Evaluation of a ferrozine based autonomous in situ lab-on-chip analyzer for dissolved iron species in coastal waters

The trace metal iron (Fe) is an essential micronutrient for phytoplankton growth and limits, or co-limits primary production across much of the world's surface ocean. Iron is a redox sensitive element, with Fe(II) and Fe(III) co-existing in natural waters. Whilst Fe(II) is the most soluble form, it is also transient with rapid oxidation rates in oxic seawater. Measurements of Fe(II) are therefore preferably undertaken in situ. For this purpose an autonomous wet chemical analyzer based on lab-on-chip technology was developed for the in situ determination of the concentration of dissolved (<0.45 μm) Fe species (Fe(II) and labile Fe) suitable for deployments in a wide range of aquatic environments. The spectrophotometric approach utilizes a buffered ferrozine solution and a ferrozine/ascorbic acid mixture for Fe(II) and labile Fe(III) analyses, respectively. Diffusive mixing, color development and spectrophotometric detection take place in three separate flow cells with different lengths such that the analyzer can measure a broad concentration range from low nM to several μM of Fe, depending on the desired application. A detection limit of 1.9 nM Fe was found. The microfluidic analyzer was tested in situ for nine days in shallow waters in the Kiel Fjord (Germany) along with other sensors as a part of the SenseOCEAN EU-project. The analyzer's performance under natural conditions was assessed with discrete samples collected and processed according to GEOTRACES protocol [acidified to pH < 2 and analyzed via inductively coupled plasma mass spectrometry (ICP-MS)]. The mechanical performance of the analyzer over the nine day period was good (consistent high precision of Fe(II) and Fe(III) standards with a standard deviation of 2.7% (n = 214) and 1.9% (n = 217), respectively, and successful completion of every programmed data point). However, total dissolved Fe was consistently low compared to ICP-MS data. Recoveries between 16 and 75% were observed, indicating that the analyzer does not measure a significant fraction of natural dissolved Fe species in coastal seawater. It is suggested that an acidification step would be necessary in order to ensure that the analyzer derived total dissolved Fe concentration is reproducible and consistent with discrete values

Air-sea gas fluxes and remineralization from a novel combination of pH and O2 sensors on a glider

Accurate, low-power sensors are needed to characterize biogeochemical variability on underwater glider missions. However, the needs for high accuracy and low power consumption can be difficult to achieve together. To overcome this difficulty, we integrated a novel sensor combination into a Seaglider, comprising a spectrophotometric lab-on-a-chip (LoC) pH sensor and a potentiometric pH sensor, in addition to the standard oxygen (O 2) optode. The stable, but less frequent (every 10 min) LoC data were used to calibrate the high-resolution (1 s) potentiometric sensor measurements. The glider was deployed for a 10-day pilot mission in August 2019. This represented the first such deployment of either type of pH sensor on a glider. The LoC pH had a mean offset of +0.005±0.008 with respect to pH calculated from total dissolved inorganic carbon content, c(DIC), and total alkalinity, A T, in co-located water samples. The potentiometric sensor required a thermal-lag correction to resolve the pH variations in the steep thermocline between surface and bottom mixed layers, in addition to scale calibration. Using the glider pH data and a regional parameterization of A T as a function of salinity, we derived the dissolved CO 2 content and glider c(DIC). Glider surface CO 2 and O 2 contents were used to derive air-sea fluxes, Φ(CO 2) and Φ(O 2). Φ(CO 2) was mostly directed into the ocean with a median of −0.4 mmol m –2 d –1. In contrast, Φ(O 2) was always out of the ocean with a median of +40 mmol m –2 d –1. Bottom water apparent oxygen utilization (AOU) was (35±1) μmol kg –1, whereas apparent carbon production (ACP) was (11±1) μmol kg –1, with mostly insignificant differences along the deployment transect. This deployment shows the potential of using pH sensors on autonomous observing platforms such as Seagliders to quantify the interactions between biogeochemical processes and the marine carbonate system at high spatiotemporal resolution

Exploring ocean biogeochemistry using a lab-on-chip phosphate analyser on an underwater glider

The ability to make measurements of phosphate (PO43–) concentrations at temporal and spatial scales beyond those offered by shipboard observations offers new opportunities for investigations of the marine phosphorus cycle. We here report the first in situ PO43– dataset from an underwater glider (Kongsberg Seaglider) equipped with a PO43– Lab-on-Chip (LoC) analyser. Over 44 days, a 120 km transect was conducted in the northern North Sea during late summer (August and September). Surface depletion of PO43– (<0.2 μM) was observed above a seasonal thermocline, with elevated, but variable concentrations within the bottom layer (0.30–0.65 μM). Part of the variability in the bottom layer is attributed to the regional circulation and across shelf exchange, with the highest PO43– concentrations being associated with elevated salinities in northernmost regions, consistent with nutrient rich North Atlantic water intruding onto the shelf. Our study represents a significant step forward in autonomous underwater vehicle sensor capabilities and presents new capability to extend research into the marine phosphorous cycle and, when combined with other recent LoC developments, nutrient stoichiometry

Toward the integrated marine debris observing system

Plastics and other artificial materials pose new risks to the health of the ocean. Anthropogenic debris travels across large distances and is ubiquitous in the water and on shorelines, yet, observations of its sources, composition, pathways, and distributions in the ocean are very sparse and inaccurate. Total amounts of plastics and other man-made debris in the ocean and on the shore, temporal trends in these amounts under exponentially increasing production, as well as degradation processes, vertical fluxes, and time scales are largely unknown. Present ocean circulation models are not able to accurately simulate drift of debris because of its complex hydrodynamics. In this paper we discuss the structure of the future integrated marine debris observing system (IMDOS) that is required to provide long-term monitoring of the state of this anthropogenic pollution and support operational activities to mitigate impacts on the ecosystem and on the safety of maritime activity. The proposed observing system integrates remote sensing and in situ observations. Also, models are used to optimize the design of the system and, in turn, they will be gradually improved using the products of the system. Remote sensing technologies will provide spatially coherent coverage and consistent surveying time series at local to global scale. Optical sensors, including high-resolution imaging, multi- and hyperspectral, fluorescence, and Raman technologies, as well as SAR will be used to measure different types of debris. They will be implemented in a variety of platforms, from hand-held tools to ship-, buoy-, aircraft-, and satellite-based sensors. A network of in situ observations, including reports from volunteers, citizen scientists and ships of opportunity, will be developed to provide data for calibration/validation of remote sensors and to monitor the spread of plastic pollution and other marine debris. IMDOS will interact with other observing systems monitoring physical, chemical, and biological processes in the ocean and on shorelines as well as the state of the ecosystem, maritime activities and safety, drift of sea ice, etc. The synthesized data will support innovative multi-disciplinary research and serve a diverse community of users

Characterisation of an irreversible bonding process for COC–COC and COC–PDMS–COC sandwich structures and application to microvalves

A novel technique for bonding heterogeneous cyclic olefin co-polymer (COC) to a thin poly(dimethylsiloxane) (PDMS) membrane is described. This improved bonding technique successfully achieved precise, well-controlled, low temperature bonding of microfluidic channels. Microchannel and fluid control patterns were embossed on a COC substrate by hot embossing technique first. The method uses aminopropyltriethoxysilane (APTES) and 3-glycidoxypropyltrimethoxysilane (GPTMS) in combination to create an irreversible bond between the two materials. The change in surface properties and the influence of different surface chemical groups on surface adhesion properties has been characterised by contact angle, surface energy measurements, scanning electron microscopy (SEM), and atomic force microscopy (AFM), revealing a change in morphology and surface roughness. A lower wettability was also observed along with a reduced hydrophobic recovery of the surfaces. Bonding efficiency of the devices was evaluated by interface evaluation of cross-sectioning, peel off tests and leak tests. In addition, the performance of the bonds achieved after different surface treatments has been compared showing that this technique results in a higher burst pressures than methods applying only oxygen plasma or APTES. Using optimised bonding conditions a robust, effective microvalve made from a PDMS membrane was fabricated and successful valve closing or opening are shown. Because of advantages of facile fabrication, low cost and biocompatibility, this hybrid device can be pave the way in many applications such as fluidic manipulation in portable and disposable microfluidic devices

Development and application of a microfluidic in-situ analyzer for dissolved Fe and Mn in natural waters

The redox sensitive trace metals iron and manganese are two important elements that help shape the biogeochemistry of aquatic systems and thus their measurement is important. Current laboratory methods are expensive, time consuming and cannot provide the spatial and temporal resolution needed to characterize these elements in natural waters. Here we describe the first autonomous analyzer capable of providing vertical profiles as well as routine in-situ determinations of dissolved Fe(II) and Mn in aquatic environments. The spectrophotometric sensor uses microfluidic methods (Lab-on-a-chip technology) and mixes reagents and samples using a novel in-cell diffusion process. Fe(II) and Mn can be measured with a frequency of up to 12 and 6 samples per hour respectively with limits of detection of 27 nM for Fe(II), 2.1% precision (n=20), and 28 nM for Mn, 2.4% precision (n=19). The device combines relatively low cost, low power usage, low reagent consumption, portability, and tolerance to pressures up to at least 170 bars, with high precision and accuracy. We present data from a successful demonstration of the sensor during a cruise to the Gotland and Landsort Deep Basins of the Baltic Sea

Development of a colorimetric microfluidic pH sensor for autonomous seawater measurements

High quality carbonate chemistry measurements are required in order to fully understand the dynamics of the oceanic carbonate system. Seawater pH data with good spatial and temporal coverage are particularly critical to apprehend ocean acidification phenomena and their consequences. There is a growing need for autonomous in situ instruments that measure pH on remote platforms. Our aim is to develop an accurate and precise autonomous in situ pH sensor for long term deployment on remote platforms. The widely used spectrophotometric pH technique is capable of the required high-quality measurements. We report a key step towards the miniaturization of a colorimetric pH sensor with the successful implementation of a simple microfluidic design with low reagent consumption. The system is particularly adapted to shipboard deployment: high quality data was obtained over a period of more than a month during a shipboard deployment in northwest European shelf waters, and less than 30 mL of indicator was consumed. The system featured a short term precision of 0.001 pH (n = 20) and an accuracy within the range of a certified Tris buffer (0.004 pH). The quality of the pH system measurements have been checked using various approaches: measurements of certified Tris buffer, measurement of certified seawater for DIC and TA, comparison of measured pH against calculated pH from pCO2, DIC and TA during the cruise in northwest European shelf waters. All showed that our measurements were of high quality. The measurements were made close to in situ temperature (+0.2 ?C) in a sampling chamber which had a continuous flow of the ship’s underway seawater supply. The optical set up was robust and relatively small due to the use of an USB mini-spectrometer, a custom made polymeric flow cell and an LED light source. The use of a three wavelength LED with detection that integrated power across the whole of each LED output spectrum indicated that low wavelength resolution detectors can be used instead of the current USB mini spectrophotometer. Artefacts due to the polychromatic light source and inhomogeneity in the absorption cell are shown to have a negligible impact on the data quality. The next step in the miniaturization of the sensor will be the incorporation of a photodiode as detector to replace the spectrophotometer

Seawater-pH measurements for ocean-acidification observations

The uptake of anthropogenic CO2 by the oceans since the onset of the industrial revolution is considered a serious challenge to marine ecosystems due to ensuing carbonate-chemistry changes (ocean acidification). Furthermore, the CO2 uptake is reducing the ocean’s capacity to absorb future CO2 emissions. In order to follow the changes in the ocean’s carbonate system, high-quality analytical measurements with good spatial and temporal resolution are necessary. High-precision and accurate pH measurements are now possible, and allow us to determine the progression of ocean acidification. The spectrophotometric pH technique is now widely used and capable of the required high-quality measurements. Spectrophotometric pH systems are deployed on ships and in situ on remote platforms. Smaller and more rugged instruments are nevertheless required for more widespread in situ application to allow routine high-resolution measurements, even in the most remote regions.We critically review oceanic pH measurements, and focus on state-of-the-art spectrophotometric pH measurement techniques and instrumentation. We present a simple microfluidic design integrated in a shipboard instrument featuring high accuracy and precision as a key step towards a targeted pH microsensor system

Spatial Variability of Antarctic Surface Snow Bacterial Communities

It was once a long-held view that the Antarctic was a pristine environment with low biomass, low biodiversity and low rates of microbial activity. However, as the intensity of scientific investigation has increased, so these views have started to change. In particular, the role and impact of human activity toward indigenous microbial communities has started to come under more intense scrutiny. During the Subglacial Lake Ellsworth exploration campaign in December 2012, a microbiological survey was conducted to determine the extent and likelihood of exogenous input into the subglacial lake system during the hot-water drilling process. Snow was collected from the surface to represent that used for melt water production for hot-water drilling. The results of this study showed that snow used to provide melt water differed in its microbiological composition from that of the surrounding area and raised the question of how the biogeography of snow-borne microorganisms might influence the potential outcome of scientific analyses. In this study, we investigated the biogeography of microorganisms in snow around a series of Antarctic logistic hubs, where human activity was clearly apparent, and from which scientific investigations have been undertaken. A change in microbial community structure with geographical location was apparent and, notably, a decrease in alpha diversity at more remote southern latitudes. Soil-related microorganisms dominated microbial assemblages suggesting terrestrial input, most likely from long-range aeolian transport into continental Antarctica. We also observed that relic DNA was not a major issue when assessing snow samples. Overall, our observations might have profound implications for future scientific activities in Antarctica, such as the need to establish “no-go” protected areas, the need for better characterization of field sites and improved protocols for sterilization and verification of ice drilling equipment

Lab-on-chip analyser for the in situ determination of dissolved manganese in seawater

A spectrophotometric approach for quantification of dissolved manganese (DMn) with 1-(2-pyridylazo)-2-naphthol (PAN) has been adapted for in situ application in coastal and estuarine waters. The analyser uses a submersible microfluidic lab-on-chip device, with low power (~ 1.5 W) and reagent consumption (63 µL per sample). Laboratory characterization showed an absorption coefficient of 40,838 ± 1127 L⋅mol−1⋅cm−1 and a detection limit of 27 nM, determined for a 34.6 mm long optical detection cell. Laboratory tests showed that long-term stability of the PAN reagent was achieved by addition of 4% v/v of a non-ionic surfactant (Triton-X100). To suppress iron (Fe) interferences with the PAN reagent, the Fe(III) masking agents deferoxamine mesylate (DFO-B) or disodium 4,5-dihydroxy-1,3-benzenedisulfonate (Tiron) were added and their Fe masking efficiencies were investigated. The analyser was tested during a deployment over several weeks in Kiel Fjord (Germany), with successful acquisition of 215 in situ data points. The time series was in good agreement with DMn concentrations determined from discretely collected samples analysed via inductively coupled plasma mass spectrometry (ICP-MS), exhibiting a mean accuracy of 87% over the full deployment duration (with an accuracy of > 99% for certain periods) and clear correlations to key hydrographic parameters