making

environmental data meaningful

Use of Semipermeable Membrane

Devices (SPMDs) to Assess Potential
Fish PAH Tissue Concentrations in
North Saskatchewan River

For Husky Energy Inc.
April 17, 2017


chemistry-matters.com
 Use of Semipermeable Membrane Devices (SPMDs) to Assess
Potential Fish
PAH Tissue Concentrations in North Saskatchewan River

Husky Energy Inc.

April 17, 2017
Introduction
Semipermeable membrane devices (SPMDs) have been used to measure organic contaminants in water for 25
years. In 1990 James N Huckins introduced the idea of passive sampling via SPMDs (Huckins et al, 1990). The
initial intent was to use them as a simple and relatively easy method to determine the role of equilibrium
partitioning in the bioaccumulation of contaminants in aquatic organisms and to monitor, in situ, the
bioavailability of aquatic organic contaminants. SPMDs consist of low density polyethylene (LDPE) lay-flat
tubing that is filled with the model lipid triolein (1,2,3-tri[cis-9-octadecenoyl]glycerol). They are a biomimetic
technique with the purpose of simulating body residues and may be used to measure concentrations of
complex organic contaminant mixtures found in water.

Polycyclic aromatic hydrocarbons (PAHs) are one group of organic contaminants where SPMDs have been used
extensively to measure water concentrations and where SPMDs have been used to assess theoretical fish PAH
exposure.

Uptake of chemicals to the SPMDs depends on their physical-chemical properties (predominantly their
octanol:water partitioning coefficient, Kow), the physical properties in the water column around them
(temperature, turbulence, flow rate) and also biofouling of the membrane (Van der Oost et al, 2003). Simply
put, organic contaminants in the water or on sediment in the water, if they come into contact with the SPMD,
will transfer to the SPMD matrix due to their lipophilic nature (fat friendly). The transfer of contaminants from
water or from sediment would equate to water passing through fish gills and transferring into the fish, thus
potentially exposing the fish to the contaminants.

SPMDs are passive samplers, meaning they are placed in the water column for a period of time, removed and
then analyzed, with no other action necessary. Water concentrations of PAHs are calculated from the SPMD
results by accounting for various environmental factors the SPMDs are exposed to during deployment.
Calculations use performance reference compounds (PRCs) which are compounds that are not found in the
environment and their release rates (loss from the SPMDs) are a measure for the exchange kinetics between
the SPMDs and water. Known concentrations of PRCs are added to each SPMD prior to deployment and the
PRC concentrations are then measured after. Decreases in concentration help account for the physical
properties in the water column (temperature, turbulence, flow rate) and also biofouling of the membrane. A
full summary of the SPMDs deployed as part of the response to the 16TAN release can be found in Chemistry
Matters Inc. report titled Forensic SPMDs Assessment Report (CMI, 2017).

Total concentrations of PAHs that collect on the SPMDs have been compared to concentrations of
contaminants in fish tissue. In a study completed by Runhui et al. (2006) in Taihu Lake, China, it was observed
that rate constants of SPMDs (uptake rate and elimination rate) are less variable than for crucian carp
(Carassius carassius). It is suspected this is, in part, a result of the reproducible, standardized design of SPMDs

making environmental data meaningful 2

 Use of Semipermeable Membrane Devices (SPMDs) to Assess
Potential Fish
PAH Tissue Concentrations in North Saskatchewan River

Husky Energy Inc.

April 17, 2017
but also because of differences in behaviour and physiological status of the individual fish. Therefore SPMDs
show very consistent results.

In a study relating SPMDs to rainbow trout, the uptake rate constants of organic contaminants (DDT) in SPMDs
were 1 to 2.5 fold higher than the compared rainbow trout (Lu and Wang, 2003). In the Runhui example, the
uptake rate constant for PAHs was 7-fold higher in the SPMDs than for the crucian carp. The ability to uptake,
process and eliminate organic contaminants changes with the reproductive state, age, size and environmental
condition of fish and with the organic contaminant present. Additionally, fish are known to metabolize PAHs
efficiently; half-lives of PAHs in rainbow trout range from 1 day for acenaphthylene to 9 days for phenanthrene
(Van der Oost et al., 2003). SPMDs do not account for metabolism; therefore, SPMD concentrations provide an
overestimate of exposure for fish.

The measured concentration of PAHs on the SPMDs, if used as a fish surrogate, would represent fish gills
whereby PAHs in the water column or on suspended sediment are transferred to the fish when passing
through their gills. As mentioned above, this is an overestimate since SPMDs show more efficient uptake than
fish in previous studies, thereby representing a conservative estimate of exposure for the fish. Once a PAH
enters a fish through its gills, it must pass from the gills, potentially passing through the liver, before being
deposited in the muscle tissue of the fish. This transfer from gills (represented by the SPMDs) to eventually
being distributed to the muscle tissue provides ample opportunity for PAHs to be metabolized and excreted,
thereby not moving to the muscle tissue. Fish microsomal enzymes, called cytochrome P4501A enzymes, are
efficient at the metabolism of PAHs to more polar metabolites facilitating excretion and preventing
accumulation of PAHs in muscle tissue.

Guidelines
In 2000, the US Environmental Protection Agency (EPA) published the third edition of Guidance for Assessing
Chemical Contaminant Data for Use in Fish Advisories, Volume 2 Risk Assessment and Fish Consumption Limits
(US EPA, 2000). The objectives were to provide guidance on the development of risk-based meal consumption
limits for PAHs. The risk-based meal consumption limits are guidelines that PAH concentrations in fish tissue
can be compared to, to ensure values are below the risk level associated with human consumption. The US
EPA screening values of 5.47 ng/g potency equivalency concentrations (PEC) and 0.673 ng/g PEC were used
and are based on the estimated consumption of fish by recreational and subsistence fishermen, respectively.
The screening values are based on an adult body weight of 70 kg and a lifespan of 70 years. The average daily
consumption for a recreational fisherman is 17.5 g/day and 142.4 g/day for a subsistence fisherman. The
subsistence consumption rate is based on an estimate of the 99th percentile of fishers and of the average
consumption of uncooked fish and shellfish from estuarine and fresh waters by subsistence fishers from EPA
studies conducted in 1998 and 2000. Screening values for carcinogens were calculated to be protective of one
excess cancer case per 100,000 (1E-5) individuals exposed over 70 years.

making environmental data meaningful 3

 Use of Semipermeable Membrane Devices (SPMDs) to Assess
Potential Fish
PAH Tissue Concentrations in North Saskatchewan River

Husky Energy Inc.

April 17, 2017
In order to compare the SPMD results to the US EPA guidelines for human consumption, analytical results
need to be converted to total PEC using individual PAH toxic equivalency factors (TEFs). The toxic equivalents
method is a risk assessment and toxicology concept used to assess PAHs. PAHs all have varying degrees of
toxicity based on their structures. The toxic equivalents method uses studies on the toxicity of PAHs to
evaluate and estimate each PAHs relative toxicity as compared to the most studied and what is generally
considered most toxic PAH, benzo(a)pyrene. The relative toxicity is based on benzo(a)pyrene having a toxicity
of 1.0. A PAH with 10% of the toxicity of benzo(a)pyrene would be given a TEF of 0.1, 10% of 1. Table 1
presents the TEFs for each of the fifteen PAHs included in the US EPA (2000) screening guidelines for fish tissue
consumption. The TEFs shown in Table 1 were originally derived by Nisbet and LaGoy (1992). The TEFs adopted
by the US EPA are more conservative than other jurisdictions, such as Health Canada, as the list includes more
compounds and has a considerably higher TEF for dibenzo(ah)anthracene.

Table 1. TEFs used to calculate the PEC of individual SPMDs to compare to the US EPA human consumption guideline.

PAH TEFs
Acenaphthylene 0.001
Acenaphthene 0.001
Fluorene 0.001
Phenanthrene 0.001
Anthracene 0.01
Fluoranthene 0.001
Pyrene 0.001
Benzo(a)anthracene 0.1
Chrysene 0.01
Benzo(b)fluoranthene 0.1
Benzo(j/k)fluoranthene 0.1
Benzo(a)pyrene 1
Dibenzo(ah)anthracene 5
Indeno(123-cd)pyrene 0.1
Benzo(ghi)perylene 0.01

North Saskatchewan River Deployment

To deploy SPMDs, because of their fragile nature, they are enclosed within a metal container that is weighted
to anchor to the bottom of a water body. The SPMDs were deployed into the North Saskatchewan River by
suspending each one from an anchor at a predetermined depth. The anchored SPMD allows the flowing water
to flow through the device thereby capturing organic contaminants as they flow past, mimicking the process
how fish would uptake the contaminants as they swim. SPMDs were deployed in two events, each one lasting
approximately 1 month. Locations were chosen based on distances to the Point of Entry (POE) of the spill. One
upstream location was chosen to assess the background PAH concentrations within the river.

making environmental data meaningful 4

 Use of Semipermeable Membrane Devices (SPMDs) to Assess
Potential Fish
PAH Tissue Concentrations in North Saskatchewan River

Husky Energy Inc.

April 17, 2017
COMPARISON
To calculate the PEC for each individual SPMD, each PAH concentration in a sample is multiplied by its
respective TEF (see Table 1) then all products are summed together to get a total PEC for each sample
(ng/g PEC) (see Table 2).

Table 2. Table of PEC values calculated using the suggested TEFs from the US EPA human fish consumption guidelines. Values
reported in ng/g PEC.

SPMD ID Calculated PEC

Deployment 1
SPMD 1 22.0
SPMD 3 10.0
SPMD 7 18.4

Deployment 2
SPMD 1 15.6
SPMD 2 9.76
SPMD 3 3.41
SPMD 4 9.83
SPMD 6 6.62
SPMD 7 7.49

After calculating the PEC for each SPMD, the values were then converted to relate to the fish tissue. For
comparison, the entire PAH amount for each SPMD (ng/sample PEC) was compared to different sizes of fish
tissue. If the amount of PAHs measured on one SPMD is divided it by a specified weight of fish tissue, the
concentration of PAHs is converted from ng/sample PEC to ng/g PEC to represent a specific size of fillet. For
example, if a large fish was caught (500 g fillet), and it was exposed to the same amount of PAHs as the SPMD,
and assuming 100% of the PAHs the fish was exposed to made their way through the blood, past the liver, and
into the tissue, without any metabolic processes occurring, then this would be a worst case scenario for the
maximum amount of PAHs that could make it into the fish tissue. If we take that same amount of PAHs
measured on the same SPMD and compare it to a smaller 200 g fillet, then the PAH concentration in the fillet
increases and shows a comparison of the PAHs between small and large size fish (see Table 3). The US EPA
screening guideline for PAHs in fish tissue samples is 5.47 ng/g PEC for recreational consumers and 0.673 ng/g
PEC for subsistence consumers.

The values in Table 3 show potential ng/g PEC concentrations of PAHs in different sizes of fish based on PAH
concentrations measured using SPMDs. When compared to the screening values of 5.47 ng/g PEC and
0.673 ng/g PEC, the values are substantially below this screening value. Also, SPMD 1 is upstream of the POE
and has the highest SPMD PEC concentration, and thus, the highest potential PAH concentration in fish tissue.

making environmental data meaningful 5

 Use of Semipermeable Membrane Devices (SPMDs) to Assess
Potential Fish
PAH Tissue Concentrations in North Saskatchewan River

Husky Energy Inc.

April 17, 2017
This indicates that background PAH concentrations in the river are dominating the uptake on the SPMDs, and
no increase of PAH concentration was seen downstream of the POE based on SPMD results. This is consistent
with the observed fingerprint of the PAHs on the SPMDs being comparable for all deployment locations.

Table 3. Comparison of fish tissue concentrations estimated from SPMD measurements. Values are reported as ng/g PEC.

SPMD ID Distance from POE 200 g Tissue 500 g Tissue

(km)
Deployment 1
SPMD 1 -17.6 (upstream) 0.11 0.044
SPMD 3 12.0 0.051 0.021
SPMD 7 379.8 0.092 0.037

Deployment 2
SPMD 1 -17.6 (upstream) 0.078 0.031
SPMD 2 0.3 0.049 0.021
SPMD 3 12.0 0.017 0.007
SPMD 4 20.7 0.049 0.021
SPMD 6 125.8 0.033 0.013
SPMD 7 379.8 0.037 0.015

Conclusion
SPMDs were developed for use as fish surrogates for monitoring organic contaminants in water bodies.
SPMDs provide an overestimate of PAH exposure since the uptake of PAHs on SPMDs is more efficient than for
fish. With this overestimation of PAH fish exposure, if it was also conservatively assumed that all PAHs were
100% retained (no loss or biotransformation) and transferred directly to the muscle tissue. Even with these
extremely conservative assumptions, the calculated concentrations of PAHs in the fish tissue are more than 50
times lower than potential screening guidelines for recreational fish consumption and more than 6 times lower
than the guidelines for a subsistence consumer. This demonstrates that PAHs in the North Saskatchewan River
do not pose significant risk to humans that may consume fish caught in the river.

These results are not surprising as the fingerprint pattern of PAHs on the SPMDs showed a source that was
upstream of the POE and that the 16TAN released was not impacting water quality based on PAH
concentrations at any of the times of deployment of the SPMDs (CMI, 2017).

Respectfully submitted,

making environmental data meaningful 6

 Use of Semipermeable Membrane Devices (SPMDs) to Assess
Potential Fish
PAH Tissue Concentrations in North Saskatchewan River

Husky Energy Inc.

April 17, 2017

Lisa N. Kates, PhD Court D. Sandau, PhD, PChem
Environmental Forensic Chemist Principal

References
Chemistry Matters Inc., 2017. Forensic SPMDs Assessment Report. Written for Husky Energy Inc. 2017. DRAFT.

Huckins et al., 1990. Semipermeable membrane devices containing model lipid: A new approach to monitoring
the bioavailability of lipophilic contaminants and estimating their bioconcentration potential. Chemosphere.
Vol. 20, No. 5, pp 533-552, 1990.

Lu and Wang, 2003. Accumulation of organochlorinated pesticides by triolein-containing semipermeable

membrane device (triolein-SPMD) and rainbow trout. Water Research. 37 (2003) 2419-2425.

Nisbet and LaGoy, 1992. Toxic Equivalency Factors (TEFs) for Polycyclic Aromatic Hydrocarbons (PAHs). Reg.
Toxicol. Pharmacol. 16:290-300

Runhio et al., 2007. Comparison of the Uptake of Polycyclic Aromatic Hydrocarbons and Organochlorine
Pesticides by Semipermeable Membrane Devices and Caged Fish (Carassius Carassius) in Taihu Lake, China.
Environmental Toxicology and Chemistry. Vol. 26, No. 6, pp. 1258-1264, 2007.

US EPA, 2000. Guidance for Assessing Chemical Contaminant Data for Use in Fish Advisories, Volume 2 Risk
Assessment and Fish Consumption Limits, Third Edition.

Van der Oost et al., 2002. Fish bioaccumulation and biomarkers in environmental risk assessment: a review.
Environmental Toxicology and Pharmacology. 13 (2003) 57-149.

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