JOURNAL OF THE AMERICAN WATER RESOURCES ASSOCIATION JUNE AMERICAN WATER RESOURCES ASSOCIATION 2004 OCCURRENCE OF TOTAL DISSOLVED PHOSPHORUS IN UNCONSOLIDATED AQUIFERS AND AQUITARDS IN IOWA1 Michael R. Burkart, William W. Simpkins, Amy J. Morrow, and J. Michael Gannon2 INTRODUCTION ABSTRACT: Seven sets of ground water samples from 103 observation wells were analyzed for total dissolved phosphorus (TDP) in four areas and five materials including loess and loess derived alluvium in the Deep Loess Hills of western Iowa, outwash and fractured till adjacent to Clear Lake in north central Iowa, fractured till in central Iowa, and a sand and gravel aquifer in northwest Iowa. Land use in ground water recharge zones in all four areas is dominated by crop or animal production or both. Concentrations of TDP exceeding the minimum laboratory detection limit of 20 µg/l as P were found in all areas and in all materials sampled. Samples from the outwash deposits associated with Clear Lake contained significantly larger concentrations than all other areas and materials with a median of 160 µg/l. Water from fractured till in three areas produced the smallest range of concentrations with a median of 40 µg/l. The mean value of TDP in all sample sets exceeded 50 µg/l, an important ecological threshold that causes increased productivity in lakes and perennial streams and one being considered as a surface water nutrient standard by regulatory agencies. These results clearly show that ground water in essentially all near-surface aquifers and aquitards discharging to Iowa’s streams and lakes is capable of sustaining P concentrations of 50 to 100 µg/l in streams, lakes, and reservoirs. Consequently, even if point discharges and sediment sources of P are substantially reduced, ground-water discharge to surface water may exceed critical thresholds under most conditions. (KEY TERMS: ground water hydrology; nonpoint source pollution; water quality; phosphorus; agriculture; till; loess; alluvium.) Increased interest in surface water impairment by nutrients has been generated by state and federal efforts to understand and mitigate nonpoint source contamination. Many surface waters in Iowa and other Midwestern states are impaired by excess nutrients, primarily nitrogen and phosphorus (P). There has been clear evidence for decades that P from a variety of sources is discharged to surface water bodies by runoff. Furthermore, it is well understood that phosphorus in runoff constitutes most of the total P (TP) loads found in streams. Stream baseflow has also been shown to carry substantial loads of P from point sources such as wastewater. Consequently, more data on P concentrations in ground water from wells will be required to distinguish P in baseflow derived from ground water and P derived directly from point discharges to streams. There is increasing discussion among state and federal regulators about establishing P standards for streams that are based on concentrations associated with aquatic ecosystem health. These concentrations are much smaller than those found in runoff. Such discussions raise the question of whether these standards can be met during periods when ground water is the only source of discharge. It is hypothesized that P concentrations in ground water of most of the materials comprising aquifers and aquitards adjacent to Iowa streams constitute sources of nutrient enrichment to streams, lakes, and reservoirs. Burkart, Michael R., William W. Simpkins, Amy J. Morrow, and J. Michael Gannon, 2004. Occurrence of Total Dissolved Phosphorus in Unconsolidated Aquifers and Aquitards in Iowa. Journal of the American Water Resources Association (JAWRA) 40(3):827-834. 1Paper No. 03118 of the Journal of the American Water Resources Association (JAWRA) (Copyright © 2004). Discussions are open until December 1, 2004. 2Respectively, Hydrologist, National Soil Tilth Laboratory, USDA-ARS, 1250 Pammel Drive, Ames, Iowa 50011; Professor, Iowa State University, Department of Geological and Atmospheric Sciences, Ames, Iowa 50011; Chemist, National Soil Tilth Laboratory, USDA-ARS, 1250 Pammel Drive, Ames, Iowa 50011; and Geologist, Iowa Geological Survey, 109 Trowbridge Hall, Iowa City, Iowa 52241-1319 (E-Mail/Burkart: burkart@nstl.gov). JOURNAL OF THE AMERICAN WATER RESOURCES ASSOCIATION 827 JAWRA BURKART, SIMPKINS, MORROW, AND GANNON The purpose of this paper is to determine if the concentrations of P in various ground water settings in agricultural areas of Iowa are sufficient to sustain nutrient enriched surface waters. A synoptic sample of ground water from a variety of aquifers and aquitards in the proximity of impaired water bodies was used to test this hypothesis in Iowa, a state with the most intensive and extensive agricultural land use in the United States. This and similar analyses will be important to the discussion of the thresholds to be established for surface water contamination in intensive agricultural regions with similar geologic materials. A national analysis of orthophosphate (Nolan and Stoner, 2000) showed no significant difference among shallow wells under agricultural areas, which had mean values of 10 µg/l and under urban land areas with mean values of 20 µg/l. The mean values of 10 µg/l were found in deeper aquifers that were assumed to have less direct influence of surface sources of P. However, samples from eastern Iowa aquifers (Savoca et al., 2000) yielded significantly different concentrations under urban and agricultural land use. These researchers reported median values for TDP of 33 µg/l in agricultural areas compared to15 µg/l in urban settings. Water samples from Midwestern aquifers, including five from Iowa were found to have median values of 20 µg/l TDP (Kolpin et al., 1996). Other samples from aquifers in Iowa yielded values with a median of 10 µg/l TDP in a heavily pumped sand and gravel aquifer adjacent to the Mississippi River (Lucy et al., 1995) and municipal wells from a variety of aquifers produced water with median values of 100 µg/l orthophosphate (Schaap and Linhart, 1998). Until recently, P transported through ground water to surface water has not been considered a critical transport pathway for agricultural nonpoint sources of P (Sims et al., 1998). However, evidence exists for both matrix and preferential flow in drainage water and dissolved P from surface sources transported through soil (Baker et al., 1975; Beauchemin et al., 1998; Sims et al., 1998; Stamm et al., 1998; Dils and Heathwaite, 1999; Hooda et al., 1999; and Simard et al., 2000). Soil leaching studies have also shown the potential for P transport through the unsaturated zone of as much as 232 µg/l TDP (Haygarth et al., 1998). Field investigations show that the introduction of large sources of P can increase the concentrations in ground water more than 10-fold within a few years (Novak et al., 2000). Long term use of inorganic fertilizer and concentration of manure P provide potential loads in soils (Sims et al., 1998) that could exceed the P sorptive capacity (PSC) of soil and enhance leaching. Leaching is of particular concern in organic and/or sandy soils (Sharpley and Rekolainen, 1997) and in soils with small PSC (Beauchemin et al., 1998). JAWRA There are few reports in North America where the PSC has been exceeded under agricultural systems (Novak et al., 2000), although studies of septic system plumes (Robertson et al., 1991; Harman et al., 1996; Robertson et al., 1998) may provide analogs for manure disposal systems. Excessive manure disposal has produced a “chemical time bomb” for leaching in Europe (Behrendt and Boekhold, 1993). Analysis of 750 wells in Nebraska Sand Hills aquifers found concentrations of TDP of as much as 300 µg/l in shallow wells with somewhat smaller concentrations in deeper wells (Helgesen et al., 1994). Piezometers and seepage meters in the bed materials of the Tualatin River, Oregon had 60 to 2,900 µg/l TDP (Rounds et al., 1994). Concentrations in baseflow from central and western Wisconsin streams yielded TDP concentrations ranging from 10 to 160 µg/l (Mason et al., 1990). These measurements established ground water as a significant source of P to streams in that region of Wisconsin. For the last few decades, research on the effects of agriculture on ground water quality in the Midwest has focused on the occurrence of nutrients, primarily nitrogen ions. More recently, renewed concerns about P in streams, lakes, and riparian corridors has stimulated the reexamination of the occurrence of P in ground water. Initial sampling for P at four Iowa ground water study sites led to the test of an hypothesis that ground water concentrations in a variety of aquifers and aquitards near agricultural sources of P may provide sustained sources of P for surface water bodies. SAMPLING AND ANALYTICAL METHODS In May 2002, 103 observation wells were sampled and TDP was selected for analysis to assure consistent comparison among sites. Areas selected for sampling were in four on-going research projects where ground water is in direct hydraulic connection to a surface water body. These studies involve the dominant materials comprising shallow unconsolidated aquifers and aquitards in Iowa and much of the glaciated Midwest. The materials include aquitards comprised of loess, fractured till, and fine grained alluvial materials, and sand and gravel aquifers. Selection of TDP eliminated the need for field acidification required by some other analytes for which delays of even minutes can precipitate P, particularly in the presence of oxidized forms of Fe. Analysis for TP from unfiltered samples was discounted because preliminary analyses showed concentrations attributable to formation sediments from wells completed in loess and till. Dissolved phosphorus is 828 JOURNAL OF THE AMERICAN WATER RESOURCES ASSOCIATION OCCURRENCE OF TOTAL DISSOLVED PHOSPHORUS IN UNCONSOLIDATED AQUIFERS AND AQUITARDS IN IOWA most representative of P transported through ground water below the water table, although colloidal P could move through small fractures and interstices as well. Samples were filtered in the field using in-line, disposable 0.45 µm filters to achieve a uniform degree of separation between TP and TDP (Eaton et al., 1995). Analysis of deionized water passed through these filters yielded no P. The automated analytical method used for TDP provides a detection limit of 20 µg/l. Water samples were stored at 4˚C until digestion of 8 ml with 0.5 ml of a 1:1 (vol/vol) solution of 7.2 N sulfuric acid and 1.4 M ammonia persulfate in an autoclave at 121˚C and 103 to 138 kPa for 30 minutes. Samples, calibration standards, and reference materials were treated equally. The digestion converts all forms of P to PO4-3 (USEPA, 1983) which was assayed by flow injection analysis (Lachat, 2002). The PO4-3 complexes with ammonium molybdate and antimony potassium tartrate under acidic conditions and is then reduced with ascorbic acid. The resulting color absorbs light at 880 nm which is proportional to the concentration of PO4-3 in the sample (Lachat, 2002). recommended rates can produce a steady accumulation of P in the soil because P removed by harvesting is only 16 kg/ha for soybean and 20 kg/ha for corn as grain (Kellogg et al., 2000). In the Clear Lake area 70 percent of the surface soils in the watershed had high, from 21 to 31 mg/kg, and very high or less than 31 mg/kg, Bray-P analyses (Iowa State University, 1999a; Klatt, 2002). Iowa State University does not recommend further P fertilization on fields of this type. The addition of manure P provides an additional source for P leaching. Manure varies substantially among livestock types, production systems and management systems, but in liquid form may contain 0.4 to 3.2 g/l P (Iowa State University, 1999b). Natural sources of P may also exist in surficial materials in these areas. Hallberg (1980) showed concentrations of TP of 364 to 550 mg/kg in pre-Illinoian fractured till. Paleosol material in southern Iowa showed values between 104 and 196 mg/kg (Woida and Thompson, 1993). FIELD AREAS Four study areas were selected for sampling where observation wells had been installed in a range of geologic materials and in settings where exchange between ground and surface water was known. The areas (Figure 1, Table 1) are underlain by loess, fractured till, fine-grained alluvium, and sand and gravel which represent the dominant materials in Iowa that store and transmit ground water under water table conditions. Multiple phosphorus sources are associated with agricultural land use in ground water recharge zones in all four areas. Crop or animal production or both dominate the land uses, although some urban areas exist near the Clear Lake and Rock Valley sites. Substrata of soils between 76 and 107 cm below land surface in all areas have been classified as having low values of Bray-Test P for crop production (Iowa Department of Agriculture and Land Stewardship, 1996). The Bray test (Bray and Kurtz, 1945) measures acid soluble forms of P. This depth of soil sample is standard for determining substrata values of available P. Classification of soils as low P means these soils have less than 7.5 mg/kg or about 30 kg/ha of Bray-test P. Annual P fertilizer recommendations from Iowa State University (1999a) for these soils are high, ranging from 19 kg/ha for soybean to 24 kg/ha for corn. These fertilizer recommendations are double for low surface soil P tests. Application of P at the low JOURNAL OF THE AMERICAN WATER RESOURCES ASSOCIATION Figure 1. Location of Areas Sampled for Phosphorus in Ground Water. The Deep Loess Research Station (DLRS) The Deep Loess Research Station (DLRS) consists of four small (30 to 40 ha) watersheds which are underlain by 20 m to 60 m of loess (Prior, 1991) in two units with similar hydraulic properties (Kramer et al., 1999; Tomer and Burkart, 2003). Divides and hill slopes are composed of the Peoria Loess of Wisconsinan age underlain by loess in the Loveland Formation of Illinoian age (Bettis, 1990). Valleys contain alluvium of the Holocene DeForest Formation that is 829 JAWRA BURKART, SIMPKINS, MORROW, AND GANNON TABLE 1. Summary of Total Dissolved Phosphorus in Ground Water From Selected Sites in Iowa. Well Depths (m) Number of Wells Minimum 10-7 to 10-5 4.5 to 20.7 13 ND* 0,640 125 050 2.1 to 2.8 Alluvium 10-8 to 10-4 3.3 to 4.50 26 ND* 1,030 077 030 1.6 to 3.2 Fractured Till 10-8 to 10-5 4.2 to 26.5 17 ND* 0,440 094 050 2.0 to 3.6 10-4 1.5 to 4.50 17 20 0,570 212 160 0.5 to 1.6 10-8 to 10-5 1.5 to 4.50 06 20 0,210 090 045 1.0 to 1.5 Walnut Creek Fractured Till 10-8 to 10-5 1.7 to 7.60 08 20 0,440 074 020 1.0 to 2.2 Rock Valley Alluvial Aquifer 10-4 to 10-3 7.5 to 150 16 20 0,260 093 080 3.6 to 6.1 Site and Material Deep Loess Station Loess Clear Lake Outwash Fractured Till TDP Concentrations (µg/l) Maximum Mean Median Water Table Depth (m) Hydraulic Conductivity (m/s) *ND is less than 20 µg/l (detection limit). stratified and reworked loess. These materials are underlain by pre-Illinoian weathered tills that form a lower, no-flow boundary to local ground water flow systems. More complete descriptions of the geology and hydrology of this study area including analysis of hydraulic conductivity values are presented in Tomer and Burkart (2003) and Kramer et al. (1999). Fifty-six wells, installed to study the general hydrology and water quality associated with agricultural watersheds, were sampled for this study (Table 1). Wells were installed using a hollow stem auger and till wells were completed by reaming the screened interval with a flared Shelby tube. Screens of either 0.3 or 0.61 m were used with a gravel pack to 0.3 m above the screen, and all wells were grouted to the surface. the early 1970s to about 190 µg/l in 2000 (Downing and Kopaska, 2001). It will become hypereutrophic, at increased concentration of 4 µg/l/yr, with concentrations of 240 µg/l by 2040. Twenty-three wells in the Clear Lake project were sampled (Table 1). Wells were installed using a hollow stem auger with outwash wells having a 0.61 m screen surrounded by a 0.91 m long silica sand pack. Till wells were installed by reaming the screened interval with a flared Shelby tube and installing a 0.61 m screen and no sand pack. Six outwash wells had hydraulic heads indicating ground water recharge from the lake and 11 showed ground water discharge to the lake. Walnut Creek Clear Lake Walnut Creek drains a 5,600 ha watershed that is underlain by late Wisconsinan fractured till (Alden Member of the Dows Formation) and pre-Illinoian fractured till of the Wolf Creek Formation. Low redox potentials, dissolved Fe, and methane production characterize most of the unweathered materials below 4.5 m in the watershed (Parkin and Simpkins, 1995). Much of the watershed has poor natural drainage that is augmented by extensive network of subsurface tile drains. More complete descriptions of the geology and hydrology of this study area including analysis of hydraulic conductivity values are presented in Eidem et al. (1999). Land use is typical of central Iowa with more than 85 percent in a corn/soybean rotation. Eight wells completed in the late Wisconsin till at three nests in upland positions in the watershed were sampled for this study (Table 1). One nest of wells is Clear Lake covers 1,467 ha making it the third largest of 34 natural lakes of glacial origin in Iowa, and it is managed for recreation and fishing. It lies in the Algona-Altamont moraine complex of the Des Moines Lobe. The surficial materials are of late Wisconsinan age. More complete descriptions of the geology and hydrology of this study area including analysis of hydraulic conductivity values are presented in Simpkins et al. (2001). The lake’s maximum depth is 5.8 m with an average depth of 2.9 m. It drains an area of 4,888 ha with slopes of 0 to 25 percent. Land use in the watershed is dominated by corn, soybean, and alfalfa crops with limited animal production. The lake was formerly oligotrophic to mesotrophic, but has increased in TP concentration from about 60 µg/l in JAWRA 830 JOURNAL OF THE AMERICAN WATER RESOURCES ASSOCIATION OCCURRENCE OF TOTAL DISSOLVED PHOSPHORUS IN UNCONSOLIDATED AQUIFERS AND AQUITARDS IN IOWA An alluvial aquifer that serves the City of Rock Valley’s well field consists of 9 to 15 m of stratified sand and gravel in the Holocene DeForest Formation overlain by finer grained recent floodplain deposits in which soils have formed. The aquifer fills the floor of a valley that is 850 to 2,100 m wide and incised into pre-Illinoian fractured till. Rogg Creek flows through the valley across the aquifer, losing discharge in the vicinity of the wells sampled for this study. More complete descriptions of the geology and hydrology of this study area including analysis of hydraulic conductivity values are presented in Thompson (1987). The land use immediately surrounding the wells is approximately 50 percent urban and 50 percent rural. Essentially all of the rural land is devoted to row crop production or row crop recently placed in the Conservation Reserve Program (CRP). Irrigated corn fields and a cattle feedlot are located in the valley immediately upgradient of the sampled wells. Sixteen wells, installed as part of a wellhead protection study by the Iowa Geological Survey, were sampled for this study (Table 1). A hollow stem auger was used to install nests of wells at 7.5 m and 15 m deep. The formation was allowed to collapse around 1.5 m long screens and the annulus grouted from 0.3 m above the screen to the land surface. from Walnut Creek produced the smallest concentrations. The range of TDP varied among the areas and among aquitards and aquifers in the same area, although the differences are dominantly in the maxima. The differences in maxima may be related to type and duration of P sources, although it may be difficult to distinguish between large sources or long term, moderate sources. The only significant difference occurs between Clear Lake and the other sites, which raises questions about the role of ground water residence time verses sources in P transport and sorption. Some of the ground water containing P near Clear Lake is about 20 years old, based on 3H analyses (Simpkins et al., 2001). Ground water flow paths may introduce bias in sampling nonpoint source pollution. Larger P concentrations may be more frequent where ground water flow converges toward a single surface feature, such as Clear Lake. In addition, sampling ground water at the very end of the flow line at the edge of the lake, as in this study, reflects all the upgradient contributions of P in the watershed. These and other explanations for the distribution of P concentrations in these areas are the subject of ongoing research. No significant differences with depth were observed at any of the sites or for any materials, although the Rock Valley aquifer samples were all from the same depth. The lack of stratification or other discernable difference related to well depth supports the conclusion that P concentrations are relatively uniformly distributed throughout these shallow ground-water systems. Substantiation of such interpretations in many other areas will be critical to understanding trends as they develop in vulnerable areas. RESULTS DISCUSSION Concentrations of TDP exceeding the laboratory detection limit of 20 µg/l were found in all areas and in all materials. Concentrations summarized in Table 1 included an assumed concentration of half the detection limit (10 µg/l) for censored values (nondetects). A limited number of samples yielded concentrations less than the detection limit, but only from the DLRS aquitards. Samples from the DLRS aquitards also produced the largest concentration (1,030 µg/l) of all samples. The samples from the outwash aquifer near Clear Lake contained significantly larger concentrations (p < 0.05) than all other areas and materials with a mean of 212 µg/l. Fractured till Specific standards for ground water P have not been established, but policy standards for P in streams and lakes are currently being debated. Threshold concentrations of 50, 76, and 100 µg/l TP are emerging as important thresholds. The U.S. Environmental Protection Agency (USEPA) proposed that TP not exceed 50 µg/l for water entering lakes and reservoirs and 100 µg/l for streams not discharging to lakes and reservoirs (USEPA, 1986). More recent ambient water quality criteria (USEPA, 2000) establishes a threshold for TP of 76 µg/l in surface waters in the Cornbelt and Northern Great Plains Ecoregion, which includes Iowa. Aquatic ecological criteria provide TP thresholds of 50 to 100 µg/l that may be located down gradient of a pasture and another is located down gradient of livestock pens that are periodically washed with water during cleaning. Wells were installed with a hollow stem auger and completed with a 0.61 m screen with no sand pack after reaming the screened interval with a flared Shelby tube. Alluvial Aquifer JOURNAL OF THE AMERICAN WATER RESOURCES ASSOCIATION 831 JAWRA BURKART, SIMPKINS, MORROW, AND GANNON useful to evaluate the effect of ground water discharge to streams. Sustained TP loads needed to support increased productivity in streams (Litke, 1999) will require ground water discharge of P in Iowa and other parts of the humid Midwest where ground water discharge dominates stream discharge during most periods. Chlorophyll concentrations of 10 µg/l are suggested as the lower boundary for a proposed trophic state in temperate streams (Dodds et al., 1998) and eutrophy in lakes (Smith, 2003). An empirical equation resulting from global analysis of temperate streams (Van Niewenhuyse and Jones, 1996) was used to determine that 50 µg/l TP correlated well with concentrations of 10 µg/l chlorophyll in streams draining generally more than 6,000 km2 and 100 µg/l TP for streams draining 50 km2. Another criterion for estimating ecological thresholds of P uses the Redfield ratio that showed algae to have an ideal elemental composition of nitrogen that is 15 or 16 times that of P (Redfield, 1958). Using this ratio, P concentrations exceeding 65 µg/l will be sufficient to support algal growth in many water bodies when nitrate-N concentrations exceed 10 mg/l, the drinking water maximum contaminant level. A substantial fraction of the TDP concentrations analyzed for this study exceed values proposed as ecological or policy thresholds. The minimum threshold proposed by USEPA for this region and the minimum value to produce critical quantities of chlorophyll is 50 µg/l. This threshold is exceeded by the mean values at all sites and in all materials (Figure 2). This threshold is exceeded by 50 percent of the samples from at least one material in each site except the late Wisconsinan till at Walnut Creek. More than 25 percent of all samples exceed 100 µg/l (Figure 2), the maximum threshold being considered by the USEPA (2000). Figure 2. Distribution of Total Dissolved Phosphorus Among Selected Sites and Materials in Iowa. Stream threshold values shown as dotted lines. Letters indicate significant groupings (p < 0.05) of sample sets. It is clear that ground water in these aquifers and aquitards can discharge the P needed to produce nutrient enriched streams. These and similar materials are capable of discharging sustained P concentrations needed to support increased productivity in perennial streams and lakes. Furthermore, because the reported concentrations are dissolved, substantial portions, if not all, are readily available to support algal growth. Consequently, it will be difficult for many surface water bodies to meet standards for TDP if they are established using thresholds that cause nutrient enrichment. It is likely that P will continue to enter surface water from aquifers and aquitards for decades, particularly since it is present throughout shallow ground water systems such as those studied here. Of particular interest for additional investigations should be areas with: CONCLUSIONS AND RECOMMENDATIONS FOR FUTURE RESEARCH High concentrations of TDP are likely to be present in ground water in all near surface aquifers and aquitards in areas of Iowa with intense agriculture. Results in this study may be typical of many similar agricultural systems in the Midwest. It is unlikely, however, that the results presented here can be used to define natural background concentrations of P because of the long term source of agricultural P in all areas sampled. Detailed analysis of sources and transport processes in each area will be needed to determine if the material characteristics, flow system, or sources play a greater role in the observed occurrence of P in ground water. JAWRA 1. Large and persistent sources of high soil concentrations of P, intensive animal production, and substantial annual P fertilizer applications, particularly in aquifer recharge areas. 832 JOURNAL OF THE AMERICAN WATER RESOURCES ASSOCIATION OCCURRENCE OF TOTAL DISSOLVED PHOSPHORUS IN UNCONSOLIDATED AQUIFERS AND AQUITARDS IN IOWA 2. Intrinsic material characteristics that support leaching and transport of P including low soil sorption capacities (sandy and/or high organic matter soils) and unconsolidated materials and bedrock with extensive fractures or other macropores. Haygarth, P.M., L. Hepworth, and S.C. Jarvis, 1998. Forms of Phosphorus Transfer in Hydrologic Pathways From Soil Under Grazed Grassland. Eur. Jour. Soil Sci. 49:65-72. Harman, J., W.D. Robertson, J.A. Cherry, and L. Zanini, 1996. Impacts on a Sand Aquifer From an Old Septic System: Nitrate and Pphosphate. Ground Water 34(6):1105-1114. Helgesen, J.O. R.B. Zelt, and J.K. Stamer, 1994. 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