HISS-1, MESS-3, PACS-2: Marine Sediment Reference Materials for Trace Metals and other Constituents

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The following tables show those constituents for which certified and information values have been established. Certified values and their uncertainties are reported as mass fractions (based on dry mass). The uncertainties represent 95% confidence limits for an individual sub-sample of 250 mg or greater.

Table 1: Certified Quantity Values – Mass Fraction

Element	HISS-1 mg/kg	MESS-3 mg/kg	PACS-2 mg/kg
Antimony (b,g,i,n,q)	(0.13)*	1.02 ± 0.09	11.3 ± 2.6
Arsenic (b,g,h,i,n,x)	0.801 ± 0.099	21.2 ± 1.1	26.2 ± 1.5
Beryllium (b,g,i)	0.129 ± 0.023	2.30 ± 0.12	1.0 ± 0.2
Cadmium (b,g,i,q)	0.024 ± 0.009	0.24 ± 0.01	2.11 ± 0.15
Chromium (b,g,i,n,q,x)	30.0 ± 6.8†	105 ± 4	90.7 ± 4.6
Cobalt (b,g,i,n,x)	(0.65)*	14.4 ± 2.0	11.5 ± 0.3
Copper (b,g,i,n,q,x)	2.29 ± 0.37	33.9 ± 1.6	310 ± 12
Lead (b,g,i,q,x)	3.13 ± 0.40	21.1 ± 0.7	183 ± 8
Lithium (b,g,i,q)	2.83 ± 0.54	73.6 ± 5.2	32.2 ± 2.0
Manganese (b,g,i,n,x)	66.1 ± 4.2	324 ± 12	440 ± 19
Mercury (a,c,q)	(0.01)*	0.091± 0.009	3.04 ± 0.20
Molybdenum (g,i,q)	(0.13)*	2.78 ± 0.07	5.43 ± 0.28
Nickel (b,g,i,q,x)	2.16 ± 0.29	46.9 ± 2.2	39.5 ± 2.3
Selenium (b,g,h)	0.050 ± 0.007	0.72 ± 0.05	0.92 ± 0.22
Silver (b,g,i,q)	0.016 ± 0.002	0.18 ± 0.02	1.22 ± 0.14
Strontium (f,i,n,q,x)	96.9 ± 11.2	129 ± 11	276 ± 30
Thallium (b,q)	(0.06)*	0.90 ± 0.06	(0.6)*
Tin (b,g,i,q)	(0.11)*	2.50 ± 0.52	19.8 ± 2.5
Uranium (q)	(0.26)*	(4)*	(3.)*
Vanadium (b,g,i,n,x)	6.80 ± 0.78	243 ± 10	133 ± 5
Zinc (b,g,i,n,q,x)	4.94 ± 0.79	159 ± 8	364 ± 23

† see page 4

Table 2: Matrix and Minor Constituents - Mass Fraction

Element	HISS-1 (g/100g)	MESS-3 (g/100g)	PACS-2 (g/100g)
Aluminum (f,i,n,x)	0.73 ± 0.05	8.59 ± 0.23	6.62 ± 0.32
Carbon (e)	---	(2.)*	(3.3)*
Calcium (f,i,n,x)	1.14 ± 0.10	1.47 ± 0.06	1.96 ± 0.18
Chlorine (n,x)	(0.35)*	—-	(3.)*
Iron (f,i,n, x)	0.246 ± 0.009	4.34 ± 0.11	4.09 ± 0.06
Potassium (f,n, x)	0.332 ± 0.013	(2.6)*	1.24 ± 0.05
Magnesium (f,i,x)	0.075 ± 0.016	(1.6)*	1.47 ± 0.13
Sodium(f,i,n)	0.373 ± 0.026	(1.6)*	3.45 ± 0.17
Phosphorus (i,x)	—-	(0.12)*	0.096 ± 0.004
Sulfur (i,x)	—-	(0.19)*	1.29 ± 0.13
Silicon (i,x)	(44.)*	(27.)*	(28.)*
Titanium (f,i,n,x)	0.076 ± 0.004	0.44 ± 0.06	0.443 ± 0.032

Coding

• a - Atomic fluorescence spectrometry
• b - Inductively coupled plasma mass spectrometry
• c - Cold vapour atomic absorption spectrometry
• e - Coulometry
• f - Flame atomic absorption spectrometry
• g - Graphite furnace atomic absorption spectrometry
• h - Hydride generation atomic absorption spectrometry
• l - Inductively coupled plasma atomic emission spectrometry
• l - High-performance liquid chromatography ICPMS
• m - Gas chromatography microwave induced plasma atomic emission
• n - Instrumental neutron activation analysis
• q - Isotope dilution inductively coupled plasma mass spectrometry
• r - Infrared spectrometry
• x - X-ray fluorescence spectrometry

Not all the methods listed above were applied to all three certified reference materials.

Table 3: Butyltin Mass Fractions in PACS-2

Butyltin	PACS-2 µg/g (as Sn)
Tributyltin (l,m)	0.832± 0.095
Dibutyltin (l,m)	1.100± 0.135
Monobutyltin (l,m)	(0.7)*

The uncertainties in the certified values of the butyltins reflect expanded uncertainties. A separate certificate for the butyltins is available upon request.

Intended use

These reference materials are primarily intended for use in the calibration of procedures and the development of methods for the analysis of marine sediments and materials with similar matrices.

Preparation of material

HISS-1 was collected from the Hibernia Shelf, off the coast of Newfoundland. MESS-3 is from the Beaufort Sea. PACS-2 was collected from Esquimalt harbour, B.C. All were freeze dried, screened to pass a No. 120 (125 μm) screen, blended and bottled by Institute staff using the facilities of the Canada Centre for Mineral and Energy Technology in Ottawa. After bottling, the samples were radiation sterilized with a minimum dose of 25 kGy by Nordion International Inc. to minimize any effects from biological activity.

Instructions for drying

Although initially free from moisture following the freeze drying, the materials, which contain sea salt, have adsorbed moisture during subsequent operations. They should be dried to a constant mass before use. Drying for several hours at 105 °C is recommended as a relatively simple method to achieve a dry mass for most purposes.

Storage and sampling

It is recommended that the material be stored in a cool, clean location. Each bottle is packaged in a trilaminate foil pouch which serves as an impermeable barrier to mercury vapour. Under conditions of high ambient levels of mercury vapour, mercury is able to penetrate the plastic cap of the bottle, thereby potentially contaminating the contents. The bottle contents should be well mixed by rotation and shaking prior to use, and tightly closed immediately thereafter.

Storage of PACS-2 for organotin stability

To ensure the stability of the organotin species in PACS-2, it is necessary to store the material at a temperature of 4 °C or lower.

Information values

Information values are considered less reliable than certified values because they are not based on the results of at least two independent methods, there were insufficient analyses performed or inhomogeneity is suspected. These values are given for information only and care should be excised not to attribute more reliability to these values than they warrant.

Homogeneity

Randomly selected bottles were used for the analytical determinations. Results from different bottles showed no significant differences compared to results from subsamples within bottles; nor was there any correlation between values obtained and bottle sequence. Thus, it is assumed that all bottles of each of these materials have essentially the same composition. An exception is Co in HISS-1, for which results indicated sample inhomogeneity.

†Chromium in HISS-1

It became apparent during the certification of HISS-1 that there is a significant fraction of Cr that is not easily solubilized. The certified value of 30 mg/kg was obtained using solid sampling techniques or prolonged digestion with hydrofluoric, sulphuric and perchloric acids. Less vigorous acid dissolution techniques (including microwave heating using closed vessels at high pressure) typically result in a Cr mass fraction between 10 and 13 mg/kg.

Metrological traceability

Results presented in this certificate are traceable to the SI through gravimetrically prepared standards of established purity and international measurement intercomparisons. As such, they serve as suitable reference materials for laboratory quality assurance programs, as outlined in ISO/IEC 17025. This CRM is registered at the Bureau International des Poids et Mesures (BIPM) in Appendix C of the Comité International des Poids et Mesures database listing Calibration and Measurement Capabilities accepted by signatories to the Mutual Recognition Arrangement of the Metre Convention.

Accreditation

The Chemical Metrology laboratory is compliant to ISO 17025 and ISO Guide 34, with approval by The Inter-American Metrology System (SIM). The certificate of approval is available upon request.

Updates

Users should ensure that the certificate they have is current. The NRC web site will contain any new information.

Acknowledgements

The following staff members of the Measurement Science and Standards portfolio at the NRC contributed to the production and certification of HISS-3, MESS-3 or PACS-2: S. Berman, V.J. Boyko, V.P. Clancy, J. Lam, P. Maxwell, J.W. McLaren, B. Methven, C. Brophy, R. Sturgeon, S. Willie and L. Yang.

The cooperation of the following during the certification of one or more of these sediments is gratefully acknowledged: 

E. Crecelius, B. Lasorsa, C.W. Apts, O.A. Cotter, R.W. Sanders and T. Gilfoil,
Battelle Pacific Northwest, Sequim, Washington.

R. Presley, P. Boothe, R. Taylor and T. Wade,
Texas A & M University, College Station, Texas.

M. Leaver, R. Beaudoin and H. Steger,
Canada Centre for Mineral and Energy Technology,
Natural Resources Canada, Ottawa, Ontario.

W. May, D.A. Becker, Rolf Zeisler, R.R. Greenberg and S. Wise,
National Institute of Standards and Technology, Gaithersburg, Maryland.

R. Parker,
Department of Geology, University of Auckland, New Zealand.

C. Davies, Z. Huang and P. Moore, Brooks Rand Ltd.,
Seattle, Washington.

Alan Jeffrey, John Stewart, Peter Lynch, Helen Walker, John Drinnan and Glenn Barry,
Department of Natural Resources Indooroopilly, Queensland, Australia.

Ms. Anne Scott,
Australian Government Analytical Laboratories, Pymble, N.S.W. Australia.

R. Smith, Skidaway Inst. of Oceanography, Savannah, GA.

Issac Pereiro and Ryszard Lobinski,
Laboratoire de Chimie Bio-Inorganique et Environnement, Pau, France.

HISS-1

Date of issue: February 1997
Date of expiry: December 2014

MESS-3

Date of issue: January 2000
Date of expiry: December 2014

PACS-2

Date of issue: August 1997
Date of expiry: December 2014
Butyltin values updated: August 2004
Date of expiry (butyltins): December 2014
Butyltin expiry dates revised: January 2012

Approved by:

Zoltan Mester, Ph. D.
Group Leader, Chemical Metrology
Measurement Science and Standards

Comments, information and inquiries should be addressed to:

National Research Council of Canada
Measurement Science and Standards
1200 Montreal Road
Building M-12
Ottawa, Ontario K1A 0R6

Telephone: 613-993-2359
Fax: 613-993-2451
Email: CRM-MRCInorganic-Inorganiques@nrc-cnrc.gc.ca