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  <front>
    <journal-meta><journal-id journal-id-type="publisher">HESS</journal-id><journal-title-group>
    <journal-title>Hydrology and Earth System Sciences</journal-title>
    <abbrev-journal-title abbrev-type="publisher">HESS</abbrev-journal-title><abbrev-journal-title abbrev-type="nlm-ta">Hydrol. Earth Syst. Sci.</abbrev-journal-title>
  </journal-title-group><issn pub-type="epub">1607-7938</issn><publisher>
    <publisher-name>Copernicus Publications</publisher-name>
    <publisher-loc>Göttingen, Germany</publisher-loc>
  </publisher></journal-meta>
    <article-meta>
      <article-id pub-id-type="doi">10.5194/hess-21-6425-2017</article-id><title-group><article-title>Prediction of storm transfers and annual loads with data-based mechanistic
models using high-frequency data</article-title>
      </title-group><?xmltex \runningtitle{Prediction of storm transfers and annual loads}?><?xmltex \runningauthor{M. C. Ockenden et al.}?>
      <contrib-group>
        <contrib contrib-type="author" corresp="no" rid="aff1">
          <name><surname>Ockenden</surname><given-names>Mary C.</given-names></name>
          
        <ext-link>https://orcid.org/0000-0002-8547-4015</ext-link></contrib>
        <contrib contrib-type="author" corresp="no" rid="aff1">
          <name><surname>Tych</surname><given-names>Wlodek</given-names></name>
          
        <ext-link>https://orcid.org/0000-0003-1655-844X</ext-link></contrib>
        <contrib contrib-type="author" corresp="no" rid="aff1">
          <name><surname>Beven</surname><given-names>Keith J.</given-names></name>
          
        <ext-link>https://orcid.org/0000-0001-7465-3934</ext-link></contrib>
        <contrib contrib-type="author" corresp="no" rid="aff2">
          <name><surname>Collins</surname><given-names>Adrian L.</given-names></name>
          
        </contrib>
        <contrib contrib-type="author" corresp="no" rid="aff3">
          <name><surname>Evans</surname><given-names>Robert</given-names></name>
          
        </contrib>
        <contrib contrib-type="author" corresp="no" rid="aff4">
          <name><surname>Falloon</surname><given-names>Peter D.</given-names></name>
          
        </contrib>
        <contrib contrib-type="author" corresp="no" rid="aff1">
          <name><surname>Forber</surname><given-names>Kirsty J.</given-names></name>
          
        </contrib>
        <contrib contrib-type="author" corresp="no" rid="aff5">
          <name><surname>Hiscock</surname><given-names>Kevin M.</given-names></name>
          
        </contrib>
        <contrib contrib-type="author" corresp="no" rid="aff1">
          <name><surname>Hollaway</surname><given-names>Michael J.</given-names></name>
          
        <ext-link>https://orcid.org/0000-0003-0386-2696</ext-link></contrib>
        <contrib contrib-type="author" corresp="no" rid="aff4">
          <name><surname>Kahana</surname><given-names>Ron</given-names></name>
          
        </contrib>
        <contrib contrib-type="author" corresp="no" rid="aff6">
          <name><surname>Macleod</surname><given-names>Christopher J. A.</given-names></name>
          
        </contrib>
        <contrib contrib-type="author" corresp="no" rid="aff7">
          <name><surname>Villamizar</surname><given-names>Martha L.</given-names></name>
          
        </contrib>
        <contrib contrib-type="author" corresp="no" rid="aff1">
          <name><surname>Wearing</surname><given-names>Catherine</given-names></name>
          
        </contrib>
        <contrib contrib-type="author" corresp="no" rid="aff8">
          <name><surname>Withers</surname><given-names>Paul J. A.</given-names></name>
          
        </contrib>
        <contrib contrib-type="author" corresp="no" rid="aff9">
          <name><surname>Zhou</surname><given-names>Jian G.</given-names></name>
          
        </contrib>
        <contrib contrib-type="author" corresp="no" rid="aff1">
          <name><surname>Benskin</surname><given-names>Clare McW. H.</given-names></name>
          
        </contrib>
        <contrib contrib-type="author" corresp="no" rid="aff10">
          <name><surname>Burke</surname><given-names>Sean</given-names></name>
          
        </contrib>
        <contrib contrib-type="author" corresp="no" rid="aff5">
          <name><surname>Cooper</surname><given-names>Richard J.</given-names></name>
          
        </contrib>
        <contrib contrib-type="author" corresp="no" rid="aff11">
          <name><surname>Freer</surname><given-names>Jim E.</given-names></name>
          
        </contrib>
        <contrib contrib-type="author" corresp="yes" rid="aff1">
          <name><surname>Haygarth</surname><given-names>Philip M.</given-names></name>
          <email>p.haygarth@lancaster.ac.uk</email>
        <ext-link>https://orcid.org/0000-0002-1672-6290</ext-link></contrib>
        <aff id="aff1"><label>1</label><institution>Lancaster Environment Centre, Lancaster University, Bailrigg,
Lancaster, LA1 4YQ, England, UK</institution>
        </aff>
        <aff id="aff2"><label>2</label><institution>Rothamsted Research North Wyke,
Okehampton, Devon, EX20 2SB, England, UK</institution>
        </aff>
        <aff id="aff3"><label>3</label><institution>Global Sustainability
Institute, Anglia Ruskin University, Cambridge, CB1 1PT, England, UK</institution>
        </aff>
        <aff id="aff4"><label>4</label><institution>Met Office Hadley Centre, Exeter, Devon, EX1 3PB, England, UK</institution>
        </aff>
        <aff id="aff5"><label>5</label><institution>School of Environmental Sciences, Norwich Research Park, University
of East Anglia, Norwich, NR4 7TJ, England, UK</institution>
        </aff>
        <aff id="aff6"><label>6</label><institution>James Hutton
Institute, Aberdeen, AB15 8QH, Scotland, UK</institution>
        </aff>
        <aff id="aff7"><label>7</label><institution>School of Engineering,
Liverpool University, Liverpool, L69 3GQ, England, UK</institution>
        </aff>
        <aff id="aff8"><label>8</label><institution>School of
Environment, Natural Resources and Geography, Bangor University, Bangor,
Gwynedd, LL57 2UW, Wales, UK</institution>
        </aff>
        <aff id="aff9"><label>9</label><institution>School of Computing, Mathematics &amp;
Digital Technology, Manchester Metropolitan University, Manchester, M1 5GD,
UK</institution>
        </aff>
        <aff id="aff10"><label>10</label><institution>British Geological Survey, Keyworth, Nottingham, NG12 5GG,
England, UK</institution>
        </aff>
        <aff id="aff11"><label>11</label><institution>School of Geographical Sciences, University of
Bristol, Bristol, BS8 1SS, UK</institution>
        </aff>
      </contrib-group>
      <author-notes><corresp id="corr1">Philip M. Haygarth (p.haygarth@lancaster.ac.uk)</corresp></author-notes><pub-date><day>18</day><month>December</month><year>2017</year></pub-date>
      
      <volume>21</volume>
      <issue>12</issue>
      <fpage>6425</fpage><lpage>6444</lpage>
      <history>
        <date date-type="received"><day>30</day><month>May</month><year>2017</year></date>
           <date date-type="rev-request"><day>6</day><month>June</month><year>2017</year></date>
           <date date-type="rev-recd"><day>8</day><month>November</month><year>2017</year></date>
           <date date-type="accepted"><day>9</day><month>November</month><year>2017</year></date>
      </history>
      <permissions>
        
        
      <license license-type="open-access"><license-p>This work is licensed under the Creative Commons Attribution 3.0 Unported License. To view a copy of this licence, visit <ext-link ext-link-type="uri" xlink:href="https://creativecommons.org/licenses/by/3.0/">https://creativecommons.org/licenses/by/3.0/</ext-link></license-p></license></permissions><self-uri xlink:href="https://hess.copernicus.org/articles/21/6425/2017/hess-21-6425-2017.html">This article is available from https://hess.copernicus.org/articles/21/6425/2017/hess-21-6425-2017.html</self-uri><self-uri xlink:href="https://hess.copernicus.org/articles/21/6425/2017/hess-21-6425-2017.pdf">The full text article is available as a PDF file from https://hess.copernicus.org/articles/21/6425/2017/hess-21-6425-2017.pdf</self-uri>
      <abstract>
    <p id="d1e322">Excess nutrients in surface waters, such as phosphorus (P) from agriculture,
result in poor water quality, with adverse effects on ecological health and
costs for remediation. However, understanding and prediction of P transfers
in catchments have been limited by inadequate data and over-parameterised
models with high uncertainty. We show that, with high temporal resolution
data, we are able to identify simple dynamic models that capture the P load
dynamics in three contrasting agricultural catchments in the UK. For a flashy
catchment, a linear, second-order (two pathways) model for discharge gave
high simulation efficiencies for short-term storm sequences and was useful in
highlighting uncertainties in out-of-bank flows. A model with non-linear
rainfall input was appropriate for predicting seasonal or annual cumulative P
loads where antecedent conditions affected the catchment response. For
second-order models, the time constant for the fast pathway varied between 2
and 15 h for all three catchments and for both discharge and P,
confirming that high temporal resolution data are necessary to capture the
dynamic responses in small catchments (10–50 km<inline-formula><mml:math id="M1" display="inline"><mml:mrow><mml:msup><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msup><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula>. The models led to a
better understanding of the dominant nutrient transfer modes, which will be
helpful in determining phosphorus transfers following changes in
precipitation patterns in the future.</p>
  </abstract>
    </article-meta>
  </front>
<body>
      

<sec id="Ch1.S1" sec-type="intro">
  <title>Introduction</title>
      <p id="d1e344">The quality of both surface waters and groundwater is under increasing
pressure from numerous sources, including intensive agricultural practices,
water abstraction, climate change, and changes in food production and housing
provisions to cope with population growth (Carpenter and Bennett,
2011). Sediment and nutrient concentrations and loads are of concern to
water utility companies and to environmental regulators who are striving to
meet stringent water quality standards. However, accurate estimation of
loads requires accurate, high temporal resolution measurements of both
discharge and nutrient concentrations (Johnes, 2007) and should
include quantification of observational uncertainties (McMillan
et al., 2012). Sediment and nitrogen are frequently and relatively easily
measured in situ. In contrast, phosphorus (P) concentrations for water
quality assessments are typically measured by manual or automatic sampling
followed by laboratory analysis, often at monthly resolution, which do not
capture the dynamic nature of P concentrations, and result in biased
estimates of P load (Cassidy and Jordan, 2011). Phosphorus concentration
in rivers and streams is controlled by many factors, including rainfall,
runoff, point sources, diffuse inputs, and in-stream P retention and
processing. Some of these factors, particularly for small catchments, change
at timescales of minutes to hours, and thus the dynamics of P concentration
and load need to be studied at similar timescales. In this study, hourly
time series of rainfall, runoff and P concentrations are used to help
understand hydrological transport pathways of P for three contrasting
agricultural catchments across the UK.</p>
      <p id="d1e347">There is a wide range of complexity in hydrological and water quality models,
applicable on a range of scales and for different purposes. In most models
there is a balance between practical simplifications and model complexity,
which depends on catchment size and knowledge (or lack thereof) of the hydrological
processes, data availability and computing power. Some of the less complex
models for diffuse pollution include export coefficient models (Johnes, 1996)
and the phosphorus indicators tool (PIT) (Heathwaite et al., 2003; Liu et
al., 2005). The most complex water quality models are idealised,
process-based representations of our best understanding of reality, with a
highly complex, fixed structure and many parameters, for which there is often
little or no site-specific data (Dean et al., 2009). These models often
include a component for sediment-bound P, where the sediment transfer is
based on a form of the universal soil loss equation (USLE), which is a
semi-empirical model known to perform poorly (Evans and Boardman, 2016).
Results generated by such process-based models are often highly uncertain,
due to the uncertainty in both the model parameters and the model structure
(Parker et al., 2013; Jackson-Blake et al., 2015). A review of pollutant loss
studies using one process-based model, the soil water assessment tool (SWAT),
revealed that most applications used a monthly time step for calibration,
with few applications using a daily time step and none using a sub-daily time
step. Model fit for total P (TP) concentration, measured by the Nash–Sutcliffe
efficiency, often exceeded 0.5 but could be as low as <inline-formula><mml:math id="M2" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">0.08</mml:mn></mml:mrow></mml:math></inline-formula> for daily
calibration. Depending on the calibration criteria, there may be many
different parameter sets that fit the calibration data equally well, but
because of a lack of data on internal variables, the models do not
necessarily fit for the right reasons. Moriasi et al. (2007) advised using
several different criteria for assessment of model fit, including a graphical
assessment as well as quantitative metrics. However, complex process-based
models still often fail to meet the acceptance criteria (Jackson-Blake et
al., 2015), even when these are relaxed to account for additional
uncertainties in the measured input data (Harmel et al., 2006) such as those
due to sampling method, sample storage or fractionation (Jarvie et al.,
2002). Less complex process-based models, with fewer parameters, have also
been developed for phosphorus transfer and have been applied with reasonable
success to specific catchments (e.g. Dupas et al., 2016; Hahn et al., 2013).
Both these studies related to small catchments (<inline-formula><mml:math id="M3" display="inline"><mml:mo>&lt;</mml:mo></mml:math></inline-formula> 10 km<inline-formula><mml:math id="M4" display="inline"><mml:mrow><mml:msup><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msup><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula>; it was
recognised that the models would only be applicable to locations where the
assumptions of the model were satisfied, which is consistent with the concept
of “uniqueness of place” (Beven, 2000).</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F1" specific-use="star"><caption><p id="d1e381">Location and topography of study catchments. Newby Beck, Eden,
Cumbria: location <bold>(a)</bold> and topography <bold>(d)</bold>; Blackwater,
Wensum, Norfolk: location <bold>(b)</bold> and topography <bold>(e)</bold>; Wylye,
Avon, Hampshire: location <bold>(c)</bold> and topography <bold>(f)</bold>.
©OS Terrain 50 DTM (ASC geospatial data), scale 1 : 50 000. Tiles ny51, ny52, ny61, ny62: updated July 2013; tiles st73, st83, tg02,
tg12: updated 2 August 2016. Downloaded on 3
January 2017 from Ordnance Survey (GB), using EDINA Digimap
Ordnance Survey Service: <uri>http://digimap.edina.ac.uk</uri>.</p></caption>
        <?xmltex \igopts{width=398.338583pt}?><graphic xlink:href="https://hess.copernicus.org/articles/21/6425/2017/hess-21-6425-2017-f01.png"/>

      </fig>

      <p id="d1e412">Hydrological models are subject to uncertainties in structure, parameters and
measurement data (both input and output observations) (Krueger et al., 2010),
and understanding the errors in measurement data is a prerequisite to better
understanding of the other uncertainties in modelling (McMillan et al.,
2012). Young et al. (1996) recommended constructing models that capture the
dominant modes of a system, with as few tuneable parameters as possible.
Transfer function models, whose structure and parameters are determined by
the information in the data, are considered to be among the most parsimonious
for rainfall–flow relationships (McGuire and McDonnell, 2006; Young, 2003).
Data-based mechanistic (DBM) modelling, which uses time-series data and fits
a range of transfer functions, allows the structure of the model to be
determined by the information in the monitoring data. There will still be
structural errors in a DBM model, as it tries to represent a continuum of
flow pathways with just the dominant modes, but this simplification will be
determined by the information in the data rather than being pre-selected.
This assists in getting the right answers for the right reasons (Kirchner,
2006). In contrast, there is a danger in process-based models that one might
fit quite different model structures or parameter sets to the available data,
i.e. the equifinality problem (Beven, 2006; Beven and Freer, 2001). An
optimal DBM model and associated parameters are identified using statistical
measures, but a model is only accepted if it has a plausible physical
explanation (Young, 1998, 2003; Young and Beven, 1994; Young et al., 2004).
With the increasing availability of high temporal resolution datasets for
additional variables alongside stream discharge (Bieroza and Heathwaite,
2015; Bowes et al., 2015; Halliday et al., 2015; Outram et al., 2014), this
technique has been used effectively for relating rainfall to hydrogen ion
concentration in rivers (Jones and Chappell, 2014), and rainfall to dissolved
organic carbon (Jones et al., 2014).</p>
      <p id="d1e416">The aim of this study was to investigate, for the first time, whether simple
dynamic models of P load could be identified to help understand the
hydrological P processes within three contrasting agricultural catchments in
the UK that represent a range of climate, topography, soil and farming
types. Specifically, the objectives were as follows:<?xmltex \hack{\newpage}?>
<list list-type="bullet"><list-item>
      <p id="d1e423">to identify rainfall–runoff models for each catchment, from hourly time
series data collected over 3 years;</p></list-item><list-item>
      <p id="d1e427">to develop models of P load exported from each catchment, using hourly time-series data of P concentrations measured with in situ bank-side
analysers;</p></list-item><list-item>
      <p id="d1e431">to improve understanding of the dominant modes of catchment response through
comparison of rainfall–runoff and rainfall–TP load models for each catchment.</p></list-item></list></p>
      <p id="d1e434">If successful, this would be the first time that DBM modelling has been
applied to high-resolution phosphorus data in catchment science.<?xmltex \hack{\newpage}?></p>
</sec>
<sec id="Ch1.S2">
  <title>Methodology</title>
<sec id="Ch1.S2.SS1">
  <title>Study sites</title>
      <p id="d1e449">Three rural catchments with different temperate climate, topography and farm
types were monitored at high temporal resolution as part of the UK
Demonstration Test Catchments (DTC) programme (Lloyd et al., 2016a, b; Outram
et al., 2014; McGonigle et al., 2014). These were Newby Beck at Newby, Eden
catchment, Cumbria (54.59<inline-formula><mml:math id="M5" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula> N, 2.62<inline-formula><mml:math id="M6" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula> W; 12.5 km<inline-formula><mml:math id="M7" display="inline"><mml:mrow><mml:msup><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msup><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula>;
Blackwater at Park Farm, Wensum catchment, Norfolk (52.78<inline-formula><mml:math id="M8" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula> N,
1.15<inline-formula><mml:math id="M9" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula> E; 19.7 km<inline-formula><mml:math id="M10" display="inline"><mml:mrow><mml:msup><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msup><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula>; Wylye at Brixton Deverill, Avon catchment,
Hampshire (51.16<inline-formula><mml:math id="M11" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula> N, 2.19<inline-formula><mml:math id="M12" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula> W; 50.2 km<inline-formula><mml:math id="M13" display="inline"><mml:mrow><mml:msup><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msup><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> (Fig. 1).
Further details of these catchments are available in Table S1 in the
Supplement.<?xmltex \hack{\newpage}?></p>
</sec>
<sec id="Ch1.S2.SS2">
  <title>Data collection</title>
      <p id="d1e550">Rainfall was measured at 15 min resolution at three sites in each of the
Newby Beck and Blackwater catchments (Outram et al., 2014; Perks et al.,
2015) and summed to give hourly totals. The hourly totals from the different
rain gauges were combined by areal weighting to give an hourly time series
for the catchment. For the Wylye catchment, only daily rainfall was available
for sites within the catchment, so raw tipping bucket data were obtained for
several sites outside the catchment and analysed to produce an hourly time
series which was considered most representative of the rainfall in the
catchment. Further details of the rainfall analysis for the Wylye catchment
are given in Sect. S1 in the Supplement.</p>
      <p id="d1e553">River water level was measured at 15 min resolution in the three catchments,
with rating curves developed for discharge estimation (Outram et al., 2014;
Perks et al., 2015; Lloyd et al., 2016b). TP concentration
was determined in situ at 30 min intervals with a Hach Lange combined
Sigmatax sampling module and Phosphax analyser using acid digestion and
colorimetry (Jordan et al., 2007, 2013; Perks et al., 2015). Total P loads
for each hour were determined by multiplying discharge (averaged to 30 min
resolution) by TP concentration for each 30 min and summing to give hourly
totals:
            <disp-formula id="Ch1.E1" content-type="numbered"><mml:math id="M14" display="block"><mml:mrow><mml:mtext>TP load</mml:mtext><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo><mml:mo>=</mml:mo><mml:mi>k</mml:mi><mml:munder><mml:mo movablelimits="false">∑</mml:mo><mml:mi>j</mml:mi></mml:munder><mml:msub><mml:mi>Q</mml:mi><mml:mi>j</mml:mi></mml:msub><mml:msub><mml:mi>C</mml:mi><mml:mi>j</mml:mi></mml:msub><mml:mo>,</mml:mo></mml:mrow></mml:math></disp-formula>
          where TP load<inline-formula><mml:math id="M15" display="inline"><mml:mrow><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> is the load (kg) exported during the hourly
timestep which ends at time <inline-formula><mml:math id="M16" display="inline"><mml:mi>t</mml:mi></mml:math></inline-formula>, <inline-formula><mml:math id="M17" display="inline"><mml:mrow><mml:msub><mml:mi>Q</mml:mi><mml:mi>j</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> is the discharge observations
(m<inline-formula><mml:math id="M18" display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msup></mml:math></inline-formula> s<inline-formula><mml:math id="M19" display="inline"><mml:mrow><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> within the hourly timestep, <inline-formula><mml:math id="M20" display="inline"><mml:mrow><mml:msub><mml:mi>C</mml:mi><mml:mi>j</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> is the corresponding
TP concentration observations (mg L<inline-formula><mml:math id="M21" display="inline"><mml:mrow><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> within the hourly timestep, and
<inline-formula><mml:math id="M22" display="inline"><mml:mi>k</mml:mi></mml:math></inline-formula> is a constant (<inline-formula><mml:math id="M23" display="inline"><mml:mo>=</mml:mo></mml:math></inline-formula> 3.6) for conversion of units to give load
in kilograms.
Visual inspection of the data indicated that aggregation of the data from 15
or 30 min resolution to hourly did not result in a significant loss of
information. This would not be the case for very small catchments or those
where the dynamics being investigated were very fast. Calculation of the load
according to Eq. (1) assumes that the TP is well mixed in the water and that
the Hach Lange sampler is taking a representative sample. It also assumes
that the rating curve is appropriate over the full range of stage recordings
made, and that the relationship between stage and discharge is stationary.
Total phosphorus load, rather than concentration, was modelled because water
utility companies are concerned about the total load which may have to be
removed and because both water flow and load are fluxes, so comparisons
between the two are easier to interpret directly than for concentration,
which is a state rather than a flux (Jones et al., 2014).</p>
</sec>
<sec id="Ch1.S2.SS3">
  <title>Transfer function model identification</title>
      <p id="d1e692">Transfer function models relating the input (here, a time series of rainfall,
<inline-formula><mml:math id="M24" display="inline"><mml:mi>R</mml:mi></mml:math></inline-formula>) to the output (here, a time series of either discharge, <inline-formula><mml:math id="M25" display="inline"><mml:mi>Q</mml:mi></mml:math></inline-formula>, or
phosphorus load, TP load) were identified using continuous-time
models (Young and Garnier, 2006) where possible, or in cases where data were
missing or identification was difficult, with discrete time models (Young,
2003), the estimation of which handles missing data more robustly. Continuous-time models are more numerically robust and have a direct interpretation as
systems of differential equations (Young, 2011). Models were identified using
the <italic>RIVCBJ identification</italic> algorithm (refined instrumental variable
continuous-time Box–Jenkins identification, for continuous-time models), or
<italic>RIVBJ identification</italic> (refined instrumental variable Box–Jenkins
identification, for discrete-time models) that are part of the CAPTAIN toolbox
(Taylor et al., 2007) for MATLAB<sup>®</sup>.</p>
      <p id="d1e718">The identification algorithm always includes a noise model; by default this
assumes normally distributed, uncorrelated errors, but an auto-regressive
moving average (ARMA) structure can be specified. The Gaussian noise model
still results in asymptotically unbiased parameter estimates, but not
necessarily the most statistically efficient (close to minimum variance)
(Taylor et al., 2007). In this study, models up to third
order were considered initially, but higher order models showed no
advantage, so only models up to second order were considered in subsequent
evaluations. Full models (input–output (I-O) plus ARMA structured residual
noise) were assessed initially and overall they did not produce better
results in all cases; therefore, in order to keep a consistent approach for
all catchments, structured noise models were not specified in later model
identification. In addition, transfer function models with a structured
noise component generally do not improve longer-term predictions of
processes which are I-O dominated. The residuals structure was not
strong enough for a structured noise model to improve the model fit
consistently. If there was a strong structure in the residuals, it would
suggest that something was being missed in the DBM system representation.
The time delay constants were estimated from the data at the same time as
the model structures.</p>
      <p id="d1e721">Continuous-time and discrete-time model structures are described below (from
Ockenden et al., 2017). The parameter estimates in both continuous-time
models and discrete-time models are formulaically related (Table S3).</p>
      <p id="d1e724">A second-order discrete linear transfer function, denoted by [2, 2,
<inline-formula><mml:math id="M26" display="inline"><mml:mi mathvariant="italic">δ</mml:mi></mml:math></inline-formula>],
takes the following form:

                <disp-formula id="Ch1.E2" content-type="numbered"><mml:math id="M27" display="block"><mml:mrow><mml:mstyle class="stylechange" displaystyle="true"/><mml:mi>y</mml:mi><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo><mml:mo>=</mml:mo><mml:mstyle displaystyle="true"><mml:mfrac style="display"><mml:mrow><mml:msub><mml:mi>b</mml:mi><mml:mn mathvariant="normal">1</mml:mn></mml:msub><mml:mo>+</mml:mo><mml:msub><mml:mi>b</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub><mml:msup><mml:mi>z</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow><mml:mrow><mml:mn mathvariant="normal">1</mml:mn><mml:mo>+</mml:mo><mml:msub><mml:mi>a</mml:mi><mml:mn mathvariant="normal">1</mml:mn></mml:msub><mml:msup><mml:mi>z</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup><mml:mo>+</mml:mo><mml:msub><mml:mi>a</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub><mml:msup><mml:mi>z</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:mfrac></mml:mstyle><mml:mi>u</mml:mi><mml:mfenced open="(" close=")"><mml:mi>t</mml:mi><mml:mo>-</mml:mo><mml:mi mathvariant="italic">δ</mml:mi></mml:mfenced><mml:mo>+</mml:mo><mml:msub><mml:mi mathvariant="italic">ξ</mml:mi><mml:mi>t</mml:mi></mml:msub><mml:mo>,</mml:mo></mml:mrow></mml:math></disp-formula>

          where <inline-formula><mml:math id="M28" display="inline"><mml:mrow><mml:mi>y</mml:mi><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> is model output at time <inline-formula><mml:math id="M29" display="inline"><mml:mi>t</mml:mi></mml:math></inline-formula>, <inline-formula><mml:math id="M30" display="inline"><mml:mrow><mml:mi>u</mml:mi><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> is model input, and <inline-formula><mml:math id="M31" display="inline"><mml:mrow><mml:msup><mml:mi>z</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula> is
the backwards step operator, i.e. <inline-formula><mml:math id="M32" display="inline"><mml:mrow><mml:msup><mml:mi>z</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup><mml:mi>y</mml:mi><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo><mml:mo>=</mml:mo><mml:mi>y</mml:mi><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula>; <inline-formula><mml:math id="M33" display="inline"><mml:mrow><mml:msub><mml:mi>b</mml:mi><mml:mn mathvariant="normal">1</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>, <inline-formula><mml:math id="M34" display="inline"><mml:mrow><mml:msub><mml:mi>b</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>,
<inline-formula><mml:math id="M35" display="inline"><mml:mrow><mml:msub><mml:mi>a</mml:mi><mml:mn mathvariant="normal">1</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>, <inline-formula><mml:math id="M36" display="inline"><mml:mrow><mml:msub><mml:mi>a</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> are parameters determined during model identification,
<inline-formula><mml:math id="M37" display="inline"><mml:mi mathvariant="italic">δ</mml:mi></mml:math></inline-formula> is the number of time steps of pure time delay and <inline-formula><mml:math id="M38" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">ξ</mml:mi><mml:mi>t</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>
represents the uncertainty arising from a combination of measurement noise,
other unmeasured inputs and modelling error. For a physical interpretation,
second-order models were only accepted it they could be decomposed by partial
fraction expansion into two first-order transfer functions with structure [1,
1, <inline-formula><mml:math id="M39" display="inline"><mml:mi mathvariant="italic">δ</mml:mi></mml:math></inline-formula>] representing fast and slow pathways, with characteristic time
constants and steady-state gains, i.e.

                <disp-formula id="Ch1.E3" content-type="numbered"><mml:math id="M40" display="block"><mml:mrow><mml:mstyle class="stylechange" displaystyle="true"/><mml:mi>y</mml:mi><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo><mml:mo>=</mml:mo><mml:mstyle displaystyle="true"><mml:mfrac style="display"><mml:mrow><mml:msub><mml:mi>b</mml:mi><mml:mtext>f</mml:mtext></mml:msub></mml:mrow><mml:mrow><mml:mn mathvariant="normal">1</mml:mn><mml:mo>-</mml:mo><mml:msub><mml:mi>a</mml:mi><mml:mtext>f</mml:mtext></mml:msub><mml:msup><mml:mi>z</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:mfrac></mml:mstyle><mml:mi>u</mml:mi><mml:mfenced close=")" open="("><mml:mi>t</mml:mi><mml:mo>-</mml:mo><mml:mi mathvariant="italic">δ</mml:mi></mml:mfenced><mml:mo>+</mml:mo><mml:mstyle displaystyle="true"><mml:mfrac style="display"><mml:mrow><mml:msub><mml:mi>b</mml:mi><mml:mtext>s</mml:mtext></mml:msub></mml:mrow><mml:mrow><mml:mn mathvariant="normal">1</mml:mn><mml:mo>-</mml:mo><mml:msub><mml:mi>a</mml:mi><mml:mtext>s</mml:mtext></mml:msub><mml:msup><mml:mi>z</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:mfrac></mml:mstyle><mml:mi>u</mml:mi><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>-</mml:mo><mml:mi mathvariant="italic">δ</mml:mi><mml:mo>)</mml:mo><mml:mo>+</mml:mo><mml:msub><mml:mi mathvariant="italic">ξ</mml:mi><mml:mi>t</mml:mi></mml:msub><mml:mo>,</mml:mo></mml:mrow></mml:math></disp-formula>

          where <inline-formula><mml:math id="M41" display="inline"><mml:mrow><mml:msub><mml:mi>b</mml:mi><mml:mtext>f</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M42" display="inline"><mml:mrow><mml:msub><mml:mi>b</mml:mi><mml:mtext>s</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> are gains on the fast and slow pathways, respectively,
and <inline-formula><mml:math id="M43" display="inline"><mml:mrow><mml:msub><mml:mi>a</mml:mi><mml:mtext>f</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M44" display="inline"><mml:mrow><mml:msub><mml:mi>a</mml:mi><mml:mtext>s</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> are parameters characterising the time constants of
the fast and slow pathways, respectively; <inline-formula><mml:math id="M45" display="inline"><mml:mrow><mml:msub><mml:mi>a</mml:mi><mml:mtext>f</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M46" display="inline"><mml:mrow><mml:msub><mml:mi>a</mml:mi><mml:mtext>s</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> are roots
of the denominator polynomial in the second-order transfer functions above
(Eq. 2). This can be interpreted as two parallel linear storages.</p>
      <p id="d1e1153">In continuous time, a transfer function model with time delay <inline-formula><mml:math id="M47" display="inline"><mml:mi mathvariant="italic">τ</mml:mi></mml:math></inline-formula> has
the following form:
            <disp-formula id="Ch1.E4" content-type="numbered"><mml:math id="M48" display="block"><mml:mrow><mml:mi>Y</mml:mi><mml:mo>(</mml:mo><mml:mi>s</mml:mi><mml:mo>)</mml:mo><mml:mo>=</mml:mo><mml:mstyle displaystyle="true"><mml:mfrac style="display"><mml:mrow><mml:mi>B</mml:mi><mml:mo>(</mml:mo><mml:mi>s</mml:mi><mml:mo>)</mml:mo></mml:mrow><mml:mrow><mml:mi>A</mml:mi><mml:mo>(</mml:mo><mml:mi>s</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:mfrac></mml:mstyle><mml:msup><mml:mi>e</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mi>s</mml:mi><mml:mi mathvariant="italic">τ</mml:mi></mml:mrow></mml:msup><mml:mi>U</mml:mi><mml:mo>(</mml:mo><mml:mi>s</mml:mi><mml:mo>)</mml:mo><mml:mo>+</mml:mo><mml:mi>E</mml:mi><mml:mo>(</mml:mo><mml:mi>s</mml:mi><mml:mo>)</mml:mo><mml:mo>,</mml:mo></mml:mrow></mml:math></disp-formula>
          where <inline-formula><mml:math id="M49" display="inline"><mml:mrow><mml:mi>Y</mml:mi><mml:mo>(</mml:mo><mml:mi>s</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula>, <inline-formula><mml:math id="M50" display="inline"><mml:mrow><mml:mi>U</mml:mi><mml:mo>(</mml:mo><mml:mi>s</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M51" display="inline"><mml:mrow><mml:mi>E</mml:mi><mml:mo>(</mml:mo><mml:mi>s</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> represent the Laplace transforms of the output, input and
noise, respectively. <inline-formula><mml:math id="M52" display="inline"><mml:mrow><mml:mi>A</mml:mi><mml:mo>(</mml:mo><mml:mi>s</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M53" display="inline"><mml:mrow><mml:mi>B</mml:mi><mml:mo>(</mml:mo><mml:mi>s</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> represent the denominator and numerator
polynomials in the derivative operator <inline-formula><mml:math id="M54" display="inline"><mml:mrow><mml:mi>s</mml:mi><mml:mo>=</mml:mo><mml:mstyle displaystyle="false"><mml:mfrac style="text"><mml:mi mathvariant="normal">d</mml:mi><mml:mrow><mml:mi mathvariant="normal">d</mml:mi><mml:mi>t</mml:mi></mml:mrow></mml:mfrac></mml:mstyle></mml:mrow></mml:math></inline-formula>
that define the relationship between the input and the output, and <inline-formula><mml:math id="M55" display="inline"><mml:mi mathvariant="italic">τ</mml:mi></mml:math></inline-formula>
represents the time delay. second-order models were only accepted if they
could be decomposed by partial fraction expansion into two parallel,
first-order transfer functions, i.e.
            <disp-formula id="Ch1.E5" content-type="numbered"><mml:math id="M56" display="block"><mml:mrow><mml:msub><mml:mtext>TP</mml:mtext><mml:mtext>load</mml:mtext></mml:msub><mml:mo>=</mml:mo><mml:mstyle displaystyle="true"><mml:mfrac style="display"><mml:mrow><mml:msub><mml:mi>b</mml:mi><mml:mi mathvariant="normal">f</mml:mi></mml:msub></mml:mrow><mml:mrow><mml:mi>s</mml:mi><mml:mo>+</mml:mo><mml:msub><mml:mi>a</mml:mi><mml:mi mathvariant="normal">f</mml:mi></mml:msub></mml:mrow></mml:mfrac></mml:mstyle><mml:msup><mml:mi>e</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mi>s</mml:mi><mml:mi mathvariant="italic">τ</mml:mi></mml:mrow></mml:msup><mml:mi>R</mml:mi><mml:mo>+</mml:mo><mml:mstyle displaystyle="true"><mml:mfrac style="display"><mml:mrow><mml:msub><mml:mi>b</mml:mi><mml:mi mathvariant="normal">s</mml:mi></mml:msub></mml:mrow><mml:mrow><mml:mi>s</mml:mi><mml:mo>+</mml:mo><mml:msub><mml:mi>a</mml:mi><mml:mi mathvariant="normal">s</mml:mi></mml:msub></mml:mrow></mml:mfrac></mml:mstyle><mml:msup><mml:mi>e</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mi>s</mml:mi><mml:mi mathvariant="italic">τ</mml:mi></mml:mrow></mml:msup><mml:mi>R</mml:mi><mml:mo>+</mml:mo><mml:mi>E</mml:mi><mml:mo>.</mml:mo></mml:mrow></mml:math></disp-formula>
          This can be interpreted as two parallel stores, which are depleted at
different rates, determined by the time constants (direct reciprocals of
<inline-formula><mml:math id="M57" display="inline"><mml:mrow><mml:msub><mml:mi>a</mml:mi><mml:mtext>f</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M58" display="inline"><mml:mrow><mml:msub><mml:mi>a</mml:mi><mml:mtext>s</mml:mtext></mml:msub><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> of the fast and slow components of the response,
respectively. The terms <inline-formula><mml:math id="M59" display="inline"><mml:mrow><mml:msub><mml:mi>b</mml:mi><mml:mtext>f</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M60" display="inline"><mml:mrow><mml:msub><mml:mi>b</mml:mi><mml:mtext>s</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> are parameters that determine the gain of
the fast and slow components, respectively. The terms “fast” and “slow” are
used here as qualitative terms, since they are not necessarily related to
specific process mechanisms; for a second-order model (two stores), one
store simply depletes at a slower rate than the other. Time constants are
catchment specific; for example, for a first-order rainfall–runoff model
which identifies just the dominant mode (one pathway), the time constant can
vary from less than an hour (e.g. for a small, flashy catchment in Malaysian
Borneo, Chappell et al., 2006) to more than 3 months
(e.g. for a chalk stream in Berkshire, UK, Ockenden and
Chappell, 2011).</p>
      <p id="d1e1456">This method of model identification requires high temporal resolution data
that capture the dynamic response to the driving input; therefore, it cannot
work if input data (in this case, rainfall) are missing, and does not perform
well if too much output data (in this case, discharge or TP load)
are missing or not showing a response. For the Newby Beck catchment, linear
models were identified for short storm sequences up to 1 month, and were
considered applicable to periods of similar conditions. These short-term
models had a simple linear structure and very few parameters (five for a
second-order model). As this paper is evaluating a methodology, successful
modelling on different timescales can be used as validation of the
approach. Models were not identified for short periods for Blackwater and
Wylye, as the presence of a much slower pathway (with a time constant of the
same order as the length of the identification period) did not allow model
parameter estimates to be sufficiently constrained over such short periods.</p>
      <p id="d1e1459">For longer time series, when seasonal change and antecedent wetness are
expected to have an impact on the response, linear models were improved by
inclusion of the rainfall–runoff non-linearity (Beven, 2012) based on
the storage state of the catchment, for which the discharge is used as a
proxy, i.e.
            <disp-formula id="Ch1.E6" content-type="numbered"><mml:math id="M61" display="block"><mml:mrow><mml:msub><mml:mi>R</mml:mi><mml:mtext>e</mml:mtext></mml:msub><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo><mml:mo>=</mml:mo><mml:mi>R</mml:mi><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo><mml:mo>(</mml:mo><mml:mi>Q</mml:mi><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn><mml:mo>)</mml:mo><mml:msup><mml:mo>)</mml:mo><mml:mi mathvariant="italic">β</mml:mi></mml:msup><mml:mo>,</mml:mo></mml:mrow></mml:math></disp-formula>
          where <inline-formula><mml:math id="M62" display="inline"><mml:mrow><mml:msub><mml:mi>R</mml:mi><mml:mtext>e</mml:mtext></mml:msub><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> is the effective rainfall at time <inline-formula><mml:math id="M63" display="inline"><mml:mi>t</mml:mi></mml:math></inline-formula>, <inline-formula><mml:math id="M64" display="inline"><mml:mi>R</mml:mi></mml:math></inline-formula> is the observed rainfall, <inline-formula><mml:math id="M65" display="inline"><mml:mi>Q</mml:mi></mml:math></inline-formula> is the
observed discharge, and <inline-formula><mml:math id="M66" display="inline"><mml:mi mathvariant="italic">β</mml:mi></mml:math></inline-formula> is a constant exponent that is optimized
from the observed data at the same time as model identification. Using a
simple non-linear function (with a single and optimised parameter) of recent
discharge measurement as catchment wetness surrogate has been tested on
catchments of different size and nature (e.g. Beven, 2012; Chappell et
al., 1999; McIntyre and Marshall, 2010; Young, 2003; Young and Beven, 1994).
A recent high flow will be highly correlated with high “overall” catchment
wetness, and using the flow at time <inline-formula><mml:math id="M67" display="inline"><mml:mrow><mml:mi>t</mml:mi><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:math></inline-formula>, as in Eq. (6), still allows estimation
of <inline-formula><mml:math id="M68" display="inline"><mml:mrow><mml:msub><mml:mi>R</mml:mi><mml:mtext>e</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M69" display="inline"><mml:mi>Q</mml:mi></mml:math></inline-formula> at time <inline-formula><mml:math id="M70" display="inline"><mml:mi>t</mml:mi></mml:math></inline-formula>. The resulting effective inputs are rescaled in fitting
the <inline-formula><mml:math id="M71" display="inline"><mml:mi>b</mml:mi></mml:math></inline-formula> parameters of the transfer function within the DBM calibration process.
A transfer function model is not subject to a direct mass balance
constraint, for example in flood forecasting applications where rainfall may
be modelled against stage rather than discharge
(e.g. Leedal et al., 2013). A simple antecedent
precipitation index (API) was also tried initially, although this introduces
additional parameterisation; it worked with reasonable success for Newby
Beck but not for the other catchments, and therefore, as a consistent method
was sought for all catchments, the API approach was not pursued in this
case. For annual TP loads, the models (still with hourly timestep) were
identified based on the data for hydrological years 2011–2012 and 2012–2013 for
Newby Beck, but, because of missing output data, just for hydrological year
2012–2013 for the Blackwater and Wylye catchments. Models were validated on
the data for all, or part, of the hydrological year 2013–2014.</p>
      <p id="d1e1601">Model fit was assessed according to model bias, to evaluate systematic over-
or under-prediction of the model, and to <inline-formula><mml:math id="M72" display="inline"><mml:mrow><mml:msubsup><mml:mi>R</mml:mi><mml:mi>t</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msubsup></mml:mrow></mml:math></inline-formula> (also known as the Nash–Sutcliffe efficiency):
            <disp-formula id="Ch1.E7" content-type="numbered"><mml:math id="M73" display="block"><mml:mrow><mml:msubsup><mml:mi>R</mml:mi><mml:mi>t</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msubsup><mml:mo>=</mml:mo><mml:mn mathvariant="normal">1</mml:mn><mml:mo>-</mml:mo><mml:mstyle displaystyle="true"><mml:mfrac style="display"><mml:mrow><mml:msup><mml:mover accent="true"><mml:mi mathvariant="italic">σ</mml:mi><mml:mo mathvariant="normal" stretchy="false">^</mml:mo></mml:mover><mml:mn mathvariant="normal">2</mml:mn></mml:msup></mml:mrow><mml:mrow><mml:msubsup><mml:mi mathvariant="italic">σ</mml:mi><mml:mi>y</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msubsup></mml:mrow></mml:mfrac></mml:mstyle><mml:mo>,</mml:mo></mml:mrow></mml:math></disp-formula>
          where

                <disp-formula specific-use="align" content-type="numbered"><mml:math id="M74" display="block"><mml:mtable displaystyle="true"><mml:mlabeledtr id="Ch1.E8"><mml:mtd/><mml:mtd><mml:mstyle displaystyle="true" class="stylechange"/></mml:mtd><mml:mtd><mml:mrow><mml:mstyle class="stylechange" displaystyle="true"/><mml:msup><mml:mover accent="true"><mml:mi mathvariant="italic">σ</mml:mi><mml:mo mathvariant="normal" stretchy="false">^</mml:mo></mml:mover><mml:mn mathvariant="normal">2</mml:mn></mml:msup><mml:mo>=</mml:mo><mml:mstyle displaystyle="true"><mml:mfrac style="display"><mml:mn mathvariant="normal">1</mml:mn><mml:mi>N</mml:mi></mml:mfrac></mml:mstyle><mml:munderover><mml:mo movablelimits="false">∑</mml:mo><mml:mrow><mml:mi>i</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow><mml:mi>N</mml:mi></mml:munderover><mml:msup><mml:mfenced open="[" close="]"><mml:msub><mml:mi>y</mml:mi><mml:mi>i</mml:mi></mml:msub><mml:mo>-</mml:mo><mml:mover accent="true"><mml:mi>y</mml:mi><mml:mo stretchy="false" mathvariant="normal">^</mml:mo></mml:mover></mml:mfenced><mml:mn mathvariant="normal">2</mml:mn></mml:msup><mml:mo>;</mml:mo><mml:mspace width="0.25em" linebreak="nobreak"/><mml:mspace linebreak="nobreak" width="0.25em"/><mml:mspace width="0.25em" linebreak="nobreak"/><mml:msubsup><mml:mi mathvariant="italic">σ</mml:mi><mml:mi>y</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msubsup><mml:mo>=</mml:mo><mml:mstyle displaystyle="true"><mml:mfrac style="display"><mml:mn mathvariant="normal">1</mml:mn><mml:mi>N</mml:mi></mml:mfrac></mml:mstyle><mml:munderover><mml:mo movablelimits="false">∑</mml:mo><mml:mrow><mml:mi>i</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow><mml:mi>N</mml:mi></mml:munderover><mml:msup><mml:mfenced open="[" close="]"><mml:msub><mml:mi>y</mml:mi><mml:mi>i</mml:mi></mml:msub><mml:mo>-</mml:mo><mml:mover accent="true"><mml:mi>y</mml:mi><mml:mo mathvariant="normal">‾</mml:mo></mml:mover></mml:mfenced><mml:mn mathvariant="normal">2</mml:mn></mml:msup><mml:mo>;</mml:mo></mml:mrow></mml:mtd></mml:mlabeledtr><mml:mtr><mml:mtd><mml:mstyle displaystyle="true" class="stylechange"/></mml:mtd><mml:mtd><mml:mrow><mml:mstyle class="stylechange" displaystyle="true"/><mml:mover accent="true"><mml:mi>y</mml:mi><mml:mo mathvariant="normal">‾</mml:mo></mml:mover><mml:mo>=</mml:mo><mml:mstyle displaystyle="true"><mml:mfrac style="display"><mml:mn mathvariant="normal">1</mml:mn><mml:mi>N</mml:mi></mml:mfrac></mml:mstyle><mml:munderover><mml:mo movablelimits="false">∑</mml:mo><mml:mrow><mml:mi>i</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow><mml:mi>N</mml:mi></mml:munderover><mml:msub><mml:mi>y</mml:mi><mml:mi>i</mml:mi></mml:msub><mml:mo>.</mml:mo></mml:mrow></mml:mtd></mml:mtr></mml:mtable></mml:math></disp-formula>

            Here, <inline-formula><mml:math id="M75" display="inline"><mml:mover accent="true"><mml:mi>y</mml:mi><mml:mo stretchy="false" mathvariant="normal">^</mml:mo></mml:mover></mml:math></inline-formula> is the model simulation, <inline-formula><mml:math id="M76" display="inline"><mml:mrow><mml:msup><mml:mover accent="true"><mml:mi mathvariant="italic">σ</mml:mi><mml:mo stretchy="false" mathvariant="normal">^</mml:mo></mml:mover><mml:mn mathvariant="normal">2</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula> is the mean
squared error of the model residuals (only equal to the variance if the mean
of the residuals is zero), and <inline-formula><mml:math id="M77" display="inline"><mml:mrow><mml:msubsup><mml:mi mathvariant="italic">σ</mml:mi><mml:mi>y</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msubsup></mml:mrow></mml:math></inline-formula> is the variance of
the observations, <inline-formula><mml:math id="M78" display="inline"><mml:mrow><mml:msub><mml:mi>y</mml:mi><mml:mi>i</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>. A balance of model fit and
over-parameterisation was sought using the Young information criterion (YIC)
and visual inspection of the model fit to the monitoring data. Model
assessment criteria are defined in Sect. S2.</p>
</sec>
<sec id="Ch1.S2.SS4">
  <title>Uncertainty estimation</title>
<sec id="Ch1.S2.SS4.SSS1">
  <title>Structural uncertainty</title>
      <p id="d1e1863">The DBM technique involves the simplified representation of complex systems,
based on the information in the data (Young, 1998, 2001; Young et
al., 2004). In practice, this means identifying models over a range of
orders, and choosing the most appropriate model order. Generally the
simplest (lowest order) model which balances model fit without
over-parameterisation is chosen. The chosen models often have a very simple
structure, which will certainly not be a true representation of all the
processes, but may model the data adequately. This structural error is
accepted as part of the DBM technique in order to reveal the dominant modes
of response.</p>
</sec>
<sec id="Ch1.S2.SS4.SSS2">
  <title>Parameter uncertainty</title>
      <p id="d1e1872">The instrumental variable algorithms (RIVCBJ and RIVBJ) allow unbiased
estimation of the model parameters and their covariance matrices. Monte
Carlo sampling within the parameter space determined by the covariance
matrices allows for uncertainty in derived quantities, such as time
constants, to be calculated. In general with DBM modelling, very little of
the total uncertainty is due to the parameters, partly because there are so
few of them and because the linear-dynamic part of the process that the
model describes is well-defined. Note that in the case of transfer function
models of the hydrograph, the models do not directly reflect the transport
of water in the system since the hydrograph represents the integrated
effects of celerities in the system rather than flow velocities
(McDonnell and Beven, 2014).</p>
</sec>
<sec id="Ch1.S2.SS4.SSS3">
  <title>Data uncertainty</title>
      <p id="d1e1881">A review of measurement data uncertainty is presented by McMillan et al. (2012),
including uncertainties in rainfall observations. For all
three catchments in this study, input data (rainfall) was based on three
rain gauges in or near each catchment. This only gives a catchment rainfall
estimate, which is affected by the non-homogeneity of the rainfall field and
the rainfall regime, and therefore some of the mismatch between model fit
and observations (for any modelling technique) may be attributed to
uncertainties in the rainfall input.</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F2" specific-use="star"><caption><p id="d1e1886">Time series of hourly rainfall, runoff and total phosphorus (TP)
concentration at the three Demonstration Test Catchments: rainfall and
runoff <bold>(a)</bold> and TP concentration <bold>(b)</bold> at Newby Beck, Eden;
rainfall and runoff <bold>(c)</bold> and TP concentration <bold>(d)</bold> at Park
Farm, Blackwater, Wensum; rainfall and runoff <bold>(e)</bold> and TP
concentration <bold>(f)</bold> at Brixton Deverill, Wylye, Avon.</p></caption>
            <?xmltex \igopts{width=455.244094pt}?><graphic xlink:href="https://hess.copernicus.org/articles/21/6425/2017/hess-21-6425-2017-f02.png"/>

          </fig>

      <p id="d1e1914">A rigorous treatment of the uncertainties in high-frequency nutrient data and
its subsequent impact on loads is given by Lloyd et al. (2016b). For Newby
Beck, where stage–discharge gaugings were available, the discharge
uncertainty was estimated using the method of McMillan and Westerberg (2015),
fitting multiple plausible rating curves and weighting with a likelihood
function. This method accounts for a mix of systematic and random measurement
errors. The uncertainty of the phosphorus concentration measurements was
estimated by comparing the time series from the bank-side analyser with the
laboratory spot samples taken for ground-truthing (Lloyd et al., 2016b),
fitting multiple regression curves and weightings according to McMillan and
Westerberg (2015). The time series of discharge and TP concentration, with
their uncertainty distributions, were then combined by resampling to give the
measurement data uncertainties on the TP loads. For the Wylye, discharge
measurement uncertainties were estimated using a standard deviation of
10 %, the maximum value calculated by Lloyd et al. (2016b) for the
gauging site at Brixton Deverill using the method of Coxon et al. (2015).
Wylye discharges were combined with a standard deviation of
0.11 mg L<inline-formula><mml:math id="M79" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> for the uncertainty of the TP concentration from the
bank-side analysers (Lloyd et al., 2016b) to give uncertainty bounds on the
TP load. For the Blackwater, discharge uncertainties were estimated by the
DTC team and supplied with the DTC data, with uncertainty bounds of
approximately <inline-formula><mml:math id="M80" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula>20 % for low flows rising to <inline-formula><mml:math id="M81" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula>30 % for high
flows. This was combined with a standard deviation of 0.01 mg L<inline-formula><mml:math id="M82" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> for
the uncertainty of the TP concentration from the bank-side analysers (Outram
et al., 2016). Measurement data uncertainty bounds are shown on plots as a
blue shaded band.</p>
</sec>
</sec>
</sec>
<sec id="Ch1.S3">
  <title>Results and discussion</title>
<sec id="Ch1.S3.SS1">
  <title>Observed hydrological response and total phosphorus load in the
three catchments</title>
      <p id="d1e1968">Time-series data from each catchment (Fig. 2) indicated large contrasts in
the hydrological response of each study catchment, with Newby Beck (Eden)
showing a very flashy response to rainfall (Fig. 2a). Although a fast
response at certain times was also evident in the Blackwater (Wensum)
catchment (Fig. 2c) and the Wylye (Avon) catchment (Fig. 2e), there was also
a more pronounced seasonal response, particularly in the Wylye where a large
groundwater component could be observed in the winter periods. This indicates
the importance of both high-frequency data and a long-term record, to capture
both fast and slower dynamics adequately. The errors resulting from sampling
well below the catchment dynamics have been well documented elsewhere (e.g.
Johnes, 2007; Jones et al., 2012; Lloyd et al., 2016b; Moatar et al., 2013).
TP concentrations in all three study catchments revealed peaks that
corresponded with runoff, with maximum values of 1.0, 0.9 and
1.5 mg L<inline-formula><mml:math id="M83" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> in the Newby Beck, Blackwater and Wylye catchments,
respectively. Newby Beck showed a very low background concentration of TP at
low flow (minimum <inline-formula><mml:math id="M84" display="inline"><mml:mo>&lt;</mml:mo></mml:math></inline-formula> 0.01 mg L<inline-formula><mml:math id="M85" display="inline"><mml:mrow><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula>, compared to
0.05–0.1 mg L<inline-formula><mml:math id="M86" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> in the Blackwater, and around 0.12 mg L<inline-formula><mml:math id="M87" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> in
the Wylye. The relationships between streamflow and TP concentration are
shown in Figs. S1–S3 in the Supplement, and the relationships between
streamflow and TP load are shown in Figs. S4–S6. The presence of a
measurable, background, non-rainfall-dependent concentration suggests an
additional source of phosphorus to the recently applied agricultural sources.
Such non-rainfall-dependent sources include legacy stores of agricultural P
in the soil, both large and smaller point source discharges, such as sewage
treatment works and domestic septic tanks (Zhang et al., 2014), and
groundwater, specifically contributions from mineral sources in the Upper
Greensand geology of the Hampshire Avon (Allen et al., 2014).</p>

<?xmltex \floatpos{t}?><table-wrap id="Ch1.T1" specific-use="star"><caption><p id="d1e2032">Observed rainfall, discharge, total phosphorus (TP) concentration
and load for the period 1 October 2012–30 September 2013, for the three
catchments.</p></caption><oasis:table frame="topbot"><oasis:tgroup cols="9">
     <oasis:colspec colnum="1" colname="col1" align="left"/>
     <oasis:colspec colnum="2" colname="col2" align="right"/>
     <oasis:colspec colnum="3" colname="col3" align="right"/>
     <oasis:colspec colnum="4" colname="col4" align="right"/>
     <oasis:colspec colnum="5" colname="col5" align="right"/>
     <oasis:colspec colnum="6" colname="col6" align="right"/>
     <oasis:colspec colnum="7" colname="col7" align="right"/>
     <oasis:colspec colnum="8" colname="col8" align="right"/>
     <oasis:colspec colnum="9" colname="col9" align="right"/>
     <oasis:thead>
       <oasis:row>  
         <oasis:entry colname="col1">Catchment</oasis:entry>  
         <oasis:entry colname="col2">Total</oasis:entry>  
         <oasis:entry colname="col3">Total</oasis:entry>  
         <oasis:entry colname="col4">Rainfall <inline-formula><mml:math id="M88" display="inline"><mml:mo>/</mml:mo></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col5">Discharge</oasis:entry>  
         <oasis:entry colname="col6">Mean annual</oasis:entry>  
         <oasis:entry colname="col7">Mean annual</oasis:entry>  
         <oasis:entry colname="col8">Total annual</oasis:entry>  
         <oasis:entry colname="col9">TP load</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1"/>  
         <oasis:entry colname="col2">rainfall</oasis:entry>  
         <oasis:entry colname="col3">runoff</oasis:entry>  
         <oasis:entry colname="col4">runoff</oasis:entry>  
         <oasis:entry colname="col5">data missing</oasis:entry>  
         <oasis:entry colname="col6">discharge</oasis:entry>  
         <oasis:entry colname="col7">TP conc.</oasis:entry>  
         <oasis:entry colname="col8">TP load</oasis:entry>  
         <oasis:entry colname="col9">data missing</oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1"/>  
         <oasis:entry colname="col2">(mm)</oasis:entry>  
         <oasis:entry colname="col3">(mm)</oasis:entry>  
         <oasis:entry colname="col4">ratio</oasis:entry>  
         <oasis:entry colname="col5">(%)</oasis:entry>  
         <oasis:entry colname="col6">(m<inline-formula><mml:math id="M89" display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msup></mml:math></inline-formula> s<inline-formula><mml:math id="M90" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula>)</oasis:entry>  
         <oasis:entry colname="col7">(mg L<inline-formula><mml:math id="M91" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula>)</oasis:entry>  
         <oasis:entry colname="col8">(kg)</oasis:entry>  
         <oasis:entry colname="col9">(%)</oasis:entry>
       </oasis:row>
     </oasis:thead>
     <oasis:tbody>
       <oasis:row>  
         <oasis:entry colname="col1">Newby Beck <?xmltex \hack{\hfill\break}?></oasis:entry>  
         <oasis:entry colname="col2">1186</oasis:entry>  
         <oasis:entry colname="col3">776</oasis:entry>  
         <oasis:entry colname="col4">0.65</oasis:entry>  
         <oasis:entry colname="col5">0.0</oasis:entry>  
         <oasis:entry colname="col6">0.31</oasis:entry>  
         <oasis:entry colname="col7">0.080</oasis:entry>  
         <oasis:entry colname="col8">1577</oasis:entry>  
         <oasis:entry colname="col9">19.7</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Eden, Cumbria</oasis:entry>  
         <oasis:entry colname="col2"/>  
         <oasis:entry colname="col3"/>  
         <oasis:entry colname="col4"/>  
         <oasis:entry colname="col5"/>  
         <oasis:entry colname="col6"/>  
         <oasis:entry colname="col7"/>  
         <oasis:entry colname="col8"/>  
         <oasis:entry colname="col9"/>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Blackwater,</oasis:entry>  
         <oasis:entry colname="col2">634</oasis:entry>  
         <oasis:entry colname="col3">195</oasis:entry>  
         <oasis:entry colname="col4">0.31</oasis:entry>  
         <oasis:entry colname="col5">13.8</oasis:entry>  
         <oasis:entry colname="col6">0.14</oasis:entry>  
         <oasis:entry colname="col7">0.092</oasis:entry>  
         <oasis:entry colname="col8">277</oasis:entry>  
         <oasis:entry colname="col9">30.6</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Wensum, Norfolk</oasis:entry>  
         <oasis:entry colname="col2"/>  
         <oasis:entry colname="col3"/>  
         <oasis:entry colname="col4"/>  
         <oasis:entry colname="col5"/>  
         <oasis:entry colname="col6"/>  
         <oasis:entry colname="col7"/>  
         <oasis:entry colname="col8"/>  
         <oasis:entry colname="col9"/>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Wylye, Avon,</oasis:entry>  
         <oasis:entry colname="col2">850</oasis:entry>  
         <oasis:entry colname="col3">273</oasis:entry>  
         <oasis:entry colname="col4">0.32</oasis:entry>  
         <oasis:entry colname="col5">0.3</oasis:entry>  
         <oasis:entry colname="col6">0.44</oasis:entry>  
         <oasis:entry colname="col7">0.149</oasis:entry>  
         <oasis:entry colname="col8">1705</oasis:entry>  
         <oasis:entry colname="col9">27.4</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Hampshire</oasis:entry>  
         <oasis:entry colname="col2"/>  
         <oasis:entry colname="col3"/>  
         <oasis:entry colname="col4"/>  
         <oasis:entry colname="col5"/>  
         <oasis:entry colname="col6"/>  
         <oasis:entry colname="col7"/>  
         <oasis:entry colname="col8"/>  
         <oasis:entry colname="col9"/>
       </oasis:row>
     </oasis:tbody>
   </oasis:tgroup></oasis:table></table-wrap>

<?xmltex \floatpos{t}?><table-wrap id="Ch1.T2" specific-use="star"><caption><p id="d1e2363">Rainfall–runoff and rainfall-total phosphorus load (TP) models
identified for Newby Beck during the period 7 November–4 December 2015, with
estimations of discharge and TP load during Storm Desmond
(5–6 December 2015). CT linear <inline-formula><mml:math id="M92" display="inline"><mml:mo>=</mml:mo></mml:math></inline-formula> continuous-time transfer function with
linear rainfall input; <inline-formula><mml:math id="M93" display="inline"><mml:mrow><mml:msubsup><mml:mi>R</mml:mi><mml:mi>t</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msubsup><mml:mo>=</mml:mo></mml:mrow></mml:math></inline-formula> model efficiency measure (Eq. 7);
TC<inline-formula><mml:math id="M94" display="inline"><mml:mrow><mml:msub><mml:mi/><mml:mtext>fast/slow</mml:mtext></mml:msub><mml:mo>=</mml:mo></mml:mrow></mml:math></inline-formula> time constant for the fast/slow pathway;
%<inline-formula><mml:math id="M95" display="inline"><mml:mrow><mml:msub><mml:mi/><mml:mtext>fast/slow</mml:mtext></mml:msub><mml:mo>=</mml:mo></mml:mrow></mml:math></inline-formula> percentage of output taking the fast/slow pathway;
Model bias <inline-formula><mml:math id="M96" display="inline"><mml:mrow><mml:mo>=</mml:mo><mml:mn mathvariant="normal">100</mml:mn><mml:mo>×</mml:mo><mml:mi mathvariant="normal">Σ</mml:mi><mml:mfenced open="(" close=")"><mml:msubsup><mml:mi>y</mml:mi><mml:mi>i</mml:mi><mml:mtext>model</mml:mtext></mml:msubsup><mml:mo>-</mml:mo><mml:msubsup><mml:mi>y</mml:mi><mml:mi>i</mml:mi><mml:mtext>obs</mml:mtext></mml:msubsup></mml:mfenced><mml:mo>/</mml:mo><mml:mi mathvariant="normal">Σ</mml:mi><mml:mfenced close=")" open="("><mml:msubsup><mml:mi>y</mml:mi><mml:mi>i</mml:mi><mml:mtext>obs</mml:mtext></mml:msubsup></mml:mfenced></mml:mrow></mml:math></inline-formula>.</p></caption><oasis:table frame="topbot"><?xmltex \begin{scaleboxenv}{.95}[.95]?><oasis:tgroup cols="11">
     <oasis:colspec colnum="1" colname="col1" align="left"/>
     <oasis:colspec colnum="2" colname="col2" align="left"/>
     <oasis:colspec colnum="3" colname="col3" align="right"/>
     <oasis:colspec colnum="4" colname="col4" align="right"/>
     <oasis:colspec colnum="5" colname="col5" align="right"/>
     <oasis:colspec colnum="6" colname="col6" align="right"/>
     <oasis:colspec colnum="7" colname="col7" align="right"/>
     <oasis:colspec colnum="8" colname="col8" align="right"/>
     <oasis:colspec colnum="9" colname="col9" align="right"/>
     <oasis:colspec colnum="10" colname="col10" align="right"/>
     <oasis:colspec colnum="11" colname="col11" align="right"/>
     <oasis:thead>
       <oasis:row>  
         <oasis:entry colname="col1">Model</oasis:entry>  
         <oasis:entry colname="col2">Model</oasis:entry>  
         <oasis:entry colname="col3"><inline-formula><mml:math id="M97" display="inline"><mml:mrow><mml:msubsup><mml:mi>R</mml:mi><mml:mi>t</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msubsup></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col4">TC<inline-formula><mml:math id="M98" display="inline"><mml:msub><mml:mi/><mml:mi mathvariant="normal">fast</mml:mi></mml:msub></mml:math></inline-formula> (h)</oasis:entry>  
         <oasis:entry colname="col5">TC<inline-formula><mml:math id="M99" display="inline"><mml:msub><mml:mi/><mml:mi mathvariant="normal">slow</mml:mi></mml:msub></mml:math></inline-formula> (h)</oasis:entry>  
         <oasis:entry colname="col6">%<inline-formula><mml:math id="M100" display="inline"><mml:msub><mml:mi/><mml:mi mathvariant="normal">fast</mml:mi></mml:msub></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col7">%<inline-formula><mml:math id="M101" display="inline"><mml:msub><mml:mi/><mml:mi mathvariant="normal">slow</mml:mi></mml:msub></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col8">Model</oasis:entry>  
         <oasis:entry colname="col9"><inline-formula><mml:math id="M102" display="inline"><mml:mi mathvariant="normal">Σ</mml:mi></mml:math></inline-formula> obs during</oasis:entry>  
         <oasis:entry colname="col10"><inline-formula><mml:math id="M103" display="inline"><mml:mi mathvariant="normal">Σ</mml:mi></mml:math></inline-formula> model during</oasis:entry>  
         <oasis:entry colname="col11">Diff.</oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1"/>  
         <oasis:entry colname="col2">structure</oasis:entry>  
         <oasis:entry colname="col3"/>  
         <oasis:entry colname="col4"/>  
         <oasis:entry colname="col5"/>  
         <oasis:entry colname="col6"/>  
         <oasis:entry colname="col7"/>  
         <oasis:entry colname="col8">bias</oasis:entry>  
         <oasis:entry colname="col9">Desmond</oasis:entry>  
         <oasis:entry colname="col10">Desmond</oasis:entry>  
         <oasis:entry colname="col11"/>
       </oasis:row>
     </oasis:thead>
     <oasis:tbody>
       <oasis:row>  
         <oasis:entry colname="col1">Rainfall–runoff</oasis:entry>  
         <oasis:entry colname="col2">CT linear</oasis:entry>  
         <oasis:entry colname="col3">0.91</oasis:entry>  
         <oasis:entry colname="col4">3.6 <inline-formula><mml:math id="M104" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.4</oasis:entry>  
         <oasis:entry colname="col5">33 <inline-formula><mml:math id="M105" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 8</oasis:entry>  
         <oasis:entry colname="col6">55 <inline-formula><mml:math id="M106" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 5</oasis:entry>  
         <oasis:entry colname="col7">45 <inline-formula><mml:math id="M107" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 5</oasis:entry>  
         <oasis:entry colname="col8">0.7 %</oasis:entry>  
         <oasis:entry colname="col9">86.6 mm</oasis:entry>  
         <oasis:entry colname="col10">106.5 mm</oasis:entry>  
         <oasis:entry colname="col11">23 %</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1"/>  
         <oasis:entry colname="col2">[2, 2, 1]</oasis:entry>  
         <oasis:entry colname="col3"/>  
         <oasis:entry colname="col4"/>  
         <oasis:entry colname="col5"/>  
         <oasis:entry colname="col6"/>  
         <oasis:entry colname="col7"/>  
         <oasis:entry colname="col8"/>  
         <oasis:entry colname="col9"/>  
         <oasis:entry colname="col10"/>  
         <oasis:entry colname="col11"/>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Rainfall–TP load</oasis:entry>  
         <oasis:entry colname="col2">CT linear</oasis:entry>  
         <oasis:entry colname="col3">0.74</oasis:entry>  
         <oasis:entry colname="col4">2.7 <inline-formula><mml:math id="M108" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.3</oasis:entry>  
         <oasis:entry colname="col5"/>  
         <oasis:entry colname="col6">100</oasis:entry>  
         <oasis:entry colname="col7"/>  
         <oasis:entry colname="col8">13 %</oasis:entry>  
         <oasis:entry colname="col9">196.5 kg</oasis:entry>  
         <oasis:entry colname="col10">273.6 kg</oasis:entry>  
         <oasis:entry colname="col11">39 %</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1"/>  
         <oasis:entry colname="col2">[1, 1, 1]</oasis:entry>  
         <oasis:entry colname="col3"/>  
         <oasis:entry colname="col4"/>  
         <oasis:entry colname="col5"/>  
         <oasis:entry colname="col6"/>  
         <oasis:entry colname="col7"/>  
         <oasis:entry colname="col8"/>  
         <oasis:entry colname="col9"/>  
         <oasis:entry colname="col10"/>  
         <oasis:entry colname="col11"/>
       </oasis:row>
     </oasis:tbody>
   </oasis:tgroup><?xmltex \end{scaleboxenv}?></oasis:table></table-wrap>

      <p id="d1e2776">A summary of the observed total rainfall, runoff, mean concentration and TP
load is given in Table 1 for the period 1 October 2012–30 September 2013
(the hydrological year with the most complete dataset). The lowest mean
annual TP concentrations were observed in the Newby Beck catchment, but
combined with the highest runoff this resulted in a high total annual TP
load. Conversely, although mean annual TP concentration in the Blackwater was
also higher than in Newby Beck, when combined with the lowest runoff, this
resulted in the lowest total annual TP load. The rainfall–runoff ratio for
Newby Beck (0.65) was much higher than for the Blackwater (0.31) or the Wylye
(0.32), indicating a larger capacity for storage in the latter two
catchments. Despite similarity in the rainfall–runoff ratio, total runoff in
the Wylye was higher than the Blackwater because of the higher total
rainfall.</p>
      <p id="d1e2779">Detailed analysis of the high-frequency data is not included here as it has
already been published by several authors (e.g. Ockenden et al., 2016; Outram
et al., 2014, including hysteresis analysis; Perks et al., 2015).
Investigation of the relationships between TP concentration and streamflow
indicated that, for all three catchments, the TP concentration was out of
phase with the streamflow; distinct hysteresis loops (Figs. S1–S3), also
observed by Outram et al. (2014), showed different TP concentrations on the
rising stage of a storm hydrograph compared to the same stage on the falling
hydrograph. This indicates that antecedent conditions and the storage state
of the catchment are important in determining the response. In order to
capture the effects of storage, dynamic models are required.</p>
</sec>
<sec id="Ch1.S3.SS2">
  <title>Identification of linear transfer function models for short storm
sequences</title>
      <p id="d1e2788">For short storm sequences up to about a month, when antecedent flows for
events were rather similar, linear models were identified for the Newby Beck
catchment. These were useful for infilling missing discharge or TP load
data, or for highlighting and estimating uncertainties in discharge and TP
load when extrapolation of the stage–discharge relationship was
inappropriate. The model is only reliable for the conditions covered during
the calibration period, but it may still be useful when there are known
problems with a stage–discharge relationship (such as during extreme
events). Indeed, the stage to discharge relationship is the weakest point of
all the catchment models relying on stage measurements. Whilst it was still
possible to identify linear models for short periods for the Blackwater and
Wylye catchments, the parameter uncertainty for these models was large; the
parameters cannot be well constrained when the (slow) time constant was of
similar order to the period of identification. For this reason, linear
models for short periods for the Blackwater and the Wylye were not
considered useful.<?xmltex \hack{\newpage}?></p>
      <p id="d1e2792">Table 2 shows results from rainfall–runoff and rainfall–TP load models
identified for Newby Beck for a series of contiguous storms in November 2015,
immediately preceding Storm Desmond (5–6 December 2015), which caused
catastrophic flooding in Cumbria and Lancashire, UK. During Storm Desmond,
Honister Pass in Cumbria received the highest 24 h rainfall on record
(341 mm) and Thirlmere received the highest 48 h rainfall on record
(405 mm). The storm was remarkable for the duration of sustained rainfall.
At Newby Beck, 156 mm of rainfall was recorded in 36 h. Although the
monitoring equipment was recording during Storm Desmond, the peak flows
during the storm were out of bank for around 31 h (compared to less than
3.5 h during more typical storms), with anecdotal evidence that the gauging
point was significantly bypassed, so these out of bank flows were highly
uncertain. This measurement uncertainty is shown by the shaded bands in
Fig. 3 (discharge model) and Fig. 4 (TP load model), which span the observed
(calculated from stage) discharge and TP load. This is more visible in the
zoomed-in periods for discharge (Fig. 3b) and TP load (Fig. 4b).
Concentrations were assumed to be reasonably accurate, but discharge was likely underestimated, therefore TP loads were consequently underestimated too. Storm Desmond was not
included in the model identification period. Using the models from the
November period to simulate flows (Fig. 3) and TP load during Storm Desmond
(Fig. 4) suggests that both discharge and TP load were underestimated. Time
series and histograms of the residuals are given in Fig. S7 for discharge and
Fig. S8 for TP load. The zoomed-in period for the TP load model (Fig. 4b)
suggests that whilst the transfer function model got the timing of the load
peak and the decay approximately right, the model generally started to
respond before the observed load responded.</p>
      <p id="d1e2795">Although there are uncertainties associated with whether it is valid to
extend the models identified above to an extreme event such as Storm
Desmond, we believe that this highlights the possible underestimation in
discharge and TP load during Storm Desmond and that the models in Table 2
might provide more realistic estimations of the true values.</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F3"><caption><p id="d1e2800">Observed and modelled discharge per unit area <bold>(a)</bold> and
zoomed section of the same <bold>(b)</bold> in Newby Beck, Eden, during November
2015, with the same model used to estimate discharge during Storm Desmond
on 5–6 December 2015. The blue band indicates the 95 % uncertainty bounds on
the measurement data and the grey band indicates the 95 % confidence
limits on the parameter uncertainty. Total model predictive uncertainty
(including the residual uncertainty) is larger than parametric uncertainty
and would enclose the observations most of the time.</p></caption>
          <?xmltex \igopts{width=236.157874pt}?><graphic xlink:href="https://hess.copernicus.org/articles/21/6425/2017/hess-21-6425-2017-f03.png"/>

        </fig>

      <?xmltex \floatpos{t}?><fig id="Ch1.F4"><caption><p id="d1e2818">Observed and modelled total phosphorus (TP) load <bold>(a)</bold> and
zoomed section of the same <bold>(b)</bold> in Newby Beck, Eden, during November
2015, with the same model used to estimate TP load during Storm Desmond
5–6 December 2015. The blue band indicates the 95 % uncertainty bounds on
the measurement data. The grey band indicates the 95 % confidence limits
on the parameter uncertainty. Total model predictive uncertainty (including
the residual uncertainty) is larger than parametric uncertainty and would
enclose the observations most of the time.</p></caption>
          <?xmltex \igopts{width=236.157874pt}?><graphic xlink:href="https://hess.copernicus.org/articles/21/6425/2017/hess-21-6425-2017-f04.png"/>

        </fig>

<?xmltex \floatpos{p}?><table-wrap id="Ch1.T3" specific-use="star" orientation="landscape"><caption><p id="d1e2836">Structure, response characteristics and model fit statistics of
rainfall–runoff and rainfall–TP load models for each catchment. Models were
calibrated on all or part of hydrological years 2012 and 2013 and validated
on all or part of hydrological year 2014. <inline-formula><mml:math id="M109" display="inline"><mml:mrow><mml:mi mathvariant="italic">β</mml:mi><mml:mo>=</mml:mo></mml:mrow></mml:math></inline-formula> exponent in the power
law used for rainfall–runoff non-linearity (Eq. 6); <inline-formula><mml:math id="M110" display="inline"><mml:mrow><mml:msubsup><mml:mi>R</mml:mi><mml:mi>t</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msubsup><mml:mo>=</mml:mo></mml:mrow></mml:math></inline-formula> model
efficiency measure (Eq. 7); <inline-formula><mml:math id="M111" display="inline"><mml:mrow><mml:msub><mml:mi>Q</mml:mi><mml:mtext>obs</mml:mtext></mml:msub><mml:mo>=</mml:mo></mml:mrow></mml:math></inline-formula> observed discharge;
<inline-formula><mml:math id="M112" display="inline"><mml:mrow><mml:msub><mml:mi>Q</mml:mi><mml:mtext>sim</mml:mtext></mml:msub><mml:mo>=</mml:mo></mml:mrow></mml:math></inline-formula> simulated discharge, using only the rainfall input; model
bias <inline-formula><mml:math id="M113" display="inline"><mml:mrow><mml:mo>=</mml:mo><mml:mn mathvariant="normal">100</mml:mn><mml:mo>×</mml:mo><mml:mi mathvariant="normal">Σ</mml:mi><mml:mfenced open="(" close=")"><mml:msubsup><mml:mi>y</mml:mi><mml:mi>i</mml:mi><mml:mtext>model</mml:mtext></mml:msubsup><mml:mo>-</mml:mo><mml:msubsup><mml:mi>y</mml:mi><mml:mi>i</mml:mi><mml:mtext>obs</mml:mtext></mml:msubsup></mml:mfenced><mml:mo>/</mml:mo><mml:mi mathvariant="normal">Σ</mml:mi><mml:mfenced close=")" open="("><mml:msubsup><mml:mi>y</mml:mi><mml:mi>i</mml:mi><mml:mtext>obs</mml:mtext></mml:msubsup></mml:mfenced></mml:mrow></mml:math></inline-formula>; TC<inline-formula><mml:math id="M114" display="inline"><mml:mrow><mml:msub><mml:mi/><mml:mtext>fast/slow</mml:mtext></mml:msub><mml:mo>=</mml:mo></mml:mrow></mml:math></inline-formula> time constant
for the fast/slow pathway; %<inline-formula><mml:math id="M115" display="inline"><mml:mrow><mml:msub><mml:mi/><mml:mtext>fast/slow</mml:mtext></mml:msub><mml:mo>=</mml:mo></mml:mrow></mml:math></inline-formula> percentage of output
taking the fast/slow pathway.</p></caption><oasis:table frame="topbot"><?xmltex \begin{scaleboxenv}{.82}[.82]?><oasis:tgroup cols="15">
     <oasis:colspec colnum="1" colname="col1" align="left"/>
     <oasis:colspec colnum="2" colname="col2" align="justify" colwidth="42.679134pt"/>
     <oasis:colspec colnum="3" colname="col3" align="left"/>
     <oasis:colspec colnum="4" colname="col4" align="left"/>
     <oasis:colspec colnum="5" colname="col5" align="right"/>
     <oasis:colspec colnum="6" colname="col6" align="right"/>
     <oasis:colspec colnum="7" colname="col7" align="right"/>
     <oasis:colspec colnum="8" colname="col8" align="right"/>
     <oasis:colspec colnum="9" colname="col9" align="right"/>
     <oasis:colspec colnum="10" colname="col10" align="right"/>
     <oasis:colspec colnum="11" colname="col11" align="right"/>
     <oasis:colspec colnum="12" colname="col12" align="right"/>
     <oasis:colspec colnum="13" colname="col13" align="justify" colwidth="42.679134pt"/>
     <oasis:colspec colnum="14" colname="col14" align="right"/>
     <oasis:colspec colnum="15" colname="col15" align="right"/>
     <oasis:thead>
       <oasis:row>  
         <oasis:entry colname="col1">Location</oasis:entry>  
         <oasis:entry colname="col2">Time</oasis:entry>  
         <oasis:entry colname="col3">Model</oasis:entry>  
         <oasis:entry colname="col4">Model</oasis:entry>  
         <oasis:entry colname="col5"><inline-formula><mml:math id="M122" display="inline"><mml:mi mathvariant="italic">β</mml:mi></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col6"><inline-formula><mml:math id="M123" display="inline"><mml:mrow><mml:msubsup><mml:mi>R</mml:mi><mml:mi>t</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msubsup></mml:mrow></mml:math></inline-formula> for calib</oasis:entry>  
         <oasis:entry colname="col7"><inline-formula><mml:math id="M124" display="inline"><mml:mrow><mml:msubsup><mml:mi>R</mml:mi><mml:mi>t</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msubsup></mml:mrow></mml:math></inline-formula> for calib</oasis:entry>  
         <oasis:entry colname="col8">Model bias</oasis:entry>  
         <oasis:entry colname="col9">TC<inline-formula><mml:math id="M125" display="inline"><mml:msub><mml:mi/><mml:mtext>fast</mml:mtext></mml:msub></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col10">TC<inline-formula><mml:math id="M126" display="inline"><mml:msub><mml:mi/><mml:mtext>slow</mml:mtext></mml:msub></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col11">%<inline-formula><mml:math id="M127" display="inline"><mml:msub><mml:mi/><mml:mtext>fast</mml:mtext></mml:msub></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col12">%<inline-formula><mml:math id="M128" display="inline"><mml:msub><mml:mi/><mml:mtext>slow</mml:mtext></mml:msub></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col13">Time</oasis:entry>  
         <oasis:entry colname="col14"><inline-formula><mml:math id="M129" display="inline"><mml:mrow><mml:msubsup><mml:mi>R</mml:mi><mml:mi>t</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msubsup></mml:mrow></mml:math></inline-formula> for valid</oasis:entry>  
         <oasis:entry colname="col15">Model bias, %</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1"/>  
         <oasis:entry colname="col2">period</oasis:entry>  
         <oasis:entry colname="col3"/>  
         <oasis:entry colname="col4">structure</oasis:entry>  
         <oasis:entry colname="col5"/>  
         <oasis:entry colname="col6">(using <inline-formula><mml:math id="M130" display="inline"><mml:mrow><mml:msub><mml:mi>Q</mml:mi><mml:mtext>obs</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula>)</oasis:entry>  
         <oasis:entry colname="col7">(using <inline-formula><mml:math id="M131" display="inline"><mml:mrow><mml:msub><mml:mi>Q</mml:mi><mml:mtext>sim</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula>)</oasis:entry>  
         <oasis:entry colname="col8">(calib) %</oasis:entry>  
         <oasis:entry colname="col9">(h)</oasis:entry>  
         <oasis:entry colname="col10">(h)</oasis:entry>  
         <oasis:entry colname="col11"/>  
         <oasis:entry colname="col12"/>  
         <oasis:entry colname="col13">period</oasis:entry>  
         <oasis:entry colname="col14">(using <inline-formula><mml:math id="M132" display="inline"><mml:mrow><mml:msub><mml:mi>Q</mml:mi><mml:mtext>sim</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula>)</oasis:entry>  
         <oasis:entry colname="col15">(valid)</oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1"/>  
         <oasis:entry colname="col2">(calib)</oasis:entry>  
         <oasis:entry colname="col3"/>  
         <oasis:entry colname="col4"/>  
         <oasis:entry colname="col5"/>  
         <oasis:entry colname="col6"/>  
         <oasis:entry colname="col7"/>  
         <oasis:entry colname="col8"/>  
         <oasis:entry colname="col9"/>  
         <oasis:entry colname="col10"/>  
         <oasis:entry colname="col11"/>  
         <oasis:entry colname="col12"/>  
         <oasis:entry colname="col13">(valid)</oasis:entry>  
         <oasis:entry colname="col14"/>  
         <oasis:entry colname="col15"/>
       </oasis:row>
     </oasis:thead>
     <oasis:tbody>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1">Newby</oasis:entry>  
         <oasis:entry colname="col2">1 Oct 11 <?xmltex \hack{\hfill\break}?>to <?xmltex \hack{\hfill\break}?>30 Sep 13</oasis:entry>  
         <oasis:entry colname="col3">R-Re-Q</oasis:entry>  
         <oasis:entry colname="col4">CT <?xmltex \hack{\hfill\break}?>[2, 2, 1]</oasis:entry>  
         <oasis:entry colname="col5">0.37</oasis:entry>  
         <oasis:entry colname="col6">0.86</oasis:entry>  
         <oasis:entry colname="col7">0.71</oasis:entry>  
         <oasis:entry colname="col8"><inline-formula><mml:math id="M133" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">9.7</mml:mn></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col9">2.9 <inline-formula><mml:math id="M134" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.1</oasis:entry>  
         <oasis:entry colname="col10">147 <inline-formula><mml:math id="M135" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 5</oasis:entry>  
         <oasis:entry colname="col11">43 <inline-formula><mml:math id="M136" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.5</oasis:entry>  
         <oasis:entry colname="col12">57 <inline-formula><mml:math id="M137" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.5</oasis:entry>  
         <oasis:entry colname="col13">1 Oct 13 <?xmltex \hack{\hfill\break}?>to <?xmltex \hack{\hfill\break}?>30 Sep 14</oasis:entry>  
         <oasis:entry colname="col14">0.78</oasis:entry>  
         <oasis:entry colname="col15"><inline-formula><mml:math id="M138" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">14.3</mml:mn></mml:mrow></mml:math></inline-formula></oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1">Newby</oasis:entry>  
         <oasis:entry colname="col2">1 Oct 11 <?xmltex \hack{\hfill\break}?>to <?xmltex \hack{\hfill\break}?>30 Sep 13</oasis:entry>  
         <oasis:entry colname="col3">R-Re – TP load<inline-formula><mml:math id="M139" display="inline"><mml:msup><mml:mi/><mml:mo>*</mml:mo></mml:msup></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col4">CT <?xmltex \hack{\hfill\break}?>[1, 1, 1]</oasis:entry>  
         <oasis:entry colname="col5"/>  
         <oasis:entry colname="col6"/>  
         <oasis:entry colname="col7">0.69</oasis:entry>  
         <oasis:entry colname="col8">2.3</oasis:entry>  
         <oasis:entry colname="col9">1.6 <inline-formula><mml:math id="M140" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.04</oasis:entry>  
         <oasis:entry colname="col10"/>  
         <oasis:entry colname="col11">100</oasis:entry>  
         <oasis:entry colname="col12"/>  
         <oasis:entry colname="col13">1 Oct 13 <?xmltex \hack{\hfill\break}?>to <?xmltex \hack{\hfill\break}?>30 Sep 14</oasis:entry>  
         <oasis:entry colname="col14">0.62</oasis:entry>  
         <oasis:entry colname="col15">5.1</oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1">Blackwater</oasis:entry>  
         <oasis:entry colname="col2">1 Dec 11 <?xmltex \hack{\hfill\break}?>to <?xmltex \hack{\hfill\break}?>31 Aug 13</oasis:entry>  
         <oasis:entry colname="col3">R-Re-Q</oasis:entry>  
         <oasis:entry colname="col4">DT <?xmltex \hack{\hfill\break}?>[2, 2, 6]</oasis:entry>  
         <oasis:entry colname="col5">0.65</oasis:entry>  
         <oasis:entry colname="col6">0.82</oasis:entry>  
         <oasis:entry colname="col7">0.37</oasis:entry>  
         <oasis:entry colname="col8"><inline-formula><mml:math id="M141" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1.5</mml:mn></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col9">14.8 <inline-formula><mml:math id="M142" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.5</oasis:entry>  
         <oasis:entry colname="col10">441 <inline-formula><mml:math id="M143" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 13</oasis:entry>  
         <oasis:entry colname="col11">25 <inline-formula><mml:math id="M144" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.6</oasis:entry>  
         <oasis:entry colname="col12">75 <inline-formula><mml:math id="M145" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.6</oasis:entry>  
         <oasis:entry colname="col13">1 Oct 13 <?xmltex \hack{\hfill\break}?>to <?xmltex \hack{\hfill\break}?>30 Sep 14</oasis:entry>  
         <oasis:entry colname="col14">0.32</oasis:entry>  
         <oasis:entry colname="col15"><inline-formula><mml:math id="M146" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">9.4</mml:mn></mml:mrow></mml:math></inline-formula></oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1">Blackwater</oasis:entry>  
         <oasis:entry colname="col2">26 Oct 12<?xmltex \hack{\hfill\break}?>to <?xmltex \hack{\hfill\break}?>28 Jul 13</oasis:entry>  
         <oasis:entry colname="col3">R – TP load</oasis:entry>  
         <oasis:entry colname="col4">CT <?xmltex \hack{\hfill\break}?>[2, 2, 4]</oasis:entry>  
         <oasis:entry colname="col5"/>  
         <oasis:entry colname="col6"/>  
         <oasis:entry colname="col7">0.67</oasis:entry>  
         <oasis:entry colname="col8">5.4</oasis:entry>  
         <oasis:entry colname="col9">12.5 <inline-formula><mml:math id="M147" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.6</oasis:entry>  
         <oasis:entry colname="col10">376 <inline-formula><mml:math id="M148" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 44</oasis:entry>  
         <oasis:entry colname="col11">54 <inline-formula><mml:math id="M149" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 2</oasis:entry>  
         <oasis:entry colname="col12">46 <inline-formula><mml:math id="M150" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 2</oasis:entry>  
         <oasis:entry colname="col13">1 Oct 13 <?xmltex \hack{\hfill\break}?>to <?xmltex \hack{\hfill\break}?>31 Mar 14</oasis:entry>  
         <oasis:entry colname="col14">0.31</oasis:entry>  
         <oasis:entry colname="col15">38.2</oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1">Wylye</oasis:entry>  
         <oasis:entry colname="col2">1 Oct 12 <?xmltex \hack{\hfill\break}?>to <?xmltex \hack{\hfill\break}?>30 Sep 13</oasis:entry>  
         <oasis:entry colname="col3">R-Re-Q</oasis:entry>  
         <oasis:entry colname="col4">DT <?xmltex \hack{\hfill\break}?>[2, 2, 6]</oasis:entry>  
         <oasis:entry colname="col5">0.59</oasis:entry>  
         <oasis:entry colname="col6">0.94</oasis:entry>  
         <oasis:entry colname="col7">0.87</oasis:entry>  
         <oasis:entry colname="col8">3.0</oasis:entry>  
         <oasis:entry colname="col9">4.1 <inline-formula><mml:math id="M151" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.2</oasis:entry>  
         <oasis:entry colname="col10">395 <inline-formula><mml:math id="M152" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 6</oasis:entry>  
         <oasis:entry colname="col11">8 <inline-formula><mml:math id="M153" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.2</oasis:entry>  
         <oasis:entry colname="col12">92 <inline-formula><mml:math id="M154" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.2</oasis:entry>  
         <oasis:entry colname="col13">1 Dec 13 <?xmltex \hack{\hfill\break}?>to <?xmltex \hack{\hfill\break}?>20 May 14</oasis:entry>  
         <oasis:entry colname="col14">0.79</oasis:entry>  
         <oasis:entry colname="col15">11.0</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Wylye</oasis:entry>  
         <oasis:entry colname="col2">1 Oct 12 <?xmltex \hack{\hfill\break}?>to <?xmltex \hack{\hfill\break}?>30 Sep 13</oasis:entry>  
         <oasis:entry colname="col3">R-Re – TP load<inline-formula><mml:math id="M155" display="inline"><mml:msup><mml:mi/><mml:mo>*</mml:mo></mml:msup></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col4">CT <?xmltex \hack{\hfill\break}?>[2, 2, 6]</oasis:entry>  
         <oasis:entry colname="col5"/>  
         <oasis:entry colname="col6"/>  
         <oasis:entry colname="col7">0.67</oasis:entry>  
         <oasis:entry colname="col8">5.5</oasis:entry>  
         <oasis:entry colname="col9">6.1 <inline-formula><mml:math id="M156" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.3</oasis:entry>  
         <oasis:entry colname="col10">570 <inline-formula><mml:math id="M157" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 54</oasis:entry>  
         <oasis:entry colname="col11">42 <inline-formula><mml:math id="M158" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 1</oasis:entry>  
         <oasis:entry colname="col12">58 <inline-formula><mml:math id="M159" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 1</oasis:entry>  
         <oasis:entry colname="col13">1 Dec 13 <?xmltex \hack{\hfill\break}?>to <?xmltex \hack{\hfill\break}?>31 Mar 14</oasis:entry>  
         <oasis:entry colname="col14">0.50</oasis:entry>  
         <oasis:entry colname="col15"><inline-formula><mml:math id="M160" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">19.7</mml:mn></mml:mrow></mml:math></inline-formula></oasis:entry>
       </oasis:row>
     </oasis:tbody>
   </oasis:tgroup><?xmltex \end{scaleboxenv}?></oasis:table><?xmltex \begin{scaleboxenv}{.82}[.82]?><table-wrap-foot><p id="d1e2958"><inline-formula><mml:math id="M116" display="inline"><mml:msup><mml:mi/><mml:mo>*</mml:mo></mml:msup></mml:math></inline-formula> The effective rainfall–TP load model is a two-stage model; it is assumed that the discharge
is unknown, so that the effective rainfall must be calculated one step at a
time, as <inline-formula><mml:math id="M117" display="inline"><mml:mrow><mml:msub><mml:mi>Q</mml:mi><mml:mtext>sim</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> is generated with the previously identified
parameters of the rainfall–discharge model. Hence <inline-formula><mml:math id="M118" display="inline"><mml:mrow><mml:msubsup><mml:mi>R</mml:mi><mml:mi>t</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msubsup></mml:mrow></mml:math></inline-formula> using
<inline-formula><mml:math id="M119" display="inline"><mml:mrow><mml:msub><mml:mi>Q</mml:mi><mml:mtext>obs</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> is a one-step ahead prediction, whereas <inline-formula><mml:math id="M120" display="inline"><mml:mrow><mml:msubsup><mml:mi>R</mml:mi><mml:mi>t</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msubsup></mml:mrow></mml:math></inline-formula> using
<inline-formula><mml:math id="M121" display="inline"><mml:mrow><mml:msub><mml:mi>Q</mml:mi><mml:mtext>sim</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> is a true simulation, only using the rainfall input.</p></table-wrap-foot><?xmltex \end{scaleboxenv}?></table-wrap>

</sec>
<sec id="Ch1.S3.SS3">
  <title>Identification of transfer function models on annual time-series
data</title>
      <p id="d1e3872">Longer-term models, based on 2 years of hourly data, were identified for
each catchment. Model fits (<inline-formula><mml:math id="M161" display="inline"><mml:mrow><mml:msubsup><mml:mi>R</mml:mi><mml:mi>t</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msubsup><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> for rainfall–runoff models for the
identification period (Table 3) were 0.71 for Newby Beck and 0.87 for Wylye,
but only 0.37 for the Blackwater. Model bias was less than <inline-formula><mml:math id="M162" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula>10 % for
all three catchments. The runoff models were all linear transfer function
models relating effective rainfall to discharge, where the exponent in the
non-linear relationship between rainfall and effective rainfall (Eq. 6) was
optimised at the same time as model parameter identification. The
non-linearity, which reflects the effect of the antecedent soil moisture
conditions in the catchments, was accounted for with the soil moisture
surrogate expressed as a power function of discharge (Beven, 2012) with
exponent <inline-formula><mml:math id="M163" display="inline"><mml:mi mathvariant="italic">β</mml:mi></mml:math></inline-formula> in Eq. (6), where a value of zero produces a linear
response to rainfall and a higher value leads to an increasingly non-linear
response. The <inline-formula><mml:math id="M164" display="inline"><mml:mi mathvariant="italic">β</mml:mi></mml:math></inline-formula> values identified for Newby Beck, Blackwater and Wylye
were 0.37, 0.65 and 0.59, respectively, indicating the most non-linear
response was in the Wensum (Blackwater) catchment, which also gave the lowest
model efficiency values. The best identified model for rainfall–runoff in
each catchment was a second-order model. In general, models higher than
second order gave little improvement in model fit but a large deterioration
in YIC, signifying over-parameterisation not warranted by the information in
the monitoring data, whereas first-order models often gave a reasonable fit
to the model peaks (and hence reasonable <inline-formula><mml:math id="M165" display="inline"><mml:mrow><mml:msubsup><mml:mi>R</mml:mi><mml:mi>t</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msubsup><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula>, but poor fit to
recession periods.</p>
      <p id="d1e3926">The dynamic response characteristics of time constant and percentage on each
flow pathway (for definitions see Table S4), determined after partial
fraction decomposition, can be compared between the study catchments for both
discrete and continuous-time models. The time constants are associated with
the dominant pathways and indicate how quickly each impulse response (of
water or TP mass) is depleted to 37 % (or fraction <inline-formula><mml:math id="M166" display="inline"><mml:mrow><mml:mn mathvariant="normal">1</mml:mn><mml:mo>/</mml:mo><mml:mi>e</mml:mi></mml:mrow></mml:math></inline-formula>) of the peak
exported. This is the standard definition of a time constant in a first-order
linear time-invariant dynamic process, e.g. <inline-formula><mml:math id="M167" display="inline"><mml:mrow><mml:mi>A</mml:mi><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo><mml:mo>=</mml:mo><mml:msub><mml:mi>A</mml:mi><mml:mn mathvariant="normal">0</mml:mn></mml:msub><mml:mi>exp⁡</mml:mi><mml:mo>(</mml:mo><mml:mo>-</mml:mo><mml:mi>t</mml:mi><mml:mo>/</mml:mo><mml:msub><mml:mi>T</mml:mi><mml:mtext>c</mml:mtext></mml:msub><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula>,
where <inline-formula><mml:math id="M168" display="inline"><mml:mrow><mml:msub><mml:mi>T</mml:mi><mml:mtext>c</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> is the time constant. In reality there will be a continuum
of runoff pathways with different time constants (Kirchner et al., 2000), but
the information in the data indicates that this continuum can be simplified
by representation as just two dominant pathways.</p>
      <p id="d1e3991">The marginal distributions of the time constants and proportion of flow or TP
load (Table 3) were determined from 1000 to 10 000 Monte Carlo realisations
using the covariance of the parameter estimates. The parameter uncertainties
estimated within the DBM methodology were small, even for the response
characteristics of the TP load models, which had higher uncertainty than
rainfall–runoff models; TP load models had coefficients of variation of less
than 3 % for fast time constants, less than 6 % for slow time
constants and less than 2 % for proportions on pathways. For the
rainfall–runoff models, the time constant for the fast pathway was
2.9 <inline-formula><mml:math id="M169" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.1 h for Newby Beck, with 43 <inline-formula><mml:math id="M170" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.5 % of the water
taking this pathway; in the Wylye, the time constant for the fast pathway was
4.1 <inline-formula><mml:math id="M171" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.2 h, but with only 8 <inline-formula><mml:math id="M172" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.2 % of the water taking
this route. This is consistent with the much higher baseflow index in the
Hampshire Avon (0.93) than the Eden (0.39) (Table S1), which is clearly
visible in the data (Fig. 1). For the Blackwater, 25 <inline-formula><mml:math id="M173" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.6 % of the
flow took the fast pathway, which is also consistent with the baseflow index
in the Wensum (0.8) being between the Eden and Hampshire Avon. The fast time
constant for the Blackwater catchment was much slower, at
14.8 <inline-formula><mml:math id="M174" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.25 h; this may be related to the average slope of the
catchment, which is much lower for the Blackwater catchment (less than
2 %) compared to 6–8 % for the Wylye and Newby Beck catchments. The
slow time constant for Newby Beck was 147 <inline-formula><mml:math id="M175" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 5 h, with
57 <inline-formula><mml:math id="M176" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.5 % of flow taking this pathway; this compared with
441 <inline-formula><mml:math id="M177" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 13 h (75 <inline-formula><mml:math id="M178" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.6 % of flow) for the Blackwater and
395 <inline-formula><mml:math id="M179" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 6 h (92 <inline-formula><mml:math id="M180" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.2 % of flow ) for the Wylye.</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F5"><caption><p id="d1e4082">First-order model between effective rainfall and total phosphorus
(TP) load at Newby Beck for the identification period
1 October 2011–30 September 2013. Continuous-time model with structure [1, 1,
1] (see Table 3); <inline-formula><mml:math id="M181" display="inline"><mml:mrow><mml:msubsup><mml:mi>R</mml:mi><mml:mi>t</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msubsup><mml:mo>=</mml:mo><mml:mn mathvariant="normal">0.69</mml:mn></mml:mrow></mml:math></inline-formula>. The light blue band indicates the
95 % uncertainty bounds on the measurement data. The grey band indicates
the 95 % confidence limits on the parameter uncertainty (on this scale,
only visible during periods where TP data are missing). See Fig. 6 for zoomed-in sections. Total model predictive uncertainty (including the residual
uncertainty) is larger than parametric uncertainty and would enclose the
observations most of the time.</p></caption>
          <?xmltex \igopts{width=236.157874pt}?><graphic xlink:href="https://hess.copernicus.org/articles/21/6425/2017/hess-21-6425-2017-f05.png"/>

        </fig>

</sec>
<sec id="Ch1.S3.SS4">
  <title>Interpretation of TP load dynamics alongside runoff dynamics</title>
      <p id="d1e4114">For the rainfall–TP load models, at Newby Beck the best identified model was
a first-order model relating the effective rainfall (from the runoff model,
i.e. calculated one step at a time using the simulated discharge,
<inline-formula><mml:math id="M182" display="inline"><mml:mrow><mml:msub><mml:mi>Q</mml:mi><mml:mtext>sim</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula>) to the TP load (Table 3, Fig. 5). Although it was possible to
identify a second-order model, this made virtually no difference to model
fit, <inline-formula><mml:math id="M183" display="inline"><mml:mrow><mml:msubsup><mml:mi>R</mml:mi><mml:mi>t</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msubsup></mml:mrow></mml:math></inline-formula>, whilst making YIC more negative
(signifying over-parameterisation), and decomposition of the model revealed
time constants for the two pathways that were both less than 8 h
(cf. 147 h for the slow pathway for
the rainfall–runoff model in Table 3). This indicates that in Newby Beck,
all the TP load is transported through a quick flow pathway. This is
consistent with most of the load being associated with P mobilised from
diffuse agricultural sources, which is transferred by surface runoff or
shallow sub-surface flow. This includes particulate P transported in surface
runoff or drain flow (Heathwaite et al., 2006), subsurface movement of fine
particles and colloids (Heathwaite et al., 2005), and displacement of fast
subsurface soluble P sources. Young (2010) recommended a minimum data
sampling rate of one-sixth of the time constant in order to avoid possible
temporal aliasing effects. Littlewood and Croke (2013) illustrated the
parameter inaccuracy and loss of data when observations were under-sampled
for discrete time transfer functions, with inaccuracy decreasing and
parameter estimates approaching stable values as the sampling interval
decreased from 24 h (daily sampling) down to hourly sampling. The time
constant for the first-order TP load model for Newby Beck was
1.6 <inline-formula><mml:math id="M184" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.04 h. In this study, daily data would not capture the true
dynamics of discharge and TP load, and that, ideally, for flashy catchments
such as Newby Beck, a sampling interval shorter than hourly would be even
more robust. However, for the other catchments in this study, the hourly data
frequency was sufficient. The time constant for the TP load model
(1.6 <inline-formula><mml:math id="M185" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.04 h) was even faster than the fast time constant for the
second-order (two pathway) rainfall–runoff model (2.9 <inline-formula><mml:math id="M186" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.1 h),
indicating that the TP mass impulse response was depleted at a faster rate
than the water response, i.e. that the store was diluted as the storms
progressed or that the sources must be readily connected and closer to the
stream, since TP depends on transport velocities and we would normally expect
velocities to be less than celerities under wet and surface runoff
conditions. Those source areas would also be the most readily exhausted, so
the effects would reinforce each other.</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F6"><caption><p id="d1e4164">First-order model between effective rainfall and total phosphorus
(TP) load at Newby Beck, expanded from Fig. 5, for storm events in May
2012 <bold>(a)</bold> and November 2012 <bold>(b)</bold> . Continuous-time model with
structure [1, 1, 1] (see Table 3); <inline-formula><mml:math id="M187" display="inline"><mml:mrow><mml:msubsup><mml:mi>R</mml:mi><mml:mi>t</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msubsup><mml:mo>=</mml:mo><mml:mn mathvariant="normal">0.69</mml:mn></mml:mrow></mml:math></inline-formula>. The light blue band
indicates the 95 % uncertainty bounds on the measurement data. The grey
band indicates the 95 % confidence limits on the parameter uncertainty
(on this scale, only visible during periods where TP data are missing). Total
model predictive uncertainty (including the residual uncertainty) is larger
than parametric uncertainty and would enclose the observations most of the
time.</p></caption>
          <?xmltex \igopts{width=236.157874pt}?><graphic xlink:href="https://hess.copernicus.org/articles/21/6425/2017/hess-21-6425-2017-f06.png"/>

        </fig>

      <p id="d1e4196"><?xmltex \hack{\newpage}?>Expanded sections of Fig. 5 are shown for storms in May 2012 (Fig. 6a) and
November 2012 (Fig 6b). Time series of residuals and residuals against
observed values are given for the discharge model in Fig. S9 and for the TP
load model in Fig. S10. Although Fig. 5 illustrates several storms where the
model underestimated the peak TP load, the model matched the shape and peak
of the May 2012 storm quite well. However, once again the model started to
respond to the rainfall before the observations showed a response. Figure 6b
shows an example of a storm in which the TP load was underestimated by the
model. The model parameter uncertainty was considerably smaller than the
measurement data uncertainty. The model did not always lie within the bands
indicated by the measurement data uncertainty, whereas the total model
prediction uncertainty (including the residual uncertainty) would span most
of the observations, indicating that the simple structure of the model does
not capture all the dynamics, and that there are other sources of uncertainty
(such as rainfall input) which are not quantified.</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F7"><caption><p id="d1e4203">Second-order model between effective rainfall and total phosphorus
(TP) load at Wylye for the identification period
1 October 2012–30 September 2013. Continuous-time model with structure [2,
2, 6] (see Table 3); <inline-formula><mml:math id="M188" display="inline"><mml:mrow><mml:msubsup><mml:mi>R</mml:mi><mml:mi>t</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msubsup><mml:mo>=</mml:mo><mml:mn mathvariant="normal">0.67</mml:mn></mml:mrow></mml:math></inline-formula>. The light blue band indicates the
95 % uncertainty bounds on the measurement data. The grey band indicates
the 95 % confidence limits on the parameter uncertainty (on this scale,
only visible during periods where TP data are missing). Total model
predictive uncertainty (including the residual uncertainty) is larger than
parametric uncertainty and would enclose the observations most of the time.
For zoomed-in periods, see Fig. 8.</p></caption>
          <?xmltex \igopts{width=236.157874pt}?><graphic xlink:href="https://hess.copernicus.org/articles/21/6425/2017/hess-21-6425-2017-f07.png"/>

        </fig>

      <p id="d1e4229">For the Wylye, the best identified TP load model was a second-order model
relating effective rainfall to TP load, with 42 <inline-formula><mml:math id="M189" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 1 % on a fast
pathway (TC <inline-formula><mml:math id="M190" display="inline"><mml:mo>=</mml:mo></mml:math></inline-formula> 6.1 <inline-formula><mml:math id="M191" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.3 h) and 58 <inline-formula><mml:math id="M192" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 1 % on a slower
pathway (570 <inline-formula><mml:math id="M193" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 54 h) (Table 3, Fig. 7). Compared to the runoff model,
this showed a much greater percentage of the TP load on faster pathways such
as surface runoff, shallow sub-surface flow or sub-surface drains.
Nevertheless, there was still a significant proportion travelling on a slower
pathway, which highlights the need for pollution mitigation efforts to
include measures that take into account sub-surface and groundwater flows and,
also, to recognise that surface runoff from farmland is not the only source
of nutrients and sediment (Allen et al., 2014; Evans, 2012). These models
cannot provide spatial information, but having identified that a slow pathway
is so important, measures which prevent pollutants getting to the slow
pathway in the first place, such as reductions at source, will be helpful.
This may require further specific measurements, such as testing P in soils or
identifying septic tanks in the catchment. With DBM models, this
interpretation is made a posteriori, after the data assimilation, and is based
on inferences from the objectively identified dominant modes of the system
response.</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F8"><caption><p id="d1e4269">Second-order model between effective rainfall and total phosphorus
(TP) load at Wylye for storm events in November 2012 <bold>(a)</bold> and
February 2013 <bold>(b)</bold>. Continuous-time model with structure [2, 2, 6]
(see Table 3); <inline-formula><mml:math id="M194" display="inline"><mml:mrow><mml:msubsup><mml:mi>R</mml:mi><mml:mi>t</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msubsup><mml:mo>=</mml:mo><mml:mn mathvariant="normal">0.67</mml:mn></mml:mrow></mml:math></inline-formula>. The light blue band indicates the 95 %
uncertainty bounds on the measurement data. The grey band indicates the
95 % confidence limits on the parameter uncertainty (on this scale, only
visible during periods where TP data are missing). Total model predictive
uncertainty (including the residual uncertainty) is larger than parametric
uncertainty and would enclose the observations most of the time.</p></caption>
          <?xmltex \igopts{width=236.157874pt}?><graphic xlink:href="https://hess.copernicus.org/articles/21/6425/2017/hess-21-6425-2017-f08.png"/>

        </fig>

      <p id="d1e4301">Figure 8 shows expanded sections of the Wylye TP load model, including a
large storm in which the load is underestimated (Fig. 8a) and two smaller
storms where the model overestimated the loads (Fig. 8b). For the Wylye
catchment, the measurement uncertainty was dominated by the uncertainty of
the data from the TP sensor, rather than the uncertainty in the discharge
(Lloyd et al., 2016b). However, some of the mismatch between model and
observations here might also be attributable to uncertainty in rainfall
input: in Fig. 8a there could be an underestimate in catchment rainfall not
captured by the rain gauges; conversely, in Fig. 8b the rain gauges may have
captured more than the catchment-average rainfall. Time series of residuals
and residuals against observed values are given for the Wylye discharge model
in Fig. S11 and for the TP load model in Fig. S12.</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F9"><caption><p id="d1e4306">Second-order model between rainfall and total phosphorus (TP) load
at Blackwater for the identification period 26 October 2012–28 July 2013.
Continuous-time model with structure [2, 2, 4] (see Table 3); <inline-formula><mml:math id="M195" display="inline"><mml:mrow><mml:msubsup><mml:mi>R</mml:mi><mml:mi>t</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msubsup><mml:mo>=</mml:mo><mml:mn mathvariant="normal">0.67</mml:mn></mml:mrow></mml:math></inline-formula>. The light blue band indicates the 95 % uncertainty bounds on the
measurement data. The grey band indicates the 95 % confidence limits on
the parameter uncertainty (on this scale, only visible during periods where
TP data are missing). Total model predictive uncertainty (including the
residual uncertainty) is larger than parametric uncertainty and would enclose
the observations most of the time. For zoomed-in periods, see Fig. 10.</p></caption>
          <?xmltex \igopts{width=236.157874pt}?><graphic xlink:href="https://hess.copernicus.org/articles/21/6425/2017/hess-21-6425-2017-f09.png"/>

        </fig>

      <p id="d1e4333">The TP load model used for the Blackwater was a linear model relating
rainfall directly to TP load. The second-order TP model gave fast and slow
time constants of 12.5 <inline-formula><mml:math id="M196" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.6 and 376 <inline-formula><mml:math id="M197" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 44 h, respectively
(Table 3, Fig. 9). The time constants were similar in magnitude to, though
both slightly shorter than, the time constants for the runoff model,
suggesting a possible exhaustion effect where, as in Newby Beck, the TP mass
store was diluted as the response progressed. For the Blackwater, as in the
other study catchments, the proportion of TP load transferred on the fast
pathway (54 <inline-formula><mml:math id="M198" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 2 %) was considerably more than the proportion of
water on the fast pathway (25 <inline-formula><mml:math id="M199" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.6 %). Although seasonal
non-linearity was still evident in the data from Blackwater, the
rainfall–runoff models that included the non-linearity did not validate
the data very well (Fig. S18),
such that the two-stage TP models using the effective rainfall calculated one
step at a time using the simulated discharge, <inline-formula><mml:math id="M200" display="inline"><mml:mrow><mml:msub><mml:mi>Q</mml:mi><mml:mtext>sim</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula>, gave a worse
fit to the data than a simple linear model. This may have been due to missing
data in the discharge and TP time series, particularly over the storm peaks,
or to inadequate representation of P inputs. An expanded section of Fig. 9,
showing a series of storms in December 2012 (Fig. 10a) indicates the seasonal
non-linearity of the response, which cannot be captured with a linear model,
with a linear rainfall input. The first storm was considerably
underestimated, but later storms were overestimated. This can usually be
accounted for by using a non-linear effective rainfall input, which was
unsuccessful in this case. A storm in May 2013 (Fig. 10b), when the land
might have been drier than during the December storms, showed considerable
overestimation of TP load by the linear model fitted to the December period.
Time series of residuals and residuals against observed values are given for
the Blackwater discharge model in Fig. S13 and for the Blackwater TP load
model in Fig. S14.</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F10"><caption><p id="d1e4377">Second-order model between rainfall and total phosphorus (TP) load
at Blackwater for storms in December 2012 <bold>(a)</bold> and May
2013 <bold>(b)</bold>. Continuous-time model with structure [2, 2, 4] (see
Table 3); <inline-formula><mml:math id="M201" display="inline"><mml:mrow><mml:msubsup><mml:mi>R</mml:mi><mml:mi>t</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msubsup><mml:mo>=</mml:mo><mml:mn mathvariant="normal">0.67</mml:mn></mml:mrow></mml:math></inline-formula>. The light blue band indicates the 95 %
uncertainty bounds on the measurement data, The grey band indicates the
95 % confidence limits on the parameter uncertainty (on this scale, only
visible during periods where TP data are missing). Total model predictive
uncertainty (including the residual uncertainty) is larger than parametric
uncertainty and would enclose the observations most of the time.</p></caption>
          <?xmltex \igopts{width=236.157874pt}?><graphic xlink:href="https://hess.copernicus.org/articles/21/6425/2017/hess-21-6425-2017-f10.png"/>

        </fig>

      <p id="d1e4409">The proportion of TP load exported on the fast pathway was considerably
greater for all catchments than the corresponding proportion of water on the
fast pathway, by a factor of approximately 2 for Newby Beck and Blackwater
and approximately 5 for the Wylye. This suggests that on the fast water
pathways, generally associated with shallower pathways such as shallow
sub-surface flow, field drains and surface runoff, there is more release of
TP than on deeper water pathways. This is consistent with soil profiles in
agricultural areas, which generally show P concentrated on the surface and
in the near-surface soil layers, with a decrease in P with depth
(Heathwaite and Dils, 2000).</p>
      <p id="d1e4412">Validation of the TP model for Blackwater and Wylye was performed on a
shorter period than for Newby Beck (half of the hydrological year 2013–2014)
because of missing data (Table 3, Figs. S15–S18). The power law used to
represent the rainfall–runoff non-linearity did not
validate the data very well in the
Blackwater catchment. Different representations of the rainfall–runoff
linearity were also investigated, such as the Bedford Ouse Sub-Model
(Chappell et al., 2006; Young, 2001; Young and Whitehead, 1977), in which the
soil storage is related to an antecedent precipitation index. Although
changes in the model non-linearity representation made minor differences to
model fit, none of the model variants validated the data well for the Blackwater catchment. This suggests that there
may be a different mechanism at work in the Blackwater catchment, in which a
fast pathway only becomes active once the soil is fully saturated, or the
groundwater level rises to a certain level (Outram et al., 2016). This could
be due to the shallow slopes, which encourage infiltration rather than
runoff. Alternatively, the response may be more dominated by point sources
which are not as rainfall-driven, or sources such as sediment-laden runoff
from impervious surfaces (roads or yards), which are rainfall-driven but do
not behave in the same non-linear way as the runoff from soil.</p>
      <p id="d1e4415">In addition, the conditions experienced during the 2 years used for model
identification may not be very similar to the validation period. From the
data in Fig. 1c, the winter of 2011 and spring of 2012 showed much lower
discharge than the same months in subsequent years. The groundwater recharge,
which is shown as an increase in the baseflow in winter, was obvious for
winter 2012–2013 and winter 2013–2014 for both the Blackwater (Fig. 2c) and the
Wylye (Fig. 2e), but was not evident for either catchment for the winter of
2011–2012. Because of the slow time constants for these catchments, the dataset
for model identification ideally needs to be longer than for the Newby Beck
catchment, where the dynamics are much faster. This study suggests that the
dataset used here was not long enough for the Blackwater catchment to capture
an adequate range of conditions.</p>

<?xmltex \floatpos{t}?><table-wrap id="Ch1.T4" specific-use="star"><caption><p id="d1e4422">Advantages and limitations of the DBM modelling method for
rainfall–TP load.</p></caption><oasis:table frame="topbot"><oasis:tgroup cols="2">
     <oasis:colspec colnum="1" colname="col1" align="justify" colwidth="227.622047pt"/>
     <oasis:colspec colnum="2" colname="col2" align="justify" colwidth="227.622047pt"/>
     <oasis:thead>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1">Advantages</oasis:entry>  
         <oasis:entry colname="col2">Limitations</oasis:entry>
       </oasis:row>
     </oasis:thead>
     <oasis:tbody>
       <oasis:row>  
         <oasis:entry colname="col1">No prior assumption of model structure required</oasis:entry>  
         <oasis:entry colname="col2">Requires complete, high temporal frequency datasets</oasis:entry>
       <?xmltex \interline{[5.690551pt]}?></oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Very few parameters required</oasis:entry>  
         <oasis:entry colname="col2">Requires long datasets to cover a full range of driving conditions</oasis:entry>
       <?xmltex \interline{[5.690551pt]}?></oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Low parameter uncertainty</oasis:entry>  
         <oasis:entry colname="col2">Models may not work well for future conditions if the range of conditions has not been included in the identification period</oasis:entry>
       <?xmltex \interline{[5.690551pt]}?></oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Makes good use of high-frequency data</oasis:entry>  
         <oasis:entry colname="col2">The power law to represent the rainfall–runoff non-linearity may not be the best representation for each catchment</oasis:entry>
       <?xmltex \interline{[5.690551pt]}?></oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Physical interpretation is made based only on the information in the data</oasis:entry>  
         <oasis:entry colname="col2">Stationary DBM model will not capture time-variable gains</oasis:entry>
       </oasis:row>
     </oasis:tbody>
   </oasis:tgroup></oasis:table></table-wrap>

</sec>
<sec id="Ch1.S3.SS5">
  <title>Advantages and limitations of the modelling method</title>
      <p id="d1e4501">The benefits and limitations of the modelling method for TP load are
summarised in Table 4. For catchments that exhibit rapidly changing dynamics,
such as response to storm events, models calibrated with daily data will have
large uncertainties associated with the parameters (and output) because the
input data do not capture the high-frequency dynamics of processes such as P
transfer. This study shows that simple transfer function models using data
with sub-daily resolution can simulate the dynamics of TP load, with model
fits at least as good as generally achieved with process-based models
(Gassman et al., 2007; Moriasi et al., 2007) and with low parameter
uncertainty. Full direct model comparisons are not currently possible, as the
published results for process-based models used different catchments and data
sets. It is still advisable to validate a fitted model using at least a split
record test (Klemes, 1986). This highlights the importance of long and
complete datasets with good time resolution for properly representing both
flow and TP loads for such catchments. The high data demand of DBM models is
noted in Table 4. Technology and monitoring methods are improving all the
time so that high-frequency data are now more readily available (e.g. Jordan
et al., 2007, 2005; Outram et al., 2014; Skeffington et al., 2015) This
requirement for adequate datasets is often an obstacle in the use of the DBM
modelling method, but as such datasets become more available, the method can
be used to improve our understanding of catchments. We should embrace efforts
to improve data coverage and ways to use it widely.</p>
      <p id="d1e4504">The models in Table 3 have been identified using a consistent method, to test
how well this modelling method copes with the different characteristics of
the three catchments. The method has been successfully applied to all the
catchments, although less successfully for the Blackwater catchment. It is
likely that the models could be improved if catchment-specific adjustments
were made or used alongside other models in a hypothetico-inductive manner
(Young, 2013). For instance, in the Blackwater catchment, the use of state-dependent parameters (Young, 1984) might be more successful to capture the
rainfall–runoff non-linearity. This means that, rather than using the form of
the non-linearity specified by Eq. (6), the parameters could be allowed to
vary according to some other observed state. In addition, model fit might be
improved by accounting for heteroscedasticity of residuals (shown in residual
analysis, Figs. S9–S14), through transformation of data and residuals (e.g.
Yang et al., 2007). Models for all catchments could be improved by having a
longer dataset, to ensure, as far as possible, that environmental conditions
during a future simulation period have already been experienced during the
identification period.</p>
      <p id="d1e4507">The models showed a pattern of underestimation of high-level TP load events
and, to a lesser extent, overestimation of lower level events (Figs. 10, 12
and 14). This was more apparent for TP load than for the discharge model
(Figs. 9, 11 and 13), although in many cases this was within the limits of
the uncertainty in the observed data. This suggests that, for the TP load
model, the non-linearity may be rainfall, discharge or load-dependent to a
greater extent than allowed for in the non-linearity of Eq. (6). This could be
explored using state-dependent parameter estimation, on which the power law
of Eq. (6) for the flow non-linearity was originally based (Young and Beven,
1994; Young, 1984). In addition, models with at least two terms in the
numerator polynomial could provide more flexibility for a differencing
effect, i.e. a consistent flushing effect with higher load occurring during
the rising limb of the discharge peak. This mechanism is not represented in
first-order models [1 1 del], as for Newby Beck, as it requires two terms of
the numerator polynomial.</p>
      <p id="d1e4510">The use of process-based models is often justified on the basis that the
inclusion of adequate process representations will lead to more robust
estimation of the response to changing environmental conditions. This is the
basis for arguing that process-based models are better suited for predicting
the impacts of future change. However, they also involve a plethora of
(often difficult to validate) assumptions in their model structures and
parameters. In practice, parameters set during calibration are rarely
changed to account for changes in the modelled processes under future
conditions, although by calibrating models for conditions similar to the
expected future conditions, it may be possible to incorporate non-stationary
parameter values (Nijzink et al., 2016). This idea
could be integrated into DBM models by choosing identification periods which
are most likely to reflect the conditions of the simulation period or
through the use of state-dependent parameters. Thus, whilst the data-based
assumption of similar conditions may be questioned when limited periods have
been used for identification, usually restricted by data availability, we
argue that many of the factors contributing to catchment response will not
have changed (e.g. catchment topography, soil type and geology) and that
this assumption will in many circumstances be no more restrictive than the
(different) assumptions made when using process-based models. Clearly, where
the factors contributing to catchment response have obviously changed (such
as if all septic tanks were upgraded or if farm budgeting reduced the
additions of P), then simple transfer function models would not be able to
predict the changes over time, whereas, in theory, process-based models
might be able to account for such changes, albeit with much uncertainty
(e.g. Dean et al., 2009; Yang et al., 2008). However, for rainfall-dominated responses, or responses to changes in rainfall patterns, simple
transfer function models can provide valuable understanding of the dominant
modes of a catchment, which, in turn, can be used to target management
interventions.</p>
</sec>
</sec>
<sec id="Ch1.S4" sec-type="conclusions">
  <title>Summary and conclusions</title>
      <p id="d1e4520">High temporal resolution data (hourly) of discharge and TP load have been
used to identify simple transfer function models that capture the dynamics of
rainfall–runoff and rainfall–phosphorus load in three diverse agricultural
catchments. Linear models were identified for short storm sequences in the
flashy Newby Beck catchment, when antecedent flows for events were similar.
Models identified for November 2015 were used to simulate flows and TP loads
in the devastating Storm Desmond (5–6 December 2015), supporting our belief
that the discharge and TP load calculated from recorded data during this
storm were considerably underestimated. In these circumstances, simple models
could be useful to infill missing data or to highlight or estimate
uncertainties in the recorded data. Linear models for short periods were not
appropriate for the less flashy Blackwater and Wylye catchments when the slow
time constant (for a second-order model) was similar in length to the time
period of identification, making the parameter uncertainty large.</p>
      <p id="d1e4523">Longer-term models were identified for each of the three catchments based on
2 years of data. Comparison of rainfall–runoff and
rainfall–TP load models for each catchment allowed a better understanding of
the dominant modes of transport within each catchment, which was based on the
time series data alone, rather than other (unmeasured) catchment parameters.
In all three catchments, a higher proportion of the TP load was exported via
a fast pathway than the corresponding proportion of water on the fast
pathway. In agreement with soil profiles in agricultural areas, this
suggested that there is more release of TP on fast (generally shallower)
water pathways such as shallow sub-surface flow, field drains and surface
runoff.</p>
      <p id="d1e4526">For successful simulations of future conditions, the models require long
datasets to ensure that a full range of driving conditions has been included
in the identification period. However, this study shows that simple transfer
function models can be successful in modelling TP loads and explaining
dominant transport modes. Transfer function models make good use of high-frequency
data, require very few parameters with low uncertainty and allow
physical interpretation based solely on the information in the data.</p>
</sec>

      
      </body>
    <back><notes notes-type="dataavailability">

      <p id="d1e4534">The data used in this study are openly available from
Lancaster University data archive (Ockenden, 2017).</p>

      <p id="d1e4537">The DTC data are available from each DTC consortium until the archive is
transferred to Defra (Department for Environment, Food &amp; Rural Affairs) as
the holding body.</p>
  </notes>
<sec id="Ch1.Sx1" specific-use="unnumbered">
  <title>Information about the Supplement</title>
      <p id="d1e4546">Information about the following can be found in the Supplement:
<list list-type="bullet"><list-item>
      <p id="d1e4551">Estimation of hourly rainfall time series for the Wylye catchment
(Sect. S1);</p></list-item><list-item>
      <p id="d1e4555">Model assessment criteria (Sect. S2);</p></list-item><list-item>
      <p id="d1e4559">Study catchment characteristics (Table S1);</p></list-item><list-item>
      <p id="d1e4563">Notation (Table S2);</p></list-item><list-item>
      <p id="d1e4567">Structure of models and relationship between
parameters from discrete-time and continuous-time models (Table S3);</p></list-item><list-item>
      <p id="d1e4571">Definition of time constants, steady-state gains and fraction on each pathway
for discrete-time and continuous-time models (Table S4);</p></list-item><list-item>
      <p id="d1e4575">Model structures and
parameters identified (Table S5);</p></list-item><list-item>
      <p id="d1e4579">Hourly streamflow against total phosphorus
concentration for the Newby Beck catchment (Fig. S1), the Blackwater
catchment (Fig. S2) and the Wylye catchment (Fig. S3);</p></list-item><list-item>
      <p id="d1e4583">Hourly streamflow
against total phosphorus load for the Newby Beck catchment (Fig. S4), the
Blackwater catchment (Fig. S5) and the Wylye catchment (Fig. S6);</p></list-item><list-item>
      <p id="d1e4587">Time series
of residuals and histograms of residuals for short term model, Newby Beck
(Figs. S7–S8);</p></list-item><list-item>
      <p id="d1e4591">Residual analysis, long-term models (Figs. S9–S14);</p></list-item><list-item>
      <p id="d1e4596">Model validation (Figs. S15–S18).</p></list-item></list></p><supplementary-material position="anchor"><p id="d1e4598"><bold>The Supplement related to this article is available online at <inline-supplementary-material xlink:href="https://doi.org/10.5194/hess-21-6425-2017-supplement" xlink:title="pdf">https://doi.org/10.5194/hess-21-6425-2017-supplement</inline-supplementary-material>.</bold></p></supplementary-material>
</sec><notes notes-type="authorcontribution">

      <p id="d1e4605">MCO ran the DBM model and led the writing of the paper. WT assisted
with DBM modelling. PMH was overall project lead with KJB, PJW, PDF and JZ
also helping manage the project. All authors participated in interpretation
of results and the writing and editing process. MCO, KJB, ALC, RE, PDF, KJF,
KMH, MJH, RK, CJAM, MLV, CW, PJW, JGZ and PMH contributed to NUTCAT 2050;
ALC, KMH, CB, SB, RJC, JEF and PMH are part of the DTC project.</p>
  </notes><notes notes-type="competinginterests">

      <p id="d1e4611">Jim Freer is a member of the editorial board of Hydrology
and Earth System Sciences.</p>
  </notes><ack><title>Acknowledgements</title><p id="d1e4617">This work was funded by the Natural Environment Research Council (NERC) as
part of the NUTCAT 2050 project, grants NE/K002392/1, NE/K002430/1 and
NE/K002406/1, and supported by the Joint UK BEIS/Defra Met Office Hadley
Centre Climate Programme (GA01101). The authors are grateful to the UK
Demonstration Test Catchments (DTC) research platform for provision of the
field data (Defra projects WQ02010, WQ0211, WQ0212 and LM0304).
<?xmltex \hack{\newline}?><?xmltex \hack{\newline}?> Edited by: Christian Stamm<?xmltex \hack{\newline}?>
Reviewed by: Sebastian Stoll and three anonymous referees</p></ack><ref-list>
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    <!--<article-title-html>Prediction of storm transfers and annual loads with data-based mechanistic models using high-frequency data</article-title-html>
<abstract-html><p class="p">Excess nutrients in surface waters, such as phosphorus (P) from agriculture,
result in poor water quality, with adverse effects on ecological health and
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models with high uncertainty. We show that, with high temporal resolution
data, we are able to identify simple dynamic models that capture the P load
dynamics in three contrasting agricultural catchments in the UK. For a flashy
catchment, a linear, second-order (two pathways) model for discharge gave
high simulation efficiencies for short-term storm sequences and was useful in
highlighting uncertainties in out-of-bank flows. A model with non-linear
rainfall input was appropriate for predicting seasonal or annual cumulative P
loads where antecedent conditions affected the catchment response. For
second-order models, the time constant for the fast pathway varied between 2
and 15 h for all three catchments and for both discharge and P,
confirming that high temporal resolution data are necessary to capture the
dynamic responses in small catchments (10–50 km<sup>2</sup>). The models led to a
better understanding of the dominant nutrient transfer modes, which will be
helpful in determining phosphorus transfers following changes in
precipitation patterns in the future.</p></abstract-html>
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