Water Air Soil Pollut (2014) 225:2103 DOI 10.1007/s11270-014-2103-x Establishment and Validation of an Amended Phosphorus Index: Refined Phosphorus Loss Assessment of an Agriculture Watershed in Northern China Bin Zhou & Rolf D. Vogt & Chongyu Xu & Xueqiang Lu & Hongliang Xu & Joshi P. Bishnu & Liang Zhu Received: 14 May 2014 / Accepted: 24 July 2014 / Published online: 6 August 2014 # Springer International Publishing Switzerland 2014 Abstract Phosphorus (P) loss from non-point sources is a main cause of freshwater eutrophication in agricultural regions. Knowledge-based watershed management plans, aimed at reducing the diffuse flux of phosphorus from specific land-use and site characteristics to freshwater resources, are needed in order to curb eutrophication in agriculture regions. In this context, the use of a phosphorus index provides a simple and practical method for identifying hot-spot source areas and to estimate their potential for contributing a flux of P to the surface waters. However, as a semi-quantitative tool, the P index is usually difficult to validate due to inadequate data representation relative to large spatial and temporal variation in P fluxes. An amended P index scheme is therefore developed and validated, based on comprehensive synoptic soil study and stream water monitoring as well as a previous study that had applied the former P index in the studied watershed in northern China (Zhang et al. 2003). The amendments include the use of data from the individual village units (mean area, ca. 30.6 ha), use of the degree of P saturation (DPS) in the B. Zhou (*) : R. D. Vogt : J. P. Bishnu : L. Zhu Department of Chemistry, University of Oslo, Oslo 0315, Norway e-mail: bin.zhou@kjemi.uio.no C. Xu : H. Xu Department of Geosciences, University of Oslo, Oslo 0315, Norway B. Zhou : X. Lu Tianjin Academy of Environmental Sciences, Tianjin 300191, China source factor scheme, adoption of flow length factor and modified water course erosion factor into the P transportation scheme, and an adjustment of the organization structure of the P index scheme. The validation of the amended P schemes was performed by comparing the modeled average P index values with the corresponding measured P fluxes for 12 different sub-catchments. The results indicate an improved precision in the simulated potential for P loss using the refined P index scheme. Measured fluxes of total P (r=0.825), particulate P (r= 0.867), and less-studied yet more relevant dissolved P (r=0.627) all showed significant correlations with the modeled P index values in the amended P scheme. The primary direct finding of the current research is that the areas with close proximity to rivers and the reservoir, as well agricultural land around villages, are found to be the main hot-spot sources for P loss to the reservoir. Keywords Amended P index . Degree of P saturation . P fluxes . Validation 1 Introduction In modern intensive agriculture, the addition of phosphorous (P) is a key factor to increase crop production (Cordell et al. 2009). Globally, 500 million tonnes of P has been applied as fertilizer during the second half of last centenary (Brown et al. 1997; FAO 1950–1995). This has led to an excess of P in the top Ap horizon of the agricultural soil, which increases the P loss from terrestrial to aquatic ecosystem. Numerous studies have 2103, Page 2 of 16 subsequently identified diffusive phosphorus loss from agricultural land as the main cause of water eutrophication in main developed countries (Agnew et al. 2006; Elliott et al. 2006). The increased flux of P from diffuse agricultural sources is thus posing a potential threat to the quality of freshwater systems (Correll 1998; Sharpley et al. 2001a). Moreover, as the contribution of P from point sources have been significantly and efficiently limited, especially in Europe and USA, the diffusive loading of P from agriculture has become the remaining cause for P flux to surface water (Orderud and Vogt 2013; Sharpley et al. 1999). Identifying and assessing potential for P loss from agricultural land is thereby the key prerequisite in order to select the most cost-efficient abatement strategies in the struggle against eutrophication. Compared to point source pollution, the sources of diffusive phosphorus loss from agricultural land are inherently more difficult to identify and quantify. The continuous development of water quality management models, especially those based on physical mechanisms, such as the SWAT and AGNPS models (Bingner et al. 2003; Neitsch et al. 2011), have greatly improved our understanding of hydro-geochemical processes governing the mobilization and transport of phosphorus in the watershed (Tominaga 2013). However, the heavy data requirements of these models greatly limit their practical application as routine management tools. Instead, the simplified P loss indicator was introduced by Lemunyon and Gilbert (1993) as a proxy for assessed potential for P flux. As a semi-quantitative tool, the P index is based on arithmetic computations of source and transportation factors, most of which are readily available data (Bechmann et al. 2005; Buczko and Kuchenbuch 2007). This indicator is therefore an applicable environmental management tool for local water quality managers: In the USA, the original P index has been routinely applied for assessments of P loss from agricultural fields and identification of critical areas with high susceptibility for P loss (Sharpley 1995; Stevens et al. 1993). In Germany, the P index combined with a GIS framework has been applied to identify areas most susceptible for phosphorus leaching (Behrendt et al. 1996). Since the P index was introduced in 1993, the system has grown more comprehensively by incorporating more governing factors: Elliott et al. (2006) introduced the phosphorus source coefficients (PSCs) into the source factor module, enabling the identification of different load rates of dissolved P in runoff from various Water Air Soil Pollut (2014) 225:2103 types of organic fertilizer. Jokela et al. (1998) introduced the role of reactive aluminum as an important P suppression factor in acid soils (Jokela 1999; Jokela et al. 1998). In the transport factor module, McFarland et al. (1998) incorporated the distance to water body factor and Sharpley et al. (2001b) introduced the leaching potential factor. More recently, Li et al. (2007) introduced the quality of receiving water factor into the modified phosphorus ranking scheme and Zhou and Gao (2011) adapted the P index in order to use it also in large-scale agricultural catchments. The development and implementation of the phosphorus index is still in its early stages in China, where a broad application of the phosphorus index system by agricultural managers is yet to be realized (Li and Guo 2010). Assessment of P loss using P index at various scales (e.g., plot, field, and watershed) have been thoroughly described in the literatures. Most watershed studies tend to use data with a relatively low spatial resolution. For example, Andersen and Kronvang (2006) introduced the use of an averaged catchment (1,000 km2) value for the measured soil test phosphorus parameter (STP, a measure of the pool of bioavailable P (BAP) in the soil), instead of applying the spatially distributed measured data. Zhou and Gao (2008) estimated the distribution of degree of phosphorus saturation (DPS %), based on measurements of only 80 soil samples, in a large agricultural watershed (13,349 km2) in southern China. By doing so, the modeling efficiency was significantly improved, and an overall estimate of phosphorus loss at a large scale was achieved. However, the use of such relatively rough input data is inherently associated with limited capability for interpretation, due to compromised spatial accuracy. The use of high-resolution spatial data, such as maps of soil texture, land use, and vegetation cover, greatly improves the possibility for interpretation at a relatively small scale by inducing their conceptual link to the potential for P loss. Most of the phosphorus mobilized during rainfall periods is found to be immobilized again by the soil. For example, Tuo et al. (2009) found that the concentration of especially particle-bound phosphorus in surface runoff was reduced (more than 80 %) upon subsequently passing through soils as interflow prior to entering the stream. Watersheds in near proximity to stream channels or the target water therefore commonly possess relatively higher risk relative to regions located at some distance away (Johnes and Heathwaite 1997). An erosion factorbased distance (water course factor) was therefore Water Air Soil Pollut (2014) 225:2103 introduced into the P index assessment system (McFarland et al. 1998). However, this relationship was initially generalized as a simple straight line distance function, with equal distance weights. This made it impossible to represent the actual transportation mechanisms, which are generally based on non-linear functions. The actual migration distance is generally longer, especially in regions with complex terrain structures. The transport length was instead considered as the actual flow distance within the given basin, meaning the distance traveled by the water from any point along the flow path (Akhtar et al. 2009). The soil parameters total P and BAP are usually selected as primary assessment indicators due to their strong correlation with the loss of P as well as their ready availability from environmental monitoring departments (Bechmann et al. 2009; Drewry et al. 2011; Sharpley 1995; Shen et al. 2011). However, the use of only BAP might lead to erroneous estimations of the potential for soil P loss due to differences in the P sorption capacity of different soil types (Wang 2010). For instance, Sharpley (1995) showed that different soil types although having the same BAP (200 mg kg−1 measured by Mehlich-3 P method) supported runoff water which differed markedly in the concentration of dissolved reactive P (0.28 and 1.36 mg L−1). The degree of phosphorus saturation (DPS) has instead been introduced as a promising indicator to improve the estimate for risk of P loss from agricultural soil. This proxy is defined as the amount of BAP in the soil relative to the P sorption capacity (PSC) of the soil. A credible validation method for the P index is a major challenge, especially on a watershed scale, as it is a semi-quantitative tool. In most of the P index studies found in the literature, the main attention has been on the comparison of P index value with the flux of total P in the stream draining the watershed, e.g., Sharpley (1995) found a strong relationship between the P index value for 30 different watersheds in the USA and the measured total P fluxes (0.1–5 kg P ha−1 year−1). Yuqiao Reservoir is the drinking water supply for the 6 million urban population of Tianjin municipality by the diversion channel (Fig. 1). The reservoir has received considerable attention due to annual algae blooms over the past decade. Several studies have concluded that increasing concentrations of phosphorus is most likely the main factor governing the algae blooming in the reservoir (Chen and Zhu 1991). Monthly mean and maximum concentrations of total P in the Page 3 of 16, 2103 reservoir reached 0.043 and 0.055 mg P L−1, respectively, in 2012.1 The reservoir water authorities have found that the major (64 %) source of P flux to the reservoir is from the local watershed (TMWA 2010; Zhang et al. 2003). Identification of hot-spot areas and assessment of risk for P loss in the local watershed of the Yuqiao reservoir is therefore a necessary prerequisite for curbing the eutrophic trend through the selection of optimum and cost-efficient abatement actions. The objective of this study has been to (1) improve the P index assessment system by modeling a set of small-scale watersheds in which a detailed database was established, compiling existing and generated high spatial resolution soil data (maps) and temporal (monitoring) data of P fractions in runoff; (2) introduce the concept of degree of P saturation (DPS%) and flow length factor to the P index assessment system to acquire an improved estimation of P loss; (3) modify the organization structure of the P index scheme in order to consider more correctly the internal relationships between indicators and thereby better capture the conceptual mechanism of P loss; (4) introduce a non-linear watercourse erosion factor in order to better assess the spatial distribution of erosion in the watercourse; and finally (5) compare and evaluate the former and amended P index through correlations with measured flux of P fractions. 2 Materials and Methods 2.1 Study Area The study area is the local watershed of the Yuqiao Reservoir (117° 25′–117° 43′ E, 39° 56′–40° 18′ N) located in the north of Tianjin municipality, in northern China (Fig. 1). The targeted watershed covers an area of 540 km2. The region has a sub-humid continental monsoon climate, with an annual mean temperature of 14 °C and an average annual precipitation of 653 mm, of which nearly three-fifths rains between July and September (JCBS 2011). Mean elevation of the local watershed is less than 200 m. The region is characterized by both flat plains and hilly morphology. The lowlands, which have an average gradient of less than 2°, account for 22 % of study area. In addition, there is an area with 1 Data source: Yuqiao Reservoir Administration Department. 2103, Page 4 of 16 Water Air Soil Pollut (2014) 225:2103 Fig. 1 Location and digital elevation map (DEM) of studied watershed relatively flat landscape, with gradients of only 2–6° (plain), comprising an additional 25 %. Together, these two landforms constitute almost half of the watershed. Hilly land with gradients of 6–15° shared 23 %, low mountain region with gradients of 15–25° account for 19 %, while gradients above 25 % (mountain region) comprise only 11 %. On a macro scale, the terrain declines from the north to the south (Fig. 1) where the reservoir is situated. Most of the soil material, especially in the lowland area, is deltaic alluvial sediments. On the hills and mountains, the soils are developed through weathering of the parent sedimentary bedrock consisting of sandstone and limestone. There have a mix of Gleysols in the lowland and Lithosols in the mountain. The majority of the ca. 130,000 local residents are living of agricultural crops and livestock breeding. Agricultural land is the dominating land use, accounting for 36 % of the targeted area. Crop rotation with “summer maize-winter wheat” is common in the lowland and plains, while agriculture in the hilly and mountainous area is predominantly orchard. The local environmental protection bureau (JCEPB 2012) reports that applying excessive amounts of inorganic P fertilizer is a general practice in this region. In addition, due to excessive livestock breeding and lack of sewage treatment system, the large amount of animal’s dung and domestic sewage were disposed of either in heaps on wasteland or directly into the drainage channels. 2.2 Background Data Background data used for the study of the P index are listed in Table 1. The soil sampling strategy aimed for an even spatial distribution as well as capturing the span in soil types and land use. Soil sampling and analysis were conducted in cooperation with Joshi (2014) as a part of their master studies. Stream water samples, used for the validation of the P indexes, were collected and a na l yz ed i n c oo pe r a t i o n w i t h t he Tia n j i n Academy of Environmental Sciences (TAES). More detailed information and further parameters on the soil and water samples may be found in their thesis. 2.3 Source Factors A total of 126 surface soil samples (0–15 cm) were collected and analyzed for soil test P (STP) and P sorption index (PSI) as part of the Master studies by (Joshi (2014)). DPS in the soils was determined using Eq. 1 (Wang 2010; Wang et al. 2010b). Water Air Soil Pollut (2014) 225:2103 Page 5 of 16, 2103 Table 1 Background data types used for the P index scheme Data type Scale Resolution Data description Source Meteorological data Four stations Daily Precipitation amount Ji County Meteorological Bureau; Yuqiao Reservoir Administration Department Hydrological data 1:25,000 River distribution Field investigation and local Water Bureau Topographic data 1:10,000 Digital elevation model The United States National Aeronautics and Space Administration (NASA) global digital elevation mapa Soil data 126 Soil samples Land use 1:10,000 30 m×30 m Soil physical and chemical Field sampling and laboratory properties (pH, STP, PSI analysis; Ji County soil (phosphors sorption index), survey report (1982); DPS, soil texture) Harmonized World Soil Database (2012)b 2.5 m×2.5 m Land-use classification Interpretation of satellite remote sensing data (Spot 5); Ji County Land Resource Bureau Vegetation cover 30 m×30 m Normalized difference vegetation index (NDVI) Landsat 8 Operational Land Imager (OLI) data Agricultural management data Village scale P fertilizer application; (mean area 30.6 ha) livestock breeding Field investigation; local bureau of agriculture; local statistics yearbook Environmental protection data Village scale (mean area 30.6 ha) Local environmental bureau Environmental protection situation/livestock manure and domestic sewage treatment situation a http://asterweb.jpl.nasa.gov/gdem.asp b http://webarchive.iiasa.ac.at/Research/LUC/External-World-soil-database/HTML/ DPSð%Þ ¼ STP STP þ PSI 100 ð1Þ The denomination for STP and PSI is mg P kg−1. Olsen P (Olsen et al. 1954), Bray-1 P test (Bray and Kurtz 1945), and Mehlich-3 P (Mehlich 1984) are commonly used methods for measuring STP: Olsen P method is suited for calcareous soil, while Bray-1P method is more reliable for acid and neutral soils. The Mehlich-3 method has been reported as well suited for a wide range of soils (Pierzynski, 2000), yet it has been argued that the Mehlich-3 method tends to overestimate the STP in calcareous soil (Basta et al. 2000; Watson and Mullen 2007). The Olsen and Bray-1 methods are therefore used, based on whether the soil pH was above or below 7.4, respectively, following the recommendation from the US Department of Agriculture (Elrashidi 2010). The final grid values of the degree of P saturation (DPS) were calculated by the inverse distance weighted interpolation method (Childs 2004). The phosphorous sorption index (PSI) is measured as an estimate of soil P sorption capacity, which was calculated by Eq. 2 (Bache and Williams 1971): X PSI Lkg−1 ¼ logC ð2Þ where X is the amount of sorbed P (mg P kg−1) on the soil, and C is the remaining P concentration in solution at equilibrium (mg P L−1). The loading of inorganic P fertilizer (P2O5) applied to the fields was calculated from the amount used by each village divided by their agricultural land area. This was subsequently recorded for each village vector and finally converted to raster format. Non-agricultural lands were considered as not fertilized. Livestock manure 2103, Page 6 of 16 Water Air Soil Pollut (2014) 225:2103 production (total P) was calculated based on various breeding species and stocks in each village. The P content in the feces of each species was based on recommended reference values issued by the Chinese Ministry of Environmental Protection (CPSC 2008) and previous research results (Fan et al. 2011). The use of this manure as an organic fertilizer product was based on village values supplied by the local agricultural management department. The final results were divided by agricultural land area of each village. The detailed calculation method is given in Eq. 3: n X Qi P i Lj ¼ ð3Þ 1 λj Sj S A ¼ R K LS C P where Lj is the average total phosphorus load applied to the fields from livestock breeding for village j (kg ha−1a−1), Qi is the breeding amount of farmed specie i, and Pi is total P emission coefficient of farmed specie i (kg unit−1a−1), determined by related emission coefficient manual from China’s Ministry of Agriculture (2009). Sj is agricultural area of village j, λj is manure utilization rate of village j. Only the P load from sanitary sewage was considered for this scheme, as there is a good mechanism of household garbage pickup though the region lacks treatment of sewage water. The P emission coefficient was determined from the recommended value (0.07 kg capital −1 a −1 ) by the People’s Republic of China Ministry of Housing and Urban (2010). The final results were divided by agricultural land area of each village, as shown in Eq. 4: where P is mean annual precipitation (mm), and Pi is the mean monthly precipitation (mm). The R values were calculated using precipitation data monitored from 2006 to 2012 at four stations distributed within and in the vicinity of the watershed. R values for the total study area were obtained through interpolating with inverse distance weight (IDW) method using Arcgis 10 spatial analysis module (Hillier 2011). The soil erodibility factor (K) is computed according to Eq. 7 (Williams et al. 1983): where A is the computed soil loss per unit area (t ha−1 year−1), R is the rainfall and runoff factor (MJ mm ha−1 h−1 year−1), K is the soil erodibility factor, LS is the topographic factor, C is the cover and management factor, and P is the support practice factor. The procedures for the determination of each factor are described below. The amount of rainfall (R) is calculated by Eq. 6 (Wischmeier and Smith 1978): R¼ Q j Ps Si ð4Þ where Dj is the average total phosphorous load from sewage of village j, Qj is the total population of village j, and Ps is the total P emission coefficient of sanitary sewage per capital, Si is agricultural area of village i. 2.4 Transportation Factors Potential for soil erosion was calculated using the Revised Universal Soil Loss Equation (RUSLE) (Eq. 5) (Renard et al. 1997). This equation is a commonly used empirically derived model that provides an improved manner of computing soil erosion based on the original Universal Soil Loss Equation (USLE) (Wischmeier and Smith 1965). 12 h X 1:1735 101:5lgðPi 2 =PÞ−0:8188 i ð6Þ i¼1 j Dj ¼ ð5Þ K Si ¼ 0:2 þ 0:3exp −0:0256S d 1 100 0:3 Si 0:25C 1 Þ C i þ S i C þ expð3:72−2:95C Sd Sd 1− þ exp −5:51 þ 22:9 1 100 100 ð7Þ where Sd, Si, and Cl are the soil sand, silt, and clay content (%), respectively. C denotes the organic carbon content (%), which was obtained from local soil survey reports and the Harmonized World Soil Database. The topographic value (LS) was calculated by Eq. 8 (Wischmeier and Smith 1978): LS ¼ λ 22:1 m 8 m ¼ 0:2 > > < m ¼ 0:3 m ¼ 0:4 > > : m ¼ 0:5 65:41 sin2 θ þ 4:56 sinθ þ 0:065 slope < 1% 1%≤ slope ≤ 3% 3% < slope < 5% slope ≥ 5% ð8Þ ð9Þ where L is slope-length factor (m), θ is slope gradient (in radians), and m is gradient exponent as specified relative to the percent slope. Related parameters were Water Air Soil Pollut (2014) 225:2103 Page 7 of 16, 2103 derived from Global Digital Elevation Map (GDEM) using the ArcGIS spatial analyst module. Crop management factor (C) was computed using Eqs. 10 and 11 (Chai et al. 2000; Ma and Ma 2001): watercourse erosion model by introducing the watercourse erosion attenuation trend weight (E) (Eq. 13), which was used in this study. 8 <C ¼ 1 C ¼ 0:6805−0:3436lgI c : C¼0 F ðxÞ ¼ Ic ¼ 0 0 < I c < 78:3 I c >78:3 ð10Þ I c ¼ 108:49NDVI þ 0:717 ð11Þ where Ic is the vegetation coverage (%), NDVI is normalized difference vegetation index, which was derived from Landsat satellite remote sensing data with Erdas software image interpreter module (Imagine 2006). The support practice factor (P) reflects the effects of best management practices (BMP) that will reduce the amount and rate of surface runoff and thus reduce the amount of soil erosion. Due to the lack of related plot experiments in this study, this factor was simply adopted from the recommended value by USLE and previous studies based on different land-use types (Huang et al. 2004; Sivertun and Prange 2003; Stone et al. 2000). The surface runoff factor (R) was calculated by Eq. 12 (Zhou and Gao 2011): Rrunoff ¼ P α ð12Þ −1 where Rrunoff is total annual runoff (mm year ), P is mean annual rainfall (mm), and α is annual runoff coefficient. The mean annual rainfall of each station was calculated using daily monitored data from 2006 to 2012. Annual runoff coefficients for different land use were adopted from previous studies in this study area (Chen and Zhu 1991). Soils with poor drainage commonly have higher soil erosion due to more surface runoff with a greater potential for P loss (Marjerison et al. 2011; Wang et al. 2006). The soil drainage class factor was therefore directly generated from the soil database (the Harmonized World Soil Database) and introduced into P index scheme. The watercourse erosion factor was determined as the actual distance from each cell to a river network. In most previous studies, a simple straight line distance function is used to assess the water course erosion factor (Bechmann et al. 2005; Wang et al. 2010a). However, the mechanism of watercourse erosion is in most cases non-linear. Sivertun and Prange (2003) improved the 0:6 e0:002x 0:4 ð13Þ where x is distance from each cell to its nearest river network (m), F(x) is the value of water course factor. The flow length factor is the actual migration distance of surface runoff. Thus was calculated using the digital elevation model data by means of the Arcgis 10 hydrological analyst module. The irrigation amount factor is the transportation factor potentially influenced by human activities. Flood irrigation is still the dominant irrigating method in the study zone due to the lack of modern irrigation (Chen and Zhu 1991; Kendy et al. 2004). The irrigation erosion factor was generated by extracting the actual irrigation water volume of each village to the corresponding agricultural land unit. 2.5 P Index Organization and Calculation A weighting value (0.75, 0.85, or 1.00) for each factor was used in order to adjust the influence of each factor on the total potential for P loss (Table 2). These values were assigned based on previous studies (Drewry et al. 2011; Sharpley 1995; Zhang et al. 2003). The weighted value for each factor was finally converted to a five-step unified risk rating value (2, 4, 6, 8, 10) relative to ascribed ranges given in Table 2. All risk rating values were determined for each 50 m×50 m grid based on the coordinate system (WGS 84/UTM zone 50N). The structure of P index scheme was re-organized in order to better account for the interactions among the factors. In previous studies, the mutual restriction between source and transportation factor group was handled through a multiplicative approach. The parallel relation, which is implied within each factor group, is accounted for through a weighted summation approach. The problem with this is that an additive approach is not sound in regards to the transportation factors since the migration distance factors have restriction to other erosion-based transportation factors, i.e., the effect of erosion-induced transport is restricted by the migration length into relevant water course. In order to account for this in the amended P index scheme, the transportation factor was sub-grouped into erosion process factor (I) and immigration distance factor (II) (Eq. 14). 2103, Page 8 of 16 Water Air Soil Pollut (2014) 225:2103 Table 2 Factor weightings and loss ratings for the amended P index scheme Factors Unit/range Weight Risk rating value Very low 2 Low 4 Medium 6 High 8 Very High 10 1.0 <5 5–10 10–15 15–25 >25 Source factors DPS % −1 −1 P fertilizer kg P ha 0.75 0 1–30 30–90 90–150 >150 Livestock manure kg P ha−1 year−1 0.75 0 1–30 30–90 90–180 >180 Daily life sewage kg P ha−1 year−1 0.75 0 0–8 8–16 16–24 >24 1.0 <5 5–10 10–15 15–25 >25 >240 year Transportation factors I: erosion process Soil erosion ton ha−1 year−1 −1 Runoff amount mm year 1.0 <195 195–210 210–225 225–240 Irrigation amount mm ha−1 year−1 0.75 0 0–380 380–420 420–460 >460 Soil drainage class 0–5 0.85 5 4 3 2 0 Transportation factors II: migration distance Water course erosion 0–1 0.85 0–0.2 0.2–0.4 0.4–0.6 0.6–0.8 >0.8 Flow length km 0.85 >50 38–50 28–38 18–28 <18 PI ¼ hX i hX i Sαwα TDβwβ hX i TEγWγ ð14Þ where Sα and wα are the source factor α rating and its weighting value, TDβ and wβ are the transportation factor β rating and its weighting value, which are based on migration distance, TEγ and Wγ are the transportation factor γ rating and its weighting value, which are based on erosion process, PI is P index value. calculation of the water course factor, was replaced by an exponential function. In addition, the flow length factor was not included in the former PI scheme. As for the organization structure, the weighted summation approach was applied within each of the transport factor groups in the amended P index, while all the transportation factors were summarized in the former model, i.e., migration distance factors were not distinguished from the other transportation factors in the former module. An overview of the changes made in the amended P index is given in Table 3. 2.6 Comparison of the Amended and Former P Index 2.7 Validation with the Measured P Losses To validate the amended P index, a previous P index (Zhang et al. 2003) applied in Yuqiao Reservoir watershed was rebuilt as a reference for the former P index scheme. In the amended P scheme, the spatial resolution was based on village scale data while in the previous study the coarser town scale was used. The finer scale was selected in order to incorporate the calculation of relevant source and transport factors (sewage emission, livestock manure emission, P fertilizer, and irrigation factor). Data on DPS were used as source factor instead of STP as DPS is considered to better reflect the potential for loss of dissolved P, which is more relevant than total P for the eutrophication issue. In the transportation module, the linear distance function, used for the How well the former and amended P index schemes manage to index the measured flux of different P fractions was evaluated using 12 different sub-catchments within the local watershed. Discharge data was collected six times a day using a portable river flow meter (LS300). Water samples were collected three times a day at the outlet of each sub-catchment during the rainy season (June 25, 2012 to July 7, 2012) as this is the only period with significant flow in the streams. During the monitoring period, the maximum daily rainfall reached 62.8 mm, while the daily average was 10.4 mm. P concentrations in all samples were determined using the colorimetric molybdenum blue method according Water Air Soil Pollut (2014) 225:2103 Page 9 of 16, 2103 Table 3 Comparison of the former and amended P index Improved content Former Source factors STP (kg ha−1) DPS (%) Transportation factors Water course erosion based on linear function Water course erosion based on exponential function – Flow length (km) Town scale (mean area 477.4 ha) Village scale (mean area 30.6 ha) PI=∑(SiWi)×∑(TjWj)* PI=[∑Sαwα]×[∑TDβwβ]×[∑TEγwγ] Data resolution: (P fertilizer application, manure and sewage P production and irrigation factor) Organization structure Amended *Si and Wi are the source factor i rating, and its weighting value, Tj and Wj, are the transportation factor j rating and its weighting value to the NS-EN-ISO 6878 (ISO 2003). Prior to analysis, the phosphorous was fractionated according to the scheme shown in Fig. 2. P load (mg s−1) from each sub-catchment was calculated by the flow (L s−1) at the time of sampling multiplied with the concentration of different P fractions (mg L−1), and the final P load of each sub-catchment is an average P load. The flux of measured P fractions were correlated with the mean P index value of each sub-catchment, which was separately clipped and extracted from the final P index grid by Arcgis 10 spatial analysis module (Hillier 2011). 3 Results and Discussion 3.1 Validation by Correlation with Fluxes of P Fractions A comparison of how well the phosphorous index (PI), generated by the amended and former P index schemes, is correlated to the measured flux of different P fractions from the 12 sub-catchments is shown in Fig. 3. The Fig. 2 P fractionation scheme applied on the water samples former scheme achieved poor correlations with fluxes of all the P fractions, having correlation coefficients (r) less than 0.48 for total P and particulate P and only 0.38 for dissolved P (sum of dissolved inorganic and organic P). With the amended P index scheme, significant correlations were achieved with the flux of total P (r= 0.825, p<0.001) and the dominating particulate P fraction (r=0.867, p<0.0002), implying that the overall phosphorus flux of P is better ranked by the amended P index scheme. Soil erosion could be the main cause of the increasing of particle P in water body, and the potential for soil erosion was relatively accurately captured by the RUSLE equation in both P index models. The main cause for the significantly better merits of the amended P index scheme regarding particulate P loss is thus the change in the model structure and data resolution. The significance level of the amended P index factors in regard to the dissolved total phosphorus (r= 0.627, p<0.029) and dissolved inorganic phosphorous flux (r=0.586, p<0.005) remained moderate. However, in comparison to the former scheme, the explanatory capacity for dissolved P fractions has improved 2103, Page 10 of 16 Water Air Soil Pollut (2014) 225:2103 Fig. 3 Comparison of the average correlation coefficients between the PI modeled by the two P index schemes and fluxes of P fractions from 12 different sub-catchments. a Former P index scheme and b amended P index scheme significantly (Fig. 3). The main cause for this improvement may be the higher resolution of the main P source factors, such as manure and sewage production factors, and the use of DPS instead of STP as the main soil source factor. The latter is likely the principal cause for the improved correlation with the dissolved P fractions as the DPS is prone to better reflect the potential for mobilization of dissolved P than the STP. These parameter sensitivity assessments are based on conceptual reasoning. A thorough statistical parameter sensitivity analysis of the model is in process and will be published in a forthcoming paper. A relatively weak correlation and significance level (r = 0.492, p < 0.105) was achieved between the new P index and the dissolved organic P. This is likely due to low concentrations of dissolved organic P (Avg. conc., 0.017 mg/L), which thus is greatly influenced by “unknown unknowns” such as direct disposal of sewage into stream channels or flushing of manure piles during storm flow. 3.2 Spatial Characteristics of Factors Governing the P Index allowing for elevated phosphorus mobilization and thereby high dissolved P concentrations in drainage water (Pautler and Sims 2000). Approximately 24.6 % of soil samples exceed the critical limit value (25 %), above which the potential for P loss through runoff is found to significantly increase (Breeuwsma et al. 1995). DPS of the soils exhibited some clear regional distribution characteristics. Areas with relatively high levels of DPS are mainly situated close to the Yuqiao Reservoir, especially in the lowlands on the northern shore of reservoir (Fig. 4a). The lowest overall DPS levels are found in the mountain region. Relatively high amounts of inorganic P fertilizers (>150 kg ha−1 year−1) were applied in the eastern part of the local catchment (Fig. 4b). This is the region containing most of the farmland, along with a high population density. A similar distribution can therefore be found for sewage loading (Fig. 4c). The area surrounding the reservoir is also the region with the majority of livestock, producing a high loading of livestock manure in this zone (Fig. 4d). Based solely on the source factors, the highest relative risk levels for loss of P appears to be mainly distributed in the region surrounding the Yuqiao Reservoir. 3.2.1 Source Factors 3.2.2 Transportation Factors The degree of phosphorous saturation (DPS) in the soils of the local watershed ranged between 0.3 and 50 %. At high DPS, the phosphorus is poorly retained by the soil, In contrast to the characteristics of the spatial distribution of source factors, the relatively high level of Water Air Soil Pollut (2014) 225:2103 Page 11 of 16, 2103 Fig. 4 Spatial distribution maps of source and transportation factors. Warm colors represent the zone with relatively high risk levels, while cold colors imply relatively low risk levels. Source factors: a degree of phosphorus saturation (DPS, %), b fertilizer phosphorus application rate (kg P ha−1), c daily life sewage emission (total P) (kg ha−1 year−1), d livestock manure emission (total P) (kg ha−1 year−1). Transportation factors: e potential soil erosion (ton ha−1 year−1), f surface runoff based on calculation (mm), g soil drainage class (0–5), h irrigation (kiloton ha−1 year−1), i water course (0–1), j flow length (km) potential soil erosion is mainly found in the mountain and hilly area, located generally further away from the Yuqiao Reservoir (Fig. 4e). Concurrently, the region that receives the highest amount of rain, and thus the highest potential for surface runoff, lies mainly in the northwest part of the study area (Fig. 4f). Soil drainage class mainly depends on soil types and texture. Soils with good drainage are mainly distributed in the mountain area with sandy soil, while soils with relative poor drainage class are found in the plain lowland area with clay soil (Fig. 4g). A fairly homogeneous distribution of irrigation on agricultural land was assumed, with the farmland near the reservoir being slightly more irrigated (Fig. 4h). The water course factor, reflecting the distance water travels before it reaches a water channel, depends on the distribution of rivers and agricultural channel. Fewer river courses are distributed in the northern part of Yuqiao Reservoir (Fig. 4i), suggesting a greater possibility for the water of losing its P load during the catchment transportation in this region. As for the flow length in the river channels, the northern mountain areas commonly had a relatively longer transportation distance, due to the greater distance to the reservoir and stronger morphology, while the transportation distance is shorter in the plain area, located close to the reservoir and with a simpler topographic situation (Fig. 4j). 3.2.3 Spatial Characteristics of PI Using the Amended and Former P Index The PI results from the two P index schemes were categorized based on Jenks natural breaks classification method (McMaster 1997). The PI was subdivided into five categories as follows: very low, low, medium, high, and very high (Table 2). Detailed comparison of the spatial distribution of PI categories from the two P Index schemes (Fig. 5) reveals that the amended P index scheme (Fig. 5b) exhibited a higher discrimination, especially in the plain lowland area with significant anthropogenic activities. This can be rationalized by that the source data from the individual village unit, rather than the town scale, provides a higher resolution in this area. In addition, a more apparent risk of P loss was found around the water courses. Furthermore, a high 2103, Page 12 of 16 Water Air Soil Pollut (2014) 225:2103 Fig. 5 P index rating maps: a results from the former P index scheme, b results from the amended P index scheme risk for P loss around the reservoir was further emphasized in the new scheme, mainly due to the relatively higher DPS of soil in this region (Fig. 4a). 3.2.4 Spatial Characteristics of the Amended PI Values In order to further explore the distribution relationship between the amended PI values and corresponding geographic factors, a total of 6,983 grid points (250 m × 250 m) were extracted from the study area. In Fig. 6, the PI for each point is plotted against the distance to each individual village and watercourses as well as its elevation. Most grid points are distributed in the regions with less than “medium” risk level categories. This implies that the critical source areas with a major potential for P loss are limited. The three geographic factors showed a general decreasing trend with increasing PI level. Most of the grids with high and very high risk for P loss are found in places that are located closer than 1 km from a village or less than 500 m from a river. A more significant negative trend was found for the elevation, indicating that most of the high and very high risk points are located at an elevation level less than 100 m above the lake level. In general, the plain lowland area, riverine zones, and village regions are the sensitive source areas for P flux to the reservoir. 3.3 Land-Use Structure Within Different Risk Levels for P Loss The areas with high and very high risk for P loss cover 29 % of the local watershed (Fig. 7). With increasing potential for P loss, there are clear trends of decreasing proportion of natural land use (forest and shrub) and increasing share of farmland, with the latter contributing 46 and 86 % of the high and very high risk zones, respectively. This reflects that the anthropogenic factors are the primary drivers for P loss within the high risk zones. 4 Conclusions The precision of the P index scheme was greatly improved by refining the spatial resolution of input data to the scale of village unit, introducing more specific indicators in both source and transport system and readjusting the organization structure of the index. The amended P index scheme is demonstrated to have the capability of capturing the spatial differences in loss of P fractions from watersheds with different land use. Despite that the correlation with the flux of dissolve P fractions remain relatively moderate, a significant improvement compared to the former scheme was Water Air Soil Pollut (2014) 225:2103 Page 13 of 16, 2103 Fig. 6 Spatial distributions of PI values relative to main explanatory geographic factors. a distance to the each village, b distance to each watercourse, c elevation above reservoir level (Jenson and Domingue 1988) achieved, thereby increasing the credibility of amended P index scheme for the estimation of dissolved P fluxes. Areas in the vicinity of the reservoir and rivers, the plain lowland area, and land surrounding the villages generally constitute a relatively high risk potential for P Fig. 7 Land-use distribution within each category of risk for P loss loss. In regard to different land use, the study demonstrates that farmlands have the highest potential risk for loss of P. The areas with “very high” and “high” potential of P loss occupy only a small proportion (29 %) of the total study area. This emphasizes the need to have 2103, Page 14 of 16 specifically targeted and differentiated abatement actions, rather than inducing a general “flat” target goal. With the amended P scheme, it is possible to significantly improve both the identification of important hotspot source areas for P flux to surface waters as well as assess their relative potential for P fluxes in streams and rivers. This refined risk discrimination and P loss assessment by means of an applicable index is a required tool for policy makers, enabling them to conduct knowledge-based decisions regarding environmental management, ensuring a more sustainable use of the ecosystem services providing our freshwater resources. Acknowledgments The authors are grateful to the Research Council of Norway for funding the SinoTropia Project (Project no. 209687/E40). 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