What do Total and Dissolved Metal

Concentrations in Groundwater
Samples Really Tell Us?

Part 1: Metal Speciation, Analytical Definition and

Toxicity

Elizabeth Haack, Ph.D., P.Chem.

WaterTech 2013, April 11 2013, Banff, AB.
 Contemplated Policy – AESRD

Wallace (2012)

Unfiltered, Field Acidified

Filtered 0.45 µm filter, Field Acidified

Note: Best way to sample metals in water is a source of ongoing

debate globally (US, European Union)

2
 Will we necessarily obtain meaningful and
scientifically-defensible data using this approach?
Meaningful Data

Exceedingly difficult question to answer

based on the sampling objectives, being:

To determine whether or not specific anthropogenic

activities are affecting natural levels?

To predict potential adverse health effects to receptors at the

point of exposure.
• Human ingestion (and dermal exposure) – treatment?
• Shallow groundwater (eco direct contact)
• Discharge point to surface water body – conditions along flow path?
Overarching Challenge:
“Operational” Definition
Absolute Total Concentration of
a Metal

“Dissolved” Particulate/Suspended
Passes through 0.45 µm filter Retained by 0.45 µM filter

Colloidal
(0.001 µm - 1 µm); Guo and Santschi 2007

“Trully” Dissolved Strong Acid Very Strong

Field
(< 1 nm: Hydrated Extractable acids
ions, Low Molecular Acidification Nitric/Hydrochloric
(solubilize metals
Acid Digestion
Weight Fraction) from crystal
(USEPA, 2010) structure)
Overarching Challenge -
Speciation
 Metals are associated with matter (ligands, colloids, particles)
that spans a continuum of sizes
• will be partitioned amongst all fractions in accordance with
properties of both metal and matter
• Not static – perturbation of conditions will affect partitioning

 A metal/trace element’s mobility, bioavailability and toxicity is

almost always dependent on its speciation.

 “Speciation” involves a myriad of considerations:

• oxidation state / redox conditions
• presence and activity of microbes
• solubility of mineral phases
• ligands
• reactions at the solid-solution interface
• presence of other metals/ions
To meet objectives….

Rigorous science requires that the following a true:

1. Field methods obtain “representative” samples

Ken’s Talk - Next
of the relevant fractions.

2. There is a good understanding of what the relevant forms (chemical

species) of the metal will be.

3. Analytical methods exist that can accurately quantify total metals as

well as relevant species concentrations

4. Toxicological data exists that allows us to assess the (relative)

bioavailability and toxicity of all forms.
Example: Chromium
Why Chromium?
Growing concern over Cr(VI)
carcinogenicity by oral exposure route

State of California:
Groundwater Ambient Monitoring and
Assessment (GAMA) Program (2011)

>47 % of wells tested, Cr(VI) exceeded

the detection limit for the purposes of
reporting of 1µ/L (1 ppb)

Public Health Goal of 20 ng/L (20 ppt)

published in 2011 (OEHHA)

Science behind existing Total Cr

criteria (50 ppb, Canada) outdated
US EPA currently considering a
Maximum Concentration Limit for Cr(VI
alone).
 1. Do we understand the
relevant forms?
Present naturally in groundwater
through weathering of Cr-containing
soils and rocks (secondary
minerals, chromic oxide, chromite)
electroplating factories, leather
tanneries and textile manufacturing
facilities

Aqueous Speciation:
Cr(III) (cationic) and Cr(VI) (anionic)

Cr (III) to Cr (VI): Mn oxides and

bacterial oxidation, kinetics slow

Not the whole story - mixed species

- Non-equilibrium conditions
McNeill et al., 2006 - Complexes with OM
1. What are the relevant forms
that are not “trully” dissolved

From McNeill et al. 2012, 4 mg/L Fe(OH)3, 5 µg/L Cr(III) or Cr(VI

2. Can we analyze total and all
the species concentrations?
Previous slides indicate that both in filtered and non-filtered samples,
may have a complex combination of species

Total Cr by ICP-MS
• No speciation
• Prone to interferences (ArC, ClO)
• Stong acid digest may not be effective (Kumar and Riyazuddin 2009)
• Detection limits are not in line with levels proposed for Cr(VI) (~0.5 µg/L)

Speciation Analysis - Cr(VI) by Ion Chromatography (McNeill et al.,

2012)
• New methodologies (US EPA Method 218.7) mean that laboratories are
capable of detection limits required for ppt-level criteria and does not require
filtration (Ask your commercial lab)
• May be some issues with respect to contamination of Cr(VI) with reagents used
to adjust pH
• Field filtration may not be necessary
 3. So what? What is important to my
receptor?
Hexaaquachromium ion; not actively transported

Cr in soils/particulates (largely Cr) does not appear to be

bioavailable through leaching tests that simulates
stomach and intestinal environment

Similarity of the Cr(VI) ion to sulphate – readily

taken up
Mammal Studies indicate mutagenic effects

Hold up on regulatory criteria:

BIOAVAILABILITY OF Cr(VI) – critical factor
linking aqueous phase concentration to the toxic
dose
-Cr(VI) reduced to Cr(III) in saliva and G.I. tract
- Amount not reduced unknown
Zhitkovich, 2011
Summary - Cr

 Speciation, analytical and toxicology are all “somewhat

understood”

 Studies suggest that risks overwhelmingly related to

Cr(VI) in samples

 Proposed approach (i.e. total vs. dissolved) is not likely

to significantly increase our understanding of risks

 Interim – reasonable because of unknown potential for

Cr(III) oxidation
Other Metals
Other Metals/Trace Elements

“Simpler Biogeochemistry” - predominantly present in groundwater

as divalent cations – behaviour largely sorption-controlled, or
complexation with organic ligands:
• Cu(II)
• Cd(II) Thermodynamic Equilibirum models (Biotic Ligand
• Zn(II) Model; WHAM) can be used with water quality data
• Ni(II) to evaluate/predict available concentrations
• Co(II)

“Complex Biogeochemistry” that includes consideration of

bioaacumulation and potential biomagnification
• Selenium and Mercury
• Studies have not shown that water concentrations are not a good
predictor of risk to higher-level organisms.
• Ecological Tissue-based criteria
Emerging/Applied
Methods
Approaches to Consider

 “Bioanalogical Sensors” (Van Leeuwen et al. 2005):

• Diffusive Gradient Thin Films Time-averaged, preconcentration - Mobile
• Gel-Integrated Microelectrodes and Labile forms Operationally Defined; Not
all elements
• Permeation Liquid Membrane
• Voltammetry
Sensitivity and Specificity may
not be sufficient
 Bioavailability to specific organisms:
• Biosensors/Bioluminescence Sensors - (Ivask et al. 2009)
• Wholeistic: In Situ effects monitoring – caged test species

Quality Control and Standards

Lacking
 Toxicology – “Omics” Sciences:
• Revolutionizing toxicology (Cohen 2004; North and Vulpe 2010)
• Cheaper, faster, number of endpoints less limited than trad. animal testing
• Can test mixed systems (i.e. where more than one contaminant is present)
Significant technical expertise to use/deploy and interpret
Concluding Thoughts

 Difficulty in assessing the meaningfulness of data from the proposed

approach is in line with ongoing debate globally (e.g. responses to the
dissolved-phase decision as part of the Water Framework Directive of
the European Union)

 Approach is arbitrary, and considered here to be an interim approach

based on current science.

 In the short term, from the standpoint of the realities of monitoring wells,
system complexity, analytical constraints, and the varied receptors to be
accounted foremost in decision-making around metals sampling should
be sound professional judgment and interpretation based on
understanding of biogeochemistry and potential risks.

 In the medium-long term - a new paradigm whereby effects monitoring,

monitoring of specific “high-risk species”, or evaluation of tissue-based
concentrations (for some elements) to emerge that provides a lines-of-
evidence approach to risks from metal/trace element concentrations at
a Site.
 Elizabeth Haack
WorleyParsons Canada Services Ltd.
905-614-2844
elizabeth.haack@worleyparsons.com

Thank You –
Questions?
References – 1 of 2

 Cohen, S. 2004. Risk Assessment in the Genomic Era. Toxicologic Pathology. 32, 3.

 Eaton, A., Ramirez, L.M. and Haghani, A., 2001. The Erin Brokovich Factor – Analysis of Total and Hexavalent
Chromium in Drinking Waters. AWWA Water Quality Technology Conference, Nashville, TN.

 Groundwater Ambient Monitoring and Assessment (GAMA) Program . Groundwater Information Sheet: Hexavalent
Chromium. www.swrcb.ca.gov/gama/docs/coc_hexchromcr6.pdf

 Guo, L., and Santschi, P.H., 2007. Ultrafiltration and its applications to sampling and characterisation of aquatic
colloids. Environmental Colloids and Particles: Behaviour, Separation and Characterisation. edited by Kevin J.
Wilkinson, Jamie R. Lead. 159-222. John Wiley & Sons, Ltd. England.

 Ivask, A., Rõlova, T., and Kahru, 2009. A. A suite of recombinant luminescent bacterial strains for the quantification
of bioavailable heavy metals and toxicity testing. BMC Biotechnology 2009, 9:41.

 Kumar, A.R., and Riyazuddin, P., 2009. Comparative Study of Analytical Methods for the Determination of
Chromium in Drinking Water Samples Containing Iron. Microchemical Journal. 93, 236.

 McNeill, A., McLean, J., Edwards, M., and Parks, J., 2012. State of the Science of Hexavalent Chromium in
Drinking Water. Water Research Foundation. Updated May 2012.
References – 2 of 2

 Morman, S.A., Plumlee, G.S., and Smith, D.B., 2009. Application of in vitro extraction studies to evaluate element
bioaccessibility in soils from a transect across the United States and Canada. Applied Geochemistry, v. 24 1454-
1463).

 North, M., and Vulpe, C.D., 2010. Functional Toxicogenomics: Mechanism-Centered Toxicology. International
Journal of Molecular Sciences. 11, 4796-4813.

 Sharma, V.K., and Sohn, M., 2009. Aquatic arsenic: Toxicity, speciation, transformations, and remediation.
Environment International 35.743–759.

 US EPA. 2010. UCMR3 Laboratory Approval Requirements and Information Document, EPA, 815-R-10-004,
USEPA Office of Water, Cincinnati, OH.

 Wallace, 2012. Alberta Water Policy Update. Brief to Water Technologies Symposium 2012. April 12, 2012.
http://www.esaa-events.com/proceedings/watertech/2012/pdf/P4.pdf

 WHO (World Health Organization), 1988. Environmental Health Criteria 61, Chromium, 1988.

 Van Leeuwen et al., 2005. Dynamic Speciation Analysis and Bioavaibility of Metals in Aquatic Systems.
Environmental Science and Technology, 39, 8545-8556.

 Zhitkovich, A, 2011. Chromium in Drinking Water: Sources, Metabolism, and Cancer Risks. Chemical Research in
Toxicology, 24., 1617–1629.