Nitrogen Isotopes as Indicators of Nitrate Sources in Minnesota Sand-Plain Aquifers by Stephen C. Komor" and Henry W, Anderson, J1 Abstract Nitrate concentrations in exces of national drinking-water standards (10 mg/L as N) ave present in certain sand-plain central Minnesota. To investigate nitrate sources in the aquifers, nitrogen-isotope values of nitrate (5'°Nyou) were measured in shallow ground water from 51 wells in five land-use settings The land-use setings and corresponding average nitrate concentrations (as N) and "°Nyos values are; livestock feedlots, 12.7 mg/1, 21.30; cultivated-irrigated fields, 13 mg/l, 7.4'/oo; residential areas with septic ‘systems, 8.3 mg/|, 6.0°/o0; cultivated-nonirrigated fields, 15.5 mg/1, 3.4°Joo; and natural, undeveloped areas, 3.8 mg/l 3. Ju. Values of 8!°Nyos less than 2° suggest that nitrogen from commercial inorganic fertilizers exists in ground water beneath all settings except the fedlots. Values of 5° No greater than 10 suggest that nitrogen from animal wast is present in ground water beneath certain feedlots, culivated-irrignted fields that are fertilized with manure, and residential areas with septic systems. Values of 6'°Nyo; between 22 and 43'/io in ground water beneath the feedlots probably result from denitrification, Values of 5'°Nwos increase with depth in many locations in the sand-plain aquifers. These increases may be caused by progressive denitrification with depth or by changes with depth in the proportions of nitrate from different sources. Similarly, variations of 6'°N yo values from 1986 to 1987 in certain locations ‘may be due to temporal variations in the amounts of d temporal frequency of sampli Introduction Sand-plain aquifers cover approximately 32,000 square kilometers of Minnesota and are important sources of water for agricultural, domestic, and municipal uses. These aqui- fers are recharged primarily by direct infiltration of precipi- tation, which makes them vulnerable to contamination by pollutants flushed through soils. Nitrate concentrations in sand-plain aquifers in Minnesota exceed the recommended limit of 10 mg/! (as N) in about 20 percent of sampled wells (Ruhl, 1987). The proportion of wells with nitrate concen- trations > 10 mg/l increases to about 50 percent in heavily farmed areas in the central part of the state (Anderson, 1989), Possible sources of nitrate contamination include ‘manure, commercial organic and inorganic fertilizers, erop residue, wastes from residential septic systems, and natural lorganie materials in soils, Because nitrate is very mobile in most soils, it can be leached from all these sources into ground water (Keeney, 1989), “U.S. Geological Survey, 2280 Woodale Drive, Mounds View, Minnesota 55112. Minnesota Department of Health-Well Management Unit, 925 SE Delaware Surcet, P.O. Box $9040, Minneapolis, Minne. sota 58459-0080, Received February 1992, revised June and August 1992, sccepted September 1992 Discussion open until September 1, 1993 260 tification or to changes i Sources. Ambiguities inthe interpretation of changes in 5"°N yo: values could be eliminated by increasing the sps the proportions of nitrate from different ial and ‘A number of studies have shown that nitrogen isotopes are useful for discriminating among nitrate sources in aground water (Kreitler et al, 1978; Kreitler and Browning, 1983; Flipse etal, 1984; Flipse and Bonner, 1985; Kaplan and Magaritz, 1986; Wells and Krothe, 1989). Nitrogen- isotope values are reported in the delta notation: BEN = [CON /"N)asmpie/("°N/'“N)aie — 1] X 1000 (1) Nitrate derived from animal wastes typically has 6'°N values in the range of 10 to 22%o, nitrate derived from natural ‘organic material in soil has 6'°N from 4 to oo, and nitrate derived from commercial fertilizers has 6'°N from —4 to 4°in (Heaton, 1986). The 6°N values that bound these categories are not rigidly defined, but do correctly classify ‘most 6?°N values according to their respective sources. In ‘unconfined aquifers recharged by precipitation, 6° N values of nitrate in shallow ground water may reflect the types of nitrate that are present on the overlying landscape. A com- plicatng factor is that nitrogen isotopes can be fractionated during transport through the unsaturated zone or aquifer. Forexample, denitrification and dissimilatory nitrate reduc- tion increase 6°°N values of residual nitrate (Smith et al, 19916). Volatile loss of ammonia from commercial fertilizers and manure also increases the 5'°N of residual nitrate (Kreitler, 1979). Mixing and exchange of nitrogen among different nitrate sources can occur. By altering the 6"°N values of nitrate, these processes can make it difficult to identify the original sources of nitrate in shallow ground water. Vol. 31, No, 2~GROUND WATER—March-April 199340 MILES 40 KILOMETERS EXPLANATION — [J sand Plains Land uses at well sites (numbers denote sampling location in Table 1): Livestock feediots Cultivated, irrigated Residential with septic system Cultivated, not irrigated Natural eouer Send plain} Location of the study area in Minnesota Fig 1 Map ofthe study area and sampling locations in central Minnesota, Welllocationsin Hubbard County are shown schematically in ‘the inset, Sand-plain boundaries from Anderson (1989). ‘The purpose of this study i to investigate whether 6°°N values ean be used to identify nitrate sources in sand-plain aquifers in Minnesota, The approach was to sample shallow ‘ground water in agricultural, residential, and undeveloped natural areas (Figure 1). Nitrogen-isotope compositions of nitrate and other chemical parameters were examined to identify nitrate sources and nitrogen-transformation pro- cesses in each land-use setting. Hydrology and Agricultural Practices Several interconnected sand-plain aquifers with similar Jithologic and hydraulic characteristics were examined (Figure 1). The sand plains are composed of glacial outwash ‘of Quaternary age (Wright and Ruhe, 1965). The deposits ‘generally are less than 30 m thick, but can be as much as 100 im thick in the western part of the study area (Van Voast, 1971; McBride, 1975). The outwash sediments consist of ‘medium to coarse sand interlayered with clay sil, silty sand, ‘and gravel (Helgesen and Lindholm, 1977; Lindholm, 1980). ‘Average mineralogical proportions ata site in the central part of the study area are 73 wi% quartz, 14 wt% plagioclase, 8 wt% potassium feldspar, and <5 wt% of carbonates, mica, ‘montmorillonite, kaolinite, amphibole, and magnetite (our ‘unpublished data). Depths to the water table generally range from 0 to 10-m, and saturated thicknesses typically are 6 10 18 m. Hydraulic conductivities in sand and gravel deposits ‘generally are 30 to 150 m/d (Lindholm, 1980). Hydraulic ‘gradients (vertical distance/ horizontal distance) of shallow ground water generally are less than 2 m/km (Magneret al, 1990), and velocities of shallow ground water average less than 0.5 m/d (Myette, 1984). Recharge is from direct infiltra- tion of precipitation and averages about 20cm/yr (Lindholm, 1980). Discharge is by evapotranspiration from the shallow water table, pumping from wells, and outflow to lakes and streams. ‘The average annual rainfall in the study area is about 66 cm. About 44 cm of rain falls between May and September, which is the growing season for corn in central Minnesota. Rain occurs, on the average, every 7-8 days uring the growing season. In irrigated fields, approxi- mately 20 to 26 cm of irrigation water are added to corn crops during the growing season (Soil Conservation Service, 1976). Corn typically is planted during the first week of May and at that time nitrogen fertilizer is applied to fields at arate ‘of approximately 28 kg N/hectare (25 lbs N/acre). Addi- tional applications of up to approximately 135 kg N/hectare (120 Ibs N/acre) occur between late May and the third week of June. Field and Analytical Procedures Ground-water samples were collected between June and August 1986, and during the third week of May 1987. ‘All samples were collected after the initial application of nitrogen to corn crops. When wells in cropped areas were 261sampled, landowners were asked whether they applied nitro- ‘gen mainly as inorganic fertilizer, manure, or a mixture of ‘both. The 51 sampled wells were a combination of steel cased wells installed for this study and existing domestic and irrigation wells. Among the wells were 15 paits of nested shallow and desp well. Shallow wells in these pairs were screened between 0 and 2.2m below the water table, whereas deeper well wee screened between 2.6 and 6.6m below the ‘water table (See note #3 inthe explanation to Table I for an exception). Water was pumped from cach well until three ‘well volumes were removed or until stable readings were achieved for pH, temperature, and specific conductivity “These practices ensured that water samples were epresenta- tive of ground-water compositions. Standard techniques Fishman and Friedman, 1989) were used for field mea- surements of alkalinity, dssolved-oxygen concentrations, pH, and specific conductance, and for laboratory measure~ ments of sulfate, chloride, nitrate, and ammonium concen- trations. Nitrogen-isotope ratios of nitrate (8"°Nos) and ammonium (6° Nass Table 1) were measured by the Global Geochemistry Corporation in Canoga Park, California; the procedures of Minagavsa etal. (1984) were followed. Preci- sion and accuracy ofthe isotope analyses are + 0.2%. (Use of firm names in this report is for identification purposes only and doesnot constitute endorsement bythe U.S. Geo- logical Survey.) Ground-water samples were collected in five land-ase settings: 1. Livestock feedlots—Eight wells were within or hydraulically downgradient from pens where cate, hogs, and poultry were fed and sheltered. Soils in these areas contain larg concentrations of manure, Sample AS0 at Site 5 (Table 1) is from a pond that drained a turkey feedlot. 2. Cultivated-ivigated settings —Filieen ‘wells were within or downgradient from cultivated fields that were irigated, commonly by centerpivot systems. 3. Residential settings with septic systems—Fourteen wells were within or downgradient from residential areas with septic tank oil-absorption systems, Well A (Table 1 vas installed in a draingield that recived effluent from a septic sytem. 4. Cultivated-noniergated settings Eleven wells were within of downgradient from cultivated fields that were not irigated. 5. Natural settings —Three wells were within or down- aradient from relatively undisturbed, uninhabitaed areas with minimal agricultural activites, Nitrogen Transformations \Nitrogen-transformation reactions that occur in shal- low aguifers include the following (Freeze and Cherry, 19795, Stumm and Morgan, 1981): Ammonification CH.O(NH)) +O; NH! + HCO, organic dissolved ammonium bicarbonate material oxygen @ 262 Nitrification NH! + 20: = NO; +2H"+H20 (3) ammonium dissolved nitrate oxygen Denitrification 4NOs + SCH:0 = 2Na(g) + SHCOy nitrate organic bicarbonate material + H+ 280 “ Dissimilatory Nitrate Reduction NOs +H,0+ 2CH0 = nitrate organic ‘material NH + 2HCOS 0 ammonium bicarbonate Ammonification and nitrification commonly occur above the water table whereas the last two reactions, which are nitrate-reduetion reactions, generally occur beneath the water table under oxygen-deticient conditions (Freeze and Cherry, 1979). Denitrification and dissimilatory nitrate reduction are microbially mediated and should result in "SN-depletion in produets and '*N-enrichment in reactants (Kaplan, 1983; Heaton, 1986). Progressive denitrification or dissimilatory nitrate reduction along ground-water flow paths should cause decreases in nitrate concentrations and increases in 8" Nos values. If ground-water flow paths were vertical, such chemical variations could be detected in nested well pairs. Geound-water flow paths are subhorizontalin the q WAdoP — LA uC “9 warmer pauaaiss ayp Jo Woweq ay) 01 sens pw] MoFaq dap — tadap IA “S 1.99 pu 97 usaming ponsaios iam daap‘q '2}qe Jae ay Moog WZ PUP Q uaAKIDg poUD9I25 ‘yep duydues awes xa pue mouse Bunuiod-premdn we yum ddoop Aumpuodsa1s09 944. "104 1 24 So1e3}pU mos parsou ® jo s9quiou ROqTeYS > cr OHSS co on vi ve 8B oe re se te sR one os = ay rr er er ove we su. oo oe | tt ove wo ost 1 09 ost ze oui yo ool ot m= oe oi one el ove so sy one 6 = ze oO Ol oe 69 Ss oe — et 0% uF our so owl oS 009 89 ee 08 tL sk OS ore sto rs te sm ge vt Lo v1 ws uw w& ee 600 ot ore se ore ad ow vo 6 6st ce so so oss out ceo oor or SST 08 rl ou TL 098 ss oz st ov so oO oz re ove re wo 6s sto ot os 9S sit ge ost re 08 LL ow eo oz sl sr Si ot 69 oor o9 wz Ye st ss cs OR hh et soot Orr ws 008 5 so ws0 (]8u) Curis) (Su) (8a) OD" Hu) (PAY Cl) wii) (a). og os "os 10 Hd ANN, or yidog (2009) srepmby URE g-PuEs wOssuUNAY [eAIUE.) Uy J97eA JO KaISHMIHPOR, “1 AGEL 265In all except the natural setting, at least 2595 of the samples have nitrate concentrations in excess ofthe drinking water standard. Average nitrate concentrations exceed the drinking-water standard in the three agricultural settings (Gee abstract for average concentrations). Ground water ‘beneath the feedlotsis characterized by ammonium concen- trations of as much as 120 mg/l and dissolved-oxygen con- centrations of less than 2 mg/l (average=0.7 mg/). A pond next toa turkey feedlot (sample ASO) contained 287 mg/ of ammonium. Ground water inthe residential settings has the largest average chloride concentration (58 mg/1) ofthe five land-use settings Nitrogen Isotope Variations Land-Use Variations Nitrogen-isotope values for nitrate are grouped by land. use in Figure 3, Three samples from natural settings that contain background nitrate concentrations (= 1.5 mg/l) have an average 6'°Nwvos value of 3.9". Two samples from natural settings with larger nitrate concentrations have an average 8"°Nwos value of 1.9%o, which is in the range of Feedlot Cultvatedrrigated Ip FO EE Residential with septic systom BPN of eo) Fig. 3, Histograms of 6 "Ns in ground water beneath the five end-use settings. At the top ofthe figure are ranges of 8” Nvo {for nitrate derived from inorganic fertilizer, natural organic ‘materials in soll, and animal wastes (Heaton, 1986). The forms of nitrogen applied to cultivated fields in the study area, ie. in- organic fertilizer, manure, or both, are indicated for the eult- vated-ireigated and cultivted-nonierigated settings. The bin Interval for the histograms is 2, 266 values for nitrate from inorganic fertilizers. Based on these comparisons the division between 6 "Nos values for natural soil nitrate and fertilizer nitrate in the study area is between 1.9 and3.9"jo, somewhat less than the general value of "jn noted by Heaton (1986) for other areas. In Figure 3, the boundary between fertilizer nitrate and soil nitrate is denoted by a range between 2 and 4 ‘The average 6"°Nxos value in the feedlot setting is 21.3'joo, whichis at the high end ofthe range for nitrate from animal waste, Seven of the 14 feedlot 5"°Nxos values are between 22 and 45°, thus exceeding the majority of pub- lished animal-waste 6°°Nyos values. The average 6”Nwos ‘value in residential setings i 6.0‘jo, Which sin the range of nitrate from natural organic material in soil. The three largest valuesin the residential setting, 9.6, 0.9, and I1.7"o, are consistent with nitrate from human waste in septic systems. Large average chloride concentrations in residen- tial areas (Figure 2) may reflect leakage from septic systems of softened water or possibly urine-contaminated water. Values of 8!Nsos in the cultivated-irrigated setting range from 0.9 to 22.6. These values span the range from fertilizer to animal-waste 6" Nwos values. In general, smaller 5™Nyos values occur where inorganic fertilizer is applied, and larger values occur where manure or fetlizer/manure mixtures are used. In the cultivated-nonirrigated setting, more than haf ofthe Nos values are within the range of soil nitrate; the average of 3.4% is within the range that divides fertilizer and natural soil ""Nxos values. Incontrast to cultivated-irigated areas, 5!°Nxos values in cultivated- nonirrigated areas are smaller where both manure and in- ‘organic fertilizer are applied than in areas where just in- organic fertilizer is applied. Depth and Yearly Variations ‘Twenty-one pairs of 6!°Nxos values from nested wells are shown in Figure 4. In 14 (679) of the pairs, 8°°Nwos values are larger in deeper wells than in shallow wels. These 14 pairs are located throughout the eastern two-thirds ofthe study area (east of location 26, Figure 1). In five pais, 8" Nwos values are smaller in the deeper wells, and in the remaining two pairs, "Nsos values are indistinguishable in deep and shallow wells Twelve wells were sampled between June 4 and August 21, 1986, and again between May 14 and 21, 1987. Changes in !"Nxos values during this period excseded Iho in eight of the wells (Figure 5) These temporal variations in 8 °Nwos values at individual localities may be due to changes in the proportions of nitrate sources or to variable amounts of fractionation of a single source. For example, 8"Nxos values in well I7 decreased from 7.8jo on August 21, 1986, to 1.5% on May 21, 1987. This change could indicate that the proportion of nitrate from inorganic fertilizer in well 17 was largerin May 1987 than in August 1986. Alternatively, it is possible that the main nitrate source was inorganic ferti- iaer at both sampling times, but that more denitefication ‘occurred in August 1986, resulting in comparatively larger 85°'N yo values at that time. Similar alternative explanations are possible for temporal variations in other wells.Cultivated- nonirrigated BENNO, (eo) Residential | Cultivated- | a Nera Ma aca” "areas Sino shit Sa.sSo Feedlot 208 irrigated Shallow fl Deep Nested well pairs Fig. 4. Variation of 6"Nyos in nested pairs of shallow and deep ground-water wells from four land-use settings. The shallow wells were screened between 0 and 2.2m below the water table, whereas the deeper wells were screened between 2.6and 6.6 m below the water table rel Pn, in exception; see explanation for Table’ 1 in deep well ~ 5'°Nyoy in shallow wel). Values of 6'"N in Ammonium ‘Ammonium concentrations were large enough to obtain 6!°Naue values in six samples from feedlots and a septic-ank drainfeld (well A31). Ammonium in these samples probably formed by ammonification of organic nitrogen from urea and proteins in animal wastes. The "Ny values in these samples range from 10.2to 21.641. Nitrate is enriched in °N by 1.2 to 8.6%oo compared to ammonium in the three samples for which both 8'°Nwos and "Nyse values are available (wells A28, $1, and 52) However, this fractionation is of limited interpretive value because ammonium in the samples may be chemically unre- lated to coexisting nitrate. Ifthe ammonium and nitrate are related, the fractionation implies that nitrate is being reduced to ammonium. Reduction-Oxidation Potentials in the Aquifer Redox potentials were estimated from the following two half-reactions: ©: 42H" +26 = H.0; © dissolved oxygen NOy + 10H’ +8 = NH! +3H0 nitrate ammonium Numbers atthe tops of the bars are differences between 8:°Nxos values in each pair Values of pe were calculated with the program WATEQUF (Ball etal, 1987); the relationship of Sato (1960) was used to caleulate pe values from dissolved-oxygen concentrations and pH values, Values of pe from the 0; / HO: couple range from about 2 to 45, whereas values from the NOs /NH couple range from 5.5 to 8.5 (Figure 6). Differences in pe values calculated from the two couples indicate that dis- solved oxygen and the nitrogen species are not in redox equilibrium (c£ Lindbergand Runnels, 1984), The pe values, do not group strongly by land use Discussion We offer two possible explanations for the common increase of 8'*Nyos values with depth in nested wells outside the feedlots (Figure 4). First, the increases could be caused. by denitrification below the water table. (Dissolved oxygen concentrations are greater than 2 mg/l in most water samples from outside the feedlots, which probably would preclude extensive dissimilatory nitrate reduction, Also, ‘only small ammonium concentrations occur in most samples ‘outside the feedlots, which argues against significant dis- similatory nitrate reduction.) If the increases of 8'°Nxos values with depth are due to denitrification, nitrate concen- trations should decrease with depth. Of the [4 well pairs in which 5"*N wos values increase with depth, however, nitrate 26740 Cultivated- Residential Feedlot nonirrigated 27 30 So 20h 9 S t Z 37 25 2 toh 4 “ 2 oe 4 oa } 44 0 Trae owen Oa See Sa aia Ow ane — TE aT (1986 1987 Se AT AB WW 2 A1B A22 Alt 7 I AIS: A2B A293 Well name Fig. 8. Variations of 3"Nyos in ay 1987.8 values in each pair (5"°Nyos in 1987 ~ 6"°Nxon im 1986). ound-wat ° 8 o = || Stes . 2 o & gots oe g Los | Ser 8 er 6 ot of o 1 2 ¢ ¢ $ pe —0,/ HO, Fig. 6. Values of pe calculated from concentrations of dissolved ‘oxygen and nitrogen species (half-eactions 6 and 7 in the text). 268 ells from three land-use settings sampled between June and August 1986 and again in umpling dates (month / day) are indicated for each sample. Numbersat the tops ofthe bars ae differences bet we 8 Nos concentrations decrease with depth in only six pairs (C4-C5, AT-A8; A2I-A22; $35-S36; SHI0-SHII; SH7-SH8), and actually increase with depth in seven of the remaining eight pairs (nitrate concentrations do not change with depth in ‘well pair 17-18), As noted earlier, the two wells in each well nest may not intercept the same ground-water flow path. ‘Therefore, changes in nitrate concentrations between nested wells cannot conclusively demonstrate the presence or absence of denitrification, Nevertheless, variations of nitrate concentrations with depth in nested wells are not supportive of denitrification in more than half ofthe well pairs in which 8!" Nxos values increase with depth, The second explanation for increases of "Nos values with depth is changes in the proportions of nitrate from various sources. For example, average 6"°Nwos values in four well pairs in the cultivated-nonirrigated setting increase with depth from 2.2 to 4.5%oo (pairs 11-12, C4-CS, and AT-A8 on 5/19/87). Such an increase could reflect a decrease with depth in the proportion of nitrate from inor- ganic fertilizer and a parallel increase in the proportion of nitrate from natural soil materials, In the residential setting, 8" Nxos values in well pair A18-A19 increase from an aver- age of 2.5‘lao in the shallow well to 9.9" in the deep well, ‘This increase with depth could reflect an increased input from septic-tank effluent. Thus, there may be no need to callupon denitrification to explain inereases of 6!"Nos values with depth in many well nests outside feedlots, Several 5"Nxos values in the feedlot settings exceed 22%, the generally accepted maximum value for animal- waste nitrate. Volatilization of ammonia from animal waste results in *N-enriched nitrate, but published 8"°Nsos values that reflect this process generally do not exceed 22%a (Heaton, 1986). Denitrification and dissimilatory nitrate reduction can produce 6""Nxos values as large as those measured beneath the feedlots (Mariotti et al., 1988; Bottcher eta, 1990; Smith eta, 1991b). The abundance of ‘organic material and comparatively small concentrations of dissolved oxygen in the feedlot settings create favorable conditions for denitrification and dissimilatory nitrate reduction, Dissolved oxygen may be depleted by oxidation ‘of organic matter or by nitrification of ammonium. Whether denitrification or dissimilatory nitrate reduction is the main nitrate-reduction pathway beneath the feediots cannot be specified unequivocally from the available data, Dissimila- tory nitrate reduction becomes thermodynamically favored ‘over denitrification as redox potentials decrease (Stumm and Morgan, 1981). Therefore, dissimilatory nitrate redue- tion might be an important nitrate-reduction pathway beneath the feedlots if redox potentials were exceptionally low. Values of pe, however, are no lower in ground water beneath the feedlots than in the other settings (Figure 6) This indirect evidence supports denitrification rather than dissimilatory nitrate reduction as the main nitrate-reduction pathway beneath the feeds. Nitrate from Fertilizer and Manure Nitrate in the cultivated-irigated setting has smaller areas where only inorganic fertilizer is applied than areas where manure and fertilizer ot only ‘manure is applied. This relationship isin accord with the expected isotopic compositions of nitrate from inorganic fertilizer and manure. Inthe cultivated-nonirrigated setting, however, 5"*Nwo: values do not correlate with the type of added nitrogen. In most samples from the cultivated- nonirrigated areas, even samples collected where manure was applied to fields, 6"°Nwvos values are in the range of nitrate from inorganic fertilizer or natural soil materials, This pattern may indicate that the amounts of manure applied to the cultivated-nonirrigated settings were not suf- ficient to appreciably affect the isotopic composition of the overall nitrate reservoir in the soi ‘There may be an additional reason why 8"*Nxics values inthe cultivated-irrigated settings reflect the types of nitro- gen applied to crops but the relationship does not hold inthe cultivated-nonirrigated settings. Cultivated-nonirrigated settings receive only about 44 cm of water during the grow- ing season, whereas culivated-irrigated areas receive about 640 70cm of water. Thus, leaching of nitrate in cultivated- nonitrigated fields may occur more slowly than in cultivated- irrigated fields. Longer residence times for nitrogen-bearing ‘materials in cultivated-nonirrigated fields would allow more exchange of nitrogen among manure, inorganic fertilizer, and natural soil materials. This homogenization of thenitro- gen poo! would mask the unique isotopic identities of nitrate from different sources. In contrast, nitrate in cultivated- irrigated fields may be transported more quickly to ground water before as much exchange can occur among different nitrate sources Conclusions Nitrogen isotopes are useful qualitative indicators of nitrate sources in central Minnesota sand-plain aquifers ‘The 5*Nwos values show that nitrate derived from animal waste enters sand-plain aquifers from certain feedlots, cultivated-irrigated fields where manures applied, and sep- ticsystems in residential areas. Nitrate from inorganic fertil izers occurs in cultivated areas and also appears to be presentin putatively natural, undisturbed areas. The presence of nitrate from fertilizers in natural areas indicates that nitrate contamination from agriculture can extend beyond the boundaries of areas under actual cultivation. ‘Temporal changes in the isotopic compositions of nitrate in individual wells can result from changes in the proportions of nitrate from different sources, Alternatively, such temporal changes could be due to variable amounts of denitrification, which would resutin variabie enrichment of "N in residual nitrate. Similarly, increases of 6° Nyos values with depth in many localities could be due to changing proportions of nitrate from various sourees orto denitrli tion, These alternative explanations illustrate that for the low sampling frequencies and densities employed here, nitrogen-isotope data can be difficult to interpret in an tunambiguous manner. To conclusively determine why 5#°Nwos values change over time and increase with depth will require that many more samples be collected through- out the year from closely spaced vertical intervals (c.f. Smith tal, 19914). Analyses ofthese samples may define isotopic and chemical gradients that clarify the causes of temporal and depth variations in 6"*Nwos values, Acknowledgments This study was funded by the Minnesota Department of Natural Resources and the U.S. Geological Survey. The manuscript was constructively reviewed by John Karl Boke, Mark Brigham, Roy Spalding, Warren Wood, and ‘wo anonymous reviewers. References Anderson, H, W, Jr, 1989, Eifects of agriculture on quality of water in surficial sand-plain aquifersin Douglas, Kandiyohi, Pope, and Stearns Counties, Minnesota. U.S. Geological Survey Water-Resoutces Investigations Report 87-8040. 52 pp. Ball, J. W,, D. K, Nordstrom, and D. W. Zachman. 1987. 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