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From High-Resolution Measurement Technologies to Lab-On-A-Chip

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From High-Resolution Measurement Technologies to Lab-On-A-Chip Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Hydrol. Earth Syst. Sci. Discuss., 9, 6457–6506, 2012 Hydrology and www.hydrol-earth-syst-sci-discuss.net/9/6457/2012/ Earth System HESSD doi:10.5194/hessd-9-6457-2012 Sciences © Author(s) 2012. CC Attribution 3.0 License. Discussions 9, 6457–6506, 2012 This discussion paper is/has been under review for the journal Hydrology and Earth System From high-resolution Sciences (HESS). Please refer to the corresponding final paper in HESS if available. measurement technologies to lab-on-a-chip A. J. Wade et al. From existing in situ, high-resolution Title Page measurement technologies to Abstract Introduction lab-on-a-chip – the future of water quality Conclusions References monitoring? Tables Figures 1 2 1 1 A. J. Wade , E. J. Palmer-Felgate , S. J. Halliday , R. A. Skeffington , J I M. Loewenthal3, H. P. Jarvie2, M. J. Bowes2, G. M. Greenway4, S. J. Haswell4, J I I. M. Bell5, E. Joly5, A. Fallatah5, C. Neal2, R. J. Williams2, E. Gozzard2, and 2 J. R. Newman Back Close 1 School of Human and Environmental Sciences, University of Reading, Reading, Full Screen / Esc RG6 6AB, UK 2 Centre for Ecology and Hydrology, Wallingford, Oxon, OX10 8BB, UK Printer-friendly Version 3Environment Agency, Fobney Mead, Reading, RG2 0SF, UK 4 Department of Chemistry, University of Hull, Hull, HU6 7RX, UK Interactive Discussion 5Department of Engineering, University of Hull, Hull, HU6 7RX, UK 6457 Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Received: 4 May 2012 – Accepted: 4 May 2012 – Published: 25 May 2012 Correspondence to: A. J. Wade ([email protected]) HESSD Published by Copernicus Publications on behalf of the European Geosciences Union. 9, 6457–6506, 2012 From high-resolution measurement technologies to lab-on-a-chip A. J. Wade et al. Title Page Abstract Introduction Conclusions References Tables Figures J I J I Back Close Full Screen / Esc Printer-friendly Version Interactive Discussion 6458 Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Abstract HESSD This paper introduces new insights into the hydrochemical functioning of lowland river-systems using field-based spectrophotometric and electrode technologies. The 9, 6457–6506, 2012 streamwater concentrations of nitrogen species and phosphorus fractions were mea- 5 sured at hourly intervals on a continuous basis at two contrasting sites on tributaries of From high-resolution the River Thames, one draining a rural catchment, the River Enborne, and one draining measurement a more urban system, The Cut. The measurements complement those from an exist- technologies to ing network of multi-parameter water quality sondes maintained across the Thames lab-on-a-chip catchment and weekly monitoring based on grab samples. The results of the sub-daily 10 monitoring show that streamwater phosphorus concentrations display highly complex, A. J. Wade et al. seemingly chaotic, dynamics under storm conditions dependent on the antecedent catchment wetness, and that diurnal phosphorus and nitrogen cycles occur under low flow conditions. The diurnal patterns highlight the dominance of sewage inputs in con- Title Page trolling the streamwater phosphorus and nitrogen concentrations at low flows, even at Abstract Introduction 15 a distance of 7 km from the nearest sewage works in the rural, River Enborne, and that the time of sample collection is important when judging water quality against ecolog- Conclusions References ical thresholds or standards. An exhaustion of the supply of phosphorus from diffuse Tables Figures and septic tank sources during storm events was evident and load estimation was not improved by sub-daily monitoring beyond that achieved by daily sampling because of J I 20 the eventual reduction in the phosphorus mass entering the stream during events. The dominance of respiration over photosynthesis in The Cut indicated a prevalence of J I heterotrophic algae, and the seasonal patterns in respiration and photosynthesis cor- responded with those of temperature and light in this nutrient over-enriched stream. Back Close These results highlight the utility of sub-daily water quality measurements but the de- Full Screen / Esc 25 ployment of modified wet-chemistry technologies into the field was limited by mains electricity availability. A new approach is therefore needed to allow measurement of Printer-friendly Version a wide range of analytes at a broader range of locations for the development of water Interactive Discussion 6459 Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | quality web-sensor networks. The development and field deployment of a miniaturised “lab-on-a-chip” ion chromatograph is proposed and justified. HESSD 9, 6457–6506, 2012 1 Introduction From high-resolution The chemical and ecological status of surface waters is an increasing concern world- measurement 5 wide as demand for water and food grows as population increases. River-system water technologies to quality is affected by changes in the controlling factors of land-use and management, lab-on-a-chip atmospheric deposition, water usage and climate and much research has been de- voted to the development of integrated catchment management strategies to protect A. J. Wade et al. and improve the freshwater resource and ecological status whilst the landscape is used 10 for homes, industry, farming, forestry and recreation (Beman et al., 2005; Boyer et al., 2006). The spatial and temporal variations in streamwater chemistry are highly complex Title Page and the links between these changes and the controlling factors are subject to intense study, yet the interactions between the physical and chemical environment of rivers and Abstract Introduction their ecological status are poorly understood (Hilton et al., 2006). More work is required Conclusions References 15 to improve understanding of the hydrochemical changes at sub-daily intervals to elu- cidate the links between the physical and chemical environment of a river-system and Tables Figures the ecological structure and function, and biodiversity (Elsenbeer et al., 1994; Bowes et al., 2009a; Neal et al., 2012a). In particular, work is needed to determine if chemical J I thresholds have meaning when assessing ecological status to implement the Water J I 20 Framework Directive (WFD) and Habitats Directive. The development of new methods of high frequency water quality measurement has Back Close been identified as likely to lead to conceptual and practical advances in the hydrolog- ical and biogeochemical sciences since the critical need for sub-daily measurements Full Screen / Esc of water quality has been established, not only for the nutrients, but also for many 25 other chemicals (Neal et al., 2012a, b). Monitoring catchment hydrochemistry for long Printer-friendly Version periods of time under diverse hydrologic regimes maximises the chances for serendip- Interactive Discussion itous discoveries and improves the characterisation of pollutant sources and pathways 6460 Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | especially during storm events (Kirchner et al., 2000, 2004). There has long been a mis- match between measurement of water fluxes over gauging structures, which are often HESSD sub-hourly, and the measurement of most nutrient fluxes, which are usually daily at 9, 6457–6506, 2012 best and more often weekly or monthly. Continuous pH, water temperature, dissolved 5 oxygen, turbidity, conductivity and chlorophyll a measurements have been available since the 1990s and these suggest that high frequency chemical analysis of these, From high-resolution and other analytes, will lead to deeper insights into the contribution of chemicals to the measurement river network via different flow pathways (Robson et al., 1995; Jarvie et al., 2001, 2003). technologies to Intensive (sub-daily) discrete sampling programmes have been employed by some re- lab-on-a-chip 10 searchers, such as Scholefield et al. (2005) in Devon, southwest England and Neal et al. (2012b) in Plynlimon, mid-Wales, to collect high frequency hydrochemical data. A. J. Wade et al. These data have demonstrated complex diurnal patterns and provided new insights into the temporal variability of nutrient fluctuations (Neal et al., 2012b). Such intensive Title Page manual sampling programmes are however impractical to sustain for prolonged peri- 15 ods, both in terms of physical and financial resources, and because samples, returned Abstract Introduction to the laboratory for analysis, are also subject to issues of sample stability (Halliday et al., 2012). Automated instrumental methods are needed to make progress by min- Conclusions References imising sample degradation and allowing the study of the short-term dynamics when Tables Figures the instream biological response is likely to be most evident (Horsburgh et al., 2010; 20 Neal et al., 2012b). J I Recent developments in field-based analytical systems are now producing the first long-term continuous in situ measurements of some nutrients in water (Jordan et al., J I 2005; Palmer-Felgate et al., 2008; Soulsby et al., 2009). The data generated from Back Close these in situ studies have been used to demonstrate the benefits of high frequency 25 sampling in areas such as load estimation accuracy (Rozemeijer et al., 2006; Jordan Full Screen / Esc and Cassidy, 2011). There are also practical applications in that industrial discharge consents are often based on load estimates, and high frequency monitoring
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