Paul J. Worsfold

Methods for the determination and speciation of mercury in natural waters—A review

This review summarises current knowledge on Hg species and their distribution in the hydrosphere and gives typical concentration ranges in open ocean, coastal and estuarine waters, as well as in rivers, lakes, rain and ground waters. The importance of reliable methods for the determination of Hg species in natural waters and the analytical challenges associated with them are discussed. Approaches for sample collection and storage, pre-concentration, separation, and detection are critically compared. The review covers well established methods for total mercury determination and identifies new approaches that offer advantages such as ease of use and reduced risk of contamination. Pre-concentration and separation techniques for Hg speciation are divided into chromatographic and non-chromatographic methods. Derivatisation methods and the coupling of pre-concentration and/or separation methods to suitable detection techniques are also discussed. Techniques for sample pre-treatment, pre-concentration, separation, and quantification of Hg species, together with examples of total Hg determination and Hg speciation analysis in different natural (non-spiked) waters are summarised in tables, with a focus on applications from the last decade.

Analytical applications of liquid-phase chemiluminescence

Abstract Solution-phase chemiluminescent reactions of analytical interest are described. Their attractions include high sensitivity, wide dynamic range and the use of simple instrumentation for monitoring emission. Selectivity can be incorporated into such reactions by means of physical and/or chemical processes (either on-line or off-line). Practical considerations and the instrumentation required are also discussed. Specific applications of chemiluminescent reactions are classified according to the nature of the analyte, i.e.; inorganic species, enzymes and nucleotides, acids and amines, carbohydrates, steroids, polycyclic aromatic compounds and drugs, with the emphasis on recent applications and salient review articles.

Atmospheric iron deposition and sea-surface dissolved iron concentrations in the eastern Atlantic Ocean

Atmospheric iron and underway sea-surface dissolved (<0.2 μm) iron (DFe) concentrations were investigated along a north-south transect in the eastern Atlantic Ocean (27°N/16°W-19°S/5°E). Fe concentrations in aerosols and dry deposition fluxes of soluble Fe were at least two orders of magnitude higher in the Saharan dust plume than at the equator or at the extreme south of the transect. A weaker source of atmospheric Fe was also observed in the South Atlantic, possibly originating in southern Africa via the north-easterly outflow of the Angolan plume. Estimations of total atmospheric deposition fluxes (dry plus wet) of soluble Fe suggested that wet deposition dominated in the intertropical convergence zone, due to the very high amount of precipitation and to the fact that a substantial part of Fe was delivered in dissolved form. On the other hand, dry deposition dominated in the other regions of the transect (73-97), where rainfall rates were much lower. Underway sea-surface DFe concentrations ranged 0.02-1.1 nM. Such low values (0.02 nM) are reported for the first time in the Atlantic Ocean and may be (co)-limiting for primary production. A significant correlation (Spearmans rho = 0.862, p<0.01) was observed between mean DFe concentrations and total atmospheric deposition fluxes, confirming the importance of atmospheric deposition on the iron cycle in the Atlantic. Residence time of DFe in the surface waters relative to atmospheric inputs were estimated in the northern part of our study area (17 ± 8 to 28 ± 16 d). These values confirmed the rapid removal of Fe from the surface waters, possibly by colloidal aggregation.

The fate of added iron during a mesoscale fertilisation experiment in the Southern Ocean

The first Southern Ocean Iron RElease Experiment (SOIREE) was performed during February 1999 in Antarctic waters south of Australia (61°S, 140°E), in order to verify whether iron supply controls the magnitude of phytoplankton production in this high nutrient low chlorophyll (HNLC) region. This paper describes iron distributions in the upper ocean during our 13-day site occupation, and presents a pelagic iron budget to account for the observed losses of dissolved and total iron from waters of the fertilised patch. Iron concentrations were measured underway during daily transects through the patch and in vertical profiles of the 65-m mixed layer. High internal consistency was noted between data obtained using contrasting sampling and analytical techniques. A pre-infusion survey confirmed the extremely low ambient dissolved (0.1 nM) and total (0.4 nM) iron concentrations. The initial enrichment elevated the dissolved iron concentration to 2.7 nM. Thereafter, dissolved iron was rapidly depleted inside the patch to 0.2-0.3 nM, necessitating three re-infusions. A distinct biological response was observed in iron-fertilised waters, relative to outside the patch, unequivocally confirming that iron limits phytoplankton growth rates and biomass at this site in summer. Our budget describing the fate of the added iron demonstrates that horizontal dispersion of fertilised waters (resulting in a quadrupling of the areal extent of the patch) and abiotic particle scavenging accounted for most of the decreases in iron concentrations inside the patch (31-58 and 12-49 of added iron, respectively). The magnitude of these loss processes altered towards the end of SOIREE, and on days 12-13 dissolved (1.1 nM) and total (2.3 nM) iron concentrations remained elevated compared to surrounding waters. At this time, the biogenic iron pool (0.1 nM) accounted for only 1-2 of the total added iron. Large pennate diatoms (> 20 μm) and autotrophic flagellates (2-20 μm) were the dominant algal groups in the patch, taking up the added iron and representing 13 and 39 of the biogenic iron pool, respectively. Iron regeneration by grazers was tightly coupled to uptake by phytoplankton and bacteria, indicating that biological Fe cycling within the bloom was self-sustaining. A concurrent increase in the concentration of iron-binding ligands on days 11-12 probably retained dissolved iron within the mixed layer. Ocean colour satellite images in late March suggest that the bloom was still actively growing 42 days after the onset of SOIREE, and hence by inference that sufficient iron was maintained in the patch for this period to meet algal requirements. This raises fundamental questions regarding the biogeochemical cycling of iron in the Southern Ocean and, in particular, how bioavailable iron was retained in surface waters and/or within the biota to sustain algal growth.

Determination of iron in seawater

Iron plays an important role in oceanic biogeochemistry and is known to limit biological activity in certain ocean regions. Such regions have a replete complement of major nutrients but low primary production of phytoplankton due to low ambient iron concentrations. The determination of iron in seawater is a major challenge, although much progress has been made during the last two decades. Techniques for total dissolved iron and iron speciation have been developed in order to rationalise its biogeochemical cycling and better understand its role in limiting phytoplankton growth. In this paper, a critical review of historical and current analytical methods for the determination of iron in seawater is presented and their capabilities evaluated. The need for standard protocols for the clean sampling and storage of low-level (<1 nM) iron seawater in order to maintain sample integrity is emphasised. The importance of laboratory and shipboard intercomparison exercises to distinguish between environmental variability and operationally measured fractions is also considered.

Determination of sub-nanomolar levels of iron in seawater using flow injection with chemiluminescence detection

The development of a highly sensitive system for the shipboard determination of dissolved iron at the sub-nM level is presented. The technique is based on a flow injection method coupled with luminol chemiluminescence detection. Dissolved Fe(II+lII) levels are determined after Fe(III) reduction using sulphite and in-line matrix elimination/preconcentration on an 8-hydroxyquinoline (8-quinolinol) chelating resin column. The detection limit (3s) is 40 pM when 1.5 ml of sample is loaded onto the column, and the relative standard deviation is 3.2 (n=5) for a 1.0 nM Fe sample. One analytical cycle can be completed in 3 min. The automated method proved reliable when employed on-board the RRS James Clark Ross during Autumn 1996, mapping dissolvable Fe(II+III) levels along the Atlantic Meridional Transect from 50°N to 50°S. Data from vertical profiles through the upper water column are presented.

Analytical applications of liquid phase chemiluminescence reactions--a review.

This paper reviews the literature on analytical applications of quantitative liquid phase chemiluminescence (CL) from 1991 to mid-1995. Other relevant reviews in this general area are also cited to provide an historical perspective. The focus is on the two major analytical techniques used in conjunction with flow-through CL detection, namely flow injection (FI) and liquid chromatography (LC). Entries have been tabulated under these two headings and are categorized in terms of the analyte, CL reaction, sample matrix and limits of detection.

Determination of carbon, phosphorus, nitrogen and silicon species in waters

Abstract This review examines the analytical chemistry of the nutrient elements carbon, phosphorus, nitrogen and silicon in environmental waters. The speciation of these elements is discussed and the terminology used for classification is described. The analytical approach is considered in general terms, with particular regard to sample collection and preservation, sample treatment and methods of analysis. A critical appraisal of the analytical methods available for each of the elements (and their speciation) is provided together with the relevant analytical figures of merit.

Sampling, sample treatment and quality assurance issues for the determination of phosphorus species in natural waters and soils

Phosphorus is an important macronutrient and the accurate determination of phosphorus species in environmental matrices such as natural waters and soils is essential for understanding the biogeochemical cycling of the element, studying its role in ecosystem health and monitoring compliance with legislation. This paper provides a critical review of sample collection, storage and treatment procedures for the determination of phosphorus species in environmental matrices. Issues such as phosphorus speciation, the molybdenum blue method, digestion procedures for organic phosphorus species, choice of model compounds for analytical studies, quality assurance and the availability of environmental CRMs for phosphate are also discussed in detail.

Characterisation and quantification of organic phosphorus and organic nitrogen components in aquatic systems: A Review

This review provides a critical assessment of knowledge regarding the determination of organic phosphorus (OP) and organic nitrogen (ON) in aquatic systems, with an emphasis on biogeochemical considerations and analytical challenges. A general background on organic phosphorus and organic nitrogen precedes a discussion of sample collection, extraction, treatment/conditioning and preconcentration of organic phosphorus/nitrogen from sediments, including suspended particulate matter, and waters, including sediment porewaters. This is followed by sections on the determination of organic phosphorus/nitrogen components. Key techniques covered for organic phosphorus components are molecular spectrometry, atomic spectrometry and enzymatic methods. For nitrogen the focus is on the measurement of total organic nitrogen concentrations by carbon hydrogen nitrogen analysis and high temperature combustion, and organic nitrogen components by gas chromatography, high-performance liquid chromatography, gel electrophoresis, mass spectrometry, nuclear magnetic resonance spectrometry, X-ray techniques and enzymatic methods. Finally future trends and needs are discussed and recommendations made.