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0.05) between Period 1 and Period 2 (Fig. 3). In contrast, outflow DRP concentrations between the two periods were significantly different (P < 0.05) from each other and statistically greater than the median inflow concentration. However, the outflow concentrations in Period 2 were more similar in magnitude to the inflow concentrations than the outflow concentrations in Period 1 (Fig. 3). Unlike DRP, median inflow TP concentrations in Period 1 were significantly greater than median inflow concentrations in Period 2 (Fig. 3). Similarly, Period 1 outflow TP concentrations were significantly greater than Period 2 outflow TP concentrations (Fig. 3). For both time periods, the median outflow TP concentrations were significantly greater than the inflow concentrations. From this point forward the results and discussion will center on the outflow of the sampling area. DRP concentrations ranged from below detection (0.003 mg L1) to 0.34 mg L1 during Period 1 and from below detection to 0.22 mg L1 during Period 2. Similarly, TP concentrations

ranged from below detection to 1.11 mg L1 during Period 1 and below detection to 0.6 mg L1 during Period 2. During the April to November time period, DRP and TP concentrations by month generally increased through the first part of the growing season and spiked in August and September before declining (Fig. 4). No monthly median TP concentrations during Period 2 exceeded the USEPA 0.05 mg L1 threshold recommendation.34 There was no significant difference (P > 0.05) in mean annual loading for either DRP or TP between Period 1 and Period 2 at the NCC site (Table 4). Similarly, no significant differences or interactions between monthly loads and time period were measured. Mean monthly DRP losses for Period 1 were greatest during the spring ‘green-up’ period (May and June) and during mid September through October when air temperatures are reduced and senescence begins and larger rainfall/runoff events were recorded (Fig. 5). The largest DRP losses during Period 2 were measured in August, September, and October. The distribution of TP losses during Period 1 followed the same pattern as for DRP (Fig. 5). TP losses in Period 2 were greatest during June but were more evenly distributed throughout the rest of the year (Fig. 5). Monthly DRP and TP loads were somewhat predictable by volumetric discharge (Fig. 6). The Period 1 DRP coefficient of determination (r2) was 0.66 compared to 0.34 during Period 2. Similarly, the TP coefficient of determination (r2) during Period 1 was 0.61 compared to 0.54 during Period 2. In both cases (DRP and TP), the slope of the lines for Period 2 loads were less than the slope of the lines for Period 1 loads. There was a significant (P < 0.05) decrease in the annual flow weighted DRP concentration between Period 1 (0.06 mg L1) and Period 2 (0.02 mg L1). For TP, there was a substantial

Table 4 Annual loading of dissolved reactive phosphorus (DRP) and total phosphorus (TP) from upland site, upland plus NCC, and NCC during data collection period April through November for Period 1 (2003–2006) and Period 2 (2007–2010)

Fig. 4 Box and whiskers plots of DRP and TP concentrations by month during different management periods. Boxes are bound by the 25th and 75th percentile. Whiskers represent the 10th and 90th percentile. Horizontal lines in the boxes correspond to median concentrations, when not present the median is equal to the lower box line (25th percentile). Dashed line corresponds to the midpoint between the oligotrophic and mesotrophic boundary condition (0.025 mg P L1 as total phosphorus) and the mesotrophic and eutrophic boundary condition (0.075 mg P L1 as total phosphorus).

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Upland

Upland + NCC

NCC

DRP (kg ha1) 2003 2004 2005 2006 Period 1 average 2007 2008 2009 2010 Period 2 average Annual average

0.00 0.02 0.03 0.01 0.015 0.02 0.03 0.02 0.05 0.03 0.022

0.02 0.05 0.08 0.02 0.043 0.04 0.05 0.02 0.06 0.043 0.04

0.11 0.17 0.25 0.07 0.15 0.11 0.13 0.02 0.09 0.088 0.12

TP (kg ha1) 2003 2004 2005 2006 Period 1 average 2007 2008 2009 2010 Period 2 average Annual average

— 0.06 0.05 0.02 0.043 0.04 0.09 0.04 0.14 0.078 0.06

— 0.11 0.11 0.04 0.087 0.07 0.16 0.05 0.15 0.108 0.10

— 0.29 0.36 0.09 0.247 0.18 0.33 0.08 0.20 0.198 0.22

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Fig. 7 Trend between annual flow-weighted DRP and TP concentrations and applied elemental phosphorus.

both annual DRP and TP flow weighted concentrations during the study period was generally in a downward direction and related to phosphorus application (Fig. 7).

Discussion Fig. 5 Mean applied elemental phosphorus by month overlaid with mean monthly DRP losses for Period 1 (2003–2006) and Period 2 (2007–2010). Whiskers for both application and loss represent one standard deviation.

decrease in the flow weighted concentration between the two periods; 0.09 mg L1 during Period 1 compared to 0.05 mg L1 for Period 2. However, the difference in calculated flow weighted TP concentrations was not statistically different. The trend in

Fig. 6 Volumetric discharge versus DRP and TP load for two management periods (2003–2006) and (2007–2010).

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A reference value of 0.05 mg P L1 as total phosphorus was selected as a basis of reference for this site and was based on data from the USEPA ambient water criteria for Eco-region VIII.34 The 0.05 mg P L1 as TP threshold corresponds to the midpoint between the oligotrophic and mesotrophic boundary condition (0.025 mg P L1 as total phosphorus) and the mesotrophic and eutrophic boundary condition (0.075 mg P L1 as total phosphorus). A smaller percentage of the TP concentrations exceeded the 0.05 mg L1 threshold in Period 2 (20%) compared to Period 1 (37%), suggesting that a combination of formulation changes and reductions in application amount will help turf managers to reduce phosphorus concentrations below recommended levels to guard against eutrophication (Fig. 3). Similarly, monthly TP concentrations exceeding the 0.05 mg L1 threshold were much more frequent in Period 1 compared to Period 2. In Period 2, only one month (August) had median TP concentration as great as the 0.05 mg L1 threshold. Since runoff was less during August we attributed the greater concentrations to smaller magnitude flows that were most likely related to irrigation and connectivity of the surface flow with tile drainage. Tile discharge was observed to occur or increase following irrigation. Conversely, in Period 1, four months had median concentrations that exceeded the threshold. Larger percentages of exceedences occurred during Period 1 in the fall when the turfgrass starts to enter dormancy (September–November). A threshold value for DRP does not exist. However, in reviews by Soldat and Petrovic14 and Sims and Sharpley,35 DRP losses in runoff typically range from 40% to 90% of TP losses. Using 50% exceedence of the TP recommendation to protect against eutrophication is a reasonable benchmark to use for DRP exceedence. At 50% of the TP threshold or 0.025 mg DRP L1, exceedences in both periods were recorded between June and October. However, the number of exceedences in Period 2 (13%) was less than Period 1 (38%), which again suggests that the change in P formulation and management can reduce the potential for eutrophication. J. Environ. Monit., 2012, 14, 2929–2938 | 2935

TP lost as a percentage of applied phosphorus increased from 3.7% in Period 1 to 6.4% in Period 2 and were expected as less phosphorus was applied during Period 2. DRP mass loss increased from 2.2% of applied in Period 1 to 2.8% in Period 2. Similar increases in percentage of amount applied were measured by Easton and Petrovic15 who measured losses following different rates and formulations and Shuman13 following ‘watering-in’ of the fertilizer after application. In the Easton and Petrovic study,15 the organic forms of fertilizer were primarily manures, rich in phosphorus. Additionally, they applied fertilizer based on nitrogen needs and thus more phosphorus was applied with the organics compared to the synthetics. In our study, the organic blends of fertilizer had minimal amounts of phosphorus, thus the actual application amounts were less compared to application amounts using synthetic blends. The increase in losses expressed as a percentage of applied was attributed to a residual phosphorus effect observed in soils with high soil test phosphorus.36–38 This effect is generally soil specific;39 however, we suspect that much of the residual phosphorus losses measured from this course are originating in the greens and tee areas where soil test phosphorus levels are three to five times greater than needed for plant growth. Based on observations of increased tile flow following irrigation, we also believe that a majority of the phosphorus may be entering the stream through tile drains rather than surface runoff. This is especially true for Period 1 when irrigation amounts were much greater. Annual loading or export coefficients (calculated as mass per unit area per year) for both Period 1 (0.15 kg DRP ha1 year1 and 0.25 kg TP ha1 year1) and Period 2 (0.09 kg DRP ha1 year1 and 0.20 kg TP ha1 year1) were generally consistent with loads reported for natural plot scale studies.15,40–42 In contrast, the loads measured here were much less than loads reported by Steinke et al.43 on frozen soil conditions and by Gaudreau et al.18 who used different sources and application rates. Our results were also comparable to watershed scale export coefficients reported by King et al.44 for a golf course in Texas and Winter and Dillon23 on a Canadian golf course. Our results were an order of magnitude less than those reported by Kunimatsu et al.25 for a golf course in Japan. In the aforementioned studies, phosphorus management was representative of typical inorganic formulations and rates. Mean annual calculated TP concentration (0.047 mg L1) during Period 2 was below the 0.05 mg L1 threshold recommended to maintain a mesotrophic condition. Similarly, flowweighted DRP concentration (0.021 mg L1) was below 0.025 mg L1 (50% of the mesotrophic threshold value). TP and DRP calculated concentrations during Period 1 exceeded the 0.05 mg L1 threshold. TP concentrations in Period 1 were approximately twice the threshold value. This suggests that the combination of reduced rates and formulations may help to obtain environmental goals. Overall, in this study, there was a greater than 50% reduction in elemental phosphorus applied to the course between the two periods (Period 1 greater than Period 2). Conversely, discharge in Period 2 was much greater than Period 1 discharge. The moderate correlation between precipitation and phosphorus loss for each of the two periods suggests that phosphorus loss may be predictable with some confidence using discharge volume. Despite the wetter period and larger discharge volumes in Period 2936 | J. Environ. Monit., 2012, 14, 2929–2938

2, the flatter slope lines associated both DRP and TP for Period 2 suggest that the reduction in phosphorus loss occurred as a result of the combined switch to organic phosphorus formulations and reduced rates of application.

Summary and conclusions Hydrology and water quality data were collected from a subarea of Northland Country Club in Duluth, MN from 2003–2010 to examine the water quality impact of two distinct phosphorus management approaches. Phosphorus management in Period 1 (2003–2006) represented a more traditional approach that could be summarized by large application amounts using synthetic formulations. Phosphorus management in Period 2 (2007–2010) was characterized by more frequent, low-dose applications, overall reduced application amounts, and organic formulations. The primary findings from this study can be highlighted as follows:  Traditional golf course phosphorus management strategies lead to a greater number of outflow flow-weighted phosphorus concentrations that exceed recommendations to protect against eutrophication in adjacent streams and waterbodies. Twenty-one percent of DRP samples and 37% of TP samples collected in the outflow during Period 1 exceeded the 0.05 mg L1 recommendation to maintain a mesotrophic condition.  Use of organic formulations coupled with low-dose applications and overall reduced rates resulted in significantly fewer flow-weighted phosphorus concentrations that exceeded the 0.05 mg L1 recommendation. In Period 2, only 4% of DRP concentrations and 20% of TP concentrations exceeded the 0.05 mg L1 threshold.  During both study periods, peak phosphorus losses had a seasonal distribution that lagged primary application by three to six months. Greater losses were measured during August, September, and October and corresponded to the time when larger rainfall runoff events were recorded and the onset of turfgrass dormancy.  For the entire period of record DRP losses accounted for approximately 2.2% of applied phosphorus while TP losses comprised 4%. DRP and TP losses expressed as a percentage of applied were slightly greater in Period 2 despite less application. The small increase in percentage lost was attributed to a residual phosphorus effect observed in soils with high soil test phosphorus. Based on these findings and the risk that phosphorus poses to the aquatic environment, it is recommended that golf courses as well as other turf managers (e.g. parks) explore the feasibility of altering their phosphorus fertility management related to phosphorus. Specifically, the recommendations are to adopt the use of organic formulations, low dose applications, and overall rate reductions. Additionally, it is recommended that the fertilizer industry develop and make more readily available fertilizer blends with little or no phosphorus.

Acknowledgements The authors would like to express our gratitude to Northland Country Club for their vision to see the relevance and importance of preserving and protecting both the environment and the This journal is ª The Royal Society of Chemistry 2012

game of golf. The authors would like to acknowledge the generosity of NCC’s members and staff in granting permission and access to conduct this research. We would also like to acknowledge the efforts of the many current and past employees of the USDA-ARS-SDRU and Spectrum Research Inc., who worked on this project: Ginny Roberts, Eric Fischer, Ann Kemble, Jeff Risley, Natalie Struble, Brad Walker, Sara Beth Scadlock, Ivy Leland, Emily Burgess, and Heather McMains. We would like to thank Dr Norm Fausey for providing a critical review of an early version of this manuscript. This research was funded in part by the U.S. Golf Association-Green Section Research.

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