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Environ Monit Assess (2012) 184:6197–6210

DOI 10.1007/s10661-011-2413-z

Application of Qual2Kw model as a tool for water quality


management: Cértima River as a case study
B. Oliveira & J. Bola & P. Quinteiro & H. Nadais &
L. Arroja

Received: 28 January 2011 / Accepted: 14 October 2011 / Published online: 3 November 2011
# Springer Science+Business Media B.V. 2011

Abstract Modelling can be a useful management tool eutrophic. By comparing in stream measurements
because models allow the understanding of water with Qual2Kw simulations, it can be concluded that it
body response to different pollution pressure scenar- would be necessary to decrease the actual pollutants
ios which may help on the decision-making process loads of nitrogen and phosphorous 5 and 10 times,
and in prosecuting the Water Framework Directive respectively, in order to change Cértima River
objectives. This study aims to evaluate the usage of classification from eutrophic to mesotrophic.
simple water quality models (Qual2Kw) applied to
small river basins in order to better understand the Keywords Modelling . Qual2Kw . Nutrients .
response of a river to different loads of nitrogen and Pollution . Cértima basin
phosphorus. Qual2Kw model was applied to Cértima
River (Portugal), a small river that ends in a shallow
lake called Pateira Fermentelos and represents a very Introduction
important ecosystem to the local community. Along
its pathway, Cértima River has a significant enrich- Water is a natural resource which availability is
ment in nutrients due to agriculture, livestock, dependent on its quantity and quality. In order to
domestic sewage and industrial effluents discharged satisfy the spatial and temporal human demands on
into the river. In case of nitrogen, the highest loads are water, it is necessary to evaluate the available
from domestic (44%) and diffuse (35%) sources. The freshwater resources and to know the pollutant loads
main sources of phosphorous are domestic (46%), generated on each river basin. In the last decades, the
livestock (24%) and diffuse sources (20%). Cértima deterioration of inland and coastal waters has been
River is strongly enriched with nutrients, and neither drastically increased due to anthropogenic discharges
nitrogen nor phosphorous is limiting the algal growth. of nutrients such as nitrogen and phosphorous to
According to the criterion of Dodds et al. (Water Res, water courses.
32(5):1455–1462, 1998), the river is classified as The European Directive 91/676/EEC of 12
December 1991 (The Council of the European
B. Oliveira (*) : J. Bola : P. Quinteiro : H. Nadais : Communities 1991b), concerning agricultural sour-
L. Arroja ces, and 91/271/EEC of 21 May 1991 (The Council
CESAM—Centre for Environmental and Marine Studies, of the European Communities 1991a), concerning
Department of Environment and Planning,
urban wastewater, refer the affluent loads of nitrogen
University of Aveiro, Campus Universitário de Santiago,
3810-193 Aveiro, Portugal and phosphorous to water courses, while the Europe-
e-mail: bruna.oliveira@ua.pt an Directive 2000/60/EC of 23 October 2000 (Water
6198 Environ Monit Assess (2012) 184:6197–6210

Framework Directive, WFD; The European Parlia- issues in Rio Blanco watershed in Jalisco, Mexico.
ment and The Council 2000) refers an integrated The results of the model were limited by the lack of
approach to the problem of eutrophication. It is data needed for input into the Qual2Kw, and the
essential to characterize the trophic status of surface model results did not necessarily represent the exact
waters in order to achieve the objectives defined in conditions present in the river, yet the model was
WFD. considered beneficial in showing what information
Each river has a different self-depuration capacity needs to be gathered to use Qual2Kw to model water
which makes necessary to know the pollutant loads quality issues in the studied river. Azzellino et al.
from different sources that the river is able to receive (2006) used the same model for apportionment of
without deteriorating its original characteristics. pollutant sources in a watershed located in Northern
Mathematical modelling is a useful tool to validate Lombardy, Italy, concluding that the model provides
the estimations of pollutant loads into an aquatic results that are of key relevance for the integrated and
environment, to establish cause–effect relations be- sustainable management and protection of European
tween pollution sources and water quality and also to freshwater resources.
assess the response of the aquatic environment to In this sense, Qual2Kw model was applied to
different scenarios. The simulations results are a Cértima River (a small river basin in Portugal) in
useful management tool that can assist policy makers order to give a simple representation to the extensive
in determining realistic strategies that take into and complex variables that govern the overall quality
account the basin specific conditions and also in of the watercourse. The model was firstly calibrated
predicting the effect of accidental discharges or using data measured at Cértima River on March 2008,
additional pollutant loads. and then the model was validated with data from
This study intends to evaluate the usage of simple January 2008. A sensitivity analysis was made to
water quality models applied to small river basins and quantify the error associated with the most important
the variations and trends in water quality as a parameters, considering March 2008 data. Finally,
consequence of different nitrogen and phosphorous nine scenarios were tested keeping the calibration
loads. Some works were done with the Qual2K model values as baseline and varying the nitrogen and
to simulate the water quality of rivers and watersheds phosphorous loads. These scenarios were then com-
using biochemical oxygen demand (BOD) (Xiaobo et pared and evaluated so as to better understand the
al. 2008), nitrogen, phosphorus and chemical oxygen trophic status of the river and its assimilative capacity,
demand (COD) (Fan et al. 2009; Grabiç et al. 2011) including feasible water management practices to
loads. The works lead to the conclusion that the improve Cértima River water quality.
model can provide the basic knowledge for a water
quality assessment even when the monitoring data are
insufficient. Other authors also used the model Methodology
Qual2K to test water quality management strategies
(Grabiç et al. 2011; Lin et al. 2010) concluding that Description of Qual2Kw
the model could form a basis for the management of
water quality issues. The mathematical model used to evaluate the water
Kannel et al. (2007) used the Qual2Kw to model quality of the river was Qual2Kw. The model frame-
water quality in the Bagmati River in Nepal. The work and documentation are available for download
model represented the field data quite, and the from the Washington State Department of Ecology at
sensitivity analysis showed that the model was highly www.ecy.wa.gov/programs/eap/models.html. It is a
sensitive for water depth and moderate to point stationary and one-dimensional model that can be
sources flow, total nitrogen (TN), BOD and nitrifica- applied when the flow and the pollution load into the
tion rate. The model was applied to simulate various river remain approximately constant. The main
water quality management strategies during critical simulated parameters are dissolved oxygen (DO),
period to maintain the targeted water quality criteria. organic matter (as BOD5), algal biomass (as chloro-
Gardner et al. (2007) constructed a Qual2K water phyll a), nitrogen compounds, phosphate compounds,
quality model to better understand the water quality faecal coliforms and conservative compounds. The
Environ Monit Assess (2012) 184:6197–6210 6199

simulated process attends to re-aeration, algal respira- direction for about 45 km until draining on Águeda
tion and growth, organic matter degradation, minerali- River. In the last 5 km, the valley of the river opens
zation, nitrification, denitrification, sedimentation and widely to form a shallow lake called Pateira
benthic activity. Also, the main input data are geometric Fermentelos (Fig. 1). The Cértima basin has approx-
properties of the river (including channel slope, channel imately 535 km2 and has a Mediterranean climate
width, side slope and Manning roughness coefficient), with strong influence from the Atlantic Ocean
flow rate, pollutant loads and meteorological parameters (Cerqueira et al. 2005). According to the climatic
(Pelletier and Chapra 2008). characterization made by Sena (2007), summers are
A real situation of a river can be represented more dry and hot, due to the effect of the Azores high-
closely using complex models. However, these are pressure system, and winters are mild and wet, with
usually reserved for larger (deep and wide) rivers strong precipitation events, resulting from the passage
where the mixing patterns are complex and also of frontal surfaces and depressions with Atlantic
require large amount of data which usually are not origin. In a typical summer, the riverbed dries up for
available and implies more costs. For modest man- a length of about 20 km from the spring.
agement purposes, this one-dimensional model may The active population mainly works in the second-
represent a good framework of water quality ary and tertiary sectors being ceramics, wine produc-
modelling. tion and metal processing the most important
industries. In addition, agriculture in the basin is
Study area mainly related with viticulture, rice and potatoes.
Table 1 summarizes the percentage of population
The Cértima River arises on the western slope of in the municipalities of the study area that has access
Bussaco Mountain in the Centre of Portugal at an to water supply, sewerage systems and wastewater
altitude of 380 m and flows in a dominant northern treatment plants (WWTP). Those not included in this

Fig. 1 Cértima basin with


reference to calibration
points and contamination
point sources. 1 WWTP
Murtede (24.2 km); 2
WWTP Mealhada
(22.3 km); 3 CST Tamegos
(17.5 km); 4 WWTP
Mogofores (15.2 km); 5
WWTP Arcos (14.5 km); 6
WWTP Sangalhos
(10.3 km); 7 WWTP
Aguada de Cima (4.9 km);
8 CST Lavandeira 1
(0.3 km); 9 CST Lavandeira
2 (0.3 km); 10 CST Oliveira
do Bairro 1 (0.3 km); 11
CST Oliveira do Bairro 2
(0.3 km) (data from SNIRH
2010)
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Table 1 Percentage of population with access to public water supply, drainage systems and wastewater treatment units (INSAAR
2010)

Municipality Population Population’s density Population served with


(No. hab) (No. hab / km2)
Water supply Sewerage Wastewater treatment
systems (%) systems (%) plants (%)

Águeda 49,800 148.7 90.0 73.0 63.0


Anadia 31,353 145.0 100.0 40.0 42.0
Mealhada 22,264 200.8 100.0 100.0 100.0
Oliveira do Bairro 23,623 269.2 97.0 84.0 72.0

list may either use community septic tanks (CST), WWTP and CST were estimated for 2007 using data
individual septic tanks or reject their effluents directly of population served by each of them and the per
into the river. capita parameters previously mentioned. At the
The stretch of Cértima River subjected to model- WWTP, the wastewater receives secondary treatment,
ling begins at Pampilhosa and extends until Perrães. and at the CST, it only receives primary treatment. It
The tributaries were indirectly introduced through was also considered that none of the treatment units
increases in the main stream flow since no data were applies auxiliary treatment to remove nutrients. For
available on water flow and quality. The modelled WWTP 4, 5, 6 and 7, there were recorded data of
stream has 25.7 km and was divided in four segments daily inflow and its composition. In order to estimate
with less than 8 km each and similar geometric and the pollution load discharged into the river after
physical properties. Each segment was sub-divided treatment, it was considered a TSS and BOD5
into 500-m intervals which formed the base grid to removal efficiency of 90% for the WWTP and 50%
solve the differential equations of the model. for CST. To estimate TN and TP removal, it was
According to Silva (2008), the channel slope varies considered the amount used by microorganisms to
between 0.003 and 0.0008, the trapezoidal cross remove 90% or 50% of BOD5, respectively, for
section has a side slope varying between 0.35 and WWTP and CST and a consumption ratio BOD5/N/
0.25 and the channel width varies between 2 and 8 m, P of 100:5:1 (Metcalf and Eddy Inc 2003).
from headstream to downstream. It was assumed a The estimated daily loads of BOD5, total N and
Manning roughness coefficient of 0.04 (Pelletier and total P for each treatment unit are represented in
Chapra 2008). Fig. 2. Industries in Cértima basin may represent a
strong anthropogenic pressure on the aquatic envi-
Contamination sources ronment. For this work only, the licensed industries
discharging its effluent directly into the river were
According to the Portuguese Inventory System of considered. Data for those industries were obtained
Water Supply and Wastewater (SNIRH 2010), in 2007 from the Management of River Basin—Center
there were six WWTP and five CST discharging their (ARH—C 2010) database, and their location was
effluents along the river (Fig. 1). Data about these associated to the centroid of the parish where they are
units were obtained from INSAAR (2010). The total located. The loads discharged into the river were
domestic pollution generated in the watershed was estimated according to the effluent volume generated
estimated from the data of resident population, their at each unit and the wastewater emission limit values
access to public drainage systems and considering a imposed by the Portuguese authorities (BOD5 ≤
typical composition of untreated domestic wastewater 40 mg O2 l−1; COD≤150 mg O2 l−1; TSS≤60 mg l−1;
of 60 gBOD5 hab−1 day−1, 90 gTSS hab−1 day−1, 8 gN TP≤10 mg Pl−1; TN ≤15 mg Nl−1) through the
hab−1 day−1 and 1.5 gP hab−1 day−1 (Metcalf and Eddy Decree-Law No. 236/98 of 1 August 1998 (Annex
Inc 2003). XVIII) (Ministry of Environment 1998).
The inflow loads of BOD5, total suspended solids Piggeries, cattle and poultry farming units were
(TSS), TN and total phosphorous (TP) to each treated separately due to their specific characteristics.
Environ Monit Assess (2012) 184:6197–6210 6201
Fig. 2 Daily flow and
BOD5, total N and total P
loads discharged into
Cértima River in 2007

The data used for estimating the pollution loads from use CORINE Land Cover 2000 (Portuguese Environ-
piggeries and cattle farming were from the Vouga mental Agency 2010) was used to determine the soil
Watershed Plan (ARH—C 2002). In case of poultry occupation.
farms, data were obtained from Management of River Diffuse pollution is very irregular throughout the
Basin—Center (ARH—C 2010), and a maximum of year and, as a consequence, for each month, it has
six growth cycles per year was considered. To been calculated a percentage of the annual load. This
estimate these loads, it was considered that the percentage was a function of the ratio between the
effluent to be discharged into the river is treated to observed average monthly precipitation and the
meet the specifications of Decree-Law No. 236/98. average annual precipitation. The loads from diffuse
The loads from livestock units were introduced in the sources introduced in the model were 84% of the
model as homogeneously distributed along the calculated load to the entire Cértima basin because
27.5 km. this is the approximate percentage corresponding to
There are various diffuse sources of pollution, but the study area.
on this study, it was only considered the export of Table 2 resumes the estimates of the total pollution
nutrients from soil to water resources. For its load generated in Cértima basin. In the case of
quantification, the load of pollutants exported per domestic loads, the values refer to the sum of treated
unit area (export rates) associated to each category of and untreated effluents. Analysing the nitrogen loads,
land occupation was considered. The total pollutant the overwhelming contribution of domestic and
load affluent to a reference section was obtained by diffuse sources is evident. Likewise, phosphorus
Eq. 1 (Novotny 2003): derives mainly from domestic, cattle farming and
diffuse sources. The high contribution of diffuse
X 
CTi ¼ Cij  Aj ð1Þ sources both to nitrogen and phosphorous loads is
mainly due to the crops and rice fields.
In order to make the division of nitrogen and
where CTi is the total load of pollutant i affluent to the phosphorous in its different forms, it was considered
reference section, Cij is the load of pollutant i per unit that the untreated domestic sewage has 60% of
area and time for the soil category j (export rate) and ammonia, 40% of organic N, 70% of inorganic P
Aj is the soil area of j category. A digital map of land and 30% of organic P, and the industrial sewage has
6202 Environ Monit Assess (2012) 184:6197–6210

Table 2 Total pollution load


generated in Cértima basin Source BOD5 TSS Total N Total P
(ton year−1) (ton year−1) (ton year−1) (ton year−1)

Domestic 668.9 989.9 153.4 27.3


Industry 31.3 46.9 11.7 2.3
Piggeries 22.4 33.5 3.4 1.1
Cattle farming 103.1 1,272.5 42.9 14.0
Poultry 35.8 53.7 13.4 2.7
Diffuse – – 122.5 11.5
pollution
Total 861.5 2,396.5 347.3 58.9

60% of ammonia, 40% of organic N, 50% of area. Perrães station is located before Pateira
inorganic P and 50% organic P (Metcalf and Eddy Fermentelos in the final segment of Cértima River.
Inc 2003). As there is a great diversity in industry Among the monitored parameters, ammonium
typologies, different distributions of nitrogen and (NH4), COD, BOD5, TP, orthophosphate (P2O5),
phosphorous were tested, and the results showed no nitrate (NO3), nitrite (NO2), DO (milligrams O2 per
significant differences in the final result. In case of litre), pH, TSS (milligrams per litre) and temperature
livestock units, it was considered a composition of (degree Celsius) were selected to assess the water
60% ammonia, 40% organic N, 60% inorganic P and quality of the river with particular attention to
40% organic P (Cosma et al. 2003). For diffuse nutrients. Despite the fact that the selected parameters
pollution, the considered distributions were 5% of are monitored at the three stations, the data obtained
ammonia, 70% organic N, 25% of nitrate, 20% between the beginning of operation and the year of
inorganic P and 80% organic P (Coelho et al. 2007). 2008 (inclusive) cannot be used for modelling
The pollutant loads from diffuse domestic sources purposes because the monitoring stations do not
and from industries were homogeneously introduced operate in continuous mode. In addition, the samples
in the model as diffuse sources according to the are not collected at the same date at the three stations,
municipality where they were generated: and the analysed parameters are not always the same
for each sample.
& Mealhada, 25.7–21.5 km
Despite this, data collected at each station were
& Anadia, 21.5–8.7 km
analysed as a whole and also in subgroups based on
& Oliveira do Bairro e Águeda, 8.7–0.0 km
their monthly and annual distribution. The rejection of
outliers was made by the method proposed by Grubbs
Monitoring stations (1948) for a confidence level of 95%. It should be
noted that at Ponte Canha and Perrães, the data for
The network of the National Institute of Water for COD and orthophosphate are limited to 2008. From a
monitoring the water quality in the modelled stretch univariate statistical analysis, it was observed that pH
consists in three stations (Fig. 1): Ponte Canha (since and temperature distributions are almost symmetric
2001), Perrães (since 2001) and Pampilhosa (since while the other parameters have asymmetric distribu-
2002). The parameters monitored are available at tions. It is natural that the most of the parameters
SNIRH (2010). present asymmetric distributions because this study
The Pampilhosa station is classified as reference makes use of surface water samples collected in
station. However, the Cértima River crosses the different seasons of the year and over several years
municipality of Pampilhosa before reaching this and possibly with different anthropogenic pressures.
station being vulnerable to anthropogenic pressures. Figure 3 presents the monthly variation of the
Ponte Canha station is downstream the urban areas of temperature at each station which influences the
Mealhada and Anadia and an important industrial processes occurring in the river.
Environ Monit Assess (2012) 184:6197–6210 6203
Fig. 3 Average monthly
variation of temperature
(degree Celsius) recorded at
each monitoring station
(SNIRH 2010)

Fig. 4 Comparison between the monthly average variation of per cubic metre) and the monthly average precipitation
ammonia (milligrams N-NH4 per cubic decimetre), nitrate (millimetres) recorded at Oliveira do Bairro between 1989 and
(milligrams N-NO3 per cubic decimetre), total P (milligrams P 2008 (SNIRH 2010)
per cubic decimetre) and orthophosphate (milligrams P-P2O5
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Table 3 Dodds et al. (1998)


suggested boundaries for trophic Variable (units) Oligotrophic–mesotrophic boundary Mesotrophic–eutrophic boundary
classification of streams
TN (mg l−1) 0.7 1.5
TP (mg l−1) 0.025 0.075

Nitrogen and phosphorous are the main nutrients and a runoff coefficient-dependent on soil type (Akan
which can cause eutrophication as a consequence of and Houghtalen 2003):
its accumulation in the aquatic environment. In order
Q ¼ 0:278  C  i  A ð2Þ
to better understand the precipitation influence on
NH4, NO3, TP and P2O5 concentration on Cértima where Q is the runoff (cubic metres per day), C is the
River, Fig. 4 shows their average monthly variation. runoff coefficient, i is the average hourly precipitation
As can be seen, NH4, TP and P2O5 concentrations are (millimetres per hour) and A is the basin area (square
the lowest in high precipitation periods, and the kilometres). The calculated values were compared
opposite occurs to NO3. The highest concentrations with the values measured by Silva (2008).
in dry months are possibly consequence of the The flow rate considered at the headstream was
decreased flow in conjunction with the constant loads that given by Silva (2008). The additional flow along
into the river, namely domestic sources, because the the river was calculated for an area of 444.9 km2
existing WWTP do not remove nitrogen nor phos- between Pampilhosa and Perrães considering the
phorous compounds. During the first months of average hourly precipitation given by Silva (2008)
precipitation, the high concentrations seem to remain and the runoff coefficient of 0.057 for uncovered
apparently due to diffuse sources. According to these surfaces (McCuen 1989). The resulting inflow is
records, Ponte Canha has the highest contamination given in Table 4 and was inserted in the model
with nitrogen and phosphorous. The use of fertilizers evenly along the 25.7 km of the river.
in the agriculture fields are probably the source of the
high concentration of nitrate recorded at Perrães. At
the studying area, fertilization is usually done in April
and October which justifies the higher concentrations Results and discussion
of nitrogen and phosphorous compounds in the
following months. According to the criterion of Model calibration
Dodds et al. (1998) in Table 3, the stretch of Cértima
River downstream Ponte Canha is classified as The calibration process aims to find values for the
eutrophic throughout the year. model parameters that best fit the system to be
modelled. Qual2Kw may be calibrated by hand or
by internal genetic algorithm which calibrates the
Flow rate model automatically based on a number of specified
stoichiometric rates and constants. In this case, it was
Runoff was estimated using the rational method that auto-calibrated using data for March 2008 measured
takes into account precipitation data, the basin area by Silva (2008) for Lagoa Seca (21.1 km), Ponte

Table 4 Data for flow rate


calculations Model Flow rate at the headstream Average precipitation Inflow
(m3 s−1) (mm h−1) (m3 s−1)

Calibration 0.04 0.134 0.95


Validation 0.1 0.333 2.36
Environ Monit Assess (2012) 184:6197–6210 6205

Table 5 Calibrated parameters for Cértima River

Parameter Value Units Min. value Max. value

Stoichiometry
Carbon 40 gC 30 50
Nitrogen 7.2 gN 3 9
Phosphorous 1 gP 0.4 2
Chlorophyll 1 gA 0.4 2
−1
ISS settling velocity 0.24696 m day 0 2
O2 re-aeration model Owens–Gibbs f (s uh)
Slow CBOD hydrolysis rate 0.25465 day−1 0 5
Slow CBOD oxidation rate 0.20485 day−1 0 0.5
−1
Fast CBOD oxidation rate 2.45565 day 0 5
Organic N hydrolysis rate 0.7866 day−1 0 5
Organic N settling velocity 0.73568 m day−1 0 2
Ammonium nitrification rate 8.3776 day−1 0 10
Nitrate denitrification rate 1.73692 day−1 0 2
−1
Sed. denitrification transfer coefficient 0.2142 m day 0 1
Organic P hydrolysis rate 0.7369 day−1 0 5
Organic P settling velocity 0.03264 m day−1 0 2
Inorganic P settling velocity 0.0336 m day−1 0 2
Sed. P oxygen attenuation half sat constant 1.60952 mgO2 l−1 0 2
Phytoplankton
Maximum growth rate 1.768515 day−1 1.5 3
Respiration rate 0.28324 day−1 0 1
Death rate 0.58812 day−1 0 1
Nitrogen half sat constant 12.9765 mgN m−3 0 150
Phosphorous half sat constant 8.491 mgP m−3 0 50
Inorganic carbon half sat constant 4.77E−05 mol l−1 1.30E−06 1.30E−04
Light model Half saturation
Light constant 64.731168 langleys day−1 28.8 115.2
Settling velocity 1.31585 m day−1 0 5
Bottom plants
Growth model Zero order
Maximum growth rate 95.383 day−1 0 100
First-order model carrying capacity 77.3645 gD m−2 50 200
Basal respiration rate 0.010659 day−1 0 0.3
Photo-respiration rate parameter 0.292002 unitless 0 0.6
Excretion rate 0.248455 day−1 0 0.5
Death rate 0.458335 day−1 0 0.5
External nitrogen half sat constant 49.872 mgN m−3 0 300
External phosphorous half sat constant 94.326 mgP m−3 0 100
−1
Inorganic carbon half sat constant 3.39E−05 mol day 1.30E−06 1.30E−04
Light model Half saturation
Light constant 6.30244 langleys day−1 1 100
Ammonia preference 83.97388 mgN m−3 1 100
Subsistence quota for nitrogen 7.63738704 mgN gD−1 0.072 72
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Table 5 (continued)

Parameter Value Units Min. value Max. value

Subsistence quota for phosphorous 8.6790223 mgP g−1 0.01 10


Maximum uptake rate for nitrogen 541.4865 mg Ng−1 D−1 350 1,500
Maximum uptake rate for phosphorous 157.118 mg PgD−1 day−1 50 200
Internal nitrogen half sat ratio 2.2144205 1.05 5
Internal phosphorous half sat ratio 4.250922 1.05 5
Nitrogen uptake water column fraction 0 1
Phosphorous uptake water column fraction 0 1
Detritus dissolution rate 2.44095 day−1 0 5
Detritus settling velocity 3.9578 m day−1 0 5

Canha (13.1 km) and S. J. Azenha (7.5 km) and data agreement, the model can be used to test different
measured by SNIRH (2010) for Pampilhosa scenarios in a general strategy to understand the river
(25.7 km) and Perrães (0 km). response to different nitrogen and phosphorous loads.
As there are no data about the tributaries of
Cértima River, assumptions had to be made in order Sensitivity analysis
to take into account the attenuation that the contam-
inants discharged on tributaries suffered previously to Sensitivity analysis is crucial to quantify the error
reach the main stream. The distance between the exact associated with the variation of the parameters of
location of the point source number 1 in the tributary greater importance and to evaluate the model robust-
and the end of Cértima River is 24.2 km. Having that, ness. The sensitivity analysis was performed in order
for the simulations with Qual2Kw, it has been to identify the parameters that have the most influence
considered that this point source was at a fictitious on the model outputs. The analysis was made varying
location in the main stream that corresponds to only one parameter at a time. Table 6 summarizes the
24.2 km. This is equivalent to assume that the tested parameters and the model results. Data for
tributary has the same attenuation capacity as the March 2008 were considered as baseline.
main stream. The same assumption has been made to It can be concluded that the model is most
point sources number 8 to 11. sensitive to Manning coefficient, ammonium nitri-
The input parameters for Qual2Kw were temperature, fication rate, bottom plants maximum growth rate
pH, conductivity, DO, BOD5, TSS, NH4, NO3, total P, and bottom plants death rate. These conclusions
average daily flow, depth profiles and flow velocity. are in accordance with the results obtained by
The model represents the field data quite well, and the Kannel et al. (2007) for nitrification rate and flow
auto-calibrated parameters are shown in Table 5. conditions. However, it seems that the forms on
which nitrogen appears are the most influenced.
Model validation Attending to that, the scenarios evaluation will be
made considering TN in spite of NH4 and NO3
In order to test the ability of the calibrated model to separately.
predict water quality under different conditions, the
model was run using data of January 2008 (Silva 2008) Scenario evaluation
without changing the calibrated parameters. As can be
seen in Fig. 5, the model response for dissolved Data for March 2008 were considered as baseline
oxygen was in good agreement with the data. The conditions for scenarios evaluation as the model has
Pearson’s correlation between the monitoring data and been calibrated for that month. According to the river
the validation results for DO is 0.723, for TN is 0.955 characteristics and location, it can be assumed that it
and for TP is 0.978. Attending to this good has no salinity, temperatures are between 14.5°C and
Environ Monit Assess (2012) 184:6197–6210 6207

river is already eutrophic according to the criterion


presented in Table 3.
The model responses for Ponte Canha are pre-
sented in Fig. 6 and for Perrães in Fig. 7. These
locations were selected because Ponte Canha is
located approximately at the middle of the river
length and Perrães is near the end and also due to
the existence of monitoring data for these locations.
Despite the absence of data of chlorophyll a for the
calibration and validation of the model, the simu-
lations results for bottom algae (BA) are presented to
help understand the river response to different
nitrogen and phosphorous concentrations. In Figs. 6
and 7 has been drawn straight lines representing DO
minimum safety threshold (4 mg l−1) and TN
(1.5 mg l−1) and TP (0.075 mg l−1) maximum
concentrations for mesotrophic classification accord-
ing to the criterion in Table 3.
Analysing the simulations results, it is evident
that the river is saturated with nitrogen and
phosphorous. The contamination seems to be
higher at Ponte Canha than at Perrães possibly due
to the depurative capacity of the river. The simu-
lations show that the river behaviour is similar at both
locations.
In order to the river not to be classified as
eutrophic at Ponte Canha, the baseline load of TP
would have to be multiplied by a factor of 0.2 and the
baseline load of TN would have to be multiplied by
0.1. This means that the actual loads of TN and TP
(baseline conditions) would have to decrease five and
ten times, respectively.
When TN load is decreased, DO slightly
increases which may be justified by the decrease
of oxygen consumption by the nitrification pro-
Fig. 5 Qual2Kw validation results for dissolved oxygen
cess. In these scenarios, the BA concentration
(milligrams per litre), total nitrogen (micrograms per litre) and remains almost the same which means that
total phosphorous (micrograms per litre) diminishing only the TN load would not affect
algae growth. However, when TP load decreases,
the DO and BA concentrations also decrease
16°C and so the DO on freshwater should be which means that this nutrient highly affects algae
approximately between 10.18 and 9.86 mg l−1 and growth, i.e. phosphorous is the limiting nutrient.
should not decrease below a safety threshold value of The individual decrease of TN load does not seem
4 mg l−1 (Metcalf and Eddy Inc 2003). to affect TP concentration and vice versa. When
Attending to that, the scenarios resumed in Table 7 the loads of TN and TP are simultaneously
were simulated using the calibrated model in order to decreased, the river has a behaviour similar to
evaluate the river response to different nitrogen and that when only TP is decreased but with smoother
phosphorous loads. Only scenarios of lower nitrogen decreases on DO and BA concentrations. For all
and phosphorous loads were simulated because the the tested scenarios, DO never drops below the
6208 Environ Monit Assess (2012) 184:6197–6210

Table 6 Sensitivity analysis results (the most influenced parameters are evidenced in bold)

Parameter Variation (%) DO BOD5 NH4 NO3 TP TSS


% of disturbance (considering March 2008 as baseline)

Manning coefficient 50.00 −2.47 −8.68 −28.80 8.84 1.75 −0.34


−50.00 8.05 10.73 27.31 −22.87 −1.72 0.55
Fast CBOD oxidation rate 50.00 −3.38 −13.05 −1.61 0.54 0.00 0.00
−50.00 4.27 12.42 2.22 −0.87 0.00 0.00
ISS settling velocity 50.00 −0.06 −0.03 −0.04 0.00 0.02 −9.85
−50.00 −0.02 0.01 0.03 −0.02 −0.04 9.37
Organic N hydrolysis rate 50.00 −0.18 0.00 1.03 0.45 0.01 0.00
−50.00 0.17 0.00 −1.18 −0.48 0.00 0.00
Organic N settling velocity 50.00 −0.65 0.01 3.37 1.91 −0.01 0.01
−50.00 0.99 0.01 5.46 −2.97 0.00 −0.01
Ammonium nitrification rate 50.00 −2.93 0.30 −38.77 11.05 −0.03 0.01
−50.00 5.29 −0.29 33.45 −34.86 0.07 −0.04
Nitrate denitrification rate 50.00 0.01 −0.10 −0.01 −0.23 0.00 0.00
−50.00 −0.03 0.10 −0.02 0.24 0.00 0.00
Sediment denitrification transfer coefficient 50.00 0.08 0.01 0.46 −7.16 0.00 0.00
−50.00 −0.09 −0.01 −0.54 6.90 0.00 0.00
Organic P hydrolysis rate 50.00 0.20 0.08 0.16 −0.04 −0.57 0.02
−50.00 −0.39 −0.14 −0.31 0.08 0.60 −0.06
Organic P settling velocity 50.00 0.07 0.03 0.01 0.00 −0.38 0.01
−50.00 −0.01 0.00 0.05 −0.03 0.34 0.00
Inorganic P settling velocity 50.00 −0.47 −0.14 −0.29 0.04 −1.20 −0.08
−50.00 0.41 0.12 0.14 0.01 1.20 0.06
Bottom plants maximum growth rate 50.00 18.82 4.84 18.02 −12.40 −7.31 2.01
−50.00 −29.76 −6.71 −15.08 4.21 12.87 −2.31
Bottom plants basal respiration rate 50.00 0.01 0.05 0.05 0.00 −0.05 0.01
−50.00 −0.11 −0.11 −0.26 0.08 0.15 −0.03
Bottom plants death rate 50.00 −3.06 3.64 −1.86 1.40 6.81 1.60
−50.00 3.92 −4.21 2.36 −2.16 −10.32 −2.08
Phytoplankton maximum growth rate 50.00 −0.06 −0.01 −0.03 0.00 0.04 −0.01
−50.00 −0.08 −0.03 −0.04 0.00 0.02 −0.02
Phytoplankton respiration rate 50.00 −0.16 −0.05 −0.11 0.02 0.04 −0.03
−50.00 −0.07 −0.02 −0.03 0.00 0.03 −0.01
Phytoplankton death rate 50.00 −0.16 −0.05 −0.11 0.02 0.04 −0.03
−50.00 −0.07 −0.02 −0.03 0.00 0.03 −0.01
Re-aeration rate 50.00 1.67 −0.35 −0.47 0.21 0.10 −0.05
−50.00 −2.94 2.44 3.45 −2.33 0.00 0.07

safety threshold of 4 mg l−1. Considering these Table 7 Nitrogen and phosphorous tested scenarios
results and the European WFD, the Portuguese water
authorities should implement management plans to Scenario Nitrogen Phosphorous
Multiplication factor of the baseline load
decrease the TN and TP loads discharges into Cértima
River basin, namely through nitrogen and phospho- N1; N2; N3 0.1; 0.2; 0.5 Equal to baseline
rous removal at the WWTP and through the adoption P1; P2; P3 Equal to baseline 0.1; 0.2; 0.5
of best practices on cattle farming and agricultural NP1; NP2; NP3 0.1; 0.2; 0.5 0.1; 0.2; 0.5
practices.
Environ Monit Assess (2012) 184:6197–6210 6209

Conclusions

The main conclusions of this study are:

& Cértima River is enriched with nutrients. In


accordance with the Dodds et al. (1998) criterion,
the river is classified as eutrophic relatively to
total P in 75% of the recorded values at
Pampilhosa, 88% at Ponte Canha and 83% at
Perrães.
& Qual2Kw was calibrated, validated and a sensi-
tivity analysis was made for Cértima River. The
model represented the field data quite well.
& Qual2Kw accurately illustrates the dynamic evo-
lution of temperature, pH, conductivity, DO,
BOD5, TSS, TN and TP along the river.
& The model was applied to simulate different
scenarios of nutrients loads, and the results
showed that the river is saturated with nitrogen
and phosphorous and only decreasing five times
the TN load and ten times the TP load would
Fig. 6 Scenarios results for DO, BA, TN and TP at Ponte
change the river classification from eutrophic to
Canha mesotrophic.
& The Qual2Kw model results suggest that there is
no correlation between nitrogen and phosphorous
concentrations at Cértima River.
& The results suggest that neither nutrient is limiting
the algal growth which indicates that on baseline
conditions, the river is saturated with both
nutrients.

The sensitivity analysis allows to understand the


parameters to which the model is more sensitive and
more effort should be applied in order to precisely
determine those parameters. Furthermore, a more
complex sensitivity analysis procedure should be
applied taking into account the simultaneous variation
of some parameters in order to evaluate their
combined influence on the model outputs.
Qual2Kw can reasonably be applied to small
basins to evaluate the effects of different modifi-
cations in an aquatic environment. This mathemat-
ical model requires simple input parameters and so
it is a good framework to simulate the water
quality when monitoring data are scarce or when
the assessment does not require great precision.
The model is also flexible as it can be used
Fig. 7 Scenarios results for DO, BA, TN and TP at Perrães without knowing all the involved parameters
6210 Environ Monit Assess (2012) 184:6197–6210

because it assumes default values. However, the INSAAR (2010). Data base—2005 and 2007. INSAAR—
National Inventory of Water Supply Systems and Waste-
quality of the model results is highly influenced
water, INAG—Water Institute, Portugal. http://insaar.inag.
by the quality of the input data. pt. Assessed 10 Jul 2010 (in Portuguese).
Kannel, P. R., Lee, S., Lee, Y. S., Kanel, S. R., & Pelletier,
G. J. (2007). Application of automated QUAL2Kw for
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