Water quality is one of the most critical indicators of environmental pollution and it affects all of us. Water contamination can be accidental or intentional and the consequences are drastic unless the appropriate measures are adopted on the spot. This review provides a critical assessment of the applicability of various technologies for real-time water quality monitoring, focusing on those that have been reportedly tested in real-life scenarios. Specifically, the performance of sensors based on molecularly imprinted polymers is evaluated in detail, also giving insights into their principle of operation, stability in real on-site applications and mass production options. Such characteristics as sensing range and limit of detection are given for the most promising systems, that were verified outside of laboratory conditions. Then, novel trends of using microwave spectroscopy and chemical materials integration for achieving a higher sensitivity to and selectivity of pollutants in water are described.
Microwave spectroscopy has been identified as a novel and inexpensive method for the monitoring of water pollutants. Integrating microwave sensors with developed coatings is a novel strategy to make the sensing system more specific for a target contaminant. This study describes the determination of copper and zinc concentration in water in both laboratory-prepared and acquired mine water samples from two abandoned mining areas in Wales, UK. Uncoated sensors immersed in samples spiked with 1.25 mg/L concentrations of copper and zinc, using the standard addition method, were able to quantify the concentration at 0.44 GHz with a strong linear correlation (R2 = 0.99) for the reflection coefficient magnitude (|S11|). Functionalised microwave sensors with l-cysteine, chitosan and bismuth zinc cobalt oxide-based coatings have shown improvement in the sensing performance. Specifically, the linear correlation at 0.91–1.00 GHz between |S11| and a polluted water sample spiked with Cu showed a higher (R2 = 0.98), sensitivity (1.65 ΔdB/mg/L) and quality factor (135) compared with uncoated sensors (R2 = 0.88, sensitivity of 0.82 ΔdB/mg/L and Q-factor 30.7). A Lorentzian peak fitting function was applied for performing advanced multiple peak analysis and identifying the changes in the resonant frequency peaks which are related to the change in metal ion content. This novel sensor platform offers the possibility of in situ monitoring of toxic metal concentrations in mining-impacted water, and multiple peak features, such as area, full width half maximum, centre and height of the peaks, have the possibility to offer higher specificity for similar toxic metals, as between copper and zinc ions.
Metal pollution in aquatic environments has attracted global attention. Current methods are not able to monitor water quality in-situ at low-cost. This paper reports on a novel approach for detecting changes in the concentration of zinc in water using electrical and a microwave sensor method, adopting two planar sensors: one was functionalised with a screen-printed β-Bi 2 O 3 based coating, while the other was uncoated. Results show that both electrical and the microwave sensor responses were dependent on the presence and concentration of Zn in water with R 2 = 0.93-0.99. The functionalised sensor with a 60 μm thick β-Bi 2 O 3 based film offers improved performance compared with both uncoated and functionalised sensors with 40 µm thick coating for detecting the changes of Zn concentrations in water for low levels (100 and 500 µg/L). This novel sensing system could be a cost-effective alternative to the current offline methods.
The feasibility of using novel electromagnetic wave sensors for real-time monitoring of metal pollution in water was assessed. Five solutions with different concentrations of lead (0, 1, 10, 50, 100 mg/L) were measured using several sensing methods: UV-Vis spectroscopy, low frequency capacitance and resistance measurements, and two sensing systems based on microwave technology. With this last approach, two sensing devices were used: a resonant cavity and a planar sensor with gold interdigitated electrode design printed on a PTFE substrate with a protective PCB lacquer coating. Results confirmed the ability of these systems to quantify the lead concentration as changes in spectrum signal at specific frequencies of the electromagnetic spectrum. Spectra were unique, with clearly observed shifts in the resonant frequencies of the sensors when placed in direct contact with different lead solutions, demonstrating the possibility of continuous monitoring with great sensitivity, selectivity, and high spatial and temporal resolution. Consequently, determination of trace and toxic metals using microwave spectroscopy is a promising alternative to traditional grab-sampling and laboratory based analyses. On-line and continuous monitoring of real-time metal concentrations offers the potential for a more effective emergency response and the platform for better scientific understanding and remediation of contaminated mine drainage.
Identifying and prioritising mine sites for remediation is challenging due to inherently complex hydrological systems and multiple potential sources of mine pollution dispersed across watersheds. Understanding mine pollution dynamics in wet temperate watersheds is particularly challenging due to substantial variability in precipitation and streamflows, which increase the importance of diffuse sources. A tracer dilution and synoptic sampling experiment was conducted in a mined watershed in Scotland to identify the main sources of mine pollution, the relative importance of point and diffuse sources of pollution, and the potential benefits of mine site remediation to stream water quality. Using high spatial resolution metal loading datasets, the major Zn and Cd source areas were identified as point sources of mine water predominantly located in the upper part of the watershed. In contrast, the main sources of Pb were diffuse sources of mine tailings and wastes located in the lower part of the watershed. In the latter case, mobilisation of Pb occurred primarily from a section of braided wetland and an uncapped tailings area. Importantly, diffuse sources of mine pollution were found to be the dominant source of Pb, and an important source of Zn and Cd, even under steady-state streamflow conditions. Mass balance calculations suggest that treatment of the main mine water sources in the upper watershed and capping of the tailings deposit in the lower watershed could reduce stream trace metal concentrations by approximately 70%. These data support the development of conceptual models of mine pollution dynamics in wet temperate watersheds. These conceptual models are important as they: (1) help prioritise those mine sites and features for remediation that will deliver the most environmental and socio-economic benefit, and; (2) provide a means to quantify the importance of diffuse pollution sources that may increase in importance in the future as a result of changes in precipitation patterns in temperate watersheds.
Exceptionally low river flows are predicted to become more frequent and more severe across many global regions as a consequence of climate change. Investigations of trace metal transport dynamics across streamflows reveal stark changes in water chemistry, metal transformation processes, and remediation effectiveness under exceptionally low-flow conditions. High spatial resolution hydrological and water quality datasets indicate that metal-rich groundwater will exert a greater control on stream water chemistry and metal concentrations because of climate change. This is because the proportion of stream water sourced from mined areas and mineralized strata will increase under predicted future low-flow scenarios (from 25% under Q45 flow to 66% under Q99 flow in this study). However, mineral speciation modelling indicates that changes in stream pH and hydraulic conditions at low flow will decrease aqueous metal transport and increase sediment metal concentrations by enhancing metal sorption directly to streambed sediments. Solute transport modelling further demonstrates how increases in the importance of metal-rich diffuse groundwater sources at low flow could minimize the benefits of point source metal contamination treatment. Understanding metal transport dynamics under exceptionally low flows, as well as under high flows, is crucial to evaluate ecosystem service provision and remediation effectiveness in watersheds under future climate change scenarios.
Thousands of pollutants are threatening our water supply, putting at risk human and environmental health. Between them, trace metals are of significant concern, due to their high toxicity at low concentrations. Abandoned mining areas are globally one of the major sources of toxic metals. Nowadays, no method can guarantee an immediate response for quantifying these pollutants. In this work, a novel technique based on microwave spectroscopy and planar sensors for in situ real-time monitoring of water quality is described. The sensors were developed to directly probe water samples, and in situ trial measurements were performed in freshwater in four polluted mining areas in the UK. Planar microwave sensors were able detect the water pollution level with an immediate response specifically depicted at three resonant peaks in the GHz range. To the authors’ best knowledge, this is the first time that planar microwave sensors were tested in situ, demonstrating the ability to use this method for classifying more and less polluted water using a multiple-peak approach.
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