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Title: Data Trend Shifts Induced by Method of Concentration for Trace Metals in Seawater: Automated Online Preconcentration vs Borohydride Reductive Coprecipitation of Nearshore Seawater Samples for Analysis of Ni, Cu, Zn, Cd, and Pb via ICP-MS

Abstract

This research compares performance, reproducibility, and detection limits of ambient seawater analysis for trace metals using both borohydride reductive co-precipitation and an automated chelation column (seaFAST™ 2) co-preconcentration for matrix interferent elimination on total and dissolved grab samples in nearshore to marine waters, over a broad concentration range, prior to ICP-MS injection. A move to an online preconcentration method both minimizes sample preparation, and eliminates correction errors when accounting for trace impurities in precipitated samples, induced via reagents. The reproducability of the online preconcentration method described, coupled with low blanks and method detection limits (MDLs), demonstrates an effective move to an automated procedure using ethylenediaminetriacetic and iminodiacetate acid chelation exchange resin and multi-analyte determination via ICP-MS for total and dissolved Ni, Cu, Zn, Cd, and Pb in marine water samples. Average CASS-5 recoveries using the online preconcentration method (n=9) were 109±7%, 104±5%, 103±7%, 101±3%, and 86±8% respectively. The MDLs obtained from the automated method for Ni, Cu, Zn, Cd and Pb were 3.3, 1.8, 13.5, 4, and 10 times lower, respectively, than for the Borohydride method. There were statistically significant differences between the methods for CASS-5 recoveries of Ni, Cu, Zn (p < 0.0001), and Pb (p = 0.0024). Comparisonmore » of methods gave high concordance (rC = 0.90) between methods for total and dissolved Ni, Cu, Zn, and Pb, and total Cd.« less

Authors:
ORCiD logo [1];  [1];  [2]
  1. BATTELLE (PACIFIC NW LAB)
  2. US Navy Space and Naval Warfare Systems Center
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1525978
Report Number(s):
PNNL-SA-140847
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Limnology and Oceanography Methods
Additional Journal Information:
Journal Volume: 17; Journal Issue: 4
Country of Publication:
United States
Language:
English
Subject:
seaFAST, borohydride, seawater, Ethylenediaminetetraacetic acid (EDTA), iminodiacetate acid, trace metals, Inductively coupled plasma mass spectrometry

Citation Formats

Strivens, Jonathan E., Brandenberger, Jill M., and Johnston, Robert K. Data Trend Shifts Induced by Method of Concentration for Trace Metals in Seawater: Automated Online Preconcentration vs Borohydride Reductive Coprecipitation of Nearshore Seawater Samples for Analysis of Ni, Cu, Zn, Cd, and Pb via ICP-MS. United States: N. p., 2019. Web. doi:10.1002/lom3.10311.
Strivens, Jonathan E., Brandenberger, Jill M., & Johnston, Robert K. Data Trend Shifts Induced by Method of Concentration for Trace Metals in Seawater: Automated Online Preconcentration vs Borohydride Reductive Coprecipitation of Nearshore Seawater Samples for Analysis of Ni, Cu, Zn, Cd, and Pb via ICP-MS. United States. doi:10.1002/lom3.10311.
Strivens, Jonathan E., Brandenberger, Jill M., and Johnston, Robert K. Mon . "Data Trend Shifts Induced by Method of Concentration for Trace Metals in Seawater: Automated Online Preconcentration vs Borohydride Reductive Coprecipitation of Nearshore Seawater Samples for Analysis of Ni, Cu, Zn, Cd, and Pb via ICP-MS". United States. doi:10.1002/lom3.10311.
@article{osti_1525978,
title = {Data Trend Shifts Induced by Method of Concentration for Trace Metals in Seawater: Automated Online Preconcentration vs Borohydride Reductive Coprecipitation of Nearshore Seawater Samples for Analysis of Ni, Cu, Zn, Cd, and Pb via ICP-MS},
author = {Strivens, Jonathan E. and Brandenberger, Jill M. and Johnston, Robert K.},
abstractNote = {This research compares performance, reproducibility, and detection limits of ambient seawater analysis for trace metals using both borohydride reductive co-precipitation and an automated chelation column (seaFAST™ 2) co-preconcentration for matrix interferent elimination on total and dissolved grab samples in nearshore to marine waters, over a broad concentration range, prior to ICP-MS injection. A move to an online preconcentration method both minimizes sample preparation, and eliminates correction errors when accounting for trace impurities in precipitated samples, induced via reagents. The reproducability of the online preconcentration method described, coupled with low blanks and method detection limits (MDLs), demonstrates an effective move to an automated procedure using ethylenediaminetriacetic and iminodiacetate acid chelation exchange resin and multi-analyte determination via ICP-MS for total and dissolved Ni, Cu, Zn, Cd, and Pb in marine water samples. Average CASS-5 recoveries using the online preconcentration method (n=9) were 109±7%, 104±5%, 103±7%, 101±3%, and 86±8% respectively. The MDLs obtained from the automated method for Ni, Cu, Zn, Cd and Pb were 3.3, 1.8, 13.5, 4, and 10 times lower, respectively, than for the Borohydride method. There were statistically significant differences between the methods for CASS-5 recoveries of Ni, Cu, Zn (p < 0.0001), and Pb (p = 0.0024). Comparison of methods gave high concordance (rC = 0.90) between methods for total and dissolved Ni, Cu, Zn, and Pb, and total Cd.},
doi = {10.1002/lom3.10311},
journal = {Limnology and Oceanography Methods},
number = 4,
volume = 17,
place = {United States},
year = {2019},
month = {4}
}

Works referenced in this record:

Measurement in Medicine: The Analysis of Method Comparison Studies
journal, September 1983

  • Altman, D. G.; Bland, J. M.
  • The Statistician, Vol. 32, Issue 3
  • DOI: 10.2307/2987937

Analysis for Cd, Cu, Ni, Zn, and Mn in estuarine water by inductively coupled plasma mass spectrometry coupled with an automated flow injection system
journal, March 2002


Statistical Methods for Assessing Agreement Between two Methods of Clinical Measurement
journal, February 1986


Direct determination of trace metals in sea-water using electrothermal vaporization inductively coupled plasma mass spectrometry
journal, January 1996

  • Chapple, Graeme; Byrne, John P.
  • Journal of Analytical Atomic Spectrometry, Vol. 11, Issue 8
  • DOI: 10.1039/ja9961100549

Trace metal enrichment by automated on-line column preconcentration for flow-injection atomic absorption spectrometry
journal, January 1989


Determination of trace metals in seawater by on-line column preconcentration inductively coupled plasma mass spectrometry
journal, July 2001


Trace metal transport by marine microorganisms: implications of metal coordination kinetics
journal, January 1993

  • Hudson, Robert J. M.; Morel, François M. M.
  • Deep Sea Research Part I: Oceanographic Research Papers, Vol. 40, Issue 1
  • DOI: 10.1016/0967-0637(93)90057-A

Determination of Mn, Fe, Co, Ni, Cu, Zn, Cd and Pb in seawater using high resolution magnetic sector inductively coupled mass spectrometry (HR-ICP-MS)
journal, April 2010


Direct determination of trace metals in sea-water by inductively coupled plasma mass spectrometry
journal, January 1998

  • Rosland, Eivind; Lund, Walter
  • Journal of Analytical Atomic Spectrometry, Vol. 13, Issue 11
  • DOI: 10.1039/a804350g

Concentration of trace elements in water samples by reductive precipitation
journal, December 1985

  • Skogerboe, R. K.; Hanagan, W. A.; Taylor, H. E.
  • Analytical Chemistry, Vol. 57, Issue 14
  • DOI: 10.1021/ac00291a016

Evaluating Agreement with a Gold Standard in Method Comparison Studies
journal, June 1998


Processes regulating cellular metal accumulation and physiological effects: Phytoplankton as model systems
journal, August 1998


Trace metal analysis of natural waters by ICP-MS with on-line preconcentration and ultrasonic nebulization
journal, January 1999

  • Warnken, Kent W.; Gill, Gary A.; Wen, Liang-Saw
  • Journal of Analytical Atomic Spectrometry, Vol. 14, Issue 2
  • DOI: 10.1039/a806822d

Method agreement analysis: A review of correct methodology
journal, June 2010