Evaluating diffuse and point phosphorus contributions to river ...
Transcript of Evaluating diffuse and point phosphorus contributions to river ...
Evaluating diffuse and point phosphorus contributions to river
transfers at different scales in the Taw catchment, Devon, UK
F.L. Wooda,b,1, A.L. Heathwaiteb,*, P.M. Haygartha
aInstitute of Grassland and Environment Research, North Wyke Research Station, Okehampton, EX20 2SB, UKbCentre for Sustainable Water Management, The Lancaster Environment Centre, Lancaster University, Lancaster LA1 4YQ, UK
Received 30 November 2003; revised 1 May 2004; accepted 1 July 2004
Abstract
This paper describes an empirical study carried out to improve understanding of how small scale transfers of mobilised
phosphorus (P) recorded at plot to field scale are mirrored by P fluxes measured at the river catchment scale. Phosphorus transfers
were studied in partially nested sites that range in area from 30 m2 to 834 km2. The work was carried out within the grassland
dominated catchment of the River Taw, south west England. The research sought to determine the characteristics of the link
between plot and river scale P fluxes for different P forms. The highest point source inputs of P were generally recorded in the
largest sub-catchments of the river. However, diffuse sources of P were estimated to constitute at least 60% of the annual P flux at
all sites. The magnitude of the diffuse P input varied with catchment land use. Detailed studies focused on the lowland catchments
showed that diffuse fluxes can be well represented by plot and field scale P transfers. The research produced no evidence for
significant inputs of P from river channel banks. However, at the hillslope scale, additional transfers of P from ‘incidental’ sources
such as re-seeded fields, open access ditches, and farmyard point sources were recorded. These inputs did not appear to
significantly affect river P fluxes, suggesting that they are either of low frequency, or that there is a corresponding decrease in
overall P transfer as the research scale is increased from field through to sub-catchment. Additional evidence of scaling was
observed where riverine P fluxes were diluted by upland or groundwater flows.
q 2005 Elsevier B.V. All rights reserved.
Keywords: Phosphorus; Diffuse pollution; Agriculture; Grassland; Scaling; Eutrophication
1. Introduction
The policies and implementation strategies designed to protect European waterbodies from P pollution are under
rapid development (e.g. Environment Agency, 2000a). To focus these policies, the processes that initiate the
Journal of Hydrology 304 (2005) 118–138
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0022-1694/$ - see front matter q 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.jhydrol.2004.07.026
Abbreviations: P, Phosphorus; TP, Total phosphorus; RP, Molybdate reactive phosphorus; UP, Phosphorus not determined by molybdatereaction (unreactive); !0.45, Less than 0.45 mm in size; STW, Sewage Treatment Works; FYM, Farm yard manure; HOST, Hydrology of SoilTypes; FAO, Food and Agriculture Organisation; USDA, United States Department of Agriculture; l.o.d., Limit of detection.
* Corresponding author. Address: Centre for Sustainable Water Management, The Lancaster Environment Centre, Lancaster University,Lancaster LAI 4YQ UK. Tel.: C44 1524 510204; fax: C44 1524 5101217.
E-mail address: [email protected] (A.L. Heathwaite).1 Present address: Institute of Grassland and Environment Research, Plas Gogerddan, Aberystwyth, SY23 3EB, UK.
F.L. Wood et al. / Journal of Hydrology 304 (2005) 118–138 119
mobilisation and drive the transfer of P from diffuse
sources to receiving waters have been investigated
extensively over the last ten years (e.g. Boesch et al.,
2001; Haygarth and Jarvis, 1999; Heathwaite and Dils,
2000; McDowell and Sharpley, 2001). Haygarth and
Condron (2004) argue that separating initial P release
(mobilisation) from subsequent P transfer (transport)
aids our understanding of the main drivers of diffuse P
losses because these two mechanisms operate at
different scales: the soil profile and plot scale,
respectively. Phosphorus mobilisation describes the
initial separation of P molecules from their source
through either solubilisation or detachment mechan-
isms,dependingonthephysical sizeof thePcompounds
that are mobilised. There is evidence to suggest that the
potential for P solubilisation increases with increased
soil P status (e.g. Heckrath et al., 1995; McDowell and
Sharpley, 2001) and that the degree of P saturation may
be used to predict the risk of P transfer by surface or
subsurface hydrological flow paths. Detachment of soil
particles and associated P is often linked to soil erosion,
which provides a physical mechanism for mobilising P
from soil into waters (Kronvang, 1990; Sharpley and
Smith, 1995).
Research on P mobilisation and transfer has resulted
in far better understanding of the processes of P
transport at the small plot to field scale. However,
better understanding of the scaling of diffuse P
transport from plot to catchment scale is still required.
This scaling is important because most of the research
examining diffuse P sources has been conducted in
intensively managed agro-ecosystems using exper-
imental plots under controlled conditions. Thus,
although there is evidence that continued inputs of P
in the form of mineral fertilisers and imported animal
feed have resulted in significant accumulation of P in
topsoil (e.g. Haygarth et al., 1998; Withers et al., 2001;
Sibbesen and Runge-Metzger, 1995; Sims et al., 2000)
there remains poorer understanding of the routing of P
through the landscape and of its contribution to P fluxes
in receiving waters. There is some evidence from
modelling (e.g. McGuckin et al., 1999; Viney et al.,
2000; Wade et al., 2002) and field studies (e.g. Vighi
and Chiaudani, 1985; Hunsaker and Levine, 1995;
Smith et al., 1995; Heathwaite et al., 1996; Hooda et
al., 1997) that diffuse P transfer significantly affect
river P fluxes. However, the routing of P from the point
of mobilisation to the point of delivery to water is
complex. It embraces: (i) differences in the relative
importance of the controls on P transfer at different
scales from point to plot, field, hillslope and catch-
ment, (ii) differences in the relative importance of
these controls over time—e.g. resulting from seaso-
nal variation, crop rotation, and as a consequence of
longer term climate change, and (iii) differences in
the relative contribution from different P fractions
according to the pathway of transfer and the
environmental controls on movement. Further com-
plexity arises because P is subject to deposition and
resuspension/dissolution during transport, and can
change form in space and time. Once transferred P
reaches surface waters, the extent, nature and
dynamics of interactions between soluble and
particulate P in water and sediments play a critical
role in the delivery and impact of P downstream
(Baldwin et al., 2002; McDowell et al., 2001).
This paper describes an empirical study carried out
to examine the transfer of P at a range of scales within
the grassland-dominated Taw river basin in southwest
England. The aim was to evaluate the link between plot
scale P transfers and river P fluxes, and to analyse any
variation in the forms of P at different scales.
2. Materials and methods
2.1. Study sites
The work reported here was undertaken at different
scales of investigation, using a nested approach where
feasible to reduce the number of variables that need to
be investigated in order to explain changes in P
transfer resulting from each incremental increase in
drainage basin area. The research was undertaken in
the 1242 km2 catchment of the River Taw in Devon,
in South West England. The southern headwaters of
the river basin rise over granite uplands c.600 m
above sea level. The lowlands and northern head-
waters flow over sandstones, a narrow east-west band
of breccias and conglomerates, shales and siltstones,
into the Bristol Channel. Most of these rocks are of
low permeability and porosity (Environment Agency,
2000b). Away from the main river valley, the
topography consists of steep sided, but rounded
hills. In the uplands, soils are peat, podzols, brown
earths, and slowly permeable gleys. Clay-rich gley
soils and typical brown earths occur over the central
F.L. Wood et al. / Journal of Hydrology 304 (2005) 118–138120
strata, with a belt of well-drained, gritty reddish loam
over the breccia (Environment Agency, 2000b).
Rainfall ranges from over 2200 mm yrK1 in the
south, and 1600 mm yrK1 in the northern uplands, to
less than 940 mm yrK1 in the lowland areas. Catch-
ment hydrology is dominated by surface water due to
the low groundwater storage capacity. There are no
major aquifers in the catchment, but groundwater,
inferred to be held in fractures in the rock bodies, is
observed to maintain river baseflow in periods of dry
weather. River discharge responds rapidly to rainfall.
Biological water quality in the catchment is generally
good, although the Taw estuary has been identified as
being eutrophic (Environment Agency, 2000b). A
sewage treatment works on the coast is the major
cause of this. (National Rivers Authority, 1995;
Environment Agency, 2000b).
Fifteen sub-catchments within the catchment of the
River Taw were studied (Fig. 1); with 6 of these sites
studied in detail (see Table 1). ‘Plot’ scale is defined
here as 30 m2, field scale lysimeters were of 1 ha size,
‘hillslope’ scale is defined as 1 ha up to 25 ha, and
‘catchment’ scale as larger than 25 ha. The plot, field
and hillslope scale sites were centred on the Rowden
drainage experiment, located in the southern part of
the Taw catchment (see Fig. 1). This facility consists
of fourteen, 1 ha, hydrologically isolated grassland
paddocks on land sloping at 5–10% (Scholefield et al.,
1993). Seven of the paddocks are mole and tile
drained to 85 cm, and this drainage water is routed
from the area separately from near-surface water,
which is constrained by an impermeable clay layer at
30 cm depth (see Armstrong et al., 1984 for a full
description of the facility, Haygarth et al., 1998 for
studies on P transfers). Adjacent to these 1 ha
lysimeters, there are twenty-four undrained 30 m2
plots, hydrologically isolated in a similar manner
(Preedy et al., 2001). The ditch draining a 19.9 ha
hillslope consisting of half of the 1 ha lysimeters and
part of an adjoining field (undrained) was also
monitored.
Soils are mainly of the Hallsworth series (FAO
dystric gleysol; USDA Typic Haplaquepts), with
small areas of Halstow series (FAO gleyic cambisol;
USDA Dystrochrepts). Both are slowly permeable,
clayey soils derived from shale dominated rock. The
subsoil lies at c. 30 cm depth, and is coarsely
structured and impermeable. The soils behave in a
similar way hydrologically, and have a hydrology of
soil types (HOST) drainage classification of 24
(Hallsworth) and 21 (Halstow; Boorman et al.,
1995). These, together, comprise the most common
hydrological soil type in England and Wales, at 14%
of the land area (Boorman et al., 1995; Fraser, 2000).
The characteristic of slowly permeable subsoil
horizons, which severely restrict the downward
movement of water is found in an additional 10% of
soils in England and Wales (Fraser, 2000). Rainfall is
c. 1067 mm per year, measured at the North Wyke
meteorological station, 2 km away.
The 1 ha lysimeters were grazed by steers/heifers
at a stocking density of 2.80 livestock units (l.s.u.) per
hectare from mid April to September, and subject to a
range of N input regimes (inorganic N: none up to
275 kg haK1, farmyard manure: none up to 10 tonnes
haK1). Inorganic P input was 26 kg haK1, applied in
early spring. The additional land contributing to the
monitored hillslope was similarly under a mixture of
low N and conventional management. The six 30 m2
plots used were hand cut, and managed convention-
ally with respect to inputs. Up to summer 1998, 10
tonnes haK1 of FYM were applied, and NPK inputs
were 275, 26, and 50 kg haK1 respectively. From
spring 1999, the plots carried a dairy slurry/inorganic
fertilizer treatment equivalent to 29 kg P haK1.
A further 9 hillslope scale sites were also studied;
their land use and soil type details are given in Table 2.
These sites were selected on the basis of representative
soil types and typical land management practice for the
area. Additional criteria were: simple topography,
single ownership, and the lack of obvious point-source
inputs. All 9 hillslope sites have Hallsworth and/or
Halstow soil series and predominantly grassland land
use that ranged in intensity from unimproved grass-
land, and beef and sheep pastures similar to Rowden, to
more intensively managed dairy farm pastures; an
arable field was included at one site. The area of the
hillslopes ranged from 5 to 18 ha and all were within 10
miles of the Rowden experimental site.
2.2. Sample and data collection
There were three consecutive phases of water
sampling to estimate diffuse P fluxes within
the catchment over a total period of three and a half
years: I (November 1996–March 1998), II (April
Fig. 1. Location of the catchment scale sampling sites and the plot to hillslope scale study areas in the River Taw catchment, Devon, UK.
F.L. Wood et al. / Journal of Hydrology 304 (2005) 118–138 121
1998–March 1999), and III (August 1999–July 2000).
Samples were collected manually in rinsed 125 ml
polyethylene sample bottles and stored at 4 8C in the
dark prior to analysis (Haygarth et al., 1995). All
analyses were carried out within 24 h of sample
collection. For each phase, water samples were
collected on the same day from a different subset of
the study sites. In Phase I samples were collected
fortnightly from the 15 catchment scale sites, the
Rowden 30 m2 and 1 ha lysimeters, and the Rowden
hillslope site (Fig. 1; Table 1). The samples were
analysed for TP and RP !0.45. In Phase II, samples
were collected at weekly intervals from the 6 of the 15
catchment scale sites because these sites had Environ-
ment Agency discharge data for P flux calculation
(Table 1); water samples were also taken from
Table 1
Soils, land use and known point source inputs for the 6 sub-catchments of the River Taw studied in Phase II
Catchment Area
(km2)
Soils Land use (expressed
as % of catchment
area)a
Catchment stocking density (head haK1) Known point-
source inputsDairy Beef Sheep Pig
Leeham
Ford
17.6 60% well-drained
podzol, 20% Poorly
drained peaty
podzols, 20% brown
earth
80% grassland, 18%
rough grazing
– 0.14 4.06 – None
Veraby 61.0 40% well-drained
brown earths, 30%
peaty but permeable
podzol, 30% peaty
gley
71% grassland, 21%
rough grazing, 3%
cereals
0.11 0.18 6.67 – Descriptiveb inputs
only-insignificant
Taw Bridge 72.4 Very mixed; well-
drained gritty loams,
slowly permeable
clays, earths, podzols
48% grassland, 29%
rough grazing, 11%
cereals, 2% other
crops/set aside
0.14 0.16 3.15 0.17 Sewage Treatment
Works (STW),
cheese factory
Collard
Bridge
79.6 50:50 well-drained
podzols and well
drained brown earths
86% grassland, 5%
rough grazing, 4%
cereals, 2% other
crops/set aside
0.21 0.17 7.86 0.05 STW, 3 fish farms
Woodleigh 328 60% well-drained
brown earth, 10%
well drained podzol,
10% poorly drained
peaty podzol, 20%
gleys.
76% grassland, 10%
rough grazing, 7%
cereals, 3% other
crops/set aside
0.19 0.14 6.54 0.04 STW, 2 fish farms,
1 wood processing
plant
Umberleigh 834 Mixed, 60% well-
drained brown-earths
and podzols, 30%
gleys.
71% grassland, 8%
rough grazing, 11%
cereals, 4% other
crops/set aside
0.27 0.11 4.93 0.15 STW, 2 cheese fac-
tories, 3 fish farms,
1 wood processing
plant, cider factory
(until Dec. 1998)
a Catchment woodland area ranges from 2 to 4% of total area.b ‘Descriptive’ STW refers to those with an effluent discharge of less than 1 m3 per day.
F.L. Wood et al. / Journal of Hydrology 304 (2005) 118–138122
the Rowden 30 m2 and 1 ha lysimeters, and the
Rowden hillslope site throughout Phase II and at the
same interval as the 6 catchment sites. For the Phase II
samples, P was fully fractionated. For Phase III,
samples were collected at weekly intervals from all
the hillslope scale sites (Fig. 1 and Tables 1 and 2),
and all P forms determined. This phase was
undertaken to confirm that the Rowden hillslope
generated P transfers typical of the hillslope scale.
For Phase I and II, river discharge data was obtained
from the Environment Agency. Discharge at Rowden
was estimated as hydrologically effective rainfall
(HER)—rainfall minus potential evapotranspiration
during the field capacity season. Potential evapotran-
spiration from grassland was estimated on a weekly
basis from open water evaporation data, using
seasonal correction factors (Penman, 1952). The
proportion of HER routed along undrained, drained
near-surface, and drained drainflow lysimeter path-
ways were 70.5, 9.5, and 66.1%, respectively
(Scholefield et al., 1993). For the hillslope scale, all
HER was assumed to exit the catchment via the basin
outlet. For Phase III, discharge at the 9 hillslope scale
sites was determined from stage readings at manually
calibrated timber/plywood weirs, installed to British
Standard 3680 4A with respect to uniformity of
channel approach. Soil samples were collected from
the 9 hillslope scale sites using a stratified grid
sampling approach. Twenty-five samples to 2 cm
depth were collected with a 25 cm2 square section
Table 2
Characteristics of the hillslope scale sites in the River Taw catchment
Site Area
(ha)
Slope
(%)
Soil series Landuse Other
characteristics
Inorganic
NPK input
(kg ha-1)
Other nutrient
inputs
Olsen P
(mg kgK1)a
H1 5.5 7 Hallsworth Unimproved sheep/
beef pasture.
Annual cutting of
rushes.
Elongated along
direction of stream
channel
0-0-0 Calcified seaweed
0.6 tonnes haK1
22.7
H2 4.8 4–9 Halstow Sheep Sampled below
farm track
92-11-10 Intermittent FYM/
slurry application,
depending on
winter ground
conditions
22.9
H3 18.1 6–12 Hallsworth/
Halstow
Sheep/beef Organically
managed
17-10-27 4 tonnes haK1
FYM plus dirty
water
44.3
H4 7.1 4 Hallsworth Beef Cattle access to
ditch
109-6-11 25 tonnes haK1
slurry
39.1
H5 19.9 5–10 Hallsworth Beef Rowden hillslope,
partly compart-
mentalised into
1 ha plots
117-24-45 5 tonnes haK1
FYM
46.0
H6 6.8 6–12 Halstow Dairy/sheep One field reseeded
in late August 1999
344-27-51 36 tonnes haK1
slurry on silage
fields
36.4
H7 12.7 10 Halstow Sheep/silage 222-24-91 32 tonnes haK1
slurry
48.7
H8 8.6 15 Halstow Dairy Dirty water from
farmyard found to
be entering runoff
195-20-54 Intermittent 86.1
H9 7.1 8 Hallsworth Barley/maize, plus
25% ‘set aside’
alongside stream
margin
Sampled from tile
drain
73-18-58 17 tonnes haK1
slurry
34.5
Data protection prevents release of farm locations.a Olsen values are relatively high; soils are acid (pH 4.9–5.9), reducing the reliability of this standard soil P test.
F.L. Wood et al. / Journal of Hydrology 304 (2005) 118–138 123
corer, to give a total sample volume of 1250 cm3.
Samples were stored for up to five days at 4 8C in the
dark. Plant matter and stones were removed prior to
passing the samples through a 2 mm sieve. The
samples were then dried at 30 8C for 12 h (equivalent
to air drying).
Estimates were made of the point-source inputs of
P to the 6 catchment scale sites monitored in Phase II.
This was undertaken using data that is publicly
available from the UK Environment Agency on
discharges from sewage treatment works and from
the main industrial discharges to rivers in the
catchment. These data were supplemented with
observations on industrial point sources noted in
Table 1 although effluent volumes are not available.
The most important of these are the fish farms. Other
point sources include small hotel and local council-
maintained sewage treatment works, and private
septic tank systems. There were no known point
sources of P into the smaller study sites (Table 1).
Accurate calculation of point source P loads is not
usually possible because records of P concentrations
and actual discharges are not recorded or are not
publicly available. Here, we calculate P loads from
sewage inputs per unit catchment area as the product
of the total daily permitted volume of effluent for
the STWs in each catchment and a P concentration of
10 mg lK1. Clearly this concentration is the upper
F.L. Wood et al. / Journal of Hydrology 304 (2005) 118–138124
boundary of the typical range of P concentrations in
effluent where there is no tertiary treatment, as in the
Taw (Brett et al., 1997; T. Griffiths, South West
Water, pers. comm.). Smaller treatment works, termed
‘descriptive’, have an effluent discharge of less than
1 m3 per day and were assumed to be discharging at
this maximum rate. Intermittent sewage discharge
data (R. Harwood, Environment Agency, pers.
comm.) indicate that these estimates are largely
accurate. The main industrial source (a cheese
factory) discharges at a relatively constant daily
rate, discharge and P concentration figures available
for 1998–1999 were used to calculate mean daily flux,
and thus the annual P input per ha. For the purposes of
comparing diffuse-source inputs with total catchment-
scale P export, estimates of point-source inputs were
subtracted from measured TP exports to give an
estimate of the diffuse export. Septic tanks are the
most commonly used method of disposing of human
waste in rural parts of Britain but P loads from this
source were not accounted for separately in our study
because no accurate means of accounting for their
contribution was available.
2.3. Analytical methods
(i) Water samples were shaken, and 50 ml vacuum
filtered (at less than 60 cm Hg, or 80 kPa) through
0.45 mm pore size cellulose nitrate filter papers (de
Haan et al., 1984). The Murphy and Riley (1962)
colorimetric technique was used to determine the
concentration of P in all the samples. The concen-
tration of TP was determined for both unfiltered and
filtered samples following an acid persulphate digest
(Rowland and Haygarth, 1997) and samples were read
at 880 nm using a manual Unicam Vis 2 spectro-
photometer. Reactive P was determined on filtered
and unfiltered samples by flow injection methods
(Karlberg and Pacey, 1989) and samples were read at
690 nm using a Tecator 5020 flow injection analyser
with autosampler. The concentration of UP in the
samples was determined by difference (TP-RP).
‘Blind’ analytical quality controls were determined
with each sample run as part of an internal QC scheme
and also as part of the external ‘Aquacheck’ Scheme
and only batches which fell within the tolerance
boundaries were accepted. Limits of detection (l.o.d.)
for the P analyses were determined every four months.
The l.o.d. was calculated as the mean blank value plus
three standard deviations of the mean (Analytical
Methods Committee, 1987). The l.o.d. calculated
from the combined datasets over the period of
sampling were 14.8 mg lK1 for TP, and 4.2 mg lK1
for RP !0.45. Concentrations of derived P forms
were only calculated where the relevant raw data were
above the l.o.d.
(ii) Soil samples were analysed for plant-available
P using Olsen soil P (Olsen et al., 1954) determined on
triplicate sub-samples of bulked hillslope site
samples. The colorimetric reagents were: (a) 6.0G0.001 g ammonium molybdate and 0.15G0.001 g
antimony potassium tartrate dissolved in 300 ml of
deionised water, to which was slowly added 74 ml of
conc. H2SO4, and the solution diluted to 500 ml. For
the working reagent, 200 ml of this was diluted to
1600 ml with deionised water (b) 7.5G0.001 g
ascorbic acid made up to 500 ml. To analyse for P,
1 ml of sample was pipetted into a test tube and 200 ml
of 1.5 M H2SO4 slowly added and mixed. Four ml of
working ammonium molybdate reagent and 1 ml of
ascorbic acid were then added. The solution was
agitated thoroughly and left to stand for 30 min to
allow colour development. Absorption was read at
880 nm on a Unicam Vis 2 spectrophotometer.
2.4. Statistical analyses
Daily mean values of the P concentration at each
scale of investigation were calculated as the arith-
metic mean of the concentrations recorded at each
replicate site. Linear regression analysis was then
used to compare the log-transformed daily mean
concentrations recorded at different scales. The
regression analysis required the P data to be log-
transformed as the time series data were not normally
distributed. Regression parameters were confirmed by
Bootstrap re-sampling (Efron and Tibshirani, 1993).
Two methods were used to calculate the mean annual
P concentration at a site, and thence the annual P flux
by multiplying by total annual discharge. First, for use
in comparisons between scales, the mean concen-
trations of the log-transformed P data over the time
series were calculated for each replicate site at a given
scale. Here, the values after re-transformation are
refered to as the antilog means. Second, where the
estimation of the diffuse contribution to river
F.L. Wood et al. / Journal of Hydrology 304 (2005) 118–138 125
catchments was made, it was possible to use flow
weighted mean concentrations, as instantaneous
discharge data were available at this scale. This
method gives a more accurate estimate of P flux in
catchments where P transfer varies with discharge
(Yaksich and Verhoff, 1983). Statistical comparison
of mean annual TP concentrations and fluxes was
performed using one way Analysis of Variance.
3. Results
The results are shown in Figs. 2–7 and Tables 3–6
and are separated here into a consideration of ‘point’
and ‘diffuse’ sources at different scales within the Taw
catchment.
3.1. Point source inputs
Large increases in RP !0.45 concentrations
occurred in some rivers when discharge was low.
However, as these high concentrations were most
pronounced when there is little or no runoff from the
land, they were taken as an indication of point-source
dominance. The summer: winter ratio of RP !0.45
concentration in the April 1997–March 1998 dataset
was used to rank the sites by a ‘point-source influence
index’. The mean seasonal concentrations of RP
!0.45 were calculated from log-transformed data
Fig. 2. Time series of total phosphorus concentration for sub-catchments of
for the period 1996–1999.
because of the log-normal frequency distribution of
the time series data. Forty-year mean monthly rainfall
data from the North Wyke meteorological station was
used to define the summer and winter periods, April–
September being designated as summer. The ratio of
summer: winter RP !0.45 concentrations for each of
the catchment scale sites is presented in Table 3. The
sites with an index greater than the median value for
the group of catchments are indicated.
Estimated point source inputs and annual catch-
ment scale TP transfers were calculated for the 1998–
1999 year (Table 4). Point source inputs were inferred
to constitute c.16% of the TP transfer for the
Umberleigh catchment, which is the largest catchment
monitored. In the Taw Bridge catchment this
contribution reached 38%. The P flux for the Taw
Bridge catchment was enriched in RP !0.45, and to a
lesser extent the other P forms, relative to the
grassland dominated sites. Transfers from Umber-
leigh were enriched in both RP O0.45 and UP O0.45.
3.2. Diffuse phosphorus transfers
Investigations on diffuse P transfers were carried
out in the sites dominated by diffuse sources, i.e. the
plot, field, and hillslope scale sites, and for the
catchment scale sites identified in Table 3. Of the 15
catchments initially monitored in Phase I, 8 catch-
ments that appeared to be principally affected by
the River Taw dominated by P inputs derived from diffuse sources,
Fig. 3. Time series of: (a) total P, and (b) reactive P!0.45 at scales ranging from 30 m2 to catchment scale for the period 1996–1999. Error bars
represent one standard error.
F.L. Wood et al. / Journal of Hydrology 304 (2005) 118–138126
diffuse inputs of P (mainly the smaller ones) were
selected for the further analysis of diffuse P transfers.
For Phase II, 4 of the 6 sites monitored were from this
group.
Within these 8 sites, TP concentrations in the
three catchments containing large proportions of
unimproved land (Belstone, Leeham Ford, and
Brayford) were low (Fig. 2). Similarly, in Phase II,
TP concentrations and annual flux in the upland
Leeham Ford catchment were low compared to the
three lowland sites (Fig. 2; Table 4), although the
proportions of different P forms exported did not
change with increased intensity of management
(Fig. 6). These less intensive upland catchments
were therefore also excluded from the study of
diffuse P transfer because the land use was different
from the smaller scale study sites. This left 5
catchment scale sites in Phase I and three in Phase
II. The selection of these catchments affected the
nested relationship with the plot and hillslope scale
sites in Phase II.
Time series data for the 4 scales of study (30 m2
plots, 1 ha field lysimeters, hillslope, and catchment)
are presented in Fig. 3 (TP and RP !0.45 from Phase
I and Phase II) and Fig. 4 (all the P forms determined
in Phase II). The 1 ha dataset is represented by the
mean of the daily undrained lysimeter and drained
lysimeter drainflow pathways-these being the domi-
nant flow pathways in the two drainage treatments.
Gaps in the record indicate periods without drainage
or interruptions in sampling (April 1999). Discharge
at Umberleigh is presented for reference. At all sites,
field observation of river discharge at the time of
sampling suggested that where samples were taken
during periods of elevated discharge, high P concen-
trations were recorded. This relationship is not,
however, strongly apparent in the time series of P
concentration and daily rainfall, or discharge. Weak
relationships between TP concentration and discharge
were identified at some sites when regression analysis
was applied to data from a 1 ha lysimeter and the
Phase II rivers (maximum r2 of 0.35).
F.L. Wood et al. / Journal of Hydrology 304 (2005) 118–138 127
Fig. 5. The percent annual export of total P derived from different P
forms at scales ranging from 30 m2 up to catchment scale for sub-
catchments representing diffuse P sources and dominated by
lowland grassland land use. The results are calculated from antilog
mean concentrations and cover the period April 1998–March 1999.
3
Fig. 6. The percent annual total P export derived from different P
forms at catchment scale for the period April 1998–March 1999.
F.L. Wood et al. / Journal of Hydrology 304 (2005) 118–138128
In general, there is a strong similarity in the
temporal patterns of concentration of all forms of P at
all scales. This was confirmed for TP by linear
regression analysis (Table 5). Regression of the P
concentrations recorded at the hillslope scale on those
at the field scale yielded a significant trend. At the 5%
level, the value of the slope parameter was indis-
tinguishable from ‘one’, and intercept indistinguish-
able from ‘zero’. The regression of catchment scale
concentrations on field scale was also significant. The
value of the slope parameter here was less than ‘one’.
The intercept parameter was not zero. At the hillslope
scale, the regression accounted for 57% of the
variance in the observed log transformed P concen-
trations, and at the catchment scale, 40%. The
concentration of UP O0.45 closely follows that of
TP (Fig. 4b), RP !0.45 and UP !0.45 show the least
temporal variation.
One way analysis of variance on the 1998–1999
data-set showed that there were no significant
differences at the 5% level in annual TP export
from the 30 m2 plots, 1 ha undrained lysimeters,
and lumped hillslope-catchment scale sites. Exports
from the 1 ha drained lysimeters were lower. By
contrast, the mean P concentrations recorded at the
hillslope-catchment scale were similar to those of
Fig. 4. Time series of different P fractions at scales ranging from 30 m2 to
RPO0.45 (d) UP!0.45 (e) RP!0.45 (note the difference in axes for the
the 1 ha drained lysimeters, whilst those from
30 m2 plots were similar to the 1 ha undrained
lysimeters. The dominant P form in terms of both
concentration and load (Tables 6 and 7; Fig. 5) was
UP O0.45 at the plot, field, and hillslope scales.
Although the TP O0.45 transfer appears to fall
below 50% of TP at the catchment scale when
estimated from antilog means, the proportions
calculated from the flow weighted mean concen-
trations are: UP O0.45 49%; RP O0.45 14%; UP
!0.45 11% and RP !0.45 26%.
During Phase III of the study, when the Rowden
hillslope appeared to generate P transfers typical of
the three other grassland hillslopes in which there
was minimal channel disturbance or point sources
(Fig. 7a). By contrast, P transfers from of the
remaining hillslopes studied in Phase III (Fig. 7b)
often recorded elevated P export.
4. Discussion
4.1. Sampling interval
For the Taw catchment, the concentration of P
varies with discharge. For reliable estimates of export
coefficients and annual mean concentrations to be
made, a sampling frequency greater than the 14–21
day interval regime sufficient for stable response
catchment scale for the period 1998–1999 (a) TP (b) UPO0.45 (c)
P fractions). Error bars represent one standard error.
Fig. 7. Time series of total P flux from hillslope scale sites (a) Rowden hillslope and 3 sites not influenced by point-sources or tillage (b) Rowden
hillslope and 5 sites influenced by disturbance, tillage or point-source inputs.
F.L. Wood et al. / Journal of Hydrology 304 (2005) 118–138 129
systems (Treunert et al., 1974) is preferable. In the
discussions that follow, the Phase II (1998–1999)
dataset used a weekly time step. Errors (expressed as
the 90% confidence interval of the mean measured
value) were found to be similar at both 1 ha and
834 km2 scale, over a six month period. Weekly
sampling was found to give rise to errors in antilog TP
exports of up to 20% when compared to daily
sampling, and errors of K46% to C121% when
compared to the flux calculated from flow weighted
mean concentrations. Estimates of P exports using
flow weighted mean concentrations were subject to an
uncertainty of K71% to C56% when calculated from
weekly rather than daily data.
Table 3
Summer to Winter ratios of P concentration used to determine point source influences for the catchment scale sites in the River Taw catchment
Site Area (km2) Mean RP !0.45
concentrationa,
summer
Mean RP !0.45
concentrationa,
winter
Point source index
(summer:winter)
Index higher than
median value
Belstone 11.1 2.36 5.01 0.47
Leeham Ford 17.6 6.92 6.18 1.12
Bow 34.7 51.26 46.93 1.09
Brayford 40.2 5.27 8.37 0.63
Veraby 61.0 11.25 11.61 0.97
Taw Bridge 72.4 396.25 178.92 2.21 †
Collard Bridge 77.4 35.15 33.89 1.04
Chumleigh 125 42.42 28.79 1.47
Lapford 127 222.60 86.90 2.56 †
George Nym 209 77.66 38.75 2.00 †
Woodleigh 328 48.17 36.49 1.32
Bridge Reeve 435 215.34 99.68 2.16 †
Kings Ford 802 95.12 56.03 1.70 †
Umberleigh 834 84.83 54.20 1.57 †
New bridge 914 81.89 53.63 1.53 †
Median value 1.47
a Mean concentration values derived from log-transformed data.
F.L. Wood et al. / Journal of Hydrology 304 (2005) 118–138130
4.2. Point sources
In this study, high RP concentrations recorded at
times of low river discharge were taken as an
indication of point-source influence. These high
concentrations could alternatively arise if at these
times there were inputs of solute-rich, long residence
time throughflow to the river, subject to only low rates
of dilution (e.g. Hooda et al., 1997). There was
however little evidence of such pathways and inputs
in the Taw catchment, owing to its low storage
capacity. It was therefore concluded that nearly all the
catchment scale study sites in the Taw catchment
showed some evidence of point source influence, with
Table 4
Point source P inputs, measured total P export and estimated diffuse P expo
1998–March 1999)
Catchment Area km2 Measured expor
(kg haK1 yrK1)
Leeham Ford 17.6 0.62
Veraby 61.0 0.94
Taw Bridge 72.4 4.25
Collard Bridge 79.6 1.30
Woodleigh 328 1.37
Umberleigh 834 2.12
the greatest influence found in the largest catchments.
There are no recorded algal problems associated with
these intermittently high P concentrations, even in
summer when there is a high potential for biological
activity.
It is rarely possible to calculate the actual point
source P load to receiving waters from STWs
because accurate records of P concentrations and
effluent discharge are not normally recorded or are
unavailable. Bennion et al. (2002) calculated the
point source P load from STWs by taking the total
human population within a catchment and applying a
per capita P export coefficient to the resident popula-
tion. In this study, we assumed a P concentration
rt from the catchment scale sites in the River Taw catchment (April
t Point-source input
(kg haK1 yrK1)
Diffuse export
(kg haK1 yrK1)
0.00 0.62
0.00 0.94
1.63 2.62
0.08 1.22
0.36 1.01
0.34 1.78
Table 5
Regression analysis of hillslope total P concentrations on field scale
concentrations, and catchment scale total P concentrations on field
scale concentrations
Hillslope on
field scale
Catchment on
field scale
n 52 54
Fprobability !0.001 !0.001
Adjusted r2 0.57 0.40
Slope 0.94 0.55
Intercept 0.340 1.749
tprobability that slope is 0 !0.001 !0.001
tprobability that slope is 1 0.299 !0.001
Bootstrapped 95%
confidence intervals:
Slope 0.783, 1.082 0.403, 0.754
Intercept K0.364, 0.982 0.963, 2.432
All concentration data are log transformed.
F.L. Wood et al. / Journal of Hydrology 304 (2005) 118–138 131
from STWs of 10 mg lK1 and used the total
permitted daily volume of effluent for the STW in
each catchment to get an estimate of the P load from
this source. Both approaches whilst providing an
estimate of the point source P load from the human
population of a catchment, have a number of
potential sources of error. Using permitted volumes
leads to an over-estimation of flux, but omits the
contribution from septic tanks; using export coeffi-
cients: (i) the method may not distinguish between
people connected to mains sewerage systems and
those served by septic tanks; (ii) no account is taken
of differences in the degree of P removal (secondary,
tertiary) from one STW to another, and (iii) no
allowance can be made for the transfer of sewage
from one catchment to another for treatment.
Furthermore, if export coefficients are used, the
accuracy of the P load estimate is dependent on the
value selected and there is no universally agreed
figure. Johnes (1996), for example, used a coefficient
of 0.38 kg P capitaK1 yK1 following secondary
treatment, whilst Carvalho et al. (2003) quote values
ranging from 0.14 kg P capitaK1 yrK1 to 1.55 kg P
capitaK1 yrK1.
In most areas of rural Britain, septic tank systems
are the main method of disposal of human waste. The
effluent from these tanks usually drains to a soakaway
where, it has always been assumed, the nutrients that
it contains are dissipated into the soil (Harper, 1992).
Recent work by Carvalho et al. (2003) suggests that P
loads from septic tank systems may be higher than
expected, primarily due to lack of maintenance. For
example, a recent survey of 24 septic tanks within the
Lough Leane catchment, in Ireland (LLCMMS,
2000), suggests that discharges from septic tanks
may account for 10–20% of the P load to some lakes
from external sources. Other researchers have
attempted to derive coefficients for the export of P
from septic tanks to surface waters; these range from
0.33 kg P capitaK1 yr1 for septic tanks within the
catchment of Loch Leven, Scotland (Frost, 1996),
0.4 kg RP capitaK1 yrK1 for septic tanks within the
catchment of the River Main, Ireland (Foy and
Lennox, 2000) and 0.26 kg RP capitaK1 yrK1 in the
Lough Leane catchment. As this methodology devel-
ops, it will be possible to refine estimates of point
source contributions.
Other point sources of increasing importance in
catchments such as the Taw include fish farms.
Although effluent P concentrations are usually low
(Dumas et al., 1998; Jokela et al., 2001), fisheries can
have a significant effect on P concentrations in
receiving waters, and on local benthic invertebrates
(Kendra, 1991).
4.3. Diffuse phosphorus transfers at the catchment
scale
Diffuse P inputs were estimated to have accounted
for at least 60% of the annual P flux of the River Taw;
rising to 84% in the largest catchment monitored, and
virtually all the flux in the Leeham Ford and Veraby
catchments. In light of the uncertainties discussed
above, the error associated with these estimates may
be of the order of a 20% underestimation of the point
source contribution to measured P flux from a
catchment, if septic tank discharges were of the
order of those reported in LLCMMS (2000).
Atmospheric P sources are generally small with
typical concentrations of P in precipitation of
c.10 mg lK1 (Jordan and Smith, 1985). However, dry
deposition rates of up to 0.97 kg P haK1 yrK1 have
been recorded in some agricultural areas (review by
Ryding and Rast, 1989). In the Taw catchment, a
positive relationship between soil type/land use and P
flux was found. This relationship has been observed
previously at scales up to two or three km2 e.g. Hooda
Table 6
Mean and range of P concentrations (mg lK1) from 30 m2 to catchment scale for diffuse-source dominated sites (1997–1999)
Scale April 1997–March 1998 April 1998–March 1999
TP RP!0.45 mm TP PO0.45 mm RPO0.45 mm UPO0.45 mm RP!0.45 mm UP!0.45 mm
30 m2 Mean 93 24 133 83 15 68 23 20
95% confidence
interval
(72–115) (16–32) (94–171) (58–109) (9–20) (48–87) (12–33) (13–28)
Range 23–451 7–84 51–363 35–224 0–63 29–202 l.o.d.–149 0–35
1 ha
Undrained Mean 96 37 123 68 22 41 16 29
95% confidence
interval
(52–139) (19–52) (86–160) (45–91) (13–30) (25–57) (12–19) (16–43)
Range 6–493 l.o.d.–188 16–857 0–822 0–216 2–606 l.o.d.–155 0–192
Drained Meana 55 16 58 26 9 12 11 12
95% confidence
interval
(42–69) (13–19) (47–68) (19–32) (6–11) (8–16) (7–14) (8–17)
Rangea – – – – – – – –
Hillslope mean 48 31 66 37 9 3 13 15
95% confidence
intervalb– – – – – – – –
Range 14–173 7–96 15–375 6–338 1–96 4–242 l.o.d.–99 1–114
Catchment Mean 55 34 60 23 5 8 24 8
‘97 (nZ5)
‘98(nZ3)
95% confidence
interval
(26–86) (16–52) (15–104) (11–34) (4–6) (0–19) (0–51) (4–11)
Range 4–284 4–157 l.o.d.–407 1–319 0–63 0–256 l.o.d.–91 0–200
a Range not possible to calculate as mean drained concentration estimated on an annual basis as total load (using anitlog means) from near-surface and drainflow pathways,
divided by total discharge. Estimation of the range of concentrations recorded in the mixed outflows on each sample date would require instantaneous discharge measurements.b Confidence interval not applicable, sample size of one.
F.L
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/Jo
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00
5)
11
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13
81
32
Table 7
Estimated annual export coefficients (kg haK1 yrK1) for different P fractions at scales ranging from 30 m2 up to catchment scale calculated from antilog mean concentrations (April
1997–March 1998 and April 1998–March 1999)
Scale April 1997–March 1998 April 1998–March 1999
Total
phosphorus
Reactive
phosphorus
!0.45 mm
Total
phosphorus
Phosphorus
O0.45 mm
Reactive
phosphorus
O0.45 mm
Unreactive
phosphorus
O0.45 mm
Reactive
phosphorus
!0.45 mm
Unreactive
phosphorus
!0.45 mm
30 m2 Mean 0.68 0.17 0.83 0.52 0.09 0.43 0.14 0.13
(nZ6) 95% confidence
interval of mean
(0.52–0.83) (0.12–0.23) (0.59–1.08) (0.36–0.69) (0.05–0.13) (0.30–0.55) (0.08–0.21) (0.08–0.17)
1 ha
Undrained Mean 0.69 0.26 0.77 0.43 0.14 0.26 0.10 0.19
(nZ7) 95% confidence
interval of mean
(0.38–1.01) (0.14–0.38) (0.54–1.01) (0.28–0.57) (0.08–0.19) (0.16–0.36) (0.08–0.12) (0.10–0.27)
Drained Mean 0.43 0.13 0.39 0.17 0.06 0.08 0.07 0.08
(nZ7) 95% confidence
interval of mean
(0.32–0.54) (0.10–0.15) (0.32–0.46) (0.13–0.22) (0.04–0.08) (0.05–0.11) (0.05–0.10) (0.05–0.11)
Hillslope Mean 0.49 0.32 0.59 0.33 0.08 0.03 0.12 0.13
(nZ1) 95% confidence
intervala– – – – – – – –
Catchment Mean 0.40 0.27 0.83 0.32 0.07 0.2 0.33 0.10
(nZ3) 95% confidence
interval of mean
(–0.01–0.81) (–0.07–0.61) (0.27–1.38) (0.13–0.50) (0.05–0.09) (0.03–0.38) (–0.03–0.70) (0.07–0.14)
a Confidence interval not applicable, sample size of one.
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33
F.L. Wood et al. / Journal of Hydrology 304 (2005) 118–138134
et al. (1997) and Withers et al. (1999). However, such
a link between land use and P transfer is less
commonly observed in larger basins, for example
the 902 km2 River Vilaine catchment in France
(Moreau et al., 1998), and the 109 km2 Gjern A
catchment in Denmark (Svendsen et al., 1995). This
may be because direct inputs to the river system from,
for example, channel or bank erosion might contribute
significantly to the diffuse P load as was the case for
the Gjern A (Svendsen et al., 1995). Other expla-
nations may be that there was little variation in small-
scale P transfers from different land uses, or that any
such differences were dampened as the scale of
observation increased. In the River Taw, the differ-
ence between upland and lowland P transfers may
have more parallels with comparisons between
forested (i.e. non-agricultural) and agricultural catch-
ments (e.g. Prairie and Kalff, 1986). For the Taw, the
average discharge per hectare is higher in the upland
catchments than in the lowland catchments. This
suggests that, unlike highly conservative and mobile
elements such as nitrate (e.g. Heathwaite et al., 1996)
P export processes specific to soil type and land use
may control P transfer rather than the volume of
discharge.
4.4. Diffuse phosphorus transfers at the 30 m2 plot
and 1 ha scale
Further insight into the likely sources and transport
dynamics for diffuse P can be gleaned by looking a P
transfer at the different scales investigated in this
study. Here, over 50% of the P transferred from both
30 m2 (undrained) plots and 1 ha (undrained) field
lysimeters is accounted for by the PO0.45 fraction,
with unreactive P forming the majority of P
transferred. Although the database for the 30 m2
plots was small compared to that generated at 1 ha
scale due to the less frequent generation of runoff from
the small plots, the temporal dynamics of P transfer
and statistical similarity in annual mean TP concen-
trations and export coefficients suggest that rapid
connectivity and similar patterns of P transport up to
the 1 ha field scale are possible. There are no exposed
channel faces to form an additional source area for P
at this scale of study, and it seems unlikely that
retention combined with additional mobilisation
processes would cancel out to produce a similar
response at the two scales. The results contrast with
research reported by Dils and Heathwaite (1996), who
recorded an increase in the downslope concentration
of TP in throughflow samples for grassland
catchments.
4.5. Diffuse phosphorus transfers from plot to
hillslope scale
At the hillslope scale, the Rowden study site
consists of a mixture of drained and undrained land.
This is typical of the Taw catchment where c.70% of
the land has been drained at some point. Several
factors suggest that the connectivity of P transport
from plot and field to hillslope may be high. For the
two years of research reported here, mean TP
concentrations and P export at the hillslope scale
lies between that recorded for the drained and
undrained 1 ha lysimeters. The regression of log-
transformed hillslope on field scale P concentrations
is also highly significant (Table 5). The regression
parameters (slope c. 1, intercept c. 0) imply that P
concentrations at the two scales are approximately
equal. However, the TP concentration recorded at the
hillslope scale during the winter of 1996–1997 was
often higher than that recorded at other scales
(Fig. 3a). Furthermore, for both years, the export of
UP O0.45 and RP !0.45 was higher than that
anticipated from the plot and field studies. The high P
concentrations and P transfer recorded for certain
period of the year may be indicative of additional
inputs of P from the channel bed or stream banks or
from unaccounted point sources such as septic tanks.
Short-term storage of P in channel beds has been
inferred in other studies (e.g. Pommel and Dorioz,
1997; Walling et al., 1998), and the major form of the
additional P transferred in 1997–1998 during the
concentration peaks (forms other than RP !0.45)
supports this interpretation. At both the field and
hillslope scales, there were pronounced peaks of P in
the UP !0.45 fraction and to a lesser extent the RP
!0.45 fraction from June to August 1998 and during
a storm in early March 1999; this contrasts with the
relatively constant concentrations of these forms
recorded at other times of the year. Drying and re-
wetting of soils, which can release large amounts of
particularly organic P to soil solution (e.g. Turner and
Haygarth, 2001) and may be a cause of this release in
F.L. Wood et al. / Journal of Hydrology 304 (2005) 118–138 135
the summer (e.g. Dils and Heathwaite, 2000). The
March release may result from freeze-thaw or from a
rapid surface soil temperature rise from 1.4 to 9.1 8C
that occurred during the 4 day period of rainfall.
In summary, the connectivity of P transfers from
plot-field up to hillslope scale may be rapid, with
little of the sediment retention that has been
observed elsewhere (Withers et al., 1998), but plot
and field scale transfers may sometimes be aug-
mented by other inputs and processes; the system is
not conservative, and plot-field scale rates of P
transfers will not accurately predict transfers at
hillslope scale.
4.6. Diffuse phosphorus transfers from plot to
catchment scales
The mean TP export from the Taw catchment
calculated from flow weighted mean concentrations,
is 1.2 kg haK1 yrK1. In contrast to the findings of
other studies in untilled sites (e.g. Sharpley et al.,
1992; Tattari and Barlund, 1998; Ekholm et al.,
1999), P O0.45 was the dominant form of P
transferred from diffuse sources in the Taw at all
scales. A significant regression relationship was
found between catchment and field scale log-
transformed TP concentrations, though it was
weaker than that recorded between hillslope and
field scale TP concentrations. The annual TP export
at the catchment scale was not significantly
different to that recorded from the undrained plots
and lysimeters. These data suggest that P flux at
the catchment scale may have contributions from P
inputs from other sources. The mean catchment
scale export of RP !0.45 (0.33 kg haK1 yrK1) is c.
three times higher than that of the mean 1 ha
concentration (0.09 kg haK1 yrK1). This difference
could account for the variation in TP export between
catchment and plot and field scales, and may be
accounted for by point source inputs at catchment
scale that are estimated to be around 0.15 kg haK
1 yrK1. Site specific inputs of P of the types observed
at the hillslope scale in Phase III of the study do not
appear to affect catchment P fluxes. Either they are of
low enough frequency to be diluted by mixing with
water of lower P concentrations or there is a decrease
in P export with increasing scale (e.g. Prairie and
Kalff, 1986). Phosphorus concentrations at the
hillslope to catchment scale are significantly lower
than those recorded for the undrained field lysimeters
but similar to P concentrations recorded in runoff
from the drained lysimeters. The lower P concen-
trations recorded at the catchment scale, despite
similar exports of most P forms, are consistent with
there being dilution of plot-field scale P transfers.
The regression equation of catchment on field scale
concentrations similarly implies that catchment scale
TP concentrations are proportional to approximately
the square root of those at field scale. The major
source of this dilution is likely to be water from the
high rainfall upland areas of the Taw catchment,
known to be low in P (antilog mean TP concen-
trations for 1997–1998 at Belstone, Leeham Ford and
Brayford were 2, 9, and 11 mg lK1, respectively; and
for 1998–1998 at Leeham Ford: 18 mg lK1).
In addition to the point source and dilution effects
discussed above, the dataset was examined for other
instances where the plot to hillslope P concentrations
or fluxes do not appear to predict catchment P
transfers. Disregarding occasional mismatches
between scales that could result from time-lags in
sampling, the time series for UP !0.45 displays a
consistent lack of response at catchment scale to
smaller scale peaks in concentration. There is only
one occasion (late April 1998) when there is
significant variation in catchment UP !0.45 con-
centration. This appears to originate in the Woodle-
igh catchment, where an unusually high
concentration of 200 mg lK1 was recorded. This
event was still apparent downstream at Umberleigh,
where the concentration had fallen to 96 mg lK1.
Significant organic P sources have been identified in
water extracts from pasture soils and have been
shown to be rapidly hydrolysable phosphodiesters or
mononucleotides (Guggenberger et al., 1996; Turner
et al., 2002). Hydrolysis of organic P forms may
account small contribution made by UP !0.45 in
downstream samples and may also contribute to the
increased export of RP !0.45 seen at the catchment
scale. The process of hydrolysis was not evaluated in
this study but several researchers have demonstrated
phosphodiesterase enzyme activity in vertical
throughflow and river waters (Christmas and Whit-
ton, 1998; Turner, 2000).
Excepting drainflow at 1 ha scale, mean TP
concentrations recorded at all scales exceed the
F.L. Wood et al. / Journal of Hydrology 304 (2005) 118–138136
OECD 35 mg lK1 threshold (OECD, 1982) for
increased risk of eutrophication in standing waters,
though not the proposed 60 mg lK1 mean annual RP
!0.45 river threshold for mesotrophic rivers
(Environment Agency, 2000a).
5. Conclusion
Point inputs of P were estimated, using the best
methods and understanding available, to account
for up to 38% of annual P fluxes at catchment
scale in the River Taw, the point source influence
tending to be greater in the larger sub-catchments.
However, the majority of the P transfer (from c.
60% to almost the entire annual P flux) at
catchment scale is estimated to be of diffuse
origin. Diffuse transfers of P measured at plot
and field scale from agricultural grassland can
account for the amount and composition of P
transfer observed at the catchment scale in diffuse
source dominated rivers, thus transport of P from
plot to catchment scale in general appears to be
conservative. There is little evidence for a signifi-
cant input of P from river channel banks in the
Taw, although there is evidence that several other
processes do affect the scaling of P transfers: the
appearance at hillslope scale of site specific source
areas such as bare soil, open access ditches, and
farm point sources; the possible hydrolysis of UP
!0.45; and the dilution of catchment scale P
concentrations by upland or groundwater sources.
These findings from the River Taw catchment are
relevant to the 14–24% of land in England and Wales
sharing similar soils and or hydrology. The P transfers
observed are not of immediate concern in the Taw
catchment, although the sediment they are associated
with might be. In the neighbouring Torridge and Tamar
catchments, however, there is no dilution from upland
headwaters, and algal blooms occur occasionally in the
Torridge and annually in the Upper Tamar Lake
(Environment Agency, 1998, 1999). Discharges from
STWs and specific farms have been identified as prime
causes of the associated eutrophication, but wide-
spread diffuse inputs of the magnitude observed in the
Taw catchment could also be contributing to the
problem.
Acknowledgements
The research was funded by a MAFF Studentship
to Fiona Wood at the University of Sheffield and
carried out at the Institute of Grassland and Environ-
mental Research North Wyke. Thanks are due to the
landowners who gave access to their farms; also to
Alison Coombs, Liz Williams, Neil Preedy, Rachel
Matthews, Trish Butler and Andrew Bristow for
technical assistance. The Environment Agency pro-
vided river hydrometric data.
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