Maxime M. Grand

Determination of dissolved zinc in seawater using micro-Sequential Injection lab-on-valve with fluorescence detection

This paper introduces the preliminary design and optimization of a micro-Sequential Injection lab-on-valve system (μSI-LOV) with fluorescence detection for the direct determination of trace Zn(2+) in an unacidified seawater matrix. The method capitalizes on the sensitivity and selectivity of FluoZin-3, which was originally designed to measure zinc in living cells. The optimum reaction conditions, sources of blank signal and physical parameters of the μSIA-LOV are evaluated with the requirements of trace metal analysis in mind, namely high sensitivity and low background signals. A detailed investigation of the effect of sample and reagent sequencing on sensitivity is presented for the first time using μSIA-LOV. We find that the order of sequencing greatly influences peak shape and analytical sensitivity with the highest and smoothest peaks obtained when a large volume of sample (75 μL) is aspirated last in the sequence prior to flow reversal and detection. The optimized reaction conditions and reagent/sample sequencing protocol yield a detection limit of 0.3 nM Zn(2+), high precision (RSD < 2.5%), a linear quantification range up to 40 nM and an analytical cycle of ∼1 min per sample. This work demonstrates that μSI-LOV is capable of attaining detection limits that are close to those needed for open ocean determinations of Zn(2+) without preconcentration or separation of the analyte from the seawater matrix. The low reagent consumption (50 μL per sample), full automation and minimal maintenance requirements of μSI-LOV make it well suited for shipboard analysis and, eventually, for development to meet the pressing need for trace element measurements in unattended locations.

Towards chemiluminescence detection in micro-sequential injection lab-on-valve format: a proof of concept based on the reaction between Fe(II) and luminol in seawater.

Micro-sequential injection lab-on-valve (µSI-LOV) is a well-established analytical platform for absorbance and fluorescence based assays but its applicability to chemiluminescence detection remains largely unexplored. In this work, we describe a novel fluidic protocol and two distinct strategies for photon collection that enable chemiluminescence detection using µSI-LOV for the first time. To illustrate this proof of concept, we selected the reaction between Fe(II) and luminol and developed a preliminary protocol for Fe(II) determinations in acidified seawater. The optimized fluidic strategy consists of holding 100 µL of the luminol reagent in a confined zone of the LOV and then displacing it with 50 µL of sample while monitoring the chemiluminescent product. Detection is achieved using two strategies: one based on a bifurcated optical fiber and the other based on a customized detection window created by mounting a photomultiplier tube atop of the LOV device. We show that detection is possible using both strategies but that the window strategy yields significantly enhanced sensitivity (355×) due to the larger detection area. In our final experimental conditions and using window detection, it was possible to achieve a limit of detection (LOD) of 1 nmol L(-1) and to quantify Fe(II) in acidified seawater samples up to 20.00 nmol L(-1) with high precision (RSD<6%). These analytical features combined with the long-term stability of luminol solution and the full automation and low reagent consumption make this approach a promising analytical tool for shipboard analysis of Fe(II). The intrinsic capacity of the LOV to operate at a low microliter level and to handle solid phases also opens up a new avenue for chemiluminescence applications. Moreover, this contribution shows that LOV can be a universal platform for optical detection, capable of absorbance, fluorescence and luminescence measurements in a single instrument setup.

Dust deposition in the eastern Indian Ocean: The ocean perspective from Antarctica to the Bay of Bengal

Atmospheric deposition is an important but still poorly constrained source of trace micronutrients to the open ocean because of the dearth of in situ measurements of total deposition (i.e., wet + dry deposition) in remote regions. In this work, we discuss the upper ocean distribution of dissolved Fe and Al in the eastern Indian Ocean along a 95°E meridional transect spanning the Antarctic margin to the Bay of Bengal. We use the mixed layer concentration of dissolved Al in conjunction with empirical data in a simple steady state model to produce 75 estimates of total dust deposition that we compare with historical observations and atmospheric model estimates. Except in the northern Bay of Bengal where the Ganges-Brahmaputra river plume contributes to the inventory of dissolved Al, the surface distribution of dissolved Al along 95°E is remarkably consistent with the large-scale gradients in mineral dust deposition and multiple-source regions impacting the eastern Indian Ocean. The lowest total dust deposition fluxes are calculated for the Southern Ocean (66 ± 60 mg m−2 yr−1) and the highest for the northern end of the south Indian subtropical gyre (up to 940 mg m−2 yr−1 at 18°S) and in the southern Bay of Bengal (2500 ± 570 mg m−2 yr−1). Our total deposition fluxes, which have an uncertainty on the order of a factor of 3.5, are comparable with the composite atmospheric model data of Mahowald et al. (2005), except in the south Indian subtropical gyre where models may underestimate total deposition. Using available measurements of the solubility of Fe in aerosols, we confirm that dust deposition is a minor source of dissolved Fe to the Southern Ocean and show that aeolian deposition of dissolved Fe in the southern Bay of Bengal may be comparable to that observed underneath the Saharan dust plume in the Atlantic Ocean.

A Lab-On-Chip Phosphate Analyzer for Long-term In Situ Monitoring at Fixed Observatories: Optimization and Performance Evaluation in Estuarine and Oligotrophic Coastal Waters

The development of phosphate sensors suitable for long-term in situ deployments in natural waters, is essential to improve our understanding of the distribution, fluxes and biogeochemical role of this key nutrient in a changing ocean. Here, we describe the optimization of the molybdenum blue method for in situ work using a lab-on-chip analyzer and evaluate its performance in the laboratory and at two contrasting field sites. The in situ performance of the LOC sensor is evaluated using hourly time-series data from a 56-day trial in Southampton Water (UK), as well as a month-long deployment in the subtropical oligotrophic waters of Kaneohe Bay (Hawaii, USA). In Kaneohe Bay, where phosphate concentrations were characteristic of the dry season (0.13 ± 0.03 M, n=704), the in situ sensor accuracy was 16 ± 12 % and a potential diurnal cycle in phosphate concentrations was observed. In Southampton Water, the sensor data (1.02 ± 0.40 µM, n=1267) were accurate to ± 0.10 µM relative to discrete reference samples. Hourly in situ monitoring revealed striking tidal and storm derived fluctuations in phosphate concentrations in Southampton Water that would not have been captured via discrete sampling. We show the impact of storms on phosphate concentrations in Southampton Water is modulated by the spring-neap tidal cycle and that the tenfold decline in phosphate concentrations observed during the later stages of the deployment was consistent with the timing of a spring phytoplankton bloom in the English Channel. Under controlled laboratory conditions in a 250 L tank, the sensor demonstrated an accuracy and precision better than 10 % irrespective of the salinity (0-30), turbidity (0-100 NTU), dissolved organic carbon concentration (0-10 mg/L) and temperature (5-20C) of the water (0.3-13 M phosphate) being analyzed. This work demonstrates that the LOC technology is mature enough to quantify the influence of stochastic events on nutrient budgets and to elucidate the role of phosphate in regulating phytoplankton productivity and community composition in estuarine and coastal regimes.

Dissolved Fe and Al in the upper 1000 m of the eastern Indian Ocean: A high‐resolution transect along 95°E from the Antarctic margin to the Bay of Bengal

A high-resolution section of dissolved iron (dFe) and aluminum (dAl) was obtained along ~95°E in the upper 1000?m of the eastern Indian Ocean from the Antarctic margin (66°S) to the Bay of Bengal (18°N) during the U.S. Climate Variability and Predictability (CLIVAR) CO2 Repeat Hydrography I08S and I09N sections (February–April 2007). In the Southern Ocean, low concentrations of dAl (