Chemical speciation of trace metals in seawater: a review.

The recent development of the chemical speciation of trace metals in seawater is described. The speciation studies reveal that metal ion complexation is one of the most important processes in seawater; especially, most bioactive trace metals, such as Fe(III) and Cu, exist as complexes with ligands in dissolved organic matter. The organic ligands in seawater are characterized with metal ions selected by the HSAB concept. A strong organic ligand, which originates from marine microorganisms, is classified as a hard base including carboxylates. The free organic ligand concentrations in seawater are buffered by complexation with excess amounts of Ca and Mg in seawater. The chemical equilibrium model suggested that the concentrations of bioactive free metal ions are at an optimal level to activities of marine microorganisms. For chemical speciation, it is important to have a better understanding of the ecological roles of trace metals in seawater.     

Determination of iron and copper in seawater at pH 1.7 with a new commercially available chelating resin, NTA Superflow

The use of a commercially available chelating resin with NTA-type functional groups for concentration of trace metals from seawater is described. Trace metal recoveries from this NTA Superflow chelating resin are pH dependent. At a pH of ≤2 only iron(III) and copper are quantitatively recovered from the resin. Iron(II) cannot be quantitatively recovered from this resin below a pH of 5. However, oxidation of acidified seawater samples (pH 1.7) with H₂O₂ prior to loading onto the resin has been demonstrated to allow quantitative recovery of total dissolved iron. Deferrioxamine and Rhodoturlic Acid, two commercially available siderophores were used to investigate the effect of strong Fe(III)-binding organic ligands on the ability to retain iron at different pH values. Acidification of seawater samples to pH 1.7 dissociates the iron complexed to these organic ligands, thereby allowing total dissolved iron and copper to be determined. Acidified samples from Monterey Bay were analyzed by a flow injection method coupled to ICP-SFMS detection using the NTA Superflow resin in the pre-concentration step. Results from this study show that when seawater samples are stored acidified (pH 1.7) over time, a portion of iron(III) is reduced to iron(II), thus necessitating the use of H₂O₂ to reoxidize the Fe(II) to Fe(III) prior to analysis. Total dissolved concentrations of iron and copper can be directly obtained on seawater samples at pH 1.7 with this method, eliminating the need to buffer the sample to a higher pH prior to column loading. This resin has the potential to be used in shipboard or in situ flow injection methods.     

铁配合物的环境光化学及其参与的环境化学过程

铁是地壳中含量最为丰富的金属元素之一,而自然界中存在的绝大多数溶解性铁都是以有机络合形式存在的。环境中的铁配合物在光照下会发生直接光解和次级的(光)化学反应过程,生成还原性的Fe(Ⅱ)和有机自由基以及衍生的活性氧物种。铁配合物的环境光化学反应将深刻影响着氧自由基的生成与衰减、有机物降解和其他元素的环境化学循环过程,因此,成为近年来国际环境科学领域的研究热点。本文介绍了铁配合物光还原反应的类型和原理,分析了Fe(Ⅱ)(光)化学氧化的可能机理和影响因素,并对国内外关于铁参与的环境化学过程所开展的研究进行了评述。在此基础上,通过分析目前研究中所存在的问题,对今后的研究方向和趋势作了展望。     

Response of the Iron Chalcogenide Glass Membrane Ion‐Selective Electrode in a Seawater Ligand Mimetic Calibration Buffer

As a continuation of recent mechanistic studies into the influence of seawater ligands on the surface chemistry of the iron chalcogenide glass membrane ion‐selective electrode (ISE), the present study has investigated the response of the iron(III) ISE in a seawater ligand mimetic system to examine its suitability as a calibration medium for the electroanalysis of raw or natural seawater. Significantly, dip method calibrations of the ISE in a mixture of salicylate, ethylene diamine tetraacetic acid (EDTA), ethylene diamine and minor amounts of dissolved iron(III) and copper(II) yielded the expected Nernstian response of 30 mV/decade according to the known ion‐exchange/electron transfer response mechanism of this ISE. Furthermore, ideal Nernstian response of the electrode is also obtained in a continuous flow analysis (CFA) mode, noting that this provides scope for using a hydrodynamic flow regime to minimize the electrode release of iron and the concomitant detection limit of the ISE. Ultimately, repetitive CFA analyses of free iron(III) in raw or natural seawater yielded a free iron(III) level commensurate with the expected inorganic and organic speciation of iron(III) in seawater.     

Anionic ligand effect on the nature of epoxidizing intermediates in iron porphyrin complex-catalyzed epoxidation reactions

We have studied an anionic ligand effect in iron porphyrin complex-catalyzed competitive epoxidations of cis- and trans-stilbenes by various terminal oxidants and found that the ratios of cis- to trans-stilbene oxide products formed in competitive epoxidations were markedly dependent on the ligating nature of the anionic ligands. The ratios of cis- to trans-stilbene oxides obtained in the reactions of Fe(TPP)X (TPP = meso-tetraphenylporphinato dianion and X(-) = anionic ligand) and iodosylbenzene (PhIO) were 14 and 0.9 when the X(-) of Fe(TPP)X was Cl(-) and CF(3)SO(3)(-), respectively. An anionic ligand effect was also observed in the reactions of an electron-deficient iron(III) porphyrin complex containing a number of different anionic ligands, Fe(TPFPP)X [TPFPP = meso-tetrakis(pentafluorophenyl)porphinato dianion and X(-) = anionic ligand], and various terminal oxidants such as PhIO, m-chloroperoxybenzoic acid (m-CPBA), tetrabutylammonium oxone (TBAO), and H(2)O(2). While high ratios of cis- to trans-stilbene oxides were obtained in the reactions of iron porphyrin catalysts containing ligating anionic ligands such as Cl(-) and OAc(-), the ratios of cis- to trans-stilbene oxide were low in the reactions of iron porphyrin complexes containing nonligating or weakly ligating anionic ligands such as SbF(6)(-), CF(3)SO(3)(-), and ClO(4)(-). When the anionic ligand was NO(3)(-), the product ratios were found to depend on terminal oxidants and olefin concentrations. We suggest that the dependence of the product ratios on the anionic ligands of iron(III) porphyrin catalysts is due to the involvement of different reactive species in olefin epoxidation reactions. That is, high-valent iron(IV) oxo porphyrin cation radicals are generated as a reactive species in the reactions of iron porphyrin catalysts containing nonligating or weakly ligating anionic ligands such as SbF(6)(-), CF(3)SO(3)(-), and ClO(4)(-), whereas oxidant-iron(III) porphyrin complexes are the reactive intermediates in the reactions of iron porphyrin catalysts containing ligating anionic ligands such as Cl(-) and OAc(-).     

Characterisation of iron binding ligands in seawater by reverse titration

Here we demonstrate the use of reverse titration - competitive ligand exchange–adsorptive cathodic stripping voltammetry (RT-CLE–ACSV) for the analysis of iron (Fe) binding ligands in seawater. In contrast to the forward titration, which examines excess ligands in solution, RT-CLE–ACSV examines the existing Fe-ligand complexes by increasing the concentration of added (electroactive) ligand (1-nitroso-2-naphthol) and analysis of the proportion of Fe bound to the added ligand. The data manipulation allows the accurate characterisation of ligands at equal or lower concentrations than Fe in seawater, and disregards electrochemically inert dissolved Fe such as some colloidal phases. The method is thus superior to the forward titration in environments with high Fe and low ligand concentrations or high concentrations of inert Fe.     

Effect of acetate and EDTA ligands on Hydrolysis of the Iron(III) Ion in sodium chloride medium

The hydrolysis of the iron(III) ion in sodium chloride medium without organic ligands and in the presence of acetate and EDTA ligands was studied by emf method, at 25°C. The data indicate the effect of the organic ligands. In the presence of acetate ion the beginning of hydrolysis of the iron(III) ion is slightly shifted toward lower pH values, while in the presence of EDTA, as a strong complex forming ligand, the beginning of hydrolysis is shifted toward higher pH values for 2.5 pH units.     

Vertical distribution and potential sources of strong ligands for copper(II) in the North Pacific

Complexing ability of natural organic ligands in seawater was determined by an approach based on coordination chemistry, i.e., thermodynamic calculations of the conditional stability constants of remarkably stable copper(II) complexes of natural ligands, which were maintained against the ligand-exchange reaction with a large excess of ethylenediaminetetraacetic acid. There exist strong ligands with the conditional stability constant of log K’_CuL > 14 at pH 5.71 and 4°?C ubiquitously in non-living dissolved organic matter, concentrated from both coastal and oceanic regimes. This type of ligand was detected at most depths from surface to 1,000 m in the oceanic regimes. The same appraoch was applied to a sample of marine organism (phytoplankton) and the strong ligand class was found out in phytoplankton. It is suggested that phytoplankton may be one of potential sources for the strong ligand.     

Photoreduction of Terrigenous Fe‐Humic Substances Leads to Bioavailable Iron in Oceans

Humic substances (HS) are important iron chelators responsible for the transport of iron from freshwater systems to the open sea, where iron is essential for marine organisms. Evidence suggests that iron complexed to HS comprises the bulk of the iron ligand pool in near‐coastal waters and shelf seas. River‐derived HS have been investigated to study their transport to, and dwell in oceanic waters. A library of iron model compounds and river‐derived Fe‐HS samples were probed in a combined X‐ray absorption spectroscopy (XAS) and valence‐to‐core X‐ray emission spectroscopy (VtC‐XES) study at the Fe K‐edge. The analyses performed revealed that iron complexation in HS samples is only dependent on oxygen‐containing HS functional groups, such as carboxyl and phenol. The photoreduction mechanism of Fe^III‐HS in oceanic conditions into bioavailable aquatic Fe^II forms, highlights the importance of river‐derived HS as an iron source for marine organisms. Consequently, such mechanisms are a vital component of the upper‐ocean iron biogeochemistry cycle.     

Petrobactin, a photoreactive siderophore produced by the oil-degrading marine bacterium Marinobacter hydrocarbonoclasticus.

Petrobactin is a bis-catecholate, alpha-hydroxy acid siderophore produced by the oil-degrading marine bacterium Marinobacter hydrocarbonoclasticus. The Fe(III)-complexed form of petrobactin is photoreactive in natural sunlight, mediated by the Fe(III)-citrate moiety. The reaction results in decarboxylation of the petrobactin ligand and reduction of Fe(III) to Fe(II). This report is one of the first to show the photoreactivity of Fe(III)-siderophores mediated by the ferric ion-alpha-hydroxy acid group. The demonstration of light-mediated decarboxylation of an Fe(III)-siderophore complex raises questions about a possible functional role for photoreactivity in siderophore-mediated iron uptake.     

Ligand substitution kinetics of the iron(III) hydroxo dimer with simple inorganic ligands

The kinetics and mechanisms of ligand substitution reactions of the iron(III) hydroxo dimer, Fe(2)(mu-OH)(2)(H(2)O)(8)(4+), with various inorganic ligands were studied by the stopped-flow method at 10.0 or 25.0 C in 1.0 M NaClO(4). The transient formation of the following di- and tetranuclear complexes was confirmed: Fe(2)(OH)SO(4)(3+), Fe(2)(OH)H(2)PO(2)(4+), Fe(2)(OH)HPO(3)(3+), Fe(2)(OH)SeO(3)(3+), and Fe(4)(AsO(4))(OH)(2)(7+). The catalytic effect of arsenic(III) on the hydrolytic reaction of iron(III) was also attributed to the formation of a dinuclear complex at very low concentration levels. Fast formation and subsequent dissociation of the multinuclear species into the corresponding mononuclear complexes (FeL) proceed via parallel reaction paths which, in general, show composite pH dependencies. The appropriate rate laws were established. The reactions of the different ligands occur at very similar rates, though the uninegatively charged singly deprotonated form reacts about 1 order of magnitude faster than the neutral form of the same ligand. The results can conveniently be interpreted in terms of a dissociative interchange mechanism which postulates the formation of an intermediate complex in which the ligand is coordinated to only one Fe(III) center of the hydroxo dimer. In a subsequent fast step, the ligand forms a bridge between the two metal ions by replacing one of the OH groups. The dissociation of the dinuclear complex into FeL most likely proceeds via the same intermediate.     

Cobalt(III) complexes of unsaturated carboxylic acids: synthesis, characterization, and photochemical studies in aqueous medium

Cobalt(III) ammine complexes coordinated to carboxylic acids are classic examples showing photoredox reactions originating from the ligand to metal charge transfer excited states. Cobalt(III) pentaammine complexes coordinated to unsaturated carboxylic acids as ligands were synthesized and characterized by spectroscopic methods. The photolysis of these complexes produces a carboxylate free radical. This free radical undergoes further transformation to form organic photoproducts. The organic photoproducts were characterized by spectroscopic methods. The nature of the decomposition products from the organic photoproduct was examined in detail. The quantum yields were also determined. The photochemical reactions have the potential to produce novel compounds from the decarboxylation of unsaturated acids, which shows interesting reaction pathways.     

Biomimetic hydrocarbon oxidation catalyzed by nonheme iron(III) complexes with peracids: evidence for an Fe(V)=O species

Mononuclear nonheme iron(III) complexes of tetradentate ligands containing two deprotonated amide moieties, [Fe(Me(2)bpb)Cl(H(2)O)] (3 a) and [Fe(bpc)Cl(H(2)O)] (4 a), were prepared by substitution reactions involving the previously synthesized iron(III) complexes [Et(3)NH][Fe(Me(2)bpb)Cl(2)] (3) and [Et(3)NH][Fe(bpc)Cl(2)] (4). Complexes 3 a and 4 a were characterized by IR and elemental analysis, and complex 3 a also by X-ray crystallography. Nonheme iron(III) complexes 3, 3 a, 4, and 4 a catalyze olefin epoxidation and alcohol oxidation on treatment with m-chloroperbenzoic acid. Pairwise comparisons of the reactivity of these complexes revealed that the nature of the axial ligand (Cl(-) versus H(2)O) influences the yield of oxidation products, whereas an electronic change in the supporting chelate ligand has little effect. Hydrocarbon oxidation by these catalysts was proposed to involve an iron(V) oxo species which is formed on heterolytic O-O bond cleavage of an iron acylperoxo intermediate (FeOOC(O)R). Evidence for this iron(V) oxo species was derived from KIE (k(H)/k(D)) values, H(2) (18)O exchange experiments, and the use of peroxyphenylacetic acid (PPAA) as the peracid. Our results suggest that an Fe(V)=O moiety can form in a system wherein the supporting chelate ligand comprises a mixture of neutral and anionic nitrogen donors. This work is relevant to the chemistry of mononuclear nonheme iron enzymes that are proposed to oxidize organic substrates via reaction pathways involving high-valent iron oxo species.     

Modeling the active site of nitrile hydratase: synthetic strategies to ensure simultaneous coordination of carboxamido-N and thiolato-S to Fe(III) centers

A general strategy for synthesizing Fe(III) complexes of ligands containing carboxamido-N and thiolato-S donors has been described. Reaction of the doubly deprotonated ligand PyPepS2- (where PyPepSH2=N-2-mercaptophenyl-2'-pyridinecarboxamide) with Fe(III) salts in DMF had previously afforded the Fe(III) complex (Et4N)[Fe(PyPepS)2] without any problem(s) associated with autoredox reactions of the thiolate functionality. In the present work, similar reactions with the doubly deprotonated ligand PiPepS2- (where PiPepSH2=2-mercapto-N-pyridin-2-yl-methylbenzamide) with Fe(III) salts, however, fail to afford any Fe(III) complex because of autoredox reactions. The break in the conjugation in the PiPepSH2 ligand frame is the key reason for this difference in behavior between these two very similar ligands. This is demonstrated by the fact that the same reaction with AqPepS2- (where AqPepSH2=2-mercapto-N-quinolin-8-yl-benzamide), another ligand with extended conjugation, affords the Fe(III) complex (Et4N)[Fe(AqPepS)2] without any synthetic complication. It is therefore evident that ligands in which the carboxamide and thiolate functionalities are kept in conjugation could be used to isolate Fe(III) complexes with carboxamido-N and thiolato-S coordination. This finding will be very helpful in future research work in the area of modeling the active site of Fe-containing nitrile hydratase.     

Axial ligand and spin-state influence on the formation and reactivity of hydroperoxo-iron(III) porphyrin complexes

The present study focuses on the formation and reactivity of hydroperoxo-iron(III) porphyrin complexes formed in the [Fe(III)(tpfpp)X]/H(2)O(2)/HOO(-) system (TPFPP=5,10,15,20-tetrakis(pentafluorophenyl)-21H,23H-porphyrin; X=Cl(-) or CF(3) SO(3)(-)) in acetonitrile under basic conditions at -15 °C. Depending on the selected reaction conditions and the active form of the catalyst, the formation of high-spin [Fe(III)(tpfpp)(OOH)] and low-spin [Fe(III)(tpfpp)(OH)(OOH)] could be observed with the application of a low-temperature rapid-scan UV/Vis spectroscopic technique. Axial ligation and the spin state of the iron(III) center control the mode of O-O bond cleavage in the corresponding hydroperoxo porphyrin species. A mechanistic changeover from homo- to heterolytic O-O bond cleavage is observed for high- [Fe(III)(tpfpp)(OOH)] and low-spin [Fe(III)(tpfpp)(OH)(OOH)] complexes, respectively. In contrast to other iron(III) hydroperoxo complexes with electron-rich porphyrin ligands, electron-deficient [Fe(III)(tpfpp)(OH)(OOH)] was stable under relatively mild conditions and could therefore be investigated directly in the oxygenation reactions of selected organic substrates. The very low reactivity of [Fe(III)(tpfpp)(OH)(OOH)] towards organic substrates implied that the ferric hydroperoxo intermediate must be a very sluggish oxidant compared with the iron(IV)-oxo porphyrin π-cation radical intermediate in the catalytic oxygenation reactions of cytochrome P450.     

Topologically constrained manganese(III) and iron(III) complexes of two cross-bridged tetraazamacrocycles

A family of Mn3+ and Fe3+ complexes of 4,11-dimethyl-1,4,8,11-tetraazabicyclo[6.6.2]hexadecane (1) and 4,10-dimethyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecane (2) has been prepared by the chemical oxidation of the divalent manganese and iron analogues. The ligands are ethylene cross-bridged tetraazamacrocycles derived from cylam and cyclen, respectively. The synthesis and characterization of these complexes, including X-ray crystal structure determinations, are described. The structural evidence demonstrates that the tetradentate ligands enforce distorted octahedral geometries on the metal ions, with two cis sites occupied by labile ligands. Magnetic measurements reveal that the complexes are high spin with typical magnetic moments. Cyclic voltammetry shows reversible redox processes for the Fe3+/Fe2+ couples of the iron(III) complexes, while Mn3+/Mn2+ and Mn4+/Mn3+ couples were observed for the complexes with manganese(III). The manganese chemistry of 1 was studied in depth. The dichloro manganese(III) cation of 1 undergoes facile ligand substitution reactions at the labile, monodentate sites, for example substituting azide for chloride ligands. Air oxidation of the dichloro complex of Mn (1)2+ in basic solution does not give the expected mu-oxo dimeric product common to manganese. Instead, an unusual manganese(III)-OH complex has been isolated from this reaction and structurally characterized. A similar reaction under slightly different conditions gives a putative MnIII(OH)2 complex that metathesizes to MnIII(OMe)2 upon recrystallization from methanol.     

Biologically active thiosemicarbazone Fe chelators and their reactions with ferrioxamine B and ferric EDTA; a kinetic study

The Fe(III) abstraction from Fe(III)/DFO and Fe(III)/EDTA complex systems by thiosemicarbazone ligands derived from 2-acetylpyridine has been studied from a kinetico-mechanistic perspective at relevant pH conditions and at varying temperatures and buffer solutions. The reactions have been found to be extremely dependent on the dominant E/Z isomeric form of the TSC ligands present in the reaction medium. Consequently the isomerisation processes occurring on the free ligands have also been monitored under equivalent conditions. The isomerisation process is found to be acid dependent, despite the absence of protonation under the conditions used, and presumably proceeds via an azo-type tautomer of the ligand. In all cases the existence of outer-sphere interaction processes has been established, both promoting the reactions and producing dead-end complexes. The better oriented forms of the ligands (EZ thiolate) have been found to react faster with the [Fe(HDFO)](+) complex, although for mono-N(4) substituted thiosemicarbazones the process is retarded by the formation of a dead-end outer-sphere complex. A comparison with the abstraction of Fe(III) from [Fe(EDTA)(H(2)O)](-) has also been conducted with significant differences in the kinetic features that implicate keystone outer-sphere interactions which dominate reactivity, even with isomeric forms that are not the best suited for direct complexation.     

Synthesis and structure of [Fe(13)O(4)F(24)(OMe)(12)](5-): the first open-shell Keggin ion

The reaction between ferric fluoride trihydrate and pyridine in hot methanol produced yellow-brown crystals of (PyH)5.[Fe13O4F24(OMe)12].4H2O.CH3OH. The anionic complex [Fe13O4F24(OMe)12]5- (1), which has a full Td symmetry, is the first example of an open-shell Keggin ion consisting of 13 high-spin d5 iron(III) atoms. The central, tetrahedral {FeO4} unit in 1 is surrounded by 12 octahedral iron atoms, which are bridged by methoxide oxygen atoms and fluoride ligands. In addition, each of the 12 iron atoms is coordinated to a terminal fluoride ligand with an Fe-F distance of 1.846(3) A. Magnetic susceptibility studies indicate strong exchange interactions between the iron atoms, the mueff value of 19.3 muB at 300 K being significantly lower than that expected for thirteen uncoupled S = 5/2 centers.     

A comparative study of high-spin manganese and iron complexes

Different metal complexes of the general form M(OH) _n (H₂O)_{6– n} have been studied for manganese and iron. Oxidation states considered for manganese are Mn(III), Mn(IV) and Mn(V) and for iron Fe(II), Fe(III) and Fe(IV). Oxygen containing ligands are used throughout with varying numbers of hydroxyl and water ligands. Some metal-oxo and some charged complexes were also studied. Large Jahn-Teller distortions were found for the Mn(III) and Fe(IV) complexes. Consequences of these distortions are that water ligands have to be placed along the weak JT-axis and that five-coordination by a loss of one of these water ligands is quite competitive with six-coordination in particular for manganese. For Fe(II) and Fe(III) lower coordinations than six are preferred due to the presence of two repulsive e _g electrons. For the metal-oxo complexes five-coordination is also preferred due to the strong trans effect from the oxo ligand. All complexes studied have high-spin ground states. An interesting effect is that the spin is much more delocalized on the ligands for the iron complexes than for the manganese complexes. This effect, which is chemically important for certain iron enzymes, is rationalized by the large number of 3d electrons on iron. For manganese with only five 3d electrons no spin delocalization is needed to obtain the proper high-spin states. Received: 4 February 1997 / Accepted: 24 February 1997     

Chemical speciation of plutonium in seawater

Concentrations of particulate and dissolved plutonium in seawater were determined together with strong organic ligands (SOL) in particulate matter (PM). The concentration of particulate 239,240Pu in surface waters of the Western North Pacific ranged from 0.03 to 0.3 mBq m(-3) during the period from 1987 to 1997. The percentage of particulate Pu to total Pu in seawater was less than 10% in surface waters, whereas its portions were less than 1% in deep waters. In order to characterize particulate Pu in seawater, the relationships between particulate Pu, dissolved Pu and SOL concentrations in surface PM were examined. The result reveals that particulate Pu was linearly related to the SOL concentration independent of dissolved Pu concentration. Mass balance analysis suggests that a dominant chemical form of Pu in surface PM, which may exist as Pu(IV), is a complex with strong organic ligands in PM.