Trends in microfluidic systems for in situ chemical analysis of natural waters

Spatially and temporally detailed measurement of ocean, river and lake chemistry is key to fully understanding the biogeochemical processes at work within them. To obtain these valuable data, miniaturised in situ chemical analysers have recently become an attractive alternative to traditional manual sampling, with microfluidic technology at the forefront of recent advances. In this short critical review we discuss the role, operation and application of in situ microfluidic analysers to measure biogeochemical parameters in natural waters. We describe recent technical developments, most notably how pumping technology has evolved to allow long-term deployments, and describe how they have been deployed in real-world situations to yield detailed, scientifically useful data. Finally, we discuss the technical challenges that still remain and the key obstacles that must be negotiated if these promising systems are to be widely adopted and used, for example, in large environmental sensor networks and on low-power underwater vehicles

Detection of ultra-low protein concentrations with the simplest possible field effect transistor

Silicon nanowire (Si NW) sensors have attracted great attention due to their ability to provide fast, low-cost, label-free, real-time detection of chemical and biological species. Usually configured as field effect transistors (FETs), they have already demonstrated remarkable sensitivity with high selectivity (through appropriate functionalisation) towards a large number of analytes in both liquid and gas phases. Despite these excellent results, Si NW FET sensors have not yet been successfully employed to detect single molecules of either a chemical or biological target species. Here we show that sensors based on silicon junctionless nanowire transistors (JNTs), the simplest possible transistors, are capable of detecting the protein streptavidin at a concentration as low as 580 zM closely approaching the single molecule level. This ultrahigh detection sensitivity is due to the intrinsic advantages of junctionless devices over conventional FETs. Apart from their superior functionality, JNTs are much easier to fabricate by standard microelectronic processes than transistors containing p–n junctions. The ability of JNT sensors to detect ultra-low concentrations (in the zeptomolar range) of target species, and their potential for low-cost mass production, will permit their deployment in numerous environments, including life sciences, biotechnology, medicine, pharmacology, product safety, environmental monitoring and security

Electrical characterization of high performance, liquid gated vertically stacked SiNW-based 3D FET for biosensing applications

A 3D vertically stacked silicon nanowire (SiNW) field effect transistor featuring a high density array of fully depleted channels gated by a backgate and one or two symmetrical platinum side-gates through a liquid has been electrically characterized for their implementation into a robust biosensing system. The structures have also been characterized electrically under vacuum when completely surrounded by a thick oxide layer. When fully suspended, the SiNWs may be surrounded by a conformal high-κ gate dielectric (HfO2) or silicon dioxide. The high density array of nanowires (up to 7 or 8 × 20 SiNWs in the vertical and horizontal direction, respectively) provides for high drive currents (1.3 mA/μm, normalized to an average NW diameter of 30 nm at VSG = 3 V, and Vd = 50 mV, for a standard structure with 7 × 10 NWs stacked) and high chances of biomolecule interaction and detection. The use of silicon on insulator substrates with a low doped device layer significantly reduces leakage currents for excellent Ion/Ioff ratios >106 of particular importance for low power applications. When the nanowires are submerged in a liquid, they feature a gate all around architecture with improved electrostatics that provides steep subthreshold slopes (SS 10 μS) while allowing for the entire surface area of the nanowire to be available for biomolecule sensing. The fabricated devices have small SiNW diameters (down to dNW ∼ 15–30 nm) in order to be fully depleted and provide also high surface to volume ratios for high sensitivities

Early warning device for detection of pollutants in water

Due to a growing need to protect water resources from contamination, there is a requirement for the development of more reliable and cost effective devices for water quality monitoring. The aim of the AQUAWARN project is to develop and deploy a fully autonomous water quality monitoring device that can measure nitrite, nitrate, phosphate and pH colorimetrically in fresh water and wastewater, and communicate the information to stakeholders in real time

Early warning pollution detection device for application in water quality

It has been well recognised that water is a valuable resource and the quality of our water systems require sampling at a higher temporal and spatial frequency than is currently taking place. The AQUAWARN project aims to meet this challenge through the development of commercially competitive water quality monitoring devices. These will be capable of performing analytical measurements in situ - primarily aimed at freshwater and wastewater systems. The analytes of interest are mainly phosphate, nitrite, nitrate, and pH. The initial focus of this project is the assessment and optimisation of appropriate colorimetric chemistries for each sensing target. These chemistries have been developed and optimised using bench-top instrumentation. Integration within microfluidic chips followed to reduce the per sample costs. Microfluidic technology uses minute amounts of reagent per sample measurement, allowing for a dramatic increase in the number of potential assays per unit volume of reagent. Moreover, the integration of LEDs and photodiodes as light sources and detectors, coupled with syringe pumps, opens the way to new generations of low-cost, portable, and autonomous devices, capable of performing multiple in-situ measurements.  For example, an analysis requiring 50 uL of reagent implies 2,000 measurements are possible per 100 mL of reagent

A miniaturised autonomous sensor based on nanowire materials platform: the SiNAPS mote

A micro-power energy harvesting system based on core(crystalline Si)-shell(amorphous Si) nanowire solar cells together with a nanowire-modified CMOS sensing platform have been developed to be used in a dust-sized autonomous chemical sensor node. The mote (SiNAPS) is augmented by low-power electronics for power management and sensor interfacing, on a chip area of 0.25mm2. Direct charging of the target battery (e.g., NiMH microbattery) is achieved with end-to-end efficiencies up to 90% at AM1.5 illumination and 80% under 100 times reduced intensity. This requires matching the voltages of the photovoltaic module and the battery circumventing maximum power point tracking. Single solar cells show efficiencies up to 10% under AM1.5 illumination and open circuit voltages, Voc, of 450-500mV. To match the battery’s voltage the miniaturised solar cells (~1mm2 area) are connected in series via wire bonding. The chemical sensor platform (mm2 area) is set up to detect hydrogen gas concentration in the low ppm range and over a broad temperature range using a low power sensing interface circuit. Using Telran TZ1053 radio to send one sample measurement of both temperature and H2 concentration every 15 seconds, the average and active power consumption for the SiNAPS mote are less than 350nW and 2.1 μW respectively. Low-power miniaturised chemical sensors of liquid analytes through microfluidic delivery to silicon nanowires are also presented. These components demonstrate the potential of further miniaturization and application of sensor nodes beyond the typical physical sensors, and are enabled by the nanowire materials platform

Autonomous reagent-based microfluidic pH sensor platform

A portable sensor has been developed for in situ measurements of pH within aqueous environments. The sensor design incorporates microfluidic technology, allowing for the use of low volume of samples and reagents, and an integrated low cost detection system that uses a light emitting diode as light source and a photodiode as the detector. Different combination of dyes has been studied in order to allow for a broader pH detection range, than can be obtained using a single dye. The optimum pH range for this particular dye combination was found to be between pH 4 and pH 9. The reagents developed for pH measurement were first tested using bench-top instrumentation and once optimised, the selected formulation was then implemented in the microfluidic system. The prototype system has been characterised in terms of pH response, linear range, reproducibility and stability. Results obtained using the prototype system are in good agreement with those obtained using reference instrumentation, i.e. a glass electrode/pH meter and analysis via spectrophotometer based assays. The reagent (mixture #3) is shown to be stable for over 8 months, which is important for long term deployments. A high reproducibility is reported with a global RSD of ≤1.8% across measurements of 90 samples, i.e. with respect to concentrations reported by a calibrated pH meter. A series of real water samples from multiple sources were also analysed using the portable sensor system, of which the global error found was 3.84% showing its feasibility for real-world applications

Riverine concentrations and export of dissolved silicon, and potential controls on nutrient stoichiometry, across the land–ocean continuum in Great Britain

Silicon (Si) is an essential nutrient element in freshwater and marine ecosystems, and its abundance relative to macro-nutrients (N, P) can impact phytoplankton communities in eutrophic rivers and estuaries. This study is the first national assessment examining (i) the primary sources (geological, biological, landcover) and controls (geomorphological, precipitation) on the transport of terrestrial dissolved silicon across Great Britain to the ocean, and (ii) the current extent and nature of its interactions with macro-nutrients in these catchments in relation to its potential impacts on phytoplankton community structure. It uses results from a year-long survey of 41 rivers along with historical data. Highest concentrations of dissolved Si (4–5.5 mg L-1) were found in rivers of the chalk- and sedimentary sandstone-based catchments of southern Great Britain and the hard sandstone catchments of Scotland. Catchment yield rates for dissolved Si varied between 0.2 and 2.6 t km−2 yr−1, with highest yields found in catchments with higher precipitation and runoff. Analysis of river N:P and dissolved Si:N ratios suggested that the sampled rivers were typically N enriched, and P limited with respect to dissolved Si. Molar dissolved Si:N ratios < 1, an indicator of river eutrophication, were associated with total nitrogen concentrations exceeding 1.8 mg L-1 or greater. The Indicator of Coastal Eutrophication index was used to assess the potential role of dissolved Si in the eutrophication of coastal waters. Negative values indicating limited eutrophication potential to non-siliceous algae were generally found, although some rivers had annual Indicator of Coastal Eutrophication index values exceeding 0, with values as high as 35 kg C km−2 day−1. In many eutrophic rivers, high dissolved Si concentrations derived from catchment lithology, kept the Indicator of Coastal Eutrophication index values below zero. Results have demonstrated that high N and P export have likely shifted most Great Britain rivers and coastal waters beyond the stoichiometric range where diatoms dominate production and into one where non-siliceous algae maybe increasingly present. Thus, future assessments of macro-nutrient management schemes, such as those involving wetlands should include dissolved Si routinely due to its stoichiometric importance