse
locations were purchased, prepped and analyzed
by ion chromatography for perchlorate. Because
of the widespread usage of kelp and fish products,
the presence of perchlorate in marine biota and/or
by-products could be considered an alternative
natural source of exposure that may be currently
overlooked.
INTRODUCTION
Sodium, potassium, and ammonium salts of
perchlorate (ClO4) have found numerous
commercial and military uses. The military uses
ammonium perchlorate chiefly as a component of
solid rocket fuel. The perchlorate is remarkably
stable in aerobic groundwater.
Perchlorate has a charge and ionic radius that is
similar to iodide and can block the uptake of
iodide by the sodium iodide symporter. Iodide is
essential to the synthesis of thyroid hormones. A
severe impairment of iodide uptake can disrupt
thyroid function. A marked impairment of
thyroid function can have potentially important
medical consequences in sensitive subpopulations
like infants.
Our understanding of the extent of perchlorate in
the environment is incomplete. In order to better
understand the extent of ambient exposure to
perchlorate, analysis of various environmental
media has been conducted. To date several
terrestrial plants such as tobacco, alfalfa, wheat,
salt cedar, soy, strawberries and Bermuda grass
have shown the ability to accumulate and
concentrate perchlorate over and above levels
found in groundwater and soil (1).
A previous study by Harvey et al. also showed
that some marine plants such as kelp are also
capable of accumulating perchlorate above an
ambient background (2). Kelp plants are
commercially harvested in numerous parts of the
world and have been found to have numerous
uses. Kelp has been used for centuries as a
fertilizer, fuel, fodder, and animal food additive
(3,4,5). Kelp meal is harvested from cold marine
environments and is processed at low
temperatures, dried, and ground to produce a
meal. This meal can then be used as animal food
supplement or plant food. Kelp is also the source
of alginates which are used extensively in the food,
textile, medical, cosmetic, and chemical industry
as water holding, jelling, stabilizing, thickening,
and emulsifying agents (3,4,5). This poster looks
at the perchlorate concentrations found in various
commercially available kelp, kelp products, fish,
and fish by-products.
Corporation WPAFB OH; and
V. Nzengung, University of Georgia-Athens Athens, GA
Materials and Methods
All ion chromatographic analyses were performed
with a Dionex DX-500 system, consisting of a
GP50 gradient pump, ED40 electrochemical
detector, and AS3500 autosampler. Instrument
control and data analysis were provided by
Dionex PeakNet 5.1 software. All analyses were
conducted in the isocratic mode with 100 mM
NaOH, which was prepared using 50% (w/w)
NaOH solution (Fisher Scientific) and deionized,
distilled water (18 megaohm). The mobile phase
was degassed for at least 30 minutes prior to use
by drawing a vacuum over it while stirring
rapidly. The conductivity mode of detection was
used, with suppression of the hydroxide ion
conductivity accomplished with the Dionex ASRS
Ultra (4 mm) Suppressor operated at 300 mA and
in the external water mode at 6–8 mL/minute.
The analytical column was a Dionex AS16 (4 x 250
mm) that was preceded by a Dionex AG16 guard
column (4 x 50 mm). Injection volume was 1 mL
for all samples. All samples were passed through
a series of filter cartridges possessing specific
functionalities in an attempt to remove the high
ionic background in these samples (1). The
Dionex OnGuard -Ba, -Ag, and -H cartridges (1
cc) were each conditioned with 10 mL of deionized
water and then connected in series. These
cartridges effect the removal or reduction of
sulfate, chloride, and metals/carbonate,
respectively, from the sample. An Acrodisc 0.2
um filter (Gelman Sciences) was placed between
the OnGuard-Ag and –H filters for removal of
AgCl colloids. Following collection of
approximately 1.5 mL of sample from each
filtration procedure, the sample was sparged with
helium for 1 minute and then analyzed.
Solid Sample Preparation (Laminaria Kelp,
Iceland Kelp, Ocean Silica, Ascoppyllum nodosum
Kelp Meal, Fish Meal 8-6-0 flakes, Alginate T-25
and T-500): Approximately one gram of sample
was accurately weighed and placed in a 50 mL
beaker with 25 mL of deionized water. The
samples were then stirred while heat was slowly
applied, until a gentle boil was achieved. Boiling
then continued for 20 minutes. The samples were
cooled and then transferred to centrifugation
tubes. The samples were centrifuged for 30
minutes at 2600 rpm. One mL of the
centrifugate/extract was then added to a 10 mL
volumetric flask, and diluted to the mark with
deionized water. Solutions that still contained
suspended particles at this point (Laminaria Kelp
and Ocean Silica) were filtered with 0.45 um
filters (Gelman Sciences). Approximately 7 mL of
this 1:10 dilution of the extract was added to a 10
mL syringe that was fitted with the series filter
arrangement described above. Approximately 4
mL of the sample was eluted through the filters
and discarded before sample was collected for
helium sparging and analysis.
Note: Both 1 gram alginate samples were
dissolved in a total of 125 mL of water, due to
their gelatinous nature in 25 mL of water.
Liquid Sample Preparation (Seaweed 0-0-1,
Organic Liquid Kelp): One mL of sample was
diluted to 10 mL in a volumetric flask, and treated
with the OnGuard cartridge/0.2 um filter system
as described above.
Preparation of Fish Meal and Fish Fertilizer 2-4-1
Liquids: These samples were inhomogeneous
suspensions. Each sample was first shaken
vigorously and then five mL of the sample was
immediately transferred to a centrifugation tube.
The samples were centrifuged at 2600 rpm for 1
hour. This resulted in three distinct layers for
each sample, with each of the two solid layers in
each sample displaying yet further differentiation.
One mL of the middle, liquid layer from each
sample was carefully sampled, transferred to a 10
mL volumetric flask, and diluted to the mark with
deionized water. The entire 10 mL solution for
each sample was then filtered with a 0.45 um
filter. Each sample was then treated with the
OnGuard cartridge/0.2 um filter system as
described above.
Perchlorate standards were prepared in water,
and a calibration curve constructed. The limit of
quantitation of perchlorate in water under the
conditions employed was approximately 10 ppb.
Perchlorate concentration in samples in which it
was found are reported on a dry weight basis, and
account for dilutions and a worst-case scenario of
69% recovery of perchlorate standard that was
subjected to the sample clean-up procedure.
1. Dionex Corp. Application Note 101, Trace Level
Determination of Bromate in Ozonated Drinking
Water Using Ion Chromatography, 1995.
Sample Result DISCUSSION
Seaweed 0-0-1 NF
Plant life abounds off-shore. People have
Laminaria Kelp 4.1 - 5.9 ppm exploited this abundance since ancient times.
Archaeological evidence from abalone middens
Iceland Kelp NF left by coastal cultures suggests that seaweeds
Organic Liquid Kelp NF have been an important resources in some cases
for almost 10,000 years (6) . Currently, in Asian
Ocean Silica NF countries seaweeds are grown in farms
Ascophyllum kelp meal 9.1 - 13.1 ppm (mariculture) and are an important part of their
diet. In other parts of the world seaweeds are
Fish Fertilizer 2-4-1 NF
harvested from kelp forests and are used as
Fish Meal (liquid) NF fodder, fertilizers, or for commercially important
Fish Meal 8-6-0 (flakes) NF phycocolloids like alginate or carrageenan
(3,4,5). Kelp forests are highly productive
Alginate T-25 NF components of cold water marine environments (
Alginate T-500 NF 6). Kelp forests are typically found in both
hemispheres between 40 and 60 degrees of latitude
(6). Kelp biomass is a significant source of
nourishment via a complex food chain for marine
ecosystems (6). Grazing herbivores like sea
urchins and abalone make kelp carbon available
to a wide variety of different organisms.
Kelp biomass is an integral part of marine
ecosystems. The presence of perchlorate in kelp
meal and kelp dietary capsules derived from the
genus Laminaria is a potentially significant
finding. It suggests that in some cold water
marine environments perchlorate may be a
natural component, one that the existing fauna in
an iodide rich environment readily tolerates.
Additional studies need to be conducted to
determine if the source of perchlorate in these dry
kelp powdered products is present also in the
unprocessed, freshly harvested kelp plants. Since
kelp meals are used as animal food supplements,
analyses of samples of actual commercial kelp
meal animal food supplements are in progress.
An interesting finding is that we did not see
perchlorate in commercially available liquid or
emulsions of either kelp or fish fertilizers. A
possible explanation for this absence of
perchlorate is that these kelp and fish liquid
emulsions, when packaged into plastic containers,
produce a reducing environment (very low
dissolved oxygen and high dissolved organic
carbon) that could remediate any perchlorate that
might be present. The presence of a reducing
environment could potentially explain also why
perchlorate was not seen in seabird guano.
Seabird guano was once a popular fertilizer (7).
Algal polysaccharides such as agar, algin,
alginates, and carrageenan extracted from
seaweeds have many uses in a variety of
industries. Exposure to these polysaccharides is
ubiquitous in food products and the absence of
perchlorate in the alginate samples analyzed
suggests that algal polysaccharides may be free
of perchlorate.
REFERENCES
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G.J., Origins of Perchlorate in Natural and
Anthropogenic Fertilizer Products, SETAC 20th
Meeting, Philadelphia, 1999.
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University Press, Philadelphia, 1985.