Voltammetric determination of inorganic arsenic in mildly acidified (pH 4.7) groundwaters from Mexico and India.

Routine monitoring of inorganic arsenic in groundwater using sensitive, reliable, easy-to-use and affordable analytical methods is integral to identifying sources, and delivering appropriate remediation solutions, to the widespread global issue of arsenic pollution. Voltammetry has many advantages over other analytical techniques, but the low electroactivity of arsenic(V) requires the use of either reducing agents or relatively strong acidic conditions, which both complicate the analytical procedures, and require more complex material handling by skilled operators. Here, we present the voltammetric determination of total inorganic arsenic in conditions of near-neutral pH using a new commercially available 25 µm diameter gold microwire (called the Gold Wirebond), which is described here for the first time. The method is based on the addition of low concentrations of permanganate (10 µM MnO4-) which fulfils two roles: (1) to ensure that all inorganic arsenic is present as arsenate by chemically oxidising arsenite to arsenate and, (2) to provide a source of manganese allowing the sensitive detection of arsenate by anodic stripping voltammetry at a gold electrode. Tests were carried out in synthetic solutions of various pH (ranging from 4.7 to 9) in presence/absence of chloride. The best response was obtained in 0.25 M chloride-containing acetate buffer resulting in analytical parameters (limit of detection of 0.28 µg L-1 for 10 s deposition time, linear range up to 20 µg L-1 and a sensitivity of 63.5 nA ppb-1. s-1) better than those obtained in acidic conditions. We used this new method to measure arsenic concentrations in contrasting groundwaters: the reducing, arsenite-rich groundwaters of India (West Bengal and Bihar regions) and the oxidising, arsenate-rich groundwaters of Mexico (Guanajuato region). Very good agreement was obtained in all groundwaters with arsenic concentrations measured by inductively coupled plasma-mass spectrometry (slope = +1.029, R2 = 0.99). The voltammetric method is sensitive, faster than other voltammetric techniques for detection of arsenic (typically 10 min per sample including triplicate measurements and 2 standard additions), easier to implement than previous methods (no acidic conditions, no chemical reduction required, reproducible sensor, can be used by non-voltammetric experts) and could enable cheaper groundwater surveying campaigns with in-the-field analysis for quick data reporting, even in remote communities.

Phycosphere pH of unicellular nano- and micro- phytoplankton cells and consequences for iron speciation.

Surface ocean pH is declining due to anthropogenic atmospheric CO2 uptake with a global decline of ~0.3 possible by 2100. Extracellular pH influences a range of biological processes, including nutrient uptake, calcification and silicification. However, there are poor constraints on how pH levels in the extracellular microenvironment surrounding phytoplankton cells (the phycosphere) differ from bulk seawater. This adds uncertainty to biological impacts of environmental change. Furthermore, previous modelling work suggests that phycosphere pH of small cells is close to bulk seawater, and this has not been experimentally verified. Here we observe under 140 µmol photons·m-2·s-1 the phycosphere pH of Chlamydomonas concordia (5 µm diameter), Emiliania huxleyi (5 µm), Coscinodiscus radiatus (50 µm) and C. wailesii (100 µm) are 0.11 ± 0.07, 0.20 ± 0.09, 0.41 ± 0.04 and 0.15 ± 0.20 (mean ± SD) higher than bulk seawater (pH 8.00), respectively. Thickness of the pH boundary layer of C. wailesii increases from 18 ± 4 to 122 ± 17 µm when bulk seawater pH decreases from 8.00 to 7.78. Phycosphere pH is regulated by photosynthesis and extracellular enzymatic transformation of bicarbonate, as well as being influenced by light intensity and seawater pH and buffering capacity. The pH change alters Fe speciation in the phycosphere, and hence Fe availability to phytoplankton is likely better predicted by the phycosphere, rather than bulk seawater. Overall, the precise quantification of chemical conditions in the phycosphere is crucial for assessing the sensitivity of marine phytoplankton to ongoing ocean acidification and Fe limitation in surface oceans.

Low-cost electrochemical detection of arsenic in the groundwater of Guanajuato state, central Mexico using an open-source potentiostat.

Arsenic is a carcinogenic groundwater contaminant that is toxic even at the parts-per-billion (ppb) level and its on-site determination remains challenging. Colorimetric test strips, though cheap and widely used, often fail to give reliable quantitative data. On the other hand, electrochemical detection is sensitive and accurate but considerably more expensive at the onset. Here, we present a study on arsenic detection in groundwater using a low-cost, open-source potentiostat based on Arduino technology. We tested different types of gold electrodes (screen-printed and microwire) with anodic stripping voltammetry (ASV), achieving low detection limits (0.7 µg L-1). In a study of arsenic contaminated groundwaters in Mexico, the microwire technique provides greater accuracy than test strips (reducing the median error from -50% to +2.9%) and greater precision (reducing uncertainties from ±25% to ±4.9%). Most importantly, the rate of false negatives versus the World Health Organisation's 10 µg L-1 limit was reduced from 50% to 0% (N = 13 samples). Arsenic determination using open-source potentiostats may offer a low-cost option for research groups and NGOs wishing to perform arsenic analysis in-house, yielding superior quantitative data than the more widely used colorimetric test strips.

Assessment of disease burden in the arsenic exposed population of Chapar village of Samastipur district, Bihar, India, and related mitigation initiative.

Fast growing arsenic menace is causing serious health hazards in Bihar, India, with an estimated 10 million people at risk. The exposed population is often unaware of the problem, which only amplifies the burden of arsenic health effects. In the present study, we have assessed the current situation of arsenic exposure in Chapar village of Samastipur district, Bihar. The health of the inhabitants was assessed and correlated with (1) arsenic concentrations in the groundwater of individual wells and (2) arsenic concentration found in their hair and urine. Altogether, 113 inhabitants were assessed, and 113 hair, urine and groundwater samples were collected. The health study reveals that the exposure to arsenic has caused serious health hazard amongst the exposed population with pronounced skin manifestations, loss of appetite, anaemia, constipation, diarrhoea, general body weakness, raised blood pressure, breathlessness, diabetes, mental disabilities, diabetes, lumps in the body and few cancer incidences. It was found that 52% of the total collected groundwater samples had arsenic levels higher than the WHO limit of 10 µg/l (with a maximum arsenic concentration of 1212 µg/l) and the reduced arsenite was the predominant form in samples tested for speciation (N = 19). In the case of hair samples, 29% of the samples had arsenic concentrations higher than the permissible limit of 0.2 mg/kg, with a maximum arsenic concentration of 46 µg/l, while in 20% exposed population, there was significant arsenic contamination in urine samples > 50 µg/l. In Chapar village, the probability of carcinogenic-related risk in the exposed population consuming arsenic contaminated water is 100% for children, 99.1% for females and 97.3% for male subjects. The assessment report shared to the government enabled the village population to receive two arsenic filter units. These units are currently operational and catering 250 households providing arsenic-free water through piped water scheme. This study therefore identified a significant solution for this arsenic-exposed population.

Revised application of copper ion selective electrode (Cu-ISE) in marine waters: A new meta-calibration approach.

Copper (Cu) is a bio-essential trace element that is of concerns due to its potential toxicity at concentrations commonly encountered in coastal waters. Here, we revisit the applicability of Cu(II) ion selective electrode (Cu-ISE) based on a jalpaite membrane for the measurement of Cufree in seawater. At high total Cu concentration (>0.1 mM), (near)Nernstian slope was obtained and determination of Cufree down to fM levels was possible. However, this slope decreases with decreasing total Cu concentration (e.g. 7 mV/decade at 15 nM total Cu) making the use of a common single calibration approach unreliable. To solve this problem, we carried out several calibrations at different levels of total Cu (15 nM - 1 mM) and ethylenediamine (EN: 5 µM - 15 mM) and fitted the calibration parameters (slope and intercept) as a function of total Cu using the Gompertz function (a meta-calibration approach). The derived empirical equations allowed the determination of Cufree at any total Cu concentration above 20 nM (determination of Cufree at lower total Cu levels is prevented by the dissolution of the electrode). We successfully tested this meta-calibration approach in UV digested seawater in presence of a synthetic ligand (EN), isolated natural organic matter (humic acid, HA) and in a natural estuarine sample. In each case, our meta-calibration approach provided a good agreement with modeled speciation data (Visual MINTEQ), while standard single approach failed. We provide here a new method for the direct determination of the free Cu ion concentration in seawater at levels relevant for coastal waters.

Evaluation of diffusive gradients in thin films (DGT) technique for speciation of trace metals in estuarine waters - A multimethodological approach.

Understanding the potential bioavailability of trace metals (TM) in marine systems is of prime importance to implement adapted regulations and efficiently protect our coastal and estuarine waters. In this study Diffusive Gradients in Thin films (DGT) technique with two different pore size was used to evaluate the potentially bioavailable fractions (DGT-labile) of Cd, Co, Cu, Ni, Pb and Zn at various depths of a highly stratified estuary (the Krka River estuary, Croatia) both in winter and summer. DGT-labile concentrations were compared to (1) total dissolved concentrations, (2) concentrations of labile species measured by anodic stripping voltammetry (ASV-labile) for Cu and (3) concentrations derived by chemical speciation modelling. High correlation between dissolved and DGT-labile concentrations was found for all metals, except for Zn where contamination problems prevented reliable conclusions. Percentages of DGT-labile fractions over total dissolved concentrations were (AVG ±â€¯SD): 92 ±â€¯3%, 64 ±â€¯2%, 23 ±â€¯5%, 61 ±â€¯3% and 57 ±â€¯6% for Cd, Pb, Cu, Ni and Co, respectively. No significant difference was found between trace metal concentrations measured with an open pore and restricted pore devices, implying the predominance of kinetically labile metal complexes smaller than 1 nm. For Cu, ASV-labile and DGT labile concentrations were highly correlated (0.97) with ASV-labile concentration being around 35% lower than that of the DGT-labile. Modelling of chemical speciation reliably predicted dynamic (free, inorganic and part of organic complexes) concentration of Cd, whereas dynamic concentrations of Cu and Pb were underestimated by 32% and 65%, respectively. In view of the relative simplicity of DGT devices, they are well suited for the monitoring effort of coastal waters, informing on potentially bioavailable concentrations of TM and thereby, helping to achieve good environmental status of coastal waters, as stipulated within the EU Water Framework Directive.

Portable and rapid arsenic speciation in synthetic and natural waters by an As(V)-selective chemisorbent, validated against anodic stripping voltammetry.

Inorganic arsenic speciation, i.e. the differentiation between arsenite and arsenate, is an important step for any program aiming to address the global issue of arsenic contaminated groundwater, whether for monitoring purposes or the development of new water treatment regimes. Reliable speciation by easy-to-use, portable and cost-effective analytical techniques is still challenging for both synthetic and natural waters. Here we demonstrate the first application of an As(V)-selective chemisorbent material for simple and portable speciation of arsenic using handheld syringes, enabling high sample throughput with minimal set-up costs. We first show that ImpAs efficiently removes As(V) from a variety of synthetic groundwaters with a single treatment, whilst As(III) is not retained. We then exemplify the potential of ImpAs for simple and fast speciation by determining rate constants for the photooxidation of As(III) in the presence of a TiO2 photocatalyst. Finally, we successfully speciate natural waters spiked with a mix of As(III) and As(V) in both Indian and UK groundwaters with less than 5 mg L-1 dissolved iron. Experimental results using ImpAs agreed with anodic stripping voltammetry (ASV), a benchmark portable technique, with analysis conditions optimised here for the groundwaters of South Asia. This new analytical tool is simple, portable and fast, and should find applications within the overall multi-disciplinary remediation effort that is taking place to tackle this worldwide arsenic problem.

Improved voltammetric methodology for chromium redox speciation in estuarine waters.

Chromium is a toxic element naturally present in natural waters whose chemical speciation regulates its cycling, mobility and bioavailability. We present here: 1- an improved analytical method for chromium speciation (Cr(VI) vs Cr(III)) in estuarine samples by catalytic adsorptive cathodic stripping voltammetric (cat-AdCSV) and 2- a study highlighting a significant change of redox speciation during summer and winter. Initial measurements first revealed that surface-active substances (SAS) present in estuarine samples strongly influenced the analytical determination of Cr by partially masking the Cr peak through an increase of the background current. We found that the application of a low negative accumulation potential (-1.65 V) resulted in much better voltammograms compared to those obtained using the usual accumulation potential of -1.0 V. Using humic acid (HA) as a model SAS of natural origin, we show that this negative potential clearly prevents adsorption of SAS on the Hg-electrode surface, which in turns benefits the adsorption of the in-situ formed Cr(III)-DTPA complex and the resulting signal. The optimised method was applied to determine chromium redox speciation and distribution along the 23 km long salinity gradient, well oxygenated, Krka River estuary (Croatia). Cr(VI) was found to be the dominant redox species in both summer and winter, with Cr(III) contribution being lower in summer (up to ∼30%, average of ∼5%) than in winter (up to ∼50%, average of ∼30%). In summer, lower concentrations of Cr(VI) were found in the freshwater end-member (2.5 nM) than in the seawater end-member (4-5 nM), while the opposite trend was found in winter. Hexavalent chromium exhibited a non-conservative behaviour along the salinity gradient for both seasons. Chromium predominantly exists in dissolved phase, and contribution of particles reactive Cr(III) was minor.

Determination of iodide and total iodine in estuarine waters by cathodic stripping voltammetry using a vibrating silver amalgam microwire electrode.

Iodide in natural waters is an important nutrient to aquatic organisms and its determination is of relevance to marine aquaculture. For this reason it is of interest to have a simple analytical method for determination of iodide in water samples. Iodide in seawater can be determined electrochemically by cathodic stripping voltammetry (CSV) with a mercury drop electrode which has environmental drawbacks. In an attempt to minimise the use of mercury in voltammetry, a vibrating silver amalgam microwire electrode is used here for the determination by CSV of iodide speciation in natural waters including seawater. Microwire electrodes were made from silver wires (diameter: 12.5µm) and electrochemically coated with mercury. The electrode surface was stable for extended periods of analyses (at least one week) and was then replaced. The optimised conditions include a pH 8, a frequency of 500Hz and a deposition time of 60s, among others. The microwire was reactivated between scans using a conditioning potential at -3 V for 1s. The detection limit for iodide in seawater was found to be 0.7nM I- at a deposition time of 60s. The response increased linearly with the concentration of iodide in seawater up to 100nM I-. The method was successfully applied to various samples from the estuary of the river Mersey (Liverpool Bay). An existing procedure for iodine speciation was modified to enable determination of iodate and total iodine as well as iodide in estuarine waters.

AGNES at vibrated gold microwire electrode for the direct quantification of free copper concentrations.

The free metal ion concentration and the dynamic features of the metal species are recognized as key to predict metal bioavailability and toxicity to aquatic organisms. Quantification of the former is, however, still challenging. In this paper, it is shown for the first time that the concentration of free copper (Cu(2+)) can be quantified by applying AGNES (Absence of Gradients and Nernstian equilibrium stripping) at a solid gold electrode. It was found that: i) the amount of deposited Cu follows a Nernstian relationship with the applied deposition potential, and ii) the stripping signal is linearly related with the free metal ion concentration. The performance of AGNES at the vibrating gold microwire electrode (VGME) was assessed for two labile systems: Cu-malonic acid and Cu-iminodiacetic acid at ionic strength 0.01 M and a range of pH values from 4.0 to 6.0. The free Cu concentrations and conditional stability constants obtained by AGNES were in good agreement with stripping scanned voltammetry and thermodynamic theoretical predictions obtained by Visual MinteQ. This work highlights the suitability of gold electrodes for the quantification of free metal ion concentrations by AGNES. It also strongly suggests that other solid electrodes may be well appropriate for such task. This new application of AGNES is a first step towards a range of applications for a number of metals in speciation, toxicological and environmental studies for the direct determination of the key parameter that is the free metal ion concentration.

Molecular recognition and scavenging of arsenate from aqueous solution using dimetallic receptors.

A series of copper(II), nickel(II) and zinc(II) dimetallic complexes were prepared and their affinities towards arsenate investigated. Indicator displacement assays (IDAs) were carried out to establish the complexes with best affinities towards arsenate. A di-zinc complex (3) was selected and its arsenate-binding abilities investigated by isothermal titration calorimetry (ITC). The X-ray crystal structure of this metallo-receptor bound to arsenate is also reported, which allowed us to establish the binding mode between 3 and this oxyanion. Immobilising 3 onto HypoGel resin yielded a novel adsorbent (Zn-HypoGel) with high affinity for arsenate. Adsorption of arsenate from competitive solutions and natural groundwater was greater than that of the commercially used iron oxide Bayoxide E33. Zn-HypoGel could be efficiently and simply regenerated by washing with sodium acetate solution.

Hepatotoxicity of pentavalent antimonial drug: possible role of residual Sb(III) and protective effect of ascorbic acid.

Pentavalent antimonial drugs such as meglumine antimoniate (Glucantime [Glu; Sanofi-Aventis, São Paulo, Brazil]) produce severe side effects, including cardiotoxicity and hepatotoxicity, during the treatment of leishmaniasis. We evaluated the role of residual Sb(III) in the hepatotoxicity of meglumine antimoniate, as well as the protective effect of the antioxidant ascorbic acid (AA) during antimonial chemotherapy in a murine model of visceral leishmaniasis. BALB/c mice infected with Leishmania infantum were treated intraperitoneally at 80 mg of Sb/kg/day with commercial meglumine antimoniate (Glu) or a synthetic meglumine antimoniate with lower Sb(III) level (MA), in association or not with AA (15 mg/kg/day), for a 20-day period. Control groups received saline or saline plus AA. Livers were evaluated for hepatocytes histological alterations, peroxidase activity, and apoptosis. Increased proportions of swollen and apoptotic hepatocytes were observed in animals treated with Glu compared to animals treated with saline or MA. The peroxidase activity was also enhanced in the liver of animals that received Glu. Cotreatment with AA reduced the extent of histological changes, the apoptotic index, and the peroxidase activity to levels corresponding to the control group. Moreover, the association with AA did not affect the hepatic uptake of Sb and the ability of Glu to reduce the liver and spleen parasite loads in infected mice. In conclusion, our data supports the use of pentavalent antimonials with low residue of Sb(III) and the association of pentavalent antimonials with AA, as effective strategies to reduce side effects in antimonial therapy.

Unexpectedly high levels of antimony (III) in the pentavalent antimonial drug Glucantime: insights from a new voltammetric approach.

Glucantime, a pentavalent antimonial drug, is commonly used for the treatment of leishmaniasis but the presence of residual trivalent antimony, Sb(III), is thought to be responsible for toxic side-effects observed in patients. Numerous analytical studies have focused on determining Sb(III) concentrations in Glucantime but without reaching a consensus: results span over 3 orders of magnitude. In this study, we present a detailed new analytical approach showing that: (1) Sb(III) levels are much higher than previously reported and represent more than 30% of total Sb; (2) determination of Sb(III) concentrations in acidic conditions is hampered by fast oxidation rates. This latter point explains the large variations in previously reported results of Sb(III) concentrations in Glucantime. Measurements were made here at a vibrated gold microwire electrode by stripping voltammetry enabling measurement of Sb(III) in acidic, neutral or alkaline conditions. The developed methods are sensitive (e.g., detection limits of 19 pM for 120 s deposition at pH 4.5), stable (<6%, N = 100), precise (5%, N = 5) and robust (same electrode used for weeks) at all pH values. In diluted solutions of Glucantime, Sb(III) levels were strongly dependent both on pH and ionic strength. At pH < 3, Sb(III) is oxidized with oxidation rates that increase as pH is decreased. At high pH, Sb(III) forms electro-inactive complexes. Highest Sb(III) levels were detected at pH ~3 and at low ionic strength. The presence of several Sb(III) and Sb(V) species was demonstrated by different reduction waves obtained by stripping scanned voltammetry. As an implication of these unexpectedly high Sb(III) concentrations, an alternative model can be proposed for the mode of action of pentavalent antimonials against leishmaniasis, in which antimony complexes may act as molecular carrier of Sb(III) and release it specifically in the acidic intracellular compartment where the Leishmania parasites reside.

Determination of lead and cadmium in seawater using a vibrating silver amalgam microwire electrode.

Silver amalgamated electrodes are a good substrate to determine lead (Pb) and cadmium (Cd) in seawater because they have properties similar to mercury but without the free mercury (Hg). Here a silver amalgamated microwire (SAM) electrode is optimised for the determination of Pb and Cd in coastal waters and uncontaminated ocean waters. The SAM was vibrated during the deposition step to increase the sensitivity, and electroanalytical parameters were optimised. The Hg coating required plating from a relatively concentrated (millimolar) solution, much greater (500×) than used for instance to coat glassy carbon electrodes. However, the coating on the ex situ amalgamated electrode was found to be stable and could be used for up to a week to determine trace levels of Pb in seawater of natural pH. The limit of detection square-wave ASV (50 Hz) using the pre-plated SAM electrode was 8 pM Pb using a 1-min plating time at pH 4.5. The limit of detection in pH 2 seawater was 4 pM using a 5-min plating time, and it was 12 pM using a 10-min plating time at natural pH in the presence of air, using a square-wave frequency of 700 Hz. The vibrating SAM electrode was tested on the determination of Pb in reference seawater samples from the open Atlantic (at the 20 pM level), Pacific, and used for a study of Pb in samples collected over 24 h in Liverpool Bay (Irish Sea).

Sulfide determination in hydrothermal seawater samples using a vibrating gold micro-wire electrode in conjunction with stripping chronopotentiometry.

A rapid electrochemical stripping chronopotentiometric procedure to determined sulfide in unaltered hydrothermal seawater samples is presented. Sulfide is deposited at -0.25 V (vs Ag/AgCl, KCl 3M) at a vibrating gold microwire and then stripped through the application of a reductive constant current (typically -2 µA). The hydrodynamic conditions are modulated by vibration allowing a short deposition step, which is shown here to be necessary to minimize H(2)S volatilization. The limit of detection (LOD) is 30 nM after a deposition step of 7s. This LOD is in the same range as the most sensitive cathodic voltammetric technique using a mercury drop electrode and is well below those reported previously for other electrodes capable of being implemented in situ.

Determination of arsenic and antimony in seawater by voltammetric and chronopotentiometric stripping using a vibrated gold microwire electrode.

The oxidation potentials of As(0)/As(III) and Sb(0)/Sb(III) on the gold electrode are very close to each other due to their similar chemistry. Arsenic concentration in seawater is low (10-20 nM), Sb occurring at ~0.1 time that of As. Methods are shown here for the electroanalytical speciation of inorganic arsenic and inorganic antimony in seawater using a solid gold microwire electrode. Anodic stripping voltammetry (ASV) and chronopotentiometry (ASC) are used at pH ≤2 and pH 8, using a vibrating gold microwire electrode. Under vibrations, the diffusion layer size at a 5 µm diameter wire is 0.7 µm. The detection limits for the As(III) and Sb(III) are below 0.1 nM using 2 min and 10 min deposition times respectively. As(III) and Sb(III) can be determined in acidic conditions (after addition of hydrazine) or at neutral pH. In the latter case, oxidation of As(0) to As(III) was found to proceed through a transient As(III) species. Adsorption of this species on the gold electrode at potentials where Sb(III) diffused away is used for selective deposition of As(III). Addition of EDTA removes the interfering effect of manganese when analysing As(III). Imposition of a desorption step for Sb(III) analysis is required. Total inorganic arsenic (iAs=As(V)+As(III)) can be determined without interference from Sb nor mono-methyl arsenious acid (MMA) at 1.6

Apparatus for in situ monitoring of copper in coastal waters.

Apparatus is designed and tested to determine metals in situ in seawater. Voltammetry with a vibrating gold microwire electrode (VGME) is combined with a battery powered potentiostat and a processor board and is tested for in situ monitoring of copper (Cu) in coastal waters. The VGME was combined with solid state reference and counter electrodes to make a single vibrating probe which was rated up to a depth of 40 m. The measuring mode for Cu was square-wave anodic stripping voltammetry whilst dissolved oxygen (DO) was monitored by a linear sweep scan in a negative potential direction. The working electrode was reactivated between measurements using a suitable potential sequence. The novelties of this work are the field-testing of apparatus incorporating a VGME for copper monitoring, which eliminates the need for pumping and reagents, but has sufficient sensitivity for low ambient levels of copper, and the use of a novel potential sequence to stabilise the response over a long time period. The apparatus has a measuring time of about 6 weeks and a measuring frequency of 12 h(-1). Measurement is reagent-free and power use is low as no pump is required. Experiments are carried out to test the stability of response of the system at various temperatures and its robustness with respect to long-term copper monitoring. Preliminary data were obtained during autonomous deployment over several weeks on a buoy in the Irish Sea. Vertical movement of the buoy caused individual measurements to have a variability of about 15%. It was found that longer term variability of the electrode could be minimised by normalisation of the Cu response over that of DO as the response was related to diffusion through the electrode surface which was similarly affected. The detected fraction of Cu (labile Cu) amounted to 1.5-4 nM during different deployments at a total Cu concentration of ∼10 nM. The same ratio was found by voltammetry in samples taken to the laboratory. The new apparatus has demonstrated that metals in coastal waters can be monitored at trace level, much facilitating the monitoring of outfalls and local water contamination. Because of its sensitivity the apparatus would be of use in estuarine as well as coastal waters, with the aim of monitoring intermittent variability in the copper concentration.

Pseudopolarography of copper complexes in seawater using a vibrating gold microwire electrode.

Copper (Cu) in seawater can be determined by anodic stripping voltammetry using a vibrating gold microwire electrode (VGME) with a much lower limit of detection than using a mercury electrode, enabling detection of labile Cu at trace level. The possibility of pseudopolarography of Cu using the VGME is investigated here and is calibrated against known chelating agents. The sensitivity much (15-fold) improved by application of a desorption step to remove adsorbed organic substances and excess anions. The notorious tendency of solid electrodes to be affected by memory effects was overcome by a conditioning interval between measurements that stabilized the electrode response. Model ligands, including EDTA, humic substances (HS), and glutathione (examples of natural ligands) were analyzed to calibrate the half-wave shift to complex stability. The half-wave shift on the VGME is much greater (~2×) than that on the mercury drop electrode which is attributed to several parameters including a much (5-fold) thinner diffusion layer on the VGME. Experiments showed that the same procedure is suitable for pseudopolarography of zinc. Application of the new method to samples from the Irish Sea showed Cu occurring in several complexes, all strongly bound, and some occurring in the electrochemically reversible region of the pseudopolarogram. The humic substance complex of Cu was also found to occur in the reversible region of the pseudopolarogram. The pseudopolarograms of Cu in seawater were unaffected by sample filtration and did not require purging to remove dissolved oxygen, suggesting that this method can be readily used as part of an in situ measuring system.

Arsenate Impact on the Metabolite Profile, Production, and Arsenic Loading of Xylem Sap in Cucumbers (Cucumis sativus L.).

Arsenic uptake and translocation studies on xylem sap focus generally on the concentration and speciation of arsenic in the xylem. Arsenic impact on the xylem sap metabolite profile and its production during short term exposure has not been reported in detail. To investigate this, cucumbers were grown hydroponically and arsenate (As(V)) and DMA were used for plant treatment for 24 h. Total arsenic and arsenic speciation in xylem sap was analyzed including a metabolite profiling under As(V) stress. Produced xylem sap was quantified and absolute arsenic transported was determined. As(V) exposure had a significant impact on the metabolite profile of xylem sap. Four m/z values corresponding to four compounds were up-regulated, one compound down-regulated by As(V) exposure. The compound down-regulated was identified to be isoleucine. Furthermore, As(V) exposure had a significant influence on sap production, leading to a reduction of up to 96% sap production when plants were exposed to 1000 µg kg(-1) As(V). No difference to control plants was observed when plants were exposed to 1000 µg kg(-1) DMA. Absolute arsenic amount in xylem sap was the lowest at high As(V) exposure. These results show that As(V) has a significant impact on the production and metabolite profile of xylem sap. The physiological importance of isoleucine needs further attention.

Determination of arsenate in natural pH seawater using a manganese-coated gold microwire electrode.

Direct electrochemical determination of arsenate (As(V)) in neutral pH waters is considered impossible due to electro-inactivity of As(V). As(III) on the other hand is readily plated as As(0) on a gold electrode and quantified by anodic stripping voltammetry (ASV). We found that the reduction of As(V) to As(III) was mediated by elemental Mn on the electrode surface in a novel redox couple in which 2 electrons are exchanged causing the Mn to be oxidised to Mn(II). Advantage is taken of this redox couple to enable for the first time the electrochemical determination of As(V) in natural waters of neutral pH including seawater by ASV using a manganese-coated gold microwire electrode. Thereto Mn is added to excess (~1 µM Mn) to the water leading to a Mn coating during the deposition of As on the electrode at a deposition potential of -1.3 V. Deposition of As(0) from dissolved As(V) caused elemental Mn to be re-oxidised to Mn(II) in a 1:1 molar ratio providing evidence for the reaction mechanism. The deposited As(V) is subsequently quantified using an ASV scan. As(III) interferes and should be quantified separately at a more positive deposition potential of -0.9 V. Combined inorganic As is quantified after oxidation of As(III) to As(V) using hypochlorite. The microwire electrode was vibrated during the deposition step to improve the sensitivity. The detection limit was 0.2 nM As(V) using a deposition time of 180 s.