Elsevier

Analytica Chimica Acta

Review

Flow injection analysis as a tool for enhancing oceanographic nutrient measurements—A review

Highlights

FIA and SIA techniques for nutrient determinations in marine waters are critically reviewed.

The advantages and suitability of FIA for underway and shipboard marine analysis are discussed.

Strategies for sensitivity improvement are considered.

Potential schlieren problems in FIA of marine samples and possible solutions proposed.

The importance of data quality and uncertainty estimation in trace analysis are emphasised.

Abstract

Macronutrient elements (C, N and P) and micronutrient elements (Fe, Co, Cu, Zn and Mn) are widely measured in their various physico-chemical forms in open ocean, shelf sea, coastal and estuarine waters. These measurements help to elucidate the biogeochemical cycling of these elements in marine waters and highlight the ecological and socio-economic importance of the oceans. Due to the dynamic nature of marine waters in terms of chemical, biological and physical processes, it is advantageous to make these measurements in situ and in this regard flow injection analysis (FIA) provides a suitable shipboard platform. This review, therefore, discusses the role of FIA in the determination of macro- and micro-nutrient elements, with an emphasis on manifold design and detection strategies for the reliable shipboard determination of specific nutrient species. The application of various FIA manifolds to oceanographic nutrient determinations is discussed, with an emphasis on sensitivity, selectivity, high throughput analysis and suitability for underway analysis and depth profiles. Strategies for enhancing sensitivity and minimizing matrix effects, e.g. refractive index (schlieren) effects and the important role of uncertainty budgets in underpinning method validation and data quality are discussed in some detail.

Abbreviations

8HQ-MAF

8-quinolinol immobilised on silica gel, metal alkoxide fluoride glass

C4 D

contactless capacitively coupled conductivity detector

CRM

certified reference material

CTAB

cetyltrimethylammonium bromide

DIC

dissolved inorganic carbon

DDAB

didodecyldimethylammonium bromide

DIC

dissolved inorganic carbon (also called "total carbonate")

DOC

dissolved organic carbon

DOP

dissolved organic phosphorus

DRP

dissolved reactive phosphorus

FIA

flow injection analysis

GF-AAS

graphite furnace atomic absorption spectrophotometry

GUM

guide to the expression of uncertainty in measurements

HNLC

high-nutrient, low-chlorophyll regions

HTCO

high temperature catalytic oxidation

ICP-SFMS

inductively coupled plasmas-sector field mass spectrometry

LWCC

liquid waveguide capillary cell

MRFC

multi-reflection flow cell

p CO 2

partial pressure of carbon dioxide

PON

particulate organic nitrogen

ROV

remotely operated vehicle

RSD

relative standard deviation

REU

relative expanded uncertainty

SAFe

sampling and analysis of iron program

SCFA

segmented continuous flow analysis

∑CO2

dissolved inorganic carbon (also called "total carbonate")

TCNQ

7,7,8,8-tetracyanoquinodimethane

T CO 2

dissolved inorganic carbon (also called "total carbonate")

TDN

total dissolved nitrogen

TDP

total dissolved phosphorus

TIC

total inorganic carbon

TPN

total particulate nitrogen

Keywords

Marine waters

Estuarine waters

Macronutrients

Micronutrients

Flow injection analysis

Data quality

Cited by (0)

Paul J. Worsfold is a Professor of Analytical Chemistry at Plymouth University (since 1990) and Co-Director of the Biogeochemistry Research Centre. He obtained his BSc from Loughborough University (1976) and his PhD from the University of Toronto (1980). He is Chair of the Division of Analytical Chemistry of the European Association for Chemical and Molecular Sciences and a Past-President of the Analytical Division of the Royal Society of Chemistry. One research interest is techniques for the determination of macronutrients and micronutrients and understanding their role in terrestrial and aquatic biogeochemical processes. Flow injection provides an integrating theme for this research and he has recently co-authored a textbook on the subject.

Robert Clough has been a research fellow in the School of Geography, Earth and Environmental Sciences at the University of Plymouth since 2003 having also obtained his BSc and PhD at Plymouth. He is currently Chair of the Western region of the Analytical Division of the Royal Society of Chemistry and a Topic Group co-ordinator for the Atomic Spectrometry Updates annual reviews. Robert's research interests focus on elemental speciation, analytical method development and chemical metrology, applying this to difficult to measure analytes in challenging sample matrices.

Maeve C. Lohan is a Professor in marine chemistry at the University of Plymouth. Her research interests focus on understanding trace metal biogeochemical cycling in both coastal and open ocean regimes with particular reference to bioactive metals such as iron, zinc, and cobalt. In particular, her research focuses on the speciation of these elements and their bioavailability and impact on aquatic ecosystems.

Philippe Monbet With a background in chemistry obtained from the University of Western Brittany, Philippe Monbet completed a PhD in "Marine Chemistry and Analytical Chemistry" at the European Institute for Marine Studies (IUEM, Brest) on the dynamics heavy metals in an estuary subject to strong agricultural inputs. He then joined French research institutes IFREMER and INERIS for missions of research and expertise. His research activities have taken him to AIMS (the Australian Institute of Marine Science, Townsville, Australia), Monash University (Melbourne, Australia) and Plymouth University (UK) where his research was mainly devoted to phosphorus biogeochemistry in coastal ecosystems.

Peter S. Ellis has been a Research Fellow in the Water Studies Centre, Monash University since 1998. With a background in electronics and optics, his recent research has focussed on the development of portable flow based analytical systems for the underway measurement of macronutrients in marine and estuarine systems. His flow systems have been extensively used for coastal marine measurements around Australia and further afield. Of particular interest has been the development of high sensitivity spectrophotometric detection systems with low susceptibility to schlieren errors.

Christophe R. Quétel graduated in 1987 in physical chemistry from the École Nationale Supérieure de Chimie Physique de Bordeaux, France. He completed a PhD thesis in marine chemistry at the Commissariat à l'Energie Atomique (Gif-sur-Yvette, France) and received his diploma from the University Paris VI in 1991. Subsequently, he held post-doctoral fellowships at the University of Bordeaux and at the National Institute for Resources and Environment in Tsukuba, Japan, before moving to the Institute for Reference Materials and Measurements (IRMM) of the Joint Research Centre of the European Commission (Geel, Belgium) in 1996. Here, he established the IRMM ICP-MS laboratory, developing projects on isotopic reference measurements and reference materials, and chemical metrology. He has published more than 75 articles and given more than 60 invited lectures at conferences and workshops. He chaired the Euramet MetChem-Technical Committee for Inorganic Analysis 2004 to 2010 and represents the IRMM on the Inorganic Analysis Working Group of the Comité Consultatif pour la Quantité de Matière. He has been the President of the French Society for Stable Isotopes from 2006 to 2012, and is Joint Editor in Chief of Geostandards and Geoanalytical Research.

Geerke H. Floor obtained her MSc from the Department of Earth Sciences, Utrecht University in 2007 and a PhD in Environmental Analytical Chemistry from the Department of Chemistry, University of Girona in 2011. Her research is at the interface between Earth Sciences and Analytical Chemistry. Geerke is working at the Institute for Reference Materials and Measurements (a European Commission Joint Research Centre) since 2011 with a main focus on the development of analytical protocols for environmental applications using the concept of isotope dilution.

Ian D. McKelvie is Principal Fellow in the School of Chemistry at the University of Melbourne and Visiting Professor, School of Geography, Earth, and Environmental Sciences, at the Plymouth University, UK. Prior to that he was Associate Professor at Monash University, where his research focused on the development of flow-based analytical systems for water quality assessment of macronutrients in marine, estuarine and freshwater systems, and on the biogeochemistry of organic phosphates. He has co-edited two monographs: Environmental Monitoring Handbook (2002) and Advances in flow injection analysis and related techniques (2008), and recently joined the journal Talanta as an associate editor.

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