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 flow-turbulence and temperature differences.

PRCs include: acenaphthene-d10, anthracene-d10, chrysene-d12, 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’,4,6-tetrachlorobiphenyl (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 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

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 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

River A C11-C34

River B C13-C33

SINTEF Reference Oil C9-C35

SINTEF Reference Oil C9-C35

Adamantanes

m/z 149

Diesel

Hydraulic Fluid

Crude Oil

River A

River B

Reference Oil

Sesquiterpanes

m/z 123 Diesel

Hydraulic Fluid

Crude Oil

River A

River B

Reference Oil

Terpanes & Hopanes

m/z 191

Diesel

Hydraulic Fluid

Crude Oil

River A

River B

Reference Oil

Regular Steranes

m/z 217

Diesel

Hydraulic Fluid

Crude Oil

River A

River B

Reference Oil

Diasteranes

m/z 218

Diesel

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

m/z 234

PAHs – C4-Phenanthrenes

Diesel

Hydraulic Fluid

Crude Oil

River A

River B

Reference Oil

m/z 192

PAHs – Methyl-Phenanthrenes/Anthracenes

Diesel

Hydraulic Fluid

Crude Oil

River A

River B

Reference Oil

m/z 216

PAHs – Fluoranthenes-Pyrenes-Benzofluorenes

Diesel

Hydraulic Fluid

Crude Oil

River A

River B

Reference Oil

m/z 270

PAHs – C3-chrysenes

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 Yes Yes No Yes Yes Sesquiterpanes Yes Yes Yes Yes Yes

Terpanes/hopanes Yes Yes Yes Yes Yes Regular steranes Yes Yes Yes Yes Yes

Diasteranes Yes Yes Yes Yes Yes Triaromatic steranes No Yes Yes No Yes C4-phenanthrenes Yes Yes Yes Yes Yes

C1-phenant./anthracenes Yes Yes Yes Yes Yes

C3-chrysenes No Yes Yes Yes Yes C2-phenanthrenes Yes Yes Yes Yes Yes

C2-dibenzothiophenes No Yes Yes Yes Yes C3-phenanthrenes Yes Yes Yes Yes Yes

C3-dibenzothiophenes No Yes Yes Yes Yes C1-fluorenes/pyrenes benzofluoranthenes

Yes Yes Yes Yes Yes

Hydrocarbon Forensics 101

PAHs

Terpanes, steranes

Triaromatic steranes

n-C17, n-C18, Pristane, Phytane

sesquiterpanes

SPMDs vs. Source

SPMDs can differentiate between different petroleum 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/C3-Chry, 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

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.

Conclusions (cont’d)

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

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

References