Passive Samplers:
Use in Forensics
Detlef (Deib) Birkholz, MSc, PhD, P. Chem.
Henri de Pennart, PhD, P. Biol., R.P. Bio
Watertech 2013: April 11, 2013
Semi-Permeable Membrane Devices, SPMDs
 SPMDs generally consist of a thin film of the neutral
triglyceride triolein, sealed in a layflat, thin-walled
tube of low density polyethylene (LDPE).
SPMD - Specifications
Triolein is used in SPMDs for the following
reasons:
 major storage lipid in most organisms;
 commercially available in high purity form;
 triolein-water partition coefficients and water
octanol partition coefficients (KOWs) are
similar
 triolein is a liquid down to -4oC.
SPMDs – Specifications (cont’d)
Choice of non porous LDPE layflat tubing based
on:
 stability in organic solvents (required for
dialysis and membrane cleaning)
 low diffusion rates of triolein relative to HOCs
(hydrophobic organic chemicals) in LDPE
during both uptake and dialytic recovery
processes
 resistance to abrasion and puncturing
SPMDs – Specifications (cont’d)
Source: Huckins et al. 2006
SPMD: target compounds
Source: Huckins et al. 2006
Field Deployment
(shallow water body)
PRCs (Performance Reference Compounds)
 The addition of PRCs is recommended to determine the effects
of SPMD membrane biofouling on the uptake of HOCs. The
PRC method can also account for the effects of flowturbulence and temperature differences.
 PRCs include: acenaphthene-d10, anthracene-d10, chrysened12, fluoranthene-d10, fluorene-d10, pyrene-d10,
phenanthrene-d10, dibenz(a,h)anthracene-d14, 2,2’dichlorobiphenyl (PCB #4), 3,5-dichlorobiphenyl (PCB#14),
2,4,5-trichlorobiphenyl (PCB#29), and 2,2’,4,6tetrachlorobiphenyl (PCB#50).
 Dibenz(a,h) anthracene-d14 is a good PRC to measure PAH
photolysis
Quality Control
 SPMD Fabrication blank – SPMDs without PRCs. The
primary purpose is to account for background
contribution due to interferences from SPMD
components, and for contamination incurred during
laboratory storage, processing and analytical procedures.
 Reagent blanks – consist of portions of all solvents
(volumes identical to those used for SPMD samples) used
during the processing, enrichment, and instrumental
analysis of an SPMD sample. Provides information on
background due to laboratory reagents and procedures.
Quality Control (cont’d)
 Field/Trip Blank SPMDs – taken to the field in sealed
metal cans and opened to the atmosphere at each site
during both deployment and retrieval of SPMDs from
aquatic systems.
 SPMD spikes – triolein spiked with analytes, PRCs and
surrogates.
Laboratory Procedures
Source: Huckins et al. 2006
Calculating Water Concentrations
History of SPMD Use in Alberta
 First employed for alkylated PAH determination by ALS Environmental
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shortly after they came on the market in the early 1990’s.
Canada Creosote site, Calgary, AB. Disconnect between water quality data
(16 L, Bow River) and analysis of fish bile downstream of site for PAHs.
Water quality showed no 4-6 ring PAHs which were abundant in fish bile
(Princess Island).
Used following Lake Wabamun derailment and spill
Have been employed for many other spills by Matrix Solutions
SPMDs often more cost effective than fish collection and analysis.
Focus has been on analysis of hydrocarbons, primarily PAHs
Have also been used to find sources of dioxins/furans and PCBs in Alberta
Currently being deployed by Environment Canada and consultants for
monitoring surface water in oil sands area.
Correlating Chemistry with Biological Response
SPMDs: A Tool for Forensics?
Petroleum Biomarkers
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All present in crude oil
Alkanes
Isoprenoids
Adamantanes
Sesquiterpanes
Terpanes/hopanes
Regular steranes/diasteranes
Triaromatic steranes
Informative PAHs
Some concentrated and/or eliminated during refining
Excellent way of differentiating between petroleum products
Petroleum Biomarkers
Methods
 Spider cage with SPMD placed in a 1-gallon stainless steel
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container
One litre of HPLC grade water added containing small amount
of diesel fuel, or environmental samples containing
hydrocarbons.
Placed in a shaking incubator at room temperature for 7-days.
SPMD removed, surface cleaned, solvent washed (acetone
and IPA), dried and then dialyzed in hexane.
Dialysates cleaned up using HRGPC followed by alumina/silica.
Analyzed for petroleum biomarkers, including informative
PAHs using gas chromatography/mass spectrometry
Alkanes
m/z 85
Diesel C10-C30
Hydraulic Fluid C11 to C31
Crude Oil C12-C31
SINTEF Reference Oil C9-C35
River A C11-C34
River B C13-C33
SINTEF Reference Oil C9-C35
Adamantanes
Diesel
m/z 149
Hydraulic Fluid
Crude Oil
River A
River B
Reference Oil
Sesquiterpanes
Diesel
m/z 123
Hydraulic Fluid
Crude Oil
River A
River B
Reference Oil
Terpanes & Hopanes
Diesel
m/z 191
Hydraulic Fluid
Crude Oil
River A
River B
Reference Oil
Regular Steranes
Diesel
m/z 217
Hydraulic Fluid
Crude Oil
River A
River B
Reference Oil
Diasteranes
Diesel
m/z 218
Hydraulic Fluid
Crude Oil
River A
River B
Reference Oil
Triaromatic Steranes
m/z 231
Diesel
Hydraulic Fluid
Crude Oil
River A
River B
Reference Oil
PAHs – C4-Phenanthrenes
Diesel
m/z 234
Hydraulic Fluid
Crude Oil
River A
River B
Reference Oil
PAHs – Methyl-Phenanthrenes/Anthracenes
Diesel
m/z 192
Hydraulic Fluid
Crude Oil
River A
River B
Reference Oil
PAHs – Fluoranthenes-Pyrenes-Benzofluorenes
Diesel
m/z 216
Hydraulic Fluid
Crude Oil
River A
River B
Reference Oil
PAHs – C3-chrysenes
m/z 270
Diesel
Hydraulic Fluid
Crude Oil
River A
River B
Reference Oil
PAHs - C2-phenanthrenes
m/z 206
Diesel
Hydraulic Fluid
Crude Oil
River A
River B
Reference Oil
PAHs - C2-Dibenzothiophenes
m/z 212
Diesel
Hydraulic Fluid
Crude Oil
River A
River B
Reference Oil
PAHs - C3-phenanthrenes
m/z 220
Diesel
Hydraulic Fluid
Crude Oil
River A
River B
Reference Oil
PAHs- C3-Dibenzothiophenes
m/z 226
Diesel
Hydraulic Fluid
Crude Oil
River A
River B
Reference Oil
Markers- summary
Analyte
Diesel
Hydraul.
Crude
River A
River B
Hydrocarbons
C10 - C30
C11 – C31
C12 – C31
C11-C34
C13-C33
C max
C14 – C16
C24 – C26
C16 – C18
C24-C28
C23-C29
Adamantanes
Sesquiterpanes
Terpanes/hopanes
Regular steranes
Diasteranes
Triaromatic steranes
C4-phenanthrenes
C1-phenant./anthracenes
Yes
Yes
Yes
Yes
Yes
No
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
No
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
No
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
C3-chrysenes
C2-phenanthrenes
C2-dibenzothiophenes
C3-phenanthrenes
C3-dibenzothiophenes
C1-fluorenes/pyrenes
benzofluoranthenes
No
Yes
No
Yes
No
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Hydrocarbon Forensics 101
SPMDs vs. Source
PAHs
sesquiterpanes
Terpanes, steranes
n-C17, n-C18, Pristane, Phytane
Triaromatic steranes
Conclusions
 SPMDs can differentiate between different petroleum
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products by comparing hydrocarbon and petroleum biomarker
profiles
Do capture all the petroleum biomarkers
Do capture PAHs which are important to determine human
and ecological risk
Although analysis of PAHs in water have been used for
forensics (e.g. C3-Dbt/C3-Phe and C2-Dbt/C2-Phe, C3-Dbt/C3Chry, etc.) these ratios are not useful when deploying SPMDs
This is not surprising because of varying KOWs for the PAHs
Analysis for petroleum biomarkers is effective at discerning
sources.
Conclusions (cont’d)
 The river samples are clearly different and show elements of
middle distillates and heavy petroleum products.
 The predominance of even alkanes in River A suggest a
synthetic product.
 Cannot dismiss that we may be looking at a mixtures of
petroleum products in both River A and River B.
Recommendations
 SPMDs could be used to determine potential seepage from
tailings ponds by sampling:
 Pond
 Groundwater downstream of dykes
 Downstream watercourses
 This could be used as a tool to limit liability when finding of PAHs
in the environment
References
 Monitors of Organic Chemicals in the Environment:
Semipermeable Membrane Devices, Eds. J.N. Huckins, J.D.
Petty and K. Booij, Springer, New York, 2006, 219+ pages
 B. Vrana et al. (2001). Use of semipermeable membrane
devices (SPMDs). Determination of bioavailable, organic,
waterborne contaminants in the industrial region of Bitterfeld,
Saxony-Anhalt, Germany. Environ. Sci. & Pollut. Res., 8: 27-34
 D. Alvarez (2010). Guidelines for the use of semipermeable
membrane device (SPMD) and the polar organic chemical
integrative sampler (POCIS) in environmental monitoring
studies. http://pubs.usgs.gov/tm/tm1d4/pdf/tm1d4.pdf