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  <front>
    <journal-meta>
<journal-id journal-id-type="publisher">BG</journal-id>
<journal-title-group>
<journal-title>Biogeosciences</journal-title>
<abbrev-journal-title abbrev-type="publisher">BG</abbrev-journal-title>
<abbrev-journal-title abbrev-type="nlm-ta">Biogeosciences</abbrev-journal-title>
</journal-title-group>
<issn pub-type="epub">1726-4189</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/bg-14-631-2017</article-id><title-group><article-title>Quantifying nutrient fluxes with a new hyporheic passive<?xmltex \hack{\break}?> flux meter (HPFM)</article-title>
      </title-group><?xmltex \runningtitle{Quantifying nutrient fluxes a new HPFM}?><?xmltex \runningauthor{J. V. Kunz et al.}?>
      <contrib-group>
        <contrib contrib-type="author" corresp="yes" rid="aff1">
          <name><surname>Kunz</surname><given-names>Julia Vanessa</given-names></name>
          <email>vanessa.kunz@ufz.de</email>
        </contrib>
        <contrib contrib-type="author" corresp="no" rid="aff2">
          <name><surname>Annable</surname><given-names>Michael D.</given-names></name>
          
        </contrib>
        <contrib contrib-type="author" corresp="no" rid="aff2">
          <name><surname>Cho</surname><given-names>Jaehyun</given-names></name>
          
        </contrib>
        <contrib contrib-type="author" corresp="no" rid="aff1">
          <name><surname>von Tümpling</surname><given-names>Wolf</given-names></name>
          
        </contrib>
        <contrib contrib-type="author" corresp="no" rid="aff2">
          <name><surname>Hatfield</surname><given-names>Kirk</given-names></name>
          
        </contrib>
        <contrib contrib-type="author" corresp="no" rid="aff3">
          <name><surname>Rao</surname><given-names>Suresh</given-names></name>
          
        </contrib>
        <contrib contrib-type="author" corresp="no" rid="aff1">
          <name><surname>Borchardt</surname><given-names>Dietrich</given-names></name>
          
        </contrib>
        <contrib contrib-type="author" corresp="no" rid="aff1">
          <name><surname>Rode</surname><given-names>Michael</given-names></name>
          
        </contrib>
        <aff id="aff1"><label>1</label><institution>Helmholtz Centre for Environmental Research UFZ, Magdeburg, Germany</institution>
        </aff>
        <aff id="aff2"><label>2</label><institution>University of Florida, Gainesville, Florida, USA</institution>
        </aff>
        <aff id="aff3"><label>3</label><institution>Purdue University, Lafayette, Indiana, USA</institution>
        </aff>
      </contrib-group>
      <author-notes><corresp id="corr1">Julia Vanessa Kunz (vanessa.kunz@ufz.de)</corresp></author-notes><pub-date><day>9</day><month>February</month><year>2017</year></pub-date>
      
      <volume>14</volume>
      <issue>3</issue>
      <fpage>631</fpage><lpage>649</lpage>
      <history>
        <date date-type="received"><day>11</day><month>August</month><year>2016</year></date>
           <date date-type="rev-request"><day>19</day><month>August</month><year>2016</year></date>
           <date date-type="rev-recd"><day>20</day><month>January</month><year>2017</year></date>
           <date date-type="accepted"><day>23</day><month>January</month><year>2017</year></date>
      </history>
      <permissions>
<license license-type="open-access">
<license-p>This work is licensed under a Creative Commons Attribution 3.0 Unported License. To view a copy of this license, visit <ext-link ext-link-type="uri" xlink:href="http://creativecommons.org/licenses/by/3.0/">http://creativecommons.org/licenses/by/3.0/</ext-link></license-p>
</license>
</permissions><self-uri xlink:href="https://bg.copernicus.org/articles/14/631/2017/bg-14-631-2017.html">This article is available from https://bg.copernicus.org/articles/14/631/2017/bg-14-631-2017.html</self-uri>
<self-uri xlink:href="https://bg.copernicus.org/articles/14/631/2017/bg-14-631-2017.pdf">The full text article is available as a PDF file from https://bg.copernicus.org/articles/14/631/2017/bg-14-631-2017.pdf</self-uri>


      <abstract>
    <p>The hyporheic zone is a hotspot of biogeochemical turnover and
nutrient removal in running waters. However, nutrient fluxes through the
hyporheic zone are highly variable in time and locally heterogeneous.
Resulting from the lack of adequate methodologies to obtain representative
long-term measurements, our quantitative knowledge on transport and turnover
in this important transition zone is still limited.</p>
    <p>In groundwater systems passive flux meters, devices which simultaneously
detect horizontal water and solute flow through a screen well in the
subsurface, are valuable tools for measuring fluxes of target solutes and
water through those ecosystems. Their functioning is based on accumulation
of target substances on a sorbent and concurrent displacement of a resident
tracer which is previously loaded on the sorbent.</p>
    <p>Here we evaluate the applicability of this methodology for investigating
water and nutrient fluxes in hyporheic zones. Based on laboratory experiments
we developed hyporheic passive flux meters (HPFMs) with a length of 50 cm
which were separated in 5–7 segments allowing for vertical resolution of
horizontal nutrient and water transport. The HPFMs were tested in a 7 day
field campaign including simultaneous measurements of oxygen and temperature
profiles and manual sampling of pore water. The results highlighted the
advantages of the novel method: with HPFMs, cumulative values for the average N
and P flux during the complete deployment time could be captured. Thereby the
two major deficits of existing methods are overcome: first, flux rates are
measured within one device instead of being calculated from separate
measurements of water flow and pore-water concentrations; second, time-integrated measurements are insensitive to short-term fluctuations and
therefore deliver more representable values for overall hyporheic nutrient
fluxes at the sampling site than snapshots from grab sampling. A remaining
limitation to the HPFM is the potential susceptibility to biofilm growth on
the resin, an issue which was not considered in previous passive flux meter
applications. Potential techniques to inhibit biofouling are discussed based
on the results of the presented work. Finally, we exemplarily demonstrate how
HPFM measurements can be used to explore hyporheic nutrient dynamics,
specifically nitrate uptake rates, based on the measurements from our field
test. Being low in costs and labour effective, many flux meters can be
installed in order to capture larger areas of river beds. This novel
technique has therefore the potential to deliver quantitative data which are
required to answer unsolved questions about transport and turnover of
nutrients in hyporheic zones.</p>
  </abstract>
    </article-meta>
  </front>
<body>
      

<sec id="Ch1.S1" sec-type="intro">
  <title>Introduction</title>
      <p>Rivers export high loads of nitrogen from inland catchments to the marine
environment (Smith et al., 2006). The ecological and economic problems caused by eutrophication of
coastal and riverine ecosystems have been recognised years ago (Patsch and
Radach, 1997; Artioli et al., 2008; Skogen et al., 2014). Decades of nutrient
studies have revealed that rivers cycle rather than only transport nutrients
(Garcia-Ruiz et al., 1998a; Seitzinger et al., 2002; Galloway et al., 2003).
In agriculturally dominated areas, in-stream processes may for example retain
up to 38 % of nitrate (NO<inline-formula><mml:math id="M1" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> and 48 % of soluble reactive
phosphate (SRP) inputs (Mortensen et al., 2016). The hyporheic zone, the
subsurface region of streams and rivers that exchanges water, solutes and
particles with the surface (Valett et al., 1993) and may mix streamwater
during the transport through the sediments with underlying groundwater
(Triska et al., 1989; Fleckenstein et al., 2010; Trauth et al., 2014), is one
key compartment for in-stream nutrient cycling (Fischer et al., 2005;
Zarnetske et al., 2011b; Basu et al., 2011; Stewart et al., 2011). For
instance, denitrification, the anaerobic reduction of NO<inline-formula><mml:math id="M2" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula> to gaseous
N<inline-formula><mml:math id="M3" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> and in most river systems the dominant dissimilatory process which
removes N out of the system (Laursen and Seitzinger, 2002; Bernot and Dodds,
2005; Lansdown et al., 2012; Kunz et al., 2017), often exclusively happens at
“reactive sites” in the hyporheic zone (Duff and Triska, 1990; Rode et al.,
2015). In addition to biological nutrient uptake, intermediate physical
storage in the hyporheic zone disperses the propagation of pollutant and
nutrient spikes which could be harmful for receiving water bodies (Runkel,
2007; Brookshire et al., 2009; Covino et al., 2010; Findlay et al., 2011).
For those reasons, it is of interest to quantify the amount of nutrients
actually reaching the reactive sites in the subsurface collateral to the
processes they undergo there (Seitzinger et al., 2006; Zarnetske et al.,
2012). Transport rates of water and nutrients from the surface to the
subsurface could be attributed to water level, sediment properties and
various other hydrological, biological, chemical and physical factors
(Böhlke et al., 2009; Boano et al., 2014; Trauth et al., 2015). The
complex interactions between these influencing factors and the temporal
variability and local heterogeneity of hyporheic processes often cause high
uncertainties in quantitative models. However, due to methodological
restrictions, experimental investigations of nutrient dynamics in the
hyporheic zone are rare and commonly exclusively of qualitative nature
(Mulholland et al., 1997; Grant et al., 2014).</p>
      <p>Attempts to quantify hyporheic nutrient processing rates have primarily been
based on benthic chamber and incubation experiments (Findlay et al., 2011;
Kessler et al., 2012). Those laboratory (mesocosm and flume) experiments can
estimate the denitrification potential of the substrates, usually via
denitrification enzyme assays. However, the realised denitrification rates
depend equally on environmental and hydrological conditions rather than on
substrate type or denitrification potential alone (Findlay et al., 2011).
Thus, owing to the high variability and complexity of natural systems,
hyporheic transport of nutrients cannot satisfactorily be mimicked in
artificial set-ups (Cook et al., 2006; Grant et al., 2014).</p>
      <p>Direct in-stream measurements of nutrient dynamics based on whole-stream
tracer injections, mass balances (McKnight et al., 2004; Böhlke et al.,
2009) and more recently high-resolution time series from automated sensors
(Pellerin et al., 2009; Hensley et al., 2014; Rode et al., 2016a, b) can be
used for determining general uptake rates on the reach scale, but do not
allow to identify the reaction sites (hyporheic versus in channel or algal
canopies) or specific local uptake processes (Ensign and Doyle, 2006; Ruehl
et al., 2007). Further, in-stream measurements  exclusively account for
water which is re-infiltrating into the main stem after passage through the
hyporheic zone. Under loosing conditions, where most of the nutrient-influx
is flowing towards the groundwater, processing rates in the subsurface cannot
be observed in the surface water. Likewise, if groundwater is contributing
significantly to surface water chemistry, surface water mass balances do not
characterise nutrient cycling in the hyporheic zone realistically (Trauth et
al., 2014).</p>
      <p>Conclusively, in situ assessments of hyporheic nutrient fluxes are
indispensable. Hyporheic nutrient fluxes are commonly calculated from
separate measurements of infiltration rates and pore-water concentrations
(Kalbus et al., 2006; Ingendahl et al., 2009). The exchange of water between
the surface and subsurface is traditionally derived from hydraulic head
differences or tracer injections (Fleckenstein et al., 2010; USEP, 2013).
Time series of high-resolution vertical temperature profiles have efficiently
been used to derive vertical Darcy velocity (<inline-formula><mml:math id="M4" display="inline"><mml:mrow><mml:msub><mml:mi>q</mml:mi><mml:mi>y</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>) (m d<inline-formula><mml:math id="M5" 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> in the
streambed. While measurements of vertical Darcy velocities are a valuable
asset, primarily horizontal fluxes are needed to assess hyporheic transport
and residence time (Binley et al., 2013; Munz et al., 2016). Active
heat-pulse tracing enables highly resolved in situ measurements of direction
and velocity of hyporheic flow (Lewandowski et al., 2011; Angermann et al.,
2012). These methods are profitable in shallow sediments (max. 15–20 cm)
and rivers with fine sediments, but may not be implementable in streams with
coarser sediments.</p>
      <p>Pore-water solute concentrations are typically determined from analysis of
grab samples extracted with drive points (Saenger and Zanke, 2009; USEP,
2013). Alternatively, dialysis cells – so-called peepers (Hesslein, 1976;
Teasdale et al., 1995) – or gels (Krom et al., 1994), based on the diffusive
equilibrium between the solute concentration in the pore water and the
receiver solution in the peeper or the gel, have been used to measure small-scale solute distribution over highly resolved profiles on the millimetre to centimetre scale. These techniques provide valuable insights into the time-specific
conditions at the target site. However, they delivers effectively a snap shot
of the highly temporally variable hyporheic zone processes (Cooke and White,
1987) that may not be representative for the overall conditions in the
system. Only repeated sampling at high frequencies and over longer time spans
as conducted for example by Duff et al. (1998) can account for the short-term
variability. Attempting to characterise larger areas with these methods is
laborious and costly.</p>
      <p>In sum, direct quantitative methods for hyporheic flux measurements have two
major deficiencies. First, separate measurements of water flow velocities
and pore-water concentrations are necessary to calculate mass fluxes. This
is not only labour intensive but can, due to the high temporal and spatial
variability of hyporheic flow, also lead to incorrect estimates of real flux
rates (Kalbus et al., 2006). Second, most techniques for measuring
pore-water concentrations exclusively capture the concentration at the
sampling time, which may not reflect the overall conditions at the sampling
location. New, affordable and efficient methods for the long-term
measurement of nutrient fluxes through the hyporheic zone are therefore
required to validate and improve models (Boyer et al., 2006; Wagenschein and
Rode, 2008; Alexander et al., 2009) and to determine the site-specific
extent of nutrient processing in the hyporheic zone (Fischer et al., 2009).</p>
      <p>In groundwater studies, passive flux meters (PFMs) have successfully been used
to quantify fluxes of contaminants (Hatfield et al., 2004; Annable et al.,
2005; Verreydt et al., 2013) through screened groundwater monitoring wells,
integrating time spans ranging from days to weeks. PFMs consist of a
cylindrical, screened PVC casing filled with activated carbon (AC) as a
porous sorbent. As long as the PFM is residing in the monitoring well,
dissolved contaminants in the groundwater flowing passively through the
meter are retained on the AC. Furthermore, the AC is preloaded with water-soluble resident tracers. The horizontal water flux through the screened
media can then be determined from the displacement of these resident tracers,
while simultaneously the contaminant flux is quantified based on the solute
mass captured on the AC. First bench-scale and column experiments for
PO<inline-formula><mml:math id="M6" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">4</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula> have been conducted in the laboratory (Cho et al., 2007). As AC
did not prove efficient in capturing nutrients, an anion-absorbing resin, a
granular matrix originally manufactured for purification processes, was used
as sorbent for PO<inline-formula><mml:math id="M7" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">4</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula> instead. In theory, the PFM principle should be
extendable to other nutrients or other environments. For example, development
of sediment bed passive flux meters (SBPFMs) for the measurement of vertical
contaminant seepage has been initiated (Layton, 2015). However, specific
tests for NO<inline-formula><mml:math id="M8" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula> as well as assessments under the complexities
associated with hyporheic zone processes have not been conducted yet.</p>
      <p>In this study we evaluate the applicability of PFMs for the measurement of
horizontal nutrient fluxes in hyporheic zones, focusing on NO<inline-formula><mml:math id="M9" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula>. We
hypothesised that, while the principal concept of PFM can be maintained,
several adaptations will still be necessary: most importantly, a suitable
sorbent for NO<inline-formula><mml:math id="M10" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula> as target nutrient is required. The market of anion-absorbing resins is large and offers a wide range of products with varying
characteristics (Annable et al., 2005; Clark et al., 2005). Various criteria,
like possible interference of resin compounds with the resident tracer
analysis or pre-existing background nutrient loads on the resin, have to be
considered. As experience on resin behaviour under field conditions is so far
rare, we also expected unforeseen associated challenges, including for
example biofouling of resin and/or nutrients. Additionally, a new deployment
and retrieval procedure had to be developed. Existing groundwater PFMs have
been installed into land-based wells. In hyporheic studies, underwater
installation requires a technique which impedes contamination with surface
water. Corrections for convergence and divergence of flowlines into or around
the flux meter have been established in earlier studies (Klammler et al.,
2007).
However, accounting for an impermeable outer casing of a flux meter is
much more complicated and requires additional factors which have to be
determined experimentally for each specific application (Hatfield et al.,
2004; Klammler et al., 2007; Annable et al., 2005). We therefore intended to
deploy the PFM in a way that allows direct contact with the surrounding
sediments and minimal manipulation of the natural flow pattern.</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F1" specific-use="star"><caption><p>Photograph of an HPFM with alternating segments before
deployment (left), schematic profile of a deployed HPFM (middle) and
schematic steps of HPFM functioning (right): (1) directly after installation,
tracer resides on activated carbon (AC), (2) infiltrating water washes out
the tracer, nutrients enter the HPFM and are absorbed on the resin, (3) after
retrieval nutrients are fixed on the resin, tracer concentration is
diluted.</p></caption>
        <?xmltex \igopts{width=312.980315pt}?><graphic xlink:href="https://bg.copernicus.org/articles/14/631/2017/bg-14-631-2017-f01.png"/>

      </fig>

      <p>Considering these requirements, we developed a modification of the PFM for
the application in the hyporheic zone (hyporheic passive flux meter, HPFM).
Based on the results from laboratory analysis and a first field test in a
nutrient-rich 3rd-order stream (Holtemme, Germany), we demonstrate prospects
and remaining limitations for hyporheic nutrient studies with HPFMs.</p>
</sec>
<sec id="Ch1.S2">
  <title>Methods</title>
<sec id="Ch1.S2.SS1">
  <title>Construction and materials</title>
      <p>The HPFMs consisted of a nylon mesh which was
filled with a mixture of a macroporous anion exchange resin as a nutrient
absorber and alcohol tracer loaded activated carbon (AC) for the water flow
quantification. In the present study HPFMs were constructed 50 cm long and
5 cm in diameter. A stainless steel rod in the middle assured the stability
of the device (Fig. 1). To measure vertical profiles of horizontal fluxes of
both nutrient and water in the hyporheic zone, the HPFM was divided into
several segments using rubber washers. Steel tube clamps were used to attach
the nylon mesh to the steel rod placed in the centre of the HPFM. The nylon
mesh was purchased from Hydro-Bios (Hydro-Bios Apparatebau GmbH,
Kiel-Holtenau, Germany) and is available in a wide range of mesh size and
thicknesses. We used a mesh size of 0.3 mm. In general, meshes should be as
wide as possible because very fine mesh may act as a barrier to water flow
limiting infiltration of water and solutes into the HPFM (Ward et al., 2011).
However, the mesh should be smaller than the finest sediments, AC or resin
granules. As final step, a rope was connected to the tube clamp on the upper
end of the HPFM in order to facilitate retrieval.</p>
</sec>
<sec id="Ch1.S2.SS2">
  <title>Selection and characterisation of resin</title>
      <p>The nutrient sorbent had to meet the following criteria:
<list list-type="order"><list-item><p>have a high loading capacity for NO<inline-formula><mml:math id="M11" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mrow><mml:mo>-</mml:mo><mml:mspace width="0.125em" linebreak="nobreak"/></mml:mrow></mml:msubsup></mml:mrow></mml:math></inline-formula>, PO<inline-formula><mml:math id="M12" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">4</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula> and
competing anions;</p></list-item><list-item><p>be free of compounds which could interfere with the alcohol tracer
measurements (e.g. organic substances);</p></list-item><list-item><p>have a low background of NO<inline-formula><mml:math id="M13" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula> and PO<inline-formula><mml:math id="M14" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">4</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula> .</p></list-item></list>
A pre-selection for anion-absorbing resins which were free of organic
compounds was made based on information provided by the manufacturers
(Purolite<sup>®</sup>,
Lewatit<sup>®</sup>,
Dowex<sup>®</sup>).</p>
<sec id="Ch1.S2.SS2.SSS1">
  <title>Nutrient background</title>
      <p>Nutrient background on the resins was determined by extracting and analysing
NO<inline-formula><mml:math id="M15" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula> and PO<inline-formula><mml:math id="M16" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">4</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula> from each resin (<inline-formula><mml:math id="M17" display="inline"><mml:mrow><mml:mi>n</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:math></inline-formula>). Therefore 30 mL of
2M KCl was added to 5 g of each pure resin and rotated for 24 h. The
solution was then analysed on a Segmented Flow Analyser Photometer (DR 5000,
Hach Lange) for NO<inline-formula><mml:math id="M18" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula> at 540 nm (detection limit 0.042 mg
NO<inline-formula><mml:math id="M19" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula>-N L<inline-formula><mml:math id="M20" 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> and for SRP at 880 nm (detection limit
0.003 mg P 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>. In order to estimate the effect of background
concentrations on final results in the actual field application of HPFM, the
extractable background concentrations were then converted to nutrient fluxes
using a Darcy flux of <inline-formula><mml:math id="M22" display="inline"><mml:mrow><mml:msub><mml:mi>q</mml:mi><mml:mi>x</mml:mi></mml:msub><mml:mo>=</mml:mo><mml:mn mathvariant="normal">4</mml:mn></mml:mrow></mml:math></inline-formula> m d<inline-formula><mml:math id="M23" 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>, an estimate based on
hyporheic flow velocities which were measured previously with salt tracer
tests at the study site. Likewise, the expected hyporheic nutrient flux was
computed from previously examined concentrations in pore-water samples and
the Darcy flux. The only resin with nutrient background below 5 % of
expected concentrations was Purolite<sup>®</sup> A500
MB Plus (Purolite GmbH, Ratingen, Germany), which had extractable background
NO<inline-formula><mml:math id="M24" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula> of 8 <inline-formula><mml:math id="M25" display="inline"><mml:mi mathvariant="normal">µ</mml:mi></mml:math></inline-formula>g NO<inline-formula><mml:math id="M26" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula>-N g<inline-formula><mml:math id="M27" 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> wetted resin
(<inline-formula><mml:math id="M28" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula>1.6 <inline-formula><mml:math id="M29" display="inline"><mml:mi mathvariant="normal">µ</mml:mi></mml:math></inline-formula>g g<inline-formula><mml:math id="M30" 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>, <inline-formula><mml:math id="M31" display="inline"><mml:mrow><mml:mi>n</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:math></inline-formula>) and
0.08 <inline-formula><mml:math id="M32" display="inline"><mml:mi mathvariant="normal">µ</mml:mi></mml:math></inline-formula>g PO<inline-formula><mml:math id="M33" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">4</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula>-P g<inline-formula><mml:math id="M34" 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> resin (<inline-formula><mml:math id="M35" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula>1.7 <inline-formula><mml:math id="M36" display="inline"><mml:mo>×</mml:mo></mml:math></inline-formula> 10<inline-formula><mml:math id="M37" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> <inline-formula><mml:math id="M38" display="inline"><mml:mi mathvariant="normal">µ</mml:mi></mml:math></inline-formula>g g<inline-formula><mml:math id="M39" 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>, <inline-formula><mml:math id="M40" display="inline"><mml:mrow><mml:mi>n</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:math></inline-formula>).
Purolite<sup>®</sup> A500 MB Plus was then considered
for testing the loading capacity. The limit of quantification LQ for the
nutrient extraction resulting from this background was calculated according
to the EPA Norm 1020B (Greenberg et al., 1992) as the sum of background
concentration and 10 times the standard deviation and amounted to
24 <inline-formula><mml:math id="M41" display="inline"><mml:mi mathvariant="normal">µ</mml:mi></mml:math></inline-formula>g NO<inline-formula><mml:math id="M42" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula>-N g<inline-formula><mml:math id="M43" 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> resin and
0.097 <inline-formula><mml:math id="M44" display="inline"><mml:mi mathvariant="normal">µ</mml:mi></mml:math></inline-formula>g PO<inline-formula><mml:math id="M45" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">4</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula>-P g<inline-formula><mml:math id="M46" 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> resin.</p>
</sec>
<sec id="Ch1.S2.SS2.SSS2">
  <title>Loading capacity and biofouling</title>
      <p>Purolite<sup>®</sup> A500 MB Plus is a macroporous
anion exchanger on the basis of polyvinylbenzyl-trimethylammonium with a
typical granular size of 0.88 mm diameter, an average density of
685 g L<inline-formula><mml:math id="M47" 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> and an effective porosity of 63 %. The theoretical
absorbing capacity is indicated in the product sheet as 1.15 eq L<inline-formula><mml:math id="M48" 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>
(molar weight equivalences per litre of resin), corresponding to
71.3 g NO<inline-formula><mml:math id="M49" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula>-N L<inline-formula><mml:math id="M50" 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>. Assuming hyporheic flow velocities of
<inline-formula><mml:math id="M51" display="inline"><mml:mrow><mml:msub><mml:mi>q</mml:mi><mml:mi>x</mml:mi></mml:msub><mml:mo>=</mml:mo><mml:mn mathvariant="normal">4</mml:mn></mml:mrow></mml:math></inline-formula> m d<inline-formula><mml:math id="M52" 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> and a concentration of
10 mg NO<inline-formula><mml:math id="M53" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula>-N L<inline-formula><mml:math id="M54" 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>, the volume of one HPFM could adsorb
NO<inline-formula><mml:math id="M55" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula> for 89 days. However, if multiple anions are present, real
loading capacities for NO<inline-formula><mml:math id="M56" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula> are expectedly lower.</p>
      <p>For the determination of a realistic loading capacity, three 5 cm diameter
columns were filled to a height of 5 cm with wetted
Purolite<sup>®</sup> A500 MB Plus resin, placed in a
vertical position and infiltrated with water collected from the study reach.
The columns were covered with tin foil to keep them dark and ensure stable
temperature. A constant supernatant of 1 cm was kept on all three columns to
ensure uniform infiltration at the surface of the column. Water was
continuously pumped (peristaltic pump,
ISMATEC<sup>®</sup> BVP Standard, ISM444) through the
columns from top to bottom for 22 days at a speed of 20 mL h<inline-formula><mml:math id="M57" 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>, which
also equals the expected Darcy velocity of <inline-formula><mml:math id="M58" display="inline"><mml:mrow><mml:msub><mml:mi>q</mml:mi><mml:mi>x</mml:mi></mml:msub><mml:mo>=</mml:mo><mml:mn mathvariant="normal">4</mml:mn></mml:mrow></mml:math></inline-formula> m d<inline-formula><mml:math id="M59" 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>. River
water was supplied from a 22 L HDPE canister (Rotilabo®EPK0.1). SRP and NO<inline-formula><mml:math id="M60" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula> concentrations in this reservoir were revised
daily. The draining water at the bottom outlet of the columns was sampled
twice a day and analysed for SRP and NO<inline-formula><mml:math id="M61" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula>.</p>
      <p>Biofilm growth on the resin was assessed by repeating the same experiment in
smaller columns (<inline-formula><mml:math id="M62" display="inline"><mml:mrow><mml:mi>n</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:math></inline-formula>) and extending it for several days after
break-through occurred. That way, nutrient consumption by biofilm after the
exhaustion of the loading capacity could be monitored. After the experiment
we coloured samples (<inline-formula><mml:math id="M63" display="inline"><mml:mrow><mml:mi>n</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:math></inline-formula>) of resin granules from the columns with
SybrGreen (C<inline-formula><mml:math id="M64" display="inline"><mml:msub><mml:mi/><mml:mn>32</mml:mn></mml:msub></mml:math></inline-formula>H<inline-formula><mml:math id="M65" display="inline"><mml:msub><mml:mi/><mml:mn>37</mml:mn></mml:msub></mml:math></inline-formula>N<inline-formula><mml:math id="M66" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula>S<inline-formula><mml:math id="M67" display="inline"><mml:mrow><mml:msup><mml:mi/><mml:mo>+</mml:mo></mml:msup><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> on nucleic acid and examined them
under a confocal laser scanning microscope to depict the degree of bacterial
fouling on the granular surface.</p>

<?xmltex \floatpos{t}?><table-wrap id="Ch1.T1" specific-use="star"><caption><p>Resident tracers per litre of aqueous solution and their
partitioning characteristics. Retardation factors (<inline-formula><mml:math id="M68" display="inline"><mml:mrow><mml:msub><mml:mi>R</mml:mi><mml:mtext>d</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula>) for the
specific set of tracers and AC used in this study had previously been
determined by Cho et al. (2007).</p></caption><oasis:table frame="topbot"><oasis:tgroup cols="3">
     <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:thead>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1">Resident tracers</oasis:entry>  
         <oasis:entry colname="col2">Aqueous concentration (g L<inline-formula><mml:math id="M69" 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></oasis:entry>  
         <oasis:entry colname="col3"><inline-formula><mml:math id="M70" display="inline"><mml:mrow><mml:msub><mml:mi>R</mml:mi><mml:mtext>d</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula></oasis:entry>
       </oasis:row>
     </oasis:thead>
     <oasis:tbody>
       <oasis:row>  
         <oasis:entry colname="col1">Methanol</oasis:entry>  
         <oasis:entry colname="col2">1.2</oasis:entry>  
         <oasis:entry colname="col3">4.9</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Ethanol</oasis:entry>  
         <oasis:entry colname="col2">1.2</oasis:entry>  
         <oasis:entry colname="col3">20</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Isopropyl alcohol (IPA)</oasis:entry>  
         <oasis:entry colname="col2">2.3</oasis:entry>  
         <oasis:entry colname="col3">109</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1"><italic>tert</italic>-Butyl alcohol (TBA)</oasis:entry>  
         <oasis:entry colname="col2">2.3</oasis:entry>  
         <oasis:entry colname="col3">309</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">2,4-Dimethyl-3-pentanol (DMP)</oasis:entry>  
         <oasis:entry colname="col2">1.2</oasis:entry>  
         <oasis:entry colname="col3"><inline-formula><mml:math id="M71" display="inline"><mml:mo>&gt;</mml:mo></mml:math></inline-formula> 1000</oasis:entry>
       </oasis:row>
     </oasis:tbody>
   </oasis:tgroup></oasis:table></table-wrap>

</sec>
</sec>
<sec id="Ch1.S2.SS3">
  <?xmltex \opttitle{Preparation of activated carbon with\hack{\break} alcohol tracers}?><title>Preparation of activated carbon with<?xmltex \hack{\break}?> alcohol tracers</title>
      <p>As designed for the groundwater PFMs, silver impregnated activated carbon
(AC) was used as sorbent for the resident alcohol tracers. The same AC as in
previous PFM applications (Annable et al., 2005) was used for the HPFM in
this study and was provided by the University of Florida, Gainesville. The AC
had a bulk density of 550 g L<inline-formula><mml:math id="M72" 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>, a grain size ranging from 0.42 to
1.68 mm and a hydraulic conductivity <inline-formula><mml:math id="M73" display="inline"><mml:mrow><mml:mi>k</mml:mi><mml:mo>=</mml:mo><mml:mn>300</mml:mn></mml:mrow></mml:math></inline-formula> m d<inline-formula><mml:math id="M74" 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>.</p>
      <p>Since the magnitude of water flow through the flux meter is unknown a priori,
multiple resident tracers with a wide range of tracer elution rates were
needed. The retardation factor of a substance <inline-formula><mml:math id="M75" display="inline"><mml:mrow><mml:msub><mml:mi>R</mml:mi><mml:mtext>d</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> is a measure for the
rate of elution of the substance from a particular carrier. Alcohols offer a
wide range of retardation factors and can easily be mixed and sorbed to the
AC (Hatfield et al., 2004; Cho et al., 2007). By choosing the same
manufacturer for the AC and the same alcohol mixture as used in the above-mentioned studies, we could rely on physical and chemical characterisations
and calculated <inline-formula><mml:math id="M76" display="inline"><mml:mrow><mml:msub><mml:mi>R</mml:mi><mml:mtext>d</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> for alcohol partitioning behaviour which have been
established by Hatfield et al. (2004), Annable et al. (2005) and Cho et
al. (2007) (Table 1).</p>
      <p>An alcohol tracer mixture for approximately 10 HPFMs was prepared by combining
100 mL of methanol, 100 mL of ethanol, 200 mL of isopropanol (IPA),
200 mL of <italic>tert</italic>-butanol (TBA) and 66 mL of 2,4-dimethyl-3-pentanol (2,4
DMP).</p>
      <p>In order to prepare the resident alcohol tracers on the AC, the AC was soaked
in an aqueous solution containing the resident alcohol tracers. A standard
ratio of 13 mL tracer mixture was added to 1 L of water in a Teflon sealed
container and was then shaken by an automated shaker over a period of several
hours. Subsequently, 1.5 L of dry activated carbon was added to the aqueous
tracer solution and rotated for 12 h to homogenise the AC tracer mixture.
After mixing, the supernatant water was discarded and the AC tracer mixture
was stored in a sealed container and refrigerated, preventing the evaporation
of the alcohol tracers.</p>
      <p>Similarly to the resins, the AC was tested for background nutrients by
extraction with 30 mL KCl per 5 g AC.</p>
      <p>The activated carbon contained 0.01 mg PO<inline-formula><mml:math id="M77" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">4</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula>-P g<inline-formula><mml:math id="M78" 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>AC
(<inline-formula><mml:math id="M79" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula>7.5 <inline-formula><mml:math id="M80" display="inline"><mml:mo>×</mml:mo></mml:math></inline-formula> 10<inline-formula><mml:math id="M81" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">4</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> mg g<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>, <inline-formula><mml:math id="M83" display="inline"><mml:mrow><mml:mi>n</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:math></inline-formula>) and
0.08 mg NO<inline-formula><mml:math id="M84" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula>-N g<inline-formula><mml:math id="M85" 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> AC (<inline-formula><mml:math id="M86" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula>5 <inline-formula><mml:math id="M87" display="inline"><mml:mo>×</mml:mo></mml:math></inline-formula> 10<inline-formula><mml:math id="M88" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> mg g<inline-formula><mml:math id="M89" 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>, <inline-formula><mml:math id="M90" display="inline"><mml:mrow><mml:mi>n</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:math></inline-formula>), which amounts to 75 % of the
expected concentration for NO<inline-formula><mml:math id="M91" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula> and 320 % for PO<inline-formula><mml:math id="M92" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">4</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula>. To
investigate whether the AC could be cleaned by washing, we repeatedly treated
AC samples with distilled water or KCl as depicted in the extraction
description above. Nutrients did not leach off under water treatment and
neither did KCl treatment satisfactorily reduce extractable background
concentration on the AC. After the third washing of AC with KCl,
0.02 mg PO<inline-formula><mml:math id="M93" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">4</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula>-P (<inline-formula><mml:math id="M94" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula>3.3 <inline-formula><mml:math id="M95" display="inline"><mml:mo>×</mml:mo></mml:math></inline-formula> 10<inline-formula><mml:math id="M96" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">4</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> mg g<inline-formula><mml:math id="M97" 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>, <inline-formula><mml:math id="M98" display="inline"><mml:mrow><mml:mi>n</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:math></inline-formula>) and 0.04 mg NO<inline-formula><mml:math id="M99" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula>-N (<inline-formula><mml:math id="M100" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula>2.3 <inline-formula><mml:math id="M101" display="inline"><mml:mo>×</mml:mo></mml:math></inline-formula> 10<inline-formula><mml:math id="M102" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> mg g<inline-formula><mml:math id="M103" 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>, <inline-formula><mml:math id="M104" display="inline"><mml:mrow><mml:mi>n</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:math></inline-formula>) could still be extracted per g AC.
Further, it was unclear to which degree replacing absorbed nutrients by KCl
would alter the alcohol tracer retardation and extraction on the AC. For
those reasons, we decided to keep the nutrient-absorbing resin separated from
the AC. As AC did not release background nutrients under water treatment,
water flowing first through AC and afterwards resin layers was not considered
problematic.</p>
</sec>
<sec id="Ch1.S2.SS4">
  <title>Deployment and retrieval procedure</title>
      <p>HPFMs were built, stored dry and transported in 70 cm long standard
polyethylene (PET) tubes (<inline-formula><mml:math id="M105" display="inline"><mml:mrow><mml:mn>58</mml:mn><mml:mo>×</mml:mo><mml:mn>5.3</mml:mn></mml:mrow></mml:math></inline-formula> SDR 11) purchased from a local
hardware store (Handelshof Bitterfeld GmbH, Bitterfeld, Germany). To avoid
resident alcohol tracer loss, the transport tubes with the HPFMs were sealed
with rubber caps and cooled during storage and transport. In the field, prior
to installation, the HPFMs were transferred to a stainless steel tube,
5.3 cm inner diameter with a loose steel drive point tip on the lower end.
The diameter of the steel tube for installation tightly fitted with the
rubber washers at the top and bottom end of the HPFM, so that vertical water
flow through tube and HPFM during installation was inhibited. The steel
casing and HPFM were driven into the river bed using a 2 kg hammer until the
upper end of the HPFM was at the same level as the surface–subsurface
interface. The metal casing was retrieved while the HPFM was held in place
using a steel rod.</p>
      <p>After 7 days of exposure, the HPFMs were retrieved by holding the transport
tube in place and quickly drawing the HPFM into the tube using the rope fixed
to the upper end of the HPFM. The required length of the transport tube,
steel drive casing and retrieval rope was determined by the depth of the
water level in the stream.</p>
      <p>After retrieval, the HPFMs were transported to the laboratory.</p>
</sec>
<sec id="Ch1.S2.SS5">
  <title>Analysis and data treatment</title>
      <p>In the laboratory, the retrieved HPFMs were instantly (after maximal 12 h)
sampled for analysis. Therefore one segment after the other was cut open and
the sorbent was segment-wise recovered, homogenised and a subsample
transferred to 40 mL glass vials. The subsamples from resin segments were
then analysed for nutrient content, the subsamples from AC segments were
analysed for the remaining alcohol tracers as described in the following
paragraphs.</p>
<sec id="Ch1.S2.SS5.SSS1">
  <title>Water flux</title>
      <p>The AC samples were shipped to the University of Florida for analysis. In the
laboratory, the mass of the previously applied mixture of alcohol tracers in
standard AC samples and the tracer mass remaining in the final AC samples
were extracted with iso-butyl alcohol (IBA). About 10 g of AC samples were
transferred into pre-weighed 40 mL vials containing 20 mL IBA. Vials were
rotated on a Glas-Col Rotator, set at 20 % rotation speed, for 24 h.
Then, subsamples were collected in 2 mL GC vials for alcohol tracer
analysis. The samples were analysed with a GC-FID (Perkin Elmer Autosystem)
(Cho et al., 2007).</p>
      <p>The relationship between time-averaged specific horizontal discharge <inline-formula><mml:math id="M106" display="inline"><mml:mrow><mml:msub><mml:mi>q</mml:mi><mml:mi>x</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>
(m s<inline-formula><mml:math id="M107" 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> through the device and tracer elution is given by
(Hatfield et al., 2004):
              <disp-formula id="Ch1.E1" content-type="numbered"><mml:math id="M108" display="block"><mml:mrow><mml:msub><mml:mi>q</mml:mi><mml:mi>x</mml:mi></mml:msub><mml:mo>=</mml:mo><mml:mstyle displaystyle="true"><mml:mfrac style="display"><mml:mrow><mml:mn>1.67</mml:mn><mml:mi>r</mml:mi><mml:mi mathvariant="italic">θ</mml:mi><mml:mo>(</mml:mo><mml:mn mathvariant="normal">1</mml:mn><mml:mo>-</mml:mo><mml:msub><mml:mi>M</mml:mi><mml:mtext>R</mml:mtext></mml:msub><mml:mo>)</mml:mo><mml:msub><mml:mi>R</mml:mi><mml:mtext>d</mml:mtext></mml:msub></mml:mrow><mml:mi>t</mml:mi></mml:mfrac></mml:mstyle><mml:mo>,</mml:mo></mml:mrow></mml:math></disp-formula>
            where <inline-formula><mml:math id="M109" display="inline"><mml:mi>r</mml:mi></mml:math></inline-formula> (m) is the radius of the HPFM, <inline-formula><mml:math id="M110" display="inline"><mml:mi mathvariant="italic">θ</mml:mi></mml:math></inline-formula> is the volumetric water
content in the HPFM (m<inline-formula><mml:math id="M111" display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msup></mml:math></inline-formula> m<inline-formula><mml:math id="M112" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula>), <inline-formula><mml:math id="M113" display="inline"><mml:mrow><mml:msub><mml:mi>M</mml:mi><mml:mtext>R</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> (–) is the relative mass
of tracer remaining in the HPFM sorbent, <inline-formula><mml:math id="M114" display="inline"><mml:mi>t</mml:mi></mml:math></inline-formula> (s) is the sampling duration and
<inline-formula><mml:math id="M115" display="inline"><mml:mrow><mml:msub><mml:mi>R</mml:mi><mml:mtext>d</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> (–) is the retardation factor of the resident tracer on the
sorbent.</p>
</sec>
<sec id="Ch1.S2.SS5.SSS2">
  <?xmltex \opttitle{Nutrient flux $J_{\text{N}}$}?><title>Nutrient flux <inline-formula><mml:math id="M116" display="inline"><mml:mrow><mml:msub><mml:mi>J</mml:mi><mml:mtext>N</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula></title>
      <p>NO<inline-formula><mml:math id="M117" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula> and PO<inline-formula><mml:math id="M118" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">4</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula> were extracted and analysed in the laboratory
at UFZ in Magdeburg, Germany, similarly to the analysis of background
concentrations on the resin: subsamples of 5 g resin were treated with
30 mL of 2 M KCl each and rotated for 24 h for extraction. The solution
was then analysed as described above.</p>
      <p>The time-averaged advective horizontal nutrient flux <inline-formula><mml:math id="M119" display="inline"><mml:mrow><mml:msub><mml:mi>J</mml:mi><mml:mtext>N</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula>
(mg m<inline-formula><mml:math id="M120" display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msup></mml:math></inline-formula> d<inline-formula><mml:math id="M121" 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> can be calculated using the following relationship
(Hatfield et al., 2004):
              <disp-formula id="Ch1.E2" content-type="numbered"><mml:math id="M122" display="block"><mml:mrow><mml:msub><mml:mi>J</mml:mi><mml:mtext>N</mml:mtext></mml:msub><mml:mo>=</mml:mo><mml:mstyle displaystyle="true"><mml:mfrac style="display"><mml:mrow><mml:msub><mml:mi>q</mml:mi><mml:mi>x</mml:mi></mml:msub><mml:msub><mml:mi>M</mml:mi><mml:mtext>N</mml:mtext></mml:msub></mml:mrow><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mi mathvariant="italic">α</mml:mi><mml:mi>r</mml:mi><mml:mi>L</mml:mi><mml:mi>t</mml:mi></mml:mrow></mml:mfrac></mml:mstyle><mml:mo>,</mml:mo></mml:mrow></mml:math></disp-formula>
            where <inline-formula><mml:math id="M123" display="inline"><mml:mrow><mml:msub><mml:mi>M</mml:mi><mml:mtext>N</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> (kg) is the mass of nutrient adsorbed, <inline-formula><mml:math id="M124" display="inline"><mml:mi>L</mml:mi></mml:math></inline-formula> (m) is the
length of the vertical thickness of the segment and <inline-formula><mml:math id="M125" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula> (–) is a
factor ranging from 0 to 2 that characterises the convergence (<inline-formula><mml:math id="M126" display="inline"><mml:mrow><mml:mi mathvariant="italic">α</mml:mi><mml:mo>&gt;</mml:mo><mml:mn mathvariant="normal">1</mml:mn><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> or divergence (<inline-formula><mml:math id="M127" display="inline"><mml:mrow><mml:mi mathvariant="italic">α</mml:mi><mml:mo>&lt;</mml:mo><mml:mn mathvariant="normal">1</mml:mn><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> of flow around the HPFM. If, like in the
case presented here, the hydraulic conductivity of the HPFM sorbent (resin or
AC) is much higher than that of the surrounding medium and the HPFM is in
direct contact with the sediments (i.e. in absence of an impermeable outer
casing or well wall), <inline-formula><mml:math id="M128" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula> can be estimated after Strack and
Haitjema (1981):
              <disp-formula id="Ch1.E3" content-type="numbered"><mml:math id="M129" display="block"><mml:mrow><mml:mi mathvariant="italic">α</mml:mi><mml:mo>=</mml:mo><mml:mfenced close=")" open="("><mml:mstyle displaystyle="true"><mml:mfrac style="display"><mml:mn mathvariant="normal">2</mml:mn><mml:mrow><mml:mn mathvariant="normal">1</mml:mn><mml:mo>+</mml:mo><mml:mstyle displaystyle="false"><mml:mfrac style="text"><mml:mn mathvariant="normal">1</mml:mn><mml:mrow><mml:msub><mml:mi>K</mml:mi><mml:mtext>D</mml:mtext></mml:msub></mml:mrow></mml:mfrac></mml:mstyle></mml:mrow></mml:mfrac></mml:mstyle></mml:mfenced><mml:mo>,</mml:mo></mml:mrow></mml:math></disp-formula>
            where <inline-formula><mml:math id="M130" display="inline"><mml:mrow><mml:msub><mml:mi>K</mml:mi><mml:mtext>D</mml:mtext></mml:msub><mml:mo>=</mml:mo><mml:msub><mml:mi>k</mml:mi><mml:mtext>D</mml:mtext></mml:msub><mml:msubsup><mml:mi>k</mml:mi><mml:mn mathvariant="normal">0</mml:mn><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msubsup></mml:mrow></mml:math></inline-formula> is the dimensionless ratio of the
uniform hydraulic conductivity of the HPFM sorptive matrix <inline-formula><mml:math id="M131" display="inline"><mml:mrow><mml:msub><mml:mi>k</mml:mi><mml:mtext>D</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula>
(L T<inline-formula><mml:math id="M132" 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> to the uniform local hydraulic conductivity of the surrounding
sediment <inline-formula><mml:math id="M133" display="inline"><mml:mrow><mml:msub><mml:mi>k</mml:mi><mml:mn mathvariant="normal">0</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> (L T<inline-formula><mml:math id="M134" 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>. For more details on the correction factor
<inline-formula><mml:math id="M135" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula> and applications where a solid casing is required or the
permeability of the surrounding sediments is higher than of the device see
Klammler et al. (2007) and Hatfield et al. (2004).</p>
</sec>
</sec>
<sec id="Ch1.S2.SS6">
  <title>Field testing of HPFMs</title>
<sec id="Ch1.S2.SS6.SSS1">
  <title>Study site</title>
      <p>A 30 m long stretch of the Holtemme River, a 3rd-order stream in the Bode
catchment, TERENO Harz/Central German Lowland Observatory, served as study
site (51<inline-formula><mml:math id="M136" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>56<inline-formula><mml:math id="M137" display="inline"><mml:msup><mml:mi/><mml:mo>′</mml:mo></mml:msup></mml:math></inline-formula>30.1<inline-formula><mml:math id="M138" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>′</mml:mo><mml:mo>′</mml:mo></mml:mrow></mml:msup></mml:math></inline-formula> N, 11<inline-formula><mml:math id="M139" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>09<inline-formula><mml:math id="M140" display="inline"><mml:msup><mml:mi/><mml:mo>′</mml:mo></mml:msup></mml:math></inline-formula>31.8<inline-formula><mml:math id="M141" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>′</mml:mo><mml:mo>′</mml:mo></mml:mrow></mml:msup></mml:math></inline-formula> E). The testing
reach is located in the lowest part of the river, where the water chemistry
is highly impacted by urban effluent and agriculture (Kamjunke et al., 2013).
Long stretches have been subjected to changes in the natural river morphology
by canalisation (Landesbetrieb für Hochwasserschutz und Wasserwirtschaft
Sachsen-Anhalt, 2009).</p>
      <p>The sediments at the selected site are sandy with gravel and small cobbles.
Sieving of sediment samples delivered the effective grain size <inline-formula><mml:math id="M142" display="inline"><mml:mrow><mml:msub><mml:mi>d</mml:mi><mml:mn>10</mml:mn></mml:msub><mml:mo>=</mml:mo><mml:mn>0.8</mml:mn></mml:mrow></mml:math></inline-formula> mm and a coefficient of uniformity <inline-formula><mml:math id="M143" display="inline"><mml:mrow><mml:msub><mml:mi>C</mml:mi><mml:mi>u</mml:mi></mml:msub><mml:mo>=</mml:mo><mml:mn>3.13</mml:mn></mml:mrow></mml:math></inline-formula>. The effective
porosity <inline-formula><mml:math id="M144" display="inline"><mml:mrow><mml:msub><mml:mi>n</mml:mi><mml:mtext>ef</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> is 13 %. After Fetter (2001) the intrinsic
permeability was estimated to be <inline-formula><mml:math id="M145" display="inline"><mml:mrow><mml:msub><mml:mi>K</mml:mi><mml:mi>i</mml:mi></mml:msub><mml:mo>=</mml:mo><mml:mn>96</mml:mn></mml:mrow></mml:math></inline-formula> m<inline-formula><mml:math id="M146" display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msup></mml:math></inline-formula> and the hydraulic
conductivity <inline-formula><mml:math id="M147" display="inline"><mml:mrow><mml:mi>k</mml:mi><mml:mo>=</mml:mo><mml:mn>81</mml:mn></mml:mrow></mml:math></inline-formula> m d<inline-formula><mml:math id="M148" 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> Clay lenses are present in the deeper
sediments below 35 cm.</p>
      <p>Mean discharge in the stream is 1.35 m<inline-formula><mml:math id="M149" 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="M150" 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> with highest peaks
around 5–6 m<inline-formula><mml:math id="M151" 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="M152" 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>. Discharge is continuously recorded by the local
authorities at the gauge Mahndorf, 15 km upstream of the testing site. In
the course of the year, NO<inline-formula><mml:math id="M153" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula> concentrations in the lower Holtemme
vary between 2 and 8 mg NO<inline-formula><mml:math id="M154" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula>-N L<inline-formula><mml:math id="M155" 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>
(Hochwasservorhersagezentrale, 2015/2016).</p>
      <p>The equipment was installed for a period of 7 days from 4 to 11 June 2015 as
illustrated in Fig. 2.</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F2"><caption><p>Overview of the instrumental setup at the Holtemme for the
testing phase in June 2015. R1, R2, resin-only HPFM; AC3, AC4, activated-carbon-only HPFM; L5, L6,
alternating layered HPFMs; MLSA, MLSB, multi-level sampler; O2 25, O2 45,
subsurface oxygen logger; <inline-formula><mml:math id="M156" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C, vertical temperature profile.</p></caption>
            <?xmltex \igopts{width=213.395669pt}?><graphic xlink:href="https://bg.copernicus.org/articles/14/631/2017/bg-14-631-2017-f02.png"/>

          </fig>

</sec>
<sec id="Ch1.S2.SS6.SSS2">
  <title>HPFM testing</title>
      <p>Based on the laboratory results for the nutrient backgrounds and the
consequent necessity to keep resin and AC separated two approaches for
constructing and deploying HPFM were tested in the field.</p>
</sec>
<sec id="Ch1.S2.SS6.SSSx1" specific-use="unnumbered">
  <title>Resin only and AC only HPFMs</title>
      <p>Four HPFMs
were constructed of which two contained only resin (R1 and R2) and the other
two contained only AC (AC3 and AC4). The HPFMs were then installed in pairs:
AC only and resin only next to each other with a separation distance of
30 cm. Those four HPFMs were sectioned in five horizontal flow segments, each with
a vertical length of 10 cm.</p>
      <p>For the calculation of the nutrient flux through each segment of R1 and R2,
we used the corresponding water flux through the respective segment of AC3
and AC4.</p>
</sec>
<sec id="Ch1.S2.SS6.SSSx2" specific-use="unnumbered">
  <title>Alternating segments of AC and resin HPFMs</title>
      <p>HPFMs L5 and L6 consisted of seven segments starting and ending with an AC
segment and adjacent segments altering between resin and AC (also see
Fig. 1). Each segment had a length of 7 cm.</p>
      <p>For the calculation of the nutrient flux through the resin segments we used
the interpolated water flow measured in the two adjacent AC segments.</p>
      <p>One additional HPFM with alternating layers was used as a control HPFM, in
order to assess potential tracer loss or nutrient contamination during
storage, transport and deployment/retrieval. This control was stored and
transported together with the other HPFMs. After deploying the control HPFM,
it was immediately retrieved, transported back to the laboratory and stored
until it was sampled and analysed along with the other HPFMs. The results
from the control HPFM also include uncertainties arising from sample
storage, analytical processing and the background concentration of nutrients
on the resin. Measurements of the other HPFMs were corrected by subtracting
the transport-, storage- and deployment-related tracer loss and nutrient
accumulation detected in the control.</p>
</sec>
<sec id="Ch1.S2.SS6.SSS3">
  <title>Additional measurements</title>
</sec>
<sec id="Ch1.S2.SS6.SSSx3" specific-use="unnumbered">
  <?xmltex \opttitle{Vertical Darcy velocity ($q_{{y}})$}?><title>Vertical Darcy velocity (<inline-formula><mml:math id="M157" display="inline"><mml:mrow><mml:msub><mml:mi>q</mml:mi><mml:mi>y</mml:mi></mml:msub><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula></title>
      <p>The vertical vector of hyporheic Darcy velocities <inline-formula><mml:math id="M158" display="inline"><mml:mrow><mml:msub><mml:mi>q</mml:mi><mml:mi>y</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> were measured
supplementary to the horizontal fluxes assessed with the HPFM in order to
estimate the general direction of flow (upwards or downwards) and to
calculate the angle of hyporheic flow.</p>
      <p>The vertical Darcy velocity (<inline-formula><mml:math id="M159" display="inline"><mml:mrow><mml:msub><mml:mi>q</mml:mi><mml:mi>y</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>) (m d<inline-formula><mml:math id="M160" 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> in the streambed was
calculated using temperature profiles measured between January and
October 2015. According to Keery et al. (2007) and Schmidt et al. (2014),
vertical flow velocities can be computed from the temporal shift of the daily
temperature signal in the subsurface water relative to the surface water. A
multi-level temperature sensor (Umwelt- und Ingenieurtechnik GmbH, Dresden,
Germany) was installed at the test site in January 2015. Temperature was
recorded at the surface–subsurface interface and at depths of 0.10, 0.125,
0.15, 0.2, 0.3 and 0.5 m in the sediment at a 10 min interval (accuracy of
0.07 <inline-formula><mml:math id="M161" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C over a range from 5 to 45 <inline-formula><mml:math id="M162" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C and a resolution of
0.04 <inline-formula><mml:math id="M163" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C). A numerical solution of the heat flow equation was then
used in conjunction with Dynamic Harmonic Regression signal processing
techniques for the analysis of these temperature time series. The coded model
was provided by Schmidt et al. (2014).</p>
</sec>
<sec id="Ch1.S2.SS6.SSSx4" specific-use="unnumbered">
  <title>Oxygen profiles</title>
      <p>We monitored the subsurface oxygen concentration as a primary indication on
the redox status of the hyporheic zone in order to evaluate the potential for
NO<inline-formula><mml:math id="M164" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula> reduction and PO<inline-formula><mml:math id="M165" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">4</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula> mobilisation. Therefore two oxygen
loggers (miniDO<inline-formula><mml:math id="M166" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>T, Precision measurement engineering Inc.) incorporated
into steel tubes acuminated at the lower end were installed in the river bed.
The tubes had filter-screens at the measuring depths of 25 and 45 cm below
surface–subsurface boundary. Installation was carried out 4 weeks prior to
the experiments, allowing enough time for re-equilibration of the surrounding
media. The measurement time step was 5 min.</p>
</sec>
<sec id="Ch1.S2.SS6.SSSx5" specific-use="unnumbered">
  <title>Multi-level samplers (MLSs)</title>
      <p>Pore-water nutrient concentrations were measured to substantiate the HPFM
results. Multi-level samplers as described in detail by Saenger and
Zanke (2009) are devices for the manual extraction of hyporheic pore water
from several distinct depths. The two samplers A and B used in these
experiments were manufactured by the institutional workshop of the UFZ. Like
the oxygen loggers both MLSs were installed 4 weeks prior to the experiment.
They consisted of an outer stainless steel tube with a length of 50 cm and a
diameter of 5 cm. Ceramic filters were inserted in this outer steel mantle
marking the extraction depths at 5, 15, 25 and 45 cm. The inner sides of the
filters were attached to steel pipes that ran to the top of the sampler so
that Teflon tubes could be attached. A protective hood was threaded on the
upper end of the sampler to preclude particles and sediment entrance. Per
sampler and depths 10 mL of pore water was manually extracted by connecting
a syringe to the open end of the Teflon tube and slowly sucking up water at a
rate of 2 mL min<inline-formula><mml:math id="M167" 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>. The four extraction depths were sampled successively,
always starting with the shallowest depths and continuing with ascendant
depths. Manual pore-water samples were taken on the 4 and 11 June 2015, both
times between 01:00 p.m. and 04:00 p.m. local time.</p>
      <p>The samples were filtered in the field through a 0.45 <inline-formula><mml:math id="M168" display="inline"><mml:mi mathvariant="normal">µ</mml:mi></mml:math></inline-formula>m membrane
filter and placed in boro-silica glass vials for transport to the laboratory.
Analysis for NO<inline-formula><mml:math id="M169" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula>, SRP, sulfate (SO<inline-formula><mml:math id="M170" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">4</mml:mn><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>-</mml:mo></mml:mrow></mml:msubsup><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> and boron (B) were
conducted in the central analytical laboratory of the UFZ, Magdeburg,
Germany. Analytical procedure for NO<inline-formula><mml:math id="M171" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula> and SRP was as in
the description above.</p>
      <p>SO<inline-formula><mml:math id="M172" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">4</mml:mn><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>-</mml:mo></mml:mrow></mml:msubsup></mml:mrow></mml:math></inline-formula> and B were used as natural tracers for groundwater and surface
water respectively. SO<inline-formula><mml:math id="M173" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">4</mml:mn><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>-</mml:mo></mml:mrow></mml:msubsup></mml:mrow></mml:math></inline-formula> was analysed on an ion chromatograph (ICS
3000, Thermo Fisher, formerly DIONEX), B was analysed on an inductively coupled
plasma mass spectrometer (ICP-MS 7500c, Agilent). As NO<inline-formula><mml:math id="M174" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula> and SRP
concentrations in the pore-water samples taken on 4 and 11 June 2015 were
unexpected and inconsistent with results from the HPFMs, the sampling was
repeated on  8 October. The aim of this repeated sampling was to
investigate whether diurnal variations in subsurface NO<inline-formula><mml:math id="M175" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula> and SRP
concentrations could explain the discrepancies between MLS and HPFM results.
We assumed that the HPFM measurements integrated temporal oscillations, while
MLS samples represented the specific concentrations around noon. In order to
test this hypothesis, both MLS were sampled twice, the first time in the
early morning before sunrise and again in the early afternoon (around
02:00 p.m.) during the sampling in October. Those samples were analysed for
NO<inline-formula><mml:math id="M176" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula>, SRP and SO<inline-formula><mml:math id="M177" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">4</mml:mn><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>-</mml:mo></mml:mrow></mml:msubsup></mml:mrow></mml:math></inline-formula>. Due to technical issues, boron could not
be measured in October.</p>

<?xmltex \floatpos{t}?><table-wrap id="Ch1.T2" specific-use="star"><caption><p>Selected morphological and hydrological parameters of the
testing site for the duration of the testing phase from
4–11 June 2015. Ranges are indicated for directly measured
parameters, the remaining parameters have been calculated from listed means.
HZ: hyporheic zone.</p></caption><oasis:table frame="topbot"><oasis:tgroup cols="5">
     <oasis:colspec colnum="1" colname="col1" align="left"/>
     <oasis:colspec colnum="2" colname="col2" align="left"/>
     <oasis:colspec colnum="3" colname="col3" align="left"/>
     <oasis:colspec colnum="4" colname="col4" align="right"/>
     <oasis:colspec colnum="5" colname="col5" align="right"/>
     <oasis:thead>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1">Surface water</oasis:entry>  
         <oasis:entry colname="col2">Abbreviation</oasis:entry>  
         <oasis:entry colname="col3">Unit</oasis:entry>  
         <oasis:entry colname="col4">Mean</oasis:entry>  
         <oasis:entry colname="col5">Range</oasis:entry>
       </oasis:row>
     </oasis:thead>
     <oasis:tbody>
       <oasis:row>  
         <oasis:entry colname="col1">Cross-sectional area</oasis:entry>  
         <oasis:entry colname="col2"><inline-formula><mml:math id="M178" display="inline"><mml:mrow><mml:msub><mml:mi>A</mml:mi><mml:mtext>SW</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col3">m<inline-formula><mml:math id="M179" display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msup></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col4">3.41</oasis:entry>  
         <oasis:entry colname="col5"/>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Depth</oasis:entry>  
         <oasis:entry colname="col2"><inline-formula><mml:math id="M180" display="inline"><mml:mi>h</mml:mi></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col3">m</oasis:entry>  
         <oasis:entry colname="col4">0.565</oasis:entry>  
         <oasis:entry colname="col5">0.54–0.61</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Width</oasis:entry>  
         <oasis:entry colname="col2"><inline-formula><mml:math id="M181" display="inline"><mml:mi>w</mml:mi></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col3">m</oasis:entry>  
         <oasis:entry colname="col4">6.03</oasis:entry>  
         <oasis:entry colname="col5">5.57–6.29</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Mean velocity</oasis:entry>  
         <oasis:entry colname="col2"><inline-formula><mml:math id="M182" display="inline"><mml:mi>v</mml:mi></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col3">m s<inline-formula><mml:math id="M183" 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="col4">0.097</oasis:entry>  
         <oasis:entry colname="col5"/>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Discharge</oasis:entry>  
         <oasis:entry colname="col2"><inline-formula><mml:math id="M184" display="inline"><mml:mrow><mml:msub><mml:mi>Q</mml:mi><mml:mtext>SW</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col3">m<inline-formula><mml:math id="M185" 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="M186" 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="col4">0.32</oasis:entry>  
         <oasis:entry colname="col5">0.30–0.34</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">NO<inline-formula><mml:math id="M187" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula> concentration</oasis:entry>  
         <oasis:entry colname="col2"><inline-formula><mml:math id="M188" display="inline"><mml:mrow><mml:msub><mml:mi>C</mml:mi><mml:mrow><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">NO</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:mrow><mml:mspace width="0.125em" linebreak="nobreak"/><mml:mtext>SW</mml:mtext></mml:mrow></mml:msub></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col3">mg NO<inline-formula><mml:math id="M189" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula>-N L<inline-formula><mml:math id="M190" 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="col4">2.86</oasis:entry>  
         <oasis:entry colname="col5">2.16–3.26</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">NO<inline-formula><mml:math id="M191" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula> mass flux</oasis:entry>  
         <oasis:entry colname="col2"><inline-formula><mml:math id="M192" display="inline"><mml:mrow><mml:msub><mml:mi>M</mml:mi><mml:mrow><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">NO</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:mrow><mml:mspace linebreak="nobreak" width="0.125em"/><mml:mtext>SW</mml:mtext></mml:mrow></mml:msub></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col3">mg NO<inline-formula><mml:math id="M193" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula>-N s<inline-formula><mml:math id="M194" 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="col4">896</oasis:entry>  
         <oasis:entry colname="col5"/>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">PO<inline-formula><mml:math id="M195" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">4</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula> concentration</oasis:entry>  
         <oasis:entry colname="col2"><inline-formula><mml:math id="M196" display="inline"><mml:mrow><mml:msub><mml:mi>C</mml:mi><mml:mrow><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">PO</mml:mi><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:mrow><mml:mspace linebreak="nobreak" width="0.125em"/><mml:mtext>SW</mml:mtext></mml:mrow></mml:msub></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col3">mg P L<inline-formula><mml:math id="M197" 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="col4">0.165</oasis:entry>  
         <oasis:entry colname="col5">0.111–0.231</oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1">PO<inline-formula><mml:math id="M198" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">4</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula> mass flux</oasis:entry>  
         <oasis:entry colname="col2"><inline-formula><mml:math id="M199" display="inline"><mml:mrow><mml:msub><mml:mi>M</mml:mi><mml:mrow><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">PO</mml:mi><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:mrow><mml:mspace linebreak="nobreak" width="0.125em"/><mml:mtext>SW</mml:mtext></mml:mrow></mml:msub></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col3">mg P s<inline-formula><mml:math id="M200" 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="col4">51</oasis:entry>  
         <oasis:entry colname="col5"/>
       </oasis:row>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1">Hyporheic zone upper 50 cm</oasis:entry>  
         <oasis:entry colname="col2"/>  
         <oasis:entry colname="col3"/>  
         <oasis:entry colname="col4"/>  
         <oasis:entry colname="col5"/>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Assessed depth of HZ</oasis:entry>  
         <oasis:entry colname="col2"><inline-formula><mml:math id="M201" display="inline"><mml:mrow><mml:msub><mml:mi>h</mml:mi><mml:mtext>HZ</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col3">m</oasis:entry>  
         <oasis:entry colname="col4">0.5</oasis:entry>  
         <oasis:entry colname="col5"/>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Cross-sectional area of HZ</oasis:entry>  
         <oasis:entry colname="col2"><inline-formula><mml:math id="M202" display="inline"><mml:mrow><mml:msub><mml:mi>A</mml:mi><mml:mtext>HZ</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col3">m<inline-formula><mml:math id="M203" display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msup></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col4">3.02</oasis:entry>  
         <oasis:entry colname="col5"/>
       </oasis:row>
     </oasis:tbody>
   </oasis:tgroup></oasis:table></table-wrap>

</sec>
<sec id="Ch1.S2.SS6.SSSx6" specific-use="unnumbered">
  <title>Surface water chemistry</title>
      <p>Surface water concentrations of SRP and NO<inline-formula><mml:math id="M204" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula> were monitored in order
to compare surface and subsurface water chemistry. Therefore we installed an
automated UV absorption sensor for NO<inline-formula><mml:math id="M205" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula> (ProPS WW, TriOS) at the
beginning of the testing reach for the duration of the experiments. The
pathway-length of the optical sensor was 10 mm, measuring at wavelengths
190–360 nm with a precision of 0.03 mg NO<inline-formula><mml:math id="M206" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula>-N L<inline-formula><mml:math id="M207" 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> and an
accuracy of <inline-formula><mml:math id="M208" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula>2 %. The measurement time step was set to 15 min. SRP,
SO<inline-formula><mml:math id="M209" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">4</mml:mn><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>-</mml:mo></mml:mrow></mml:msubsup></mml:mrow></mml:math></inline-formula> and B concentrations in the surface water were assessed with
grab samples taken simultaneously to the MLS measurements.</p>
      <p>The UV sensor was supplemented with a multi-parameter probe YSI 6600 V2/4
(YSI Environmental, Yellow Springs, Ohio) recording the following parameters:
pH (precision 0.01 units, accuracy <inline-formula><mml:math id="M210" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula>0.2 units), specific conductivity
(precision 0.001 mS cm<inline-formula><mml:math id="M211" 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>, accuracy <inline-formula><mml:math id="M212" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula>0.5 %), dissolved oxygen
(precision 0.01 mg L<inline-formula><mml:math id="M213" 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>, accuracy <inline-formula><mml:math id="M214" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula>1 %), temperature (precision
0.01 <inline-formula><mml:math id="M215" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C, accuracy <inline-formula><mml:math id="M216" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula>0.15 <inline-formula><mml:math id="M217" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C) and turbidity (precision
0.1 NTU, accuracy <inline-formula><mml:math id="M218" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula>2 %).</p>
</sec>
<sec id="Ch1.S2.SS6.SSS4">
  <title>Estimates of nitrate turnover rates based on HPFM
measurements</title>
      <p>Estimates for hyporheic removal activity <inline-formula><mml:math id="M219" display="inline"><mml:mrow><mml:msub><mml:mi>R</mml:mi><mml:mi>N</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> for the specific conditions
at the study site during the HPFM testing phase were calculated using the
morphological and hydrological parameters summarised in Table 2.</p>
      <p>The absolute amount of water passing the screened area of the hyporheic zone
<inline-formula><mml:math id="M220" display="inline"><mml:mrow><mml:msub><mml:mi>Q</mml:mi><mml:mtext>HZ</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> (m s<inline-formula><mml:math id="M221" 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> is the product of the average horizontal vector
of the Darcy velocity <inline-formula><mml:math id="M222" display="inline"><mml:mrow><mml:msub><mml:mi>q</mml:mi><mml:mi>x</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> (m s<inline-formula><mml:math id="M223" 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> measured in the HPFM and the
cross-sectional area of the upper 50 cm of the hyporheic zone <inline-formula><mml:math id="M224" display="inline"><mml:mrow><mml:msub><mml:mi>A</mml:mi><mml:mtext>HZ</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula>
(m<inline-formula><mml:math id="M225" display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msup></mml:math></inline-formula>). The proportion of water infiltrating the hyporheic zone
%<inline-formula><mml:math id="M226" display="inline"><mml:mrow><mml:msub><mml:mi>Q</mml:mi><mml:mtext>HZ</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> (%) was then calculated from the ratio
<inline-formula><mml:math id="M227" display="inline"><mml:mstyle displaystyle="false"><mml:mfrac style="text"><mml:mrow><mml:msub><mml:mi>Q</mml:mi><mml:mtext>HZ</mml:mtext></mml:msub></mml:mrow><mml:mrow><mml:msub><mml:mi>Q</mml:mi><mml:mtext>SW</mml:mtext></mml:msub></mml:mrow></mml:mfrac></mml:mstyle></mml:math></inline-formula>, where <inline-formula><mml:math id="M228" display="inline"><mml:mrow><mml:msub><mml:mi>Q</mml:mi><mml:mtext>SW</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> (m<inline-formula><mml:math id="M229" 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="M230" 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> is
the average discharge at the study site during the days of measurements,
derived from continuous records at the gauche Mahndorf, which were provided
by the local authority Landesbetrieb für Hochwasserschutz und
Wasserwirtschaft Sachsen-Anhalt.</p>
      <p>The NO<inline-formula><mml:math id="M231" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula> removal activity of the hyporheic zone <inline-formula><mml:math id="M232" display="inline"><mml:mrow><mml:msub><mml:mi>R</mml:mi><mml:mi>N</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> (%) was
calculated from the difference in average surface water concentration
<inline-formula><mml:math id="M233" display="inline"><mml:mrow><mml:msub><mml:mi>C</mml:mi><mml:mrow><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">NO</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:mrow><mml:mtext>-SW</mml:mtext></mml:mrow></mml:msub></mml:mrow></mml:math></inline-formula> (mg NO<inline-formula><mml:math id="M234" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula>-N L<inline-formula><mml:math id="M235" 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> and the average
concentrations measured with the HPFM <inline-formula><mml:math id="M236" display="inline"><mml:mrow><mml:msub><mml:mi>C</mml:mi><mml:mrow><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">NO</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:mrow><mml:mtext>-HZ</mml:mtext></mml:mrow></mml:msub></mml:mrow></mml:math></inline-formula>
(mg NO<inline-formula><mml:math id="M237" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula>-N L<inline-formula><mml:math id="M238" 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>, were <inline-formula><mml:math id="M239" display="inline"><mml:mrow><mml:msub><mml:mi>C</mml:mi><mml:mrow><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">NO</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:mrow><mml:mtext>-HZ</mml:mtext></mml:mrow></mml:msub></mml:mrow></mml:math></inline-formula> is the
quotient <inline-formula><mml:math id="M240" display="inline"><mml:mstyle displaystyle="false"><mml:mfrac style="text"><mml:mrow><mml:msub><mml:mi>J</mml:mi><mml:mtext>N</mml:mtext></mml:msub></mml:mrow><mml:mrow><mml:msub><mml:mi>q</mml:mi><mml:mi>x</mml:mi></mml:msub></mml:mrow></mml:mfrac></mml:mstyle></mml:math></inline-formula>.</p>
</sec>
</sec>
</sec>
<sec id="Ch1.S3">
  <title>Results</title>
<sec id="Ch1.S3.SS1">
  <title>Laboratory experiments</title>
<sec id="Ch1.S3.SS1.SSSx1" specific-use="unnumbered">
  <title>Loading capacity and biofouling</title>
      <p>Break-through in the sorbent
column experiments occurred after 300 pore volumes (PVs) or 21 days at
selected drainage for both NO<inline-formula><mml:math id="M241" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula> and SRP.</p>
      <p>In the biofouling experiment, the NO<inline-formula><mml:math id="M242" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula> concentration in the draining
water gradually decreased again after break-through. SRP in the draining
water was completely depleted 6 h after the break-through. The calculated
amount of retained nutrient in comparison to manufacturer value loading
capacities of Purolite<sup>®</sup> A 500MB Plus
indicate that the absorbing capacity of the resin in this small column
experiment was exhausted after 25.5 h (Supplement S1). We attributed the
decrease of nutrients in the draining solution after breakthrough to biotic
consumption of SRP (limiting nutrient) and NO<inline-formula><mml:math id="M243" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula>. Under the laser
scanning microscope growth of biofilm could be observed on obviously brown
stained Purolite<sup>®</sup> beads of the columns from
the biofouling experiment and to a very low degree on beads from the same
column which appeared still clean (Supplement S1). Browning of
Purolite<sup>®</sup> beads was not observed on
Purolite®beads from the loading experiment (bigger columns,
experiment not extended after break-through) but on the top 2 cm of the HPFM
R2 after exposure at the study site.</p>
</sec>
</sec>
<sec id="Ch1.S3.SS2">
  <title>Field testing</title>
<sec id="Ch1.S3.SS2.SSS1">
  <title>HPFMs and additional measurements</title>
</sec>
<sec id="Ch1.S3.SS2.SSSx1" specific-use="unnumbered">
  <title>HPFMs</title>
      <p>Deployment required approximately 15 min per HPFM and could be conducted by
two persons. The water depth during the installation was 40 to 100 cm,
depending on the specific location in the stream.</p>
      <p>The average horizontal water flow <italic>q</italic><inline-formula><mml:math id="M244" display="inline"><mml:msub><mml:mi/><mml:mi>x</mml:mi></mml:msub></mml:math></inline-formula> and nutrient flux
<inline-formula><mml:math id="M245" display="inline"><mml:mrow><mml:msub><mml:mi>J</mml:mi><mml:mtext>N</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> measured in the HPFM during the 7 day field testing are
illustrated in Fig. 3. All flux meter except 5 L showed declining
<inline-formula><mml:math id="M246" display="inline"><mml:mrow><mml:msub><mml:mi>J</mml:mi><mml:mtext>N</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M247" display="inline"><mml:mrow><mml:msub><mml:mi>q</mml:mi><mml:mi>x</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> with depth. Average horizontal <inline-formula><mml:math id="M248" display="inline"><mml:mrow><mml:msub><mml:mi>q</mml:mi><mml:mi>x</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> was
76 cm d<inline-formula><mml:math id="M249" 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>, ranging from 115 cm d<inline-formula><mml:math id="M250" 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 shallowest layer of
5 L to 20 cm d<inline-formula><mml:math id="M251" 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 deepest layer of AC4. Over the 7 days
duration of the experiment, accumulated horizontal flow velocities of <inline-formula><mml:math id="M252" display="inline"><mml:mrow><mml:msub><mml:mi>q</mml:mi><mml:mi>x</mml:mi></mml:msub><mml:mo>=</mml:mo><mml:mn>8.4</mml:mn></mml:mrow></mml:math></inline-formula> cm 7 d<inline-formula><mml:math id="M253" 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> (<inline-formula><mml:math id="M254" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula>0.02 cm 7 d<inline-formula><mml:math id="M255" 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>, <inline-formula><mml:math id="M256" display="inline"><mml:mrow><mml:mi>n</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:math></inline-formula>) and nutrient
fluxes of 29.4 mg NO<inline-formula><mml:math id="M257" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula>-N m<inline-formula><mml:math id="M258" display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msup></mml:math></inline-formula> 7 d<inline-formula><mml:math id="M259" 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>
(<inline-formula><mml:math id="M260" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula>0.7 mg m<inline-formula><mml:math id="M261" display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msup></mml:math></inline-formula> d<inline-formula><mml:math id="M262" 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>, <inline-formula><mml:math id="M263" display="inline"><mml:mrow><mml:mi>n</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:math></inline-formula>) and
36.4 mg SRP m<inline-formula><mml:math id="M264" display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msup></mml:math></inline-formula> 7 d<inline-formula><mml:math id="M265" 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> (<inline-formula><mml:math id="M266" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula>6.3 mg m<inline-formula><mml:math id="M267" display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msup></mml:math></inline-formula> d<inline-formula><mml:math id="M268" 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>, <inline-formula><mml:math id="M269" display="inline"><mml:mrow><mml:mi>n</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:math></inline-formula>)
were detected in the control HPFM. Breaking these results down to dial
values yields <inline-formula><mml:math id="M270" display="inline"><mml:mrow><mml:msub><mml:mi>q</mml:mi><mml:mi>x</mml:mi></mml:msub><mml:mo>=</mml:mo><mml:mn>1.2</mml:mn></mml:mrow></mml:math></inline-formula> cm d<inline-formula><mml:math id="M271" 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> (<inline-formula><mml:math id="M272" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula>0.003 cm d<inline-formula><mml:math id="M273" 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>, <inline-formula><mml:math id="M274" display="inline"><mml:mrow><mml:mi>n</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:math></inline-formula>)
and nutrient fluxes of 4.2 mg NO<inline-formula><mml:math id="M275" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula>-N m<inline-formula><mml:math id="M276" display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msup></mml:math></inline-formula> d<inline-formula><mml:math id="M277" 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>
(<inline-formula><mml:math id="M278" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula>0.1 mg m<inline-formula><mml:math id="M279" display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msup></mml:math></inline-formula> d<inline-formula><mml:math id="M280" 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>, <inline-formula><mml:math id="M281" display="inline"><mml:mrow><mml:mi>n</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:math></inline-formula>) and 5.2 mg SRP m<inline-formula><mml:math id="M282" display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msup></mml:math></inline-formula> d<inline-formula><mml:math id="M283" 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>
(<inline-formula><mml:math id="M284" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula>0.9 mg m<inline-formula><mml:math id="M285" display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msup></mml:math></inline-formula> d<inline-formula><mml:math id="M286" 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>, <inline-formula><mml:math id="M287" display="inline"><mml:mrow><mml:mi>n</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:math></inline-formula>). Comparing these fluxes to the
<inline-formula><mml:math id="M288" display="inline"><mml:mrow><mml:msub><mml:mi>J</mml:mi><mml:mtext>N</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> values measured with the other HPFM, an average 0.3 % of the
uncorrected NO<inline-formula><mml:math id="M289" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula> flux and 5 % of the uncorrected SRP flux were
attributed to tracer loss or nutrient accumulation resulting from transport,
deployment, retrieval, analytical processing of samples and the background
concentrations on the resin.</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F3" specific-use="star"><caption><p>Time-integrative measurements for  4–11 June 2015. Left: horizontal NO<inline-formula><mml:math id="M290" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula>-N and SRP-P flux
in mg m<inline-formula><mml:math id="M291" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> d<inline-formula><mml:math id="M292" 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> through the resin HPFM R1 <bold>(a)</bold>, R2 <bold>(b)</bold> and the layered HPFM
L5 <bold>(c)</bold>
and L6 <bold>(d)</bold>. Right: corresponding Darcy velocities
<inline-formula><mml:math id="M293" display="inline"><mml:mrow><mml:msub><mml:mi>q</mml:mi><mml:mi>x</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> in cm d<inline-formula><mml:math id="M294" 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>
through the activated carbon HPFM AC3 <bold>(e)</bold> and AC4 <bold>(f)</bold> and the layered HPFMs
5L <bold>(g)</bold> and 6L <bold>(h)</bold>.</p></caption>
            <?xmltex \igopts{width=341.433071pt}?><graphic xlink:href="https://bg.copernicus.org/articles/14/631/2017/bg-14-631-2017-f03.png"/>

          </fig>

</sec>
<sec id="Ch1.S3.SS2.SSSx2" specific-use="unnumbered">
  <?xmltex \opttitle{Vertical Darcy velocity ($q_{{y}}$)}?><title>Vertical Darcy velocity (<inline-formula><mml:math id="M295" display="inline"><mml:mrow><mml:msub><mml:mi>q</mml:mi><mml:mi>y</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>)</title>
      <p>Vertical water flow <inline-formula><mml:math id="M296" display="inline"><mml:mrow><mml:msub><mml:mi>q</mml:mi><mml:mi>y</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> in the streambed was predominantly downward from
January to October 2015. It was exclusively downward during the HPFM testing
phase, ranging from 40 to 55 cm d<inline-formula><mml:math id="M297" 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>. With this, vertical flow <inline-formula><mml:math id="M298" display="inline"><mml:mrow><mml:msub><mml:mi>q</mml:mi><mml:mi>y</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>
was slightly lower than average horizontal flow <inline-formula><mml:math id="M299" display="inline"><mml:mrow><mml:msub><mml:mi>q</mml:mi><mml:mi>x</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>. Resulting from the
relationship between <inline-formula><mml:math id="M300" display="inline"><mml:mrow><mml:msub><mml:mi>q</mml:mi><mml:mi>y</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M301" display="inline"><mml:mrow><mml:msub><mml:mi>q</mml:mi><mml:mi>x</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> the angle of hyporheic flow
(tan<inline-formula><mml:math id="M302" display="inline"><mml:mrow><mml:mi mathvariant="italic">α</mml:mi><mml:mo>=</mml:mo><mml:mstyle displaystyle="false"><mml:mfrac style="text"><mml:mrow><mml:msub><mml:mi>q</mml:mi><mml:mi>y</mml:mi></mml:msub></mml:mrow><mml:mrow><mml:msub><mml:mi>q</mml:mi><mml:mi>x</mml:mi></mml:msub></mml:mrow></mml:mfrac></mml:mstyle><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> was 32<inline-formula><mml:math id="M303" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula> downwards.</p>
</sec>
<sec id="Ch1.S3.SS2.SSSx3" specific-use="unnumbered">
  <title>Oxygen profiles</title>
      <p>We observed strong diel variations in oxygen concentration in the hyporheic
zone. During several nights oxygen was nearly depleted (Fig. 4). The minima
and maxima oxygen concentrations in the subsurface occurred contemporarily
with the respective extremes in the surface water. Interestingly the
amplitude in O<inline-formula><mml:math id="M304" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> oscillation was higher at 45 cm depths than at 25 cm
depths.</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F4"><caption><p>Time series of dissolved oxygen concentrations in the
surface water (green) and the subsurface water (depth 25 cm, purple;
depth 45 cm, orange) at the study site from 4–11 June 2015.<?xmltex \hack{\vspace*{11mm}}?></p></caption>
            <?xmltex \igopts{width=236.157874pt}?><graphic xlink:href="https://bg.copernicus.org/articles/14/631/2017/bg-14-631-2017-f04.png"/>

          </fig>

</sec>
<sec id="Ch1.S3.SS2.SSSx4" specific-use="unnumbered">
  <title>Multi-level samplers</title>
      <p>In order to facilitate direct comparison, nutrient fluxes as measured in the
HPFM were converted to flux-averaged concentrations which are the quotient of
<inline-formula><mml:math id="M305" display="inline"><mml:mrow><mml:msub><mml:mi>J</mml:mi><mml:mtext>N</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> and the respective <inline-formula><mml:math id="M306" display="inline"><mml:mrow><mml:msub><mml:mi>q</mml:mi><mml:mi>x</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> (Fig. 5). Overall, nutrient
concentrations in the manually sampled pore water taken in June 2015 were
higher than the average concentration derived from the HPFM. While the
expected increase of SRP and decrease of NO<inline-formula><mml:math id="M307" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula> and water flow with
depths was observed in the HPFM, pore water extracted with the MLS showed no
change over depth neither for NO<inline-formula><mml:math id="M308" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula> nor SRP. In the repeated manual
pore-water samples taken in October (Fig. 6) NO<inline-formula><mml:math id="M309" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula> concentrations were
uniformly lower in the early morning than in the afternoon, whereas SRP
behaved the other way round. This trend was consistent in both samplers even
though the average concentration and distribution over depths differed
between the samplers A and B.</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F5"><caption><p>Comparison between manually sampled pore water from MLS
(red) and HPFM (blue) for NO<inline-formula><mml:math id="M310" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula>-N (top)
and SRP (bottom). Each MLS was sampled on  4 and 11 June 2015. Average
surface water concentration during the deployment time and the
concentrations at the time point of MLS sampling are marked in green.</p></caption>
            <?xmltex \igopts{width=236.157874pt}?><graphic xlink:href="https://bg.copernicus.org/articles/14/631/2017/bg-14-631-2017-f05.png"/>

          </fig>

      <?xmltex \floatpos{t}?><fig id="Ch1.F6"><caption><p>Concentrations of NO<inline-formula><mml:math id="M311" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula>-N and SRP in time differentiating manually taken pore-water
samples from MLS A (bottom) and MLS B (top) on 8 October 2015. Corresponding surface water concentrations are marked as
vertical lines.</p></caption>
            <?xmltex \igopts{width=219.08622pt}?><graphic xlink:href="https://bg.copernicus.org/articles/14/631/2017/bg-14-631-2017-f06.png"/>

          </fig>

      <p>On both sampling dates in June (4 and 11 June 2015) neither SO<inline-formula><mml:math id="M312" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">4</mml:mn><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>-</mml:mo></mml:mrow></mml:msubsup></mml:mrow></mml:math></inline-formula> nor
boron showed a vertical gradient in concentrations in the pore-water samples.
SO<inline-formula><mml:math id="M313" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">4</mml:mn><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>-</mml:mo></mml:mrow></mml:msubsup></mml:mrow></mml:math></inline-formula> concentrations of 170 mg L<inline-formula><mml:math id="M314" 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> on  4 June and
190 mg L<inline-formula><mml:math id="M315" 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> on  11 June were in the same range as surface water
concentrations. So too were boron concentrations with 50 to
60 <inline-formula><mml:math id="M316" display="inline"><mml:mi mathvariant="normal">µ</mml:mi></mml:math></inline-formula>g L<inline-formula><mml:math id="M317" 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>, consistent with the concentrations in the surface
water, indicating no or only minor groundwater influence. Also in October
SO<inline-formula><mml:math id="M318" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">4</mml:mn><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>-</mml:mo></mml:mrow></mml:msubsup></mml:mrow></mml:math></inline-formula> concentrations in the pore-water samples were in the range of
surface water concentrations, slightly declining with depth.</p>
</sec>
<sec id="Ch1.S3.SS2.SSSx5" specific-use="unnumbered">
  <title>Surface water chemistry</title>
      <p>Temperature, O<inline-formula><mml:math id="M319" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> and pH showed the expected diurnal amplitudes whereas
specific conductivity and NO<inline-formula><mml:math id="M320" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula> did not display a distinct diurnal
pattern (Table 4).</p>
</sec>
<sec id="Ch1.S3.SS2.SSS2">
  <title>Estimates of nitrate turnover rates based on HPFM
measurements</title>
      <p>With an average water flow of <inline-formula><mml:math id="M321" display="inline"><mml:mrow><mml:msub><mml:mi>Q</mml:mi><mml:mtext>HZ</mml:mtext></mml:msub><mml:mo>=</mml:mo><mml:mn>2.65</mml:mn><mml:mo>×</mml:mo><mml:msup><mml:mn>10</mml:mn><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">5</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula> m<inline-formula><mml:math id="M322" 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="M323" 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> through the assessed upper 50 cm of the hyporheic
zone and across the 6 m width of the stream, 0.008 % of water
transported in the river entered the hyporheic zone (Table 3).</p>

<?xmltex \floatpos{t}?><table-wrap id="Ch1.T3" specific-use="star"><caption><p>Summarised parameters of NO<inline-formula><mml:math id="M324" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula> transport and removal through the upper 50 cm of the hyporheic
zone at the test site for the testing phase from 4–11 June 2015. Ranges
are indicated for directly measured parameters, the remaining parameters
have been calculated from listed means.</p></caption><oasis:table frame="topbot"><oasis:tgroup cols="5">
     <oasis:colspec colnum="1" colname="col1" align="left"/>
     <oasis:colspec colnum="2" colname="col2" align="left"/>
     <oasis:colspec colnum="3" colname="col3" align="left"/>
     <oasis:colspec colnum="4" colname="col4" align="right"/>
     <oasis:colspec colnum="5" colname="col5" align="right"/>
     <oasis:thead>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1"/>  
         <oasis:entry colname="col2">Abbreviation</oasis:entry>  
         <oasis:entry colname="col3">Unit</oasis:entry>  
         <oasis:entry colname="col4">Mean</oasis:entry>  
         <oasis:entry colname="col5">Range</oasis:entry>
       </oasis:row>
     </oasis:thead>
     <oasis:tbody>
       <oasis:row>  
         <oasis:entry colname="col1">Water flow through HZ</oasis:entry>  
         <oasis:entry colname="col2"><inline-formula><mml:math id="M325" display="inline"><mml:mrow><mml:msub><mml:mi>Q</mml:mi><mml:mtext>HZ</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col3">L s<inline-formula><mml:math id="M326" 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="col4">0.0265</oasis:entry>  
         <oasis:entry colname="col5"/>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">% of river water entering HZ</oasis:entry>  
         <oasis:entry colname="col2">%<inline-formula><mml:math id="M327" display="inline"><mml:mrow><mml:msub><mml:mi>Q</mml:mi><mml:mtext>HZ</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col3">%</oasis:entry>  
         <oasis:entry colname="col4">0.008</oasis:entry>  
         <oasis:entry colname="col5"/>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Horizontal Darcy velocity</oasis:entry>  
         <oasis:entry colname="col2"><inline-formula><mml:math id="M328" display="inline"><mml:mrow><mml:msub><mml:mi>q</mml:mi><mml:mi>x</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col3">cm d<inline-formula><mml:math id="M329" 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="col4">76</oasis:entry>  
         <oasis:entry colname="col5">20–116</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Average NO<inline-formula><mml:math id="M330" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula> concentration in the HZ</oasis:entry>  
         <oasis:entry colname="col2"><inline-formula><mml:math id="M331" display="inline"><mml:mrow><mml:msub><mml:mi>C</mml:mi><mml:mrow><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">NO</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:mrow><mml:mspace width="0.125em" linebreak="nobreak"/><mml:mtext>HZ</mml:mtext></mml:mrow></mml:msub></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col3">mg NO<inline-formula><mml:math id="M332" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula>-N L<inline-formula><mml:math id="M333" 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="col4">1.39</oasis:entry>  
         <oasis:entry colname="col5">0.31–2.86</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">% NO<inline-formula><mml:math id="M334" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula> entering the HZ which is removed</oasis:entry>  
         <oasis:entry colname="col2"><inline-formula><mml:math id="M335" display="inline"><mml:mrow><mml:msub><mml:mi>R</mml:mi><mml:mi>N</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col3">%</oasis:entry>  
         <oasis:entry colname="col4">52</oasis:entry>  
         <oasis:entry colname="col5"/>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Potential NO<inline-formula><mml:math id="M336" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula> load entering HZ</oasis:entry>  
         <oasis:entry colname="col2"><inline-formula><mml:math id="M337" display="inline"><mml:mrow><mml:msub><mml:mi>M</mml:mi><mml:mtext>HZ theory</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col3">mg NO<inline-formula><mml:math id="M338" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula>-N s<inline-formula><mml:math id="M339" 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="col4">0.08</oasis:entry>  
         <oasis:entry colname="col5"/>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">NO<inline-formula><mml:math id="M340" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula> load measured in HZ</oasis:entry>  
         <oasis:entry colname="col2"><inline-formula><mml:math id="M341" display="inline"><mml:mrow><mml:msub><mml:mi>M</mml:mi><mml:mtext>HZ measured</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col3">mg NO<inline-formula><mml:math id="M342" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula>-N s<inline-formula><mml:math id="M343" 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="col4">0.037</oasis:entry>  
         <oasis:entry colname="col5"/>
       </oasis:row>
     </oasis:tbody>
   </oasis:tgroup></oasis:table></table-wrap>

<?xmltex \floatpos{t}?><table-wrap id="Ch1.T4" specific-use="star"><caption><p>Benchmark surface water parameters derived from the
continuous sensor records from 4–11 June and 8–11 October 2015:
Temp: temperature; SpC: specific conductivity; O<inline-formula><mml:math id="M344" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>: dissolved oxygen.</p></caption><oasis:table frame="topbot"><oasis:tgroup cols="7">
     <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:thead>
       <oasis:row>  
         <oasis:entry colname="col1"/>  
         <oasis:entry colname="col2"/>  
         <oasis:entry colname="col3">Temp</oasis:entry>  
         <oasis:entry colname="col4">SpC</oasis:entry>  
         <oasis:entry colname="col5">pH</oasis:entry>  
         <oasis:entry colname="col6">O<inline-formula><mml:math id="M345" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col7">NO<inline-formula><mml:math id="M346" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula></oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1"/>  
         <oasis:entry colname="col2"/>  
         <oasis:entry colname="col3"><inline-formula><mml:math id="M347" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C</oasis:entry>  
         <oasis:entry colname="col4"><inline-formula><mml:math id="M348" display="inline"><mml:mi mathvariant="normal">µ</mml:mi></mml:math></inline-formula>S cm<inline-formula><mml:math id="M349" 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="col5">–</oasis:entry>  
         <oasis:entry colname="col6">mg L<inline-formula><mml:math id="M350" 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 NO<inline-formula><mml:math id="M351" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula>-N L<inline-formula><mml:math id="M352" 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:row>
     </oasis:thead>
     <oasis:tbody>
       <oasis:row>  
         <oasis:entry colname="col1">4–11 June 2015</oasis:entry>  
         <oasis:entry colname="col2">mean</oasis:entry>  
         <oasis:entry colname="col3">17.81</oasis:entry>  
         <oasis:entry colname="col4">1063</oasis:entry>  
         <oasis:entry colname="col5">8.42</oasis:entry>  
         <oasis:entry colname="col6">9.37</oasis:entry>  
         <oasis:entry colname="col7">2.86</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1"/>  
         <oasis:entry colname="col2">SD</oasis:entry>  
         <oasis:entry colname="col3">2.57</oasis:entry>  
         <oasis:entry colname="col4">46</oasis:entry>  
         <oasis:entry colname="col5">0.27</oasis:entry>  
         <oasis:entry colname="col6">2.01</oasis:entry>  
         <oasis:entry colname="col7">0.32</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1"/>  
         <oasis:entry colname="col2">min</oasis:entry>  
         <oasis:entry colname="col3">13.38</oasis:entry>  
         <oasis:entry colname="col4">886</oasis:entry>  
         <oasis:entry colname="col5">7.75</oasis:entry>  
         <oasis:entry colname="col6">6.13</oasis:entry>  
         <oasis:entry colname="col7">2.16</oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1"/>  
         <oasis:entry colname="col2">max</oasis:entry>  
         <oasis:entry colname="col3">23.79</oasis:entry>  
         <oasis:entry colname="col4">1224</oasis:entry>  
         <oasis:entry colname="col5">8.84</oasis:entry>  
         <oasis:entry colname="col6">13.12</oasis:entry>  
         <oasis:entry colname="col7">3.26</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">8–11 October 2015</oasis:entry>  
         <oasis:entry colname="col2">mean</oasis:entry>  
         <oasis:entry colname="col3">11.22</oasis:entry>  
         <oasis:entry colname="col4">951</oasis:entry>  
         <oasis:entry colname="col5">8.21</oasis:entry>  
         <oasis:entry colname="col6">10.48</oasis:entry>  
         <oasis:entry colname="col7">2.75</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1"/>  
         <oasis:entry colname="col2">SD</oasis:entry>  
         <oasis:entry colname="col3">2.75</oasis:entry>  
         <oasis:entry colname="col4">59</oasis:entry>  
         <oasis:entry colname="col5">0.10</oasis:entry>  
         <oasis:entry colname="col6">0.91</oasis:entry>  
         <oasis:entry colname="col7">0.28</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1"/>  
         <oasis:entry colname="col2">min</oasis:entry>  
         <oasis:entry colname="col3">6.02</oasis:entry>  
         <oasis:entry colname="col4">818</oasis:entry>  
         <oasis:entry colname="col5">7.99</oasis:entry>  
         <oasis:entry colname="col6">9.09</oasis:entry>  
         <oasis:entry colname="col7">1.95</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1"/>  
         <oasis:entry colname="col2">max</oasis:entry>  
         <oasis:entry colname="col3">15.32</oasis:entry>  
         <oasis:entry colname="col4">1056</oasis:entry>  
         <oasis:entry colname="col5">8.44</oasis:entry>  
         <oasis:entry colname="col6">12.44</oasis:entry>  
         <oasis:entry colname="col7">3.40</oasis:entry>
       </oasis:row>
     </oasis:tbody>
   </oasis:tgroup></oasis:table></table-wrap>

      <p>While the average surface water concentration was
2.86 mg NO<inline-formula><mml:math id="M353" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula>-N L<inline-formula><mml:math id="M354" 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>, the average concentration in the
subsurface measured with the HPFM was only
1.39 mg NO<inline-formula><mml:math id="M355" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula>-N L<inline-formula><mml:math id="M356" 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>. Assuming that the difference between
surface and subsurface concentration arose from hyporheic consumption of
infiltrating NO<inline-formula><mml:math id="M357" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula>, the average removal rate <inline-formula><mml:math id="M358" display="inline"><mml:mrow><mml:msub><mml:mi>R</mml:mi><mml:mi>N</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> was 52 %. For
SRP the average surface water concentration from 4 to 11 June 2015 was
0.165 mg P L<inline-formula><mml:math id="M359" 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>, the average concentration in the hyporheic zone was
0.11 mg P L<inline-formula><mml:math id="M360" 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>.</p>
</sec>
</sec>
</sec>
<sec id="Ch1.S4">
  <title>Discussion</title>
      <p>The application of the HPFM for quantitative in situ measurement of
horizontal NO<inline-formula><mml:math id="M361" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula> and SRP fluxes through the hyporheic zone is novel.
An earlier study on passive flux meter (SBPFM) in river beds (Layton, 2015)
only assessed vertical flow of contaminants and is therefore not comparable
to the application presented here. In the current work, adaptations were
developed, tested and improved. Those include the choice of an appropriate
resin, assessment of biofilm growth on the instruments and an approach that
avoids challenges with contamination of the sorbent with nutrients. The
results from the control HPFM showed that the uncertainty in measurement
related to handling of the HPFM and processing of samples as conducted in
this study is acceptable. Finally, the minimum and maximum deployment time
will depend on the Darcy velocity and nutrient concentrations at a study
site. Since the values derived from the control incorporate all the
processing steps of HPFM and samples, they can be regarded as the method
detection limit (MDL) (Greenberg et al., 1992). The MDL defines the
lower limit for the use of HPFM in cases where nutrient fluxes are very low
and deployment time cannot be extended. Based on the accumulated values
detected in the control, the minimum deployment time can be estimated. In
systems with high nutrient concentrations, usually the flow velocity <inline-formula><mml:math id="M362" display="inline"><mml:mrow><mml:msub><mml:mi>q</mml:mi><mml:mi>x</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>
will be the limiting factor. In our application the MDL for <inline-formula><mml:math id="M363" display="inline"><mml:mrow><mml:msub><mml:mi>q</mml:mi><mml:mi>x</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> derived
from the control was 8.4 cm for the complete deployment time (7 days). If
the method inherited uncertainty should not be more than 5 % of the total
measurement, the product of duration (in days) and velocity (in cm) should be
at least 168 (<inline-formula><mml:math id="M364" display="inline"><mml:mrow><mml:mn>20</mml:mn><mml:mo>×</mml:mo><mml:mn>8.4</mml:mn></mml:mrow></mml:math></inline-formula>). As an example: if measured <inline-formula><mml:math id="M365" display="inline"><mml:mrow><mml:msub><mml:mi>q</mml:mi><mml:mi>x</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> is around
200 cm d<inline-formula><mml:math id="M366" 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>, 1 day (24 h) of deployment is sufficient. The lowest
<inline-formula><mml:math id="M367" display="inline"><mml:mrow><mml:msub><mml:mi>q</mml:mi><mml:mi>x</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> detected in our assessment was 21 cm d<inline-formula><mml:math id="M368" 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 HPFM AC4, see
Fig. 3f), so that actually a deployment duration of 8 days would have been
optimal. The same estimation can additionally be derived for expected
nutrient fluxes. In systems with low nutrient concentrations, it would be
preferable to start estimating the minimum deployment time based on the
nutrient fluxes. We recommend that a control HPFM is incorporated in each
field application of HPFM in order to determine the specific MDL. The upper
limit is given by the loading capacity of the resin or complete displacement
of all resident alcohol tracers.</p>
      <p>The high-nutrient background on the AC required the separation of resin and
AC in the HPFMs. We tested two different HPFM designs in this study, of which
each inherits designated characteristics being more or less beneficial for
different specifications. The first approach consists of pairs of two HPFMs where one is
used to assess the water flux and the second to capture nutrients, and  is
preferable if a highly resolved depth profile is needed (a heterogeneous
horizontal flux in the vertical direction). Since this approach assumes that
local horizontal heterogeneity is negligible in the range of 20–30 cm, we
recommend this type only for the use in uniform systems such as channelised
river reaches. Even in those systems however, small-scale variability in
streambed and sediment characteristics can cause spatially heterogeneous
flow distributions (Lewandowski et al., 2011; Mendoza-Lera and Mutz, 2013).
The second approach with alternating nutrient sorbents and water flux
measuring segments is therefore preferable in most other cases as long as a
high resolution over the vertical profile is not required. In general,
several HPFMs should be grouped together in order to obtain representative
results.</p>
      <p>Further improvements of the HPFM for nutrient studies in the subsurface of
rivers could be achieved by identifying a nutrient-free carrier for the
tracers. First, because this would allow measuring nutrient and water flux at
the same location within the device and thereby increase spatial resolution, and second, because in a mixed texture of nutrient absorber and tracer carrier
the antibacterial nature of the activated carbon would suppress biofouling on
the absorbent. We observed substantial biofilm growth on the resin in the
laboratory and on the top 2 cm of the field-deployed HPFM R2. The results of
the column experiments suggest that biofilm growth on the resin porous media
did not affect its loading capacity. Further, biofilm growth was only visible
on columns which were run beyond breakthrough, suggesting that considerable
biofouling only started after the loading capacity of the tracer was
exhausted. R2 detected higher NO<inline-formula><mml:math id="M369" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula> fluxes in the top layer than the
other HPFM. This could be due to contamination of the top layer of this HPFM
with surface water (if the HPFM was not introduced sufficiently deep into the
sediments). The further implication would be that this layer was exposed to
much higher water and nutrient infiltration, so that the loading capacity was
exhausted before the end of the experiment allowing biofilm accumulation. At
the current state it is unclear to what extent the biofilm bound nutrients
can be extracted by the procedure used here. Further experiments would also
be needed to clarify under which conditions biofilm growth can occur and if
bacterial uptake, transformation and release of nutrients influence the
concentrations of nutrients inside the HPFM. HPFM segments on which biofilm
is visible should be interpreted with caution. Finally, identifying a
procedure or materials which completely inhibit biofouling will be an
important step in the further development of HPFM.</p>
      <p>In addition to instrumental adaptations we presented an installation
procedure, which allows for smooth deployment with minimal disturbance of
the system. Unlike typical well screen deployments where PFMs (Annable et
al., 2005; Verreydt et al., 2013) or SBPFMs (Layton, 2015) have been inserted
into a screened plastic or steel casing, our technique enabled the direct
contact of the HPFM with the surrounding river sediments. Disturbing the
natural structure of the sediment, potentially resulting in artificial flow
paths, is intrinsic to all intrusive techniques, including HPFMs. Still,
dispensing of a solid wall improves the integration of  HPFMs in the
natural system and prevents the generation of preferential flow paths along
the wall of the device. Additionally, the HPFMs include a measurement time
that is long relative to the duration of the installation, suggesting that
the presented method causes lower disturbance compared to other intrusive
measurements. While the installation of mini-drive points or heat pulse
sensors in sediments coarser than sand may be difficult or even impossible
and also proved unfeasible at our field site, installation of the HPFM with
the presented technique was successful. The correction for convergence of
flowlines into the device or divergence around it is relatively simple and
already incorporated in the equation for the flux calculation. Heterogeneous
permeability of the hyporheic zone around the HPFM does not distort the
correction term as long as the permeability of the surrounding is coherently
higher or coherently lower than the permeability of the HPFM matrix.
Pre-measurements are therefore necessary for the selection of a suitable
resin and tracer carrier. We believe that the presented approach and
equations are applicable for a wide range of field conditions. However, for
very coarse sediments, a protection of the HPFM with a solid screen might
still be preferred. If fine particles are observed to bypass the mesh and
enter the HPFM, a finer mesh should be chosen. We did not observe clogging
of the mesh or intrusion of particles at our study, though in highly
permeable systems with fine particle transport this might have to be
considered.</p>
      <p>A major advantage of the HPFM method is highlighted by the findings of the
7 day long field testing. In June, we found discrepancies between the average
concentrations measured in the HPFM and the concentration found using the
MLS. From our measurements it is not possible to prove that the HPFM results
are correct and the MLS results biased. Nevertheless, the HPFM showed the
expected decline in <inline-formula><mml:math id="M370" display="inline"><mml:mrow><mml:msub><mml:mi>J</mml:mi><mml:mtext>N</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> with depths, whereas the MLS pore-water
concentrations were similar at all depths. This can be related to two
reasons. First, we might have sampled surface water which bypassed along the
wall of the MLS. The question would then be why that happened in June but not
in October; second, we might have sampled the MLS at a time point when the
hyporheic zone was inactive in respect to nutrient processing. Considering
the high diurnal amplitudes in hyporheic oxygen concentration, we assumed
that the discrepancy between HPFM and MLS arose from oscillations in
hyporheic nutrient concentrations similar to the oxygen pattern. Microbial
consumption of O<inline-formula><mml:math id="M371" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> in the sediments can, depending on nutrient
concentration in surface water and transfer of these nutrients to the
sediments, result in O<inline-formula><mml:math id="M372" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> depletion in the subsurface. Especially in
nutrient-rich streams the related diurnal oscillations in O<inline-formula><mml:math id="M373" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>
concentration favour night time denitrification in the hyporheic zone
(Christensen et al., 1990; Laursen and Seitzinger, 2004; Harrison et al.,
2005; O'Connor and Hondzo, 2008; Nimick et al., 2011). The redox conditions
in the subsurface may also regulate the mobilisation/demobilisation of
phosphate (Smith et al., 2011). The repeated manual sampling of pore water
from MLS in October showed diurnal variations of SRP and NO<inline-formula><mml:math id="M374" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula> in the
subsurface of the testing reach, supporting the hypothesis that diurnal
cycles in benthic metabolism caused temporal variations in hyporheic SRP and
NO<inline-formula><mml:math id="M375" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula> concentrations at our study site. As the majority of sampling is
commonly conducted during daylight hours, night time conditions are
under-represented in studies relying on single manual sampling events. Flux
average concentrations can deviate by more than 50 % from estimates based
on single event sampling, as was illustrated by comparison between our manual
samples and the average pore-water concentrations calculated from the HPFM
data.</p>
      <p>Repeated pore-water sampling at high frequencies can be used to determine
diurnal dynamics. However, continuing this over a longer time span is
laborious, whereas if only few single time-specific snap shot samplings are
conducted, the results may not realistically represent the overall conditions
at the target site. Our comparison between MLS and HPFM reinforce the need
for long-term recording of nutrient transport through the hyporheic zone. In
general, most of our knowledge on hyporheic nutrient dynamics is based on
measured surface water dynamics and models which project these dynamics on
hyporheic processing. Theoretically, we could measure nutrient fluxes in the
hyporheic zone and estimate whole-stream uptake rates from these
measurements. However, the substantially higher effort to obtain subsurface
data is not justified in most cases. As long as the overall in-stream
retention is the focus, surface water monitoring will remain the method of
choice. Innovative tracer experiments may even allow quantifying hyporheic
exchange in streams. Haggerty et al. (2009) proposed a “smart” tracer
approach, where the injected substance resazurin converts irreversibly to
resofurin under metabolic activity. While a promising tool for detecting
metabolic activity at the sediment–water interface in streams, first,
uncertainties about sorption and transformation characteristics of these
tracers remain (Lemke et al., 2014) and second, those methods give no
evidence about nutrient transport to those reactive sites.</p>
      <p>Thus, whenever the nutrient processing function of the hyporheic zone and
its quantitative contribution to stream nutrient retention is of interest,
for example in the evaluation of restoration measures including a
rehabilitation of the river bed, direct measurements of hyporheic fluxes are
indispensable. The HPFMs are a valuable approach that can be efficiently
used to characterise and quantify nutrient dynamics in a sediment system. We
consider that a combination of HPFM, MLS and concurrent measurements of pore
water oxygen concentrations, as presented in this study, provide a practical
set-up to interpret hyporheic nutrient dynamics.</p>
      <p>Like solute concentrations and water flow patterns, the vertical extension of
the hyporheic zone varies in time and space and between different rivers and
reaches. Our set-up assessed exclusively the upper 50 cm of the hyporheic
zone. We found continuously decreasing NO<inline-formula><mml:math id="M376" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula> concentrations with
depths, suggesting that this entire area (and potentially deeper) of the
subsurface contained active sites for nitrate removal. While it was stated
that denitrification is limited to the upper few cm of the hyporheic zone
close to the sediment–water interface (Hill et al., 1998; Harvey et al.,
2013), our results are in accordance to findings by Zarnetske et al. (2011b)
and Kessler et al. (2012) who also report extended active hyporheic zones.
Conducting collateral tracer tests, as suggested for example by Abbott et al. (2016),
could deliver further evidence and characterise distinct flow paths.
Nevertheless, since vertical water movement was overall downward and the
lowest concentrations of NO<inline-formula><mml:math id="M377" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula> were observed in the deepest segments
of the HPFM, it is very likely that the hyporheic zone at our study site
extends deeper than the 50 cm evaluated. The length of an HPFM can easily be
increased, depending on the individual site conditions.</p>
      <p>Considering the high spatial heterogeneity of the hyporheic zone, a larger
number of HPFM would be needed to derive reliable and statistically
supportable rates of hyporheic nutrient dynamics. The following example aims
to display further possibilities of interpreting HPFM measurements. At our
study site, the hyporheic removal potential <inline-formula><mml:math id="M378" display="inline"><mml:mrow><mml:msub><mml:mi>R</mml:mi><mml:mtext>N</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> of more than
50 % of infiltrating NO<inline-formula><mml:math id="M379" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula> and 30 % of SRP suggests an active
hyporheus. Evaluation of the effect of hyporheic removal activity on overall
NO<inline-formula><mml:math id="M380" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula> removal in the stream or the normalisation of hyporheic uptake
to a benthic area requires a flow path length. In the presented example, this
length refers to the horizontal vector of the distance the water travels in
the subsurface before infiltrating the HPFM. The horizontal vector can be
derived from the residence time of water and solutes in the hyporheic zone
<inline-formula><mml:math id="M381" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">τ</mml:mi><mml:mtext>HZ</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> and the horizontal Darcy velocity <inline-formula><mml:math id="M382" display="inline"><mml:mrow><mml:msub><mml:mi>q</mml:mi><mml:mi>x</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>. Assuming a
downward flow direction, <inline-formula><mml:math id="M383" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">τ</mml:mi><mml:mtext>HZ</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> could be inferred from the
vertical Darcy velocity <inline-formula><mml:math id="M384" display="inline"><mml:mrow><mml:msub><mml:mi>q</mml:mi><mml:mi>y</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> as assessed from the temperature profiling
and the hyporheic zone depths of 50 cm. Thereafter, <inline-formula><mml:math id="M385" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">τ</mml:mi><mml:mtext>HZ</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula>
conceptually corresponds to the time the water travels through the hyporheic
zone before exiting to groundwater and <inline-formula><mml:math id="M386" display="inline"><mml:mrow><mml:msub><mml:mi>s</mml:mi><mml:mtext>HZ</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> to the horizontal vector
of the flow paths. The nitrate uptake rate <inline-formula><mml:math id="M387" display="inline"><mml:mrow><mml:msub><mml:mi>U</mml:mi><mml:mrow><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">NO</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:mrow><mml:mtext>-HZ</mml:mtext></mml:mrow></mml:msub></mml:mrow></mml:math></inline-formula>
(mg NO<inline-formula><mml:math id="M388" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula>-N m<inline-formula><mml:math id="M389" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> d<inline-formula><mml:math id="M390" 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> is then the difference between the
theoretically transported NO<inline-formula><mml:math id="M391" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula> mass
<inline-formula><mml:math id="M392" display="inline"><mml:mrow><mml:msub><mml:mi>M</mml:mi><mml:mrow><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">NO</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:mrow><mml:mtext>-HZ theor</mml:mtext></mml:mrow></mml:msub></mml:mrow></mml:math></inline-formula>, which is the product of <inline-formula><mml:math id="M393" display="inline"><mml:mrow><mml:msub><mml:mi>Q</mml:mi><mml:mtext>HZ</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> and
<inline-formula><mml:math id="M394" display="inline"><mml:mrow><mml:msub><mml:mi>C</mml:mi><mml:mrow><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">NO</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:mrow><mml:mtext>-SW</mml:mtext></mml:mrow></mml:msub></mml:mrow></mml:math></inline-formula> and the measured mass flux
<inline-formula><mml:math id="M395" display="inline"><mml:mrow><mml:msub><mml:mi>M</mml:mi><mml:mrow><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">NO</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:mrow><mml:mtext>-HZ real</mml:mtext></mml:mrow></mml:msub></mml:mrow></mml:math></inline-formula>. During the testing phase
<inline-formula><mml:math id="M396" display="inline"><mml:mrow><mml:msub><mml:mi>U</mml:mi><mml:mrow><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">NO</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:mrow><mml:mtext>-HZ</mml:mtext></mml:mrow></mml:msub></mml:mrow></mml:math></inline-formula> was calculated as
693 mg NO<inline-formula><mml:math id="M397" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula>-N m<inline-formula><mml:math id="M398" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> d<inline-formula><mml:math id="M399" 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>. The same procedure yields a
removal (uptake or adsorption) rate for SRP of <inline-formula><mml:math id="M400" display="inline"><mml:mrow><mml:msub><mml:mi>U</mml:mi><mml:mrow><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">PO</mml:mi><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:mrow><mml:mtext>-HZ</mml:mtext></mml:mrow></mml:msub><mml:mo>=</mml:mo><mml:mn>24</mml:mn></mml:mrow></mml:math></inline-formula> mg PO<inline-formula><mml:math id="M401" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">4</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula> m<inline-formula><mml:math id="M402" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> d<inline-formula><mml:math id="M403" 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>. Calculating
<inline-formula><mml:math id="M404" display="inline"><mml:mrow><mml:msub><mml:mi>U</mml:mi><mml:mrow><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">NO</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:mrow><mml:mtext>-HZ</mml:mtext></mml:mrow></mml:msub></mml:mrow></mml:math></inline-formula> in the same way for each single depth assessed
with the HPFM can deliver additional information about vertical gradients on
nutrient processing rates and help to identify the most active depth in
hyporheic zone. <inline-formula><mml:math id="M405" display="inline"><mml:mrow><mml:msub><mml:mi>U</mml:mi><mml:mrow><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">NO</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:mrow><mml:mtext>-HZi</mml:mtext></mml:mrow></mml:msub></mml:mrow></mml:math></inline-formula> of a particular layer in the
hyporheic zone can be derived by the differences in uptake rate between the
regarded layer and the overlying layer. For instance the removal rates
attributed to the different layers of HPFM L6 would be
<inline-formula><mml:math id="M406" display="inline"><mml:mrow><mml:msub><mml:mi>U</mml:mi><mml:mrow><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">NO</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:mrow><mml:mtext>-HZ15</mml:mtext></mml:mrow></mml:msub><mml:mo>=</mml:mo><mml:mn>567</mml:mn></mml:mrow></mml:math></inline-formula> mg NO<inline-formula><mml:math id="M407" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula>-N m<inline-formula><mml:math id="M408" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> d<inline-formula><mml:math id="M409" 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 shallow layer (0 to 15 cm depths), <inline-formula><mml:math id="M410" display="inline"><mml:mrow><mml:msub><mml:mi>U</mml:mi><mml:mrow><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">NO</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:mrow><mml:mtext>-HZ30</mml:mtext></mml:mrow></mml:msub><mml:mo>=</mml:mo><mml:mn>174</mml:mn></mml:mrow></mml:math></inline-formula> mg NO<inline-formula><mml:math id="M411" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula>-N m<inline-formula><mml:math id="M412" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> d<inline-formula><mml:math id="M413" 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 layer from 15 to 30 cm
depths and <inline-formula><mml:math id="M414" display="inline"><mml:mrow><mml:msub><mml:mi>U</mml:mi><mml:mrow><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">NO</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:mrow><mml:mtext>-HZ45</mml:mtext></mml:mrow></mml:msub><mml:mo>=</mml:mo><mml:mn>256</mml:mn></mml:mrow></mml:math></inline-formula> mg NO<inline-formula><mml:math id="M415" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula>-N m<inline-formula><mml:math id="M416" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> d<inline-formula><mml:math id="M417" 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 deepest layer from 30 to
45 cm depths. From this example one could conclude that the shallowest
sediments are the most efficient ones in terms of nitrate removal. While
removal activity is first declining with depths it later increases again.
This finding is consistent with the higher amplitudes of oxygen concentration
in 45 cm depths compared to 25 cm depths, also suggesting higher biotic
activity at the deepest layer. Potential reasons for this pattern could be
decreasing NO<inline-formula><mml:math id="M418" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula> penetration with depth (lower uptake at the middle
layer than the shallowest one) which is in the deepest parts counter-balanced
by increased residence time and stronger reducing conditions.</p>
</sec>
<sec id="Ch1.S5" sec-type="conclusions">
  <title>Conclusion and outlook</title>
      <p>The role of the hyporheic zone as a hotspot for in-stream nutrient cycling is
indisputable (Mulholland et al., 1997; Fellows et al., 2001; Fischer et al.,
2005; Rode et al., 2015). Quantitative and qualitative knowledge about the
influence of mass transfer on hyporheic nutrient removal is crucial to manage
streams and river, especially in the light of increasing worldwide
morphological alterations (Borchardt and Pusch, 2009), eutrophication
(Ingendahl et al., 2009) and sediment loading (Hartwig and Borchardt, 2015).
Despite decades of research on hyporheic nutrient cycling, robust
quantitative data on nutrient fluxes through the hyporheic zone are limited,
which is mainly due to methodological constraints in measuring nutrient
concentrations and water flux in the subsurface of streams (O'Connor et al.,
2010; Boano et al., 2014; Gonzalez-Pinzon et al., 2015). Passive flux meters
have the potential to fill the gap in measured quantitative nutrient fluxes
to the reactive sites in the sediments of rivers. To date, HPFMs are
virtually the only method which can simultaneously capture nutrient and water
flux through hyporheic zone within the same device and at the same spatial
location. The field testing of several devices proved the general
applicability of passive flux meters for quantifying NO<inline-formula><mml:math id="M419" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula> and
PO<inline-formula><mml:math id="M420" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">4</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula> flux to reactive sites in the hyporheic zone. The hyporheic flux
rates of nutrients and nitrate uptake rates measured in an agricultural 3rd-order stream were generally in agreement with rates reported in the
literature. Our results clearly highlight the advantages of HPFM compared to
commonly used methods (i.e. grab sampling of pore water and separate
measurements of hyporheic exchange and Darcy velocities), first of all the
capacity to integrate over longer time periods.</p>
      <p>Quantifying nutrient flux to the potentially reactive sites in the hyporheic
zone is an essential step to further improve our process-based knowledge on
hyporheic nutrient cycling. In the future, long-term measurements of
nutrient fluxes as obtained from HPFM can feed into and advance the
transport part of nutrient cycling models.</p>
      <p>We anticipate further improvement and increased use of passive flux meter
approaches in order to advance conceptual models of nutrient cycling in the
hyporheic zone. We demonstrated modifications which extended PFM application
from groundwater to hyporheic zones. Current limitations related to the
potential bias of results due to biofilm growth on sorbents require further
analysis for the identification of more suitable sorbents. While we focused
on nutrients, PFMs may also be used for a wide range of other substances like
contaminants or trace elements.</p>
      <p>Being labour efficient and attractive with respect to relatively low costs,
numerous HPFMs can be efficiently used to cover larger areas and assess the
degree of local heterogeneity. Further, neither advanced technology,
maintenance, or power supply are needed which can be extremely advantageous
for the use in remote areas or study sites without infrastructure.</p>
</sec>
<sec id="Ch1.S6">
  <title>Data availability</title>
      <p>All relevant data are either incorporated in figures/tables in the article or provided in the
Supplement.</p>
</sec>

      
      </body>
    <back><app-group>
        <supplementary-material position="anchor"><p><bold>The Supplement related to this article is available online at <inline-supplementary-material xlink:href="http://dx.doi.org/10.5194/bg-14-631-2017-supplement" xlink:title="zip">doi:10.5194/bg-14-631-2017-supplement</inline-supplementary-material>.</bold></p></supplementary-material>
        </app-group><notes notes-type="competinginterests">

      <p>The authors declare that they have no conflict of
interest.</p>
  </notes><ack><title>Acknowledgements</title><p>We thank Uwe Kiwel for his technical support during the field work and Andrea
Hoff and Christina Hoffmeister from the analytical department of the UFZ for
their assistance in the laboratory experiments. We are also grateful for
fruitful discussions with James Jawitz, Andreas Musolff, Christian Schmidt
and Nico Trauth.<?xmltex \hack{\newline}?><?xmltex \hack{\newline}?> The article processing
charges for this open-access <?xmltex \hack{\newline}?> publication were covered by a
Research <?xmltex \hack{\newline}?> Centre of the Helmholtz Association. <?xmltex \hack{\newline}?><?xmltex \hack{\newline}?> Edited by: T. J. Battin<?xmltex \hack{\newline}?> Reviewed by: R.
González-Pinzón, J. Rozemeijer, J. Lewandowski, and one anonymous
referee</p></ack><ref-list>
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    <!--<article-title-html>Quantifying nutrient fluxes with a new hyporheic passive flux meter (HPFM)</article-title-html>
<abstract-html><p class="p">The hyporheic zone is a hotspot of biogeochemical turnover and
nutrient removal in running waters. However, nutrient fluxes through the
hyporheic zone are highly variable in time and locally heterogeneous.
Resulting from the lack of adequate methodologies to obtain representative
long-term measurements, our quantitative knowledge on transport and turnover
in this important transition zone is still limited.</p><p class="p">In groundwater systems passive flux meters, devices which simultaneously
detect horizontal water and solute flow through a screen well in the
subsurface, are valuable tools for measuring fluxes of target solutes and
water through those ecosystems. Their functioning is based on accumulation
of target substances on a sorbent and concurrent displacement of a resident
tracer which is previously loaded on the sorbent.</p><p class="p">Here we evaluate the applicability of this methodology for investigating
water and nutrient fluxes in hyporheic zones. Based on laboratory experiments
we developed hyporheic passive flux meters (HPFMs) with a length of 50 cm
which were separated in 5–7 segments allowing for vertical resolution of
horizontal nutrient and water transport. The HPFMs were tested in a 7 day
field campaign including simultaneous measurements of oxygen and temperature
profiles and manual sampling of pore water. The results highlighted the
advantages of the novel method: with HPFMs, cumulative values for the average N
and P flux during the complete deployment time could be captured. Thereby the
two major deficits of existing methods are overcome: first, flux rates are
measured within one device instead of being calculated from separate
measurements of water flow and pore-water concentrations; second, time-integrated measurements are insensitive to short-term fluctuations and
therefore deliver more representable values for overall hyporheic nutrient
fluxes at the sampling site than snapshots from grab sampling. A remaining
limitation to the HPFM is the potential susceptibility to biofilm growth on
the resin, an issue which was not considered in previous passive flux meter
applications. Potential techniques to inhibit biofouling are discussed based
on the results of the presented work. Finally, we exemplarily demonstrate how
HPFM measurements can be used to explore hyporheic nutrient dynamics,
specifically nitrate uptake rates, based on the measurements from our field
test. Being low in costs and labour effective, many flux meters can be
installed in order to capture larger areas of river beds. This novel
technique has therefore the potential to deliver quantitative data which are
required to answer unsolved questions about transport and turnover of
nutrients in hyporheic zones.</p></abstract-html>
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