Agriculture, Ecosystems and Environment, 47 ( t 993 ) 117-134

Elsevier Science Publishers B.V., Amsterdam

117

Soil solution response to acidic deposition in a northern hardwood forest

L.E. Rustad *,a, I.J. Fernandeza, R.D. Fullerb, M.B. David c, S.C. Nodvin d, W.A. H a l t e m a n e
aDepartment of Plant, Soil, and Environmental Science, Universityof Maine, Orono, ME 04469, USA bCenterfor Earth and Environmental Science, SUNY-Plattsburgh, Plattsburgh, NY 12901, USA CDepartment of Forestry, University of Illinois, Urbana, IL 61801, USA aNational Park Service-Cooperative Park Studies Unit, Forestry, Wildlife and Fisheries, University of Tennessee, Knoxville, TN 37901, USA eDepartment of Mathematics, Universityof Maine, Orono, ME 04469, USA

Abstract

An intensive plot-scale acidification experiment evaluated the effects of H2SO4, HNO3, and combined H2SO4 and HNO3 treatments on the chemistry of soils and soil solutions in a northern hardwood forest. Treatments were delivered to 18 plots (each of 15 m 15 m, three plots per treatment) during 20-week field seasons by a hill-slope irrigation system and consisted of two levels of H2SO4 ( ~ 2000 and 4000 eq ha- 1year- 1), two levels of HNO3 ( ~ 2000 and 4000 eq ha- ~year- ~), one level of combined H2SO4/HNO3 ( ~ 2000 eq ha-t year-~ each of SO2- and NO3- ), and a control (water only). Soil solutions responded rapidly to all treatments with increased leaching of SO2- and/or NO~(depending on treatment) accompanied by increased leaching of Ca2+ and Mg2+ from the upper B horizon. As solutions passed through the upper 25 cm of soil, mean SO~- concentrations decreased by 50--86% of initial values in all S treatments and mean NO~- concentrations decreased by 71-93% of initial values in the low nitrogen treatments. This reflected the importance of anion adsorption for SO2- and biological immobilization for NO~- in these forested Spodosols. Mean NO~- concentrations, however, remained constant with depth in the high nitrogen treatment, suggesting that this high rate of NO~- input exceeded the plant/soil capacity to immobilize N. During the autumn and winter following the treatment period, soil solution SO~- and NO~- concentrations were greater for treated soils than for those of the control for 2-7 months. This suggests that anion desorption from soil exchange sites occurred in response to lowered soil solution concentrations of these strong acid anions.

Introduction Over the last two decades there has been considerable concern that acidic deposition may decrease the productivity of forest soils. Studies have shown that atmospheric deposition of strong acids can increase base cation leaching and the mobilization of toxic metals (e.g. AP ), decrease soil pH and base saturation, change mineral weathering rates, and alter soil biology (National
*Corresponding author.

1993 Elsevier Science Publishers B.V. All fights reserved 0167-8809/93/$06.00

1 18

L.E. Rustad et al./Agriculture, Ecosystems and Environment 47 (1993) 117-134

Acid Precipitation Assessment Program, 1987; Fernandez, 1989). In addition, changes in the chemistry of soil solutions, such as elevated levels of strong acid anions, H + and A1n+, may have adverse impacts on the chemistry and biology of associated surface waters (Goldstein et al., 1984). Investigations into the complex interactions between atmospheric deposition, forest soils, and surface waters have been limited because of the longterm nature of forest ecosystem development, the hypothesized subtle but chronic effects of acidic deposition, and the high heterogeneity of forest soils. Ideally, long-term, highly replicated studies of the response of whole ecosystems to ambient levels of acidic deposition should be used to evaluate the effects of elevated strong acid additions to forested ecosystems. An alternative is to experimentally manipulate whole ecosystems or ecosystem components with acid additions to simulate altered deposition scenarios. The External Plot Experiment (EPE) of the Watershed Manipulation Project (WMP) is a multiple-year study designed to evaluate dose-response relationships for HzSO4 and HNO3 additions to soils at the Bear Brook Watershed in Maine (BBWM), and to assess the biogeochemical mechanisms controlling these responses. The objective of this paper is to report on the response of soil solutions to the first year and a half of chemical manipulation.
Methods

Site description
The EPE study site is located in eastern Maine (4451'55 " N, 686'25 " W) approximately 50 km from the Atlantic Ocean. It is on the southeastfacing slope of Lead Mountain, approximately 100 m due east of the BBWM catchments. The vegetation is dominated by America beech (Fagus grandifolia Ehrb. ) (approximately 40 years old ) with a small component of yellow birch (Betula alleghaniensis Britt.), sugar maple (Acer saccharum Marsh. ), red maple (Acer rubrum L. ), and red spruce (Picea rubens Sarg. ). Spodosol soils are coarse-loamy, mixed, frigid Typic Haplorthods formed from compact basal till (David et al., 1990), and the bedrock is primarily metamorphosed quartzites and calc-silicates with granitic intrusions.

Experimental design
In the spring of 1987, six 15 mX 15 m plots were established within the experimental area on each of three elevational contours (245, 260 and 275 m), making a total of 18 plots of 225 m 2 each. Each plot was surrounded by a 1 m treated buffer strip to avoid edge effects. The plots on the same contour were situated 15 m apart with approximately 30 m between contours (Fig. 1 ). Six treatments were randomly assigned to one plot on each of the three

L.E. Rustad et aL /Agriculture, Ecosystems and Environment 47 (1993) 117-134

1 19

'~- ~"
~ ~ ,.j

~I
'<~-'~. ~, .

[] LowN ~ HighN
LOW S

~~.
Dosi Flushing Tanks

~
.,//

1
~
-.

HighS
Control

C5

C6

Water Source

I.~
B2 3 ~\ B4 ~

~
8'5

'J
B6

ii

,}

A1

A2

A3

A4 ,

A5 I A 6 ~ A 6

,"-

~I

~'~

, Water Storage " Tanks

"-r"

Fig. 1. Experimentaldesign.
contours (i.e. blocks) for a total of three plots per treatment in a randomized block design. Target treatments consisted of two levels of HESO4 (2000 and 4000 eq ha -~ year-1; referred to as LS and HS, respectively), two levels of HNO3 (2000 and 4000 eq ha-~ year-~; LN and HN, respectively), one level of combined HESO4/HNO3 (2000 eq ha-1 year-1 each of SO 2- and N O ; NS), and a control receiving water only (C). Exact treatment levels (Table 1 ) differed slightly from target doses owing to field season differences. During the summer of 1987, soils in each plot were mapped and sampled (David et al., 1990), and all plots were instrumented with: ( 1 ) two pairs of tension lysimeters with one lysimeter of each pair located in the upper Bhs horizon directly below the E horizon and the second located 25 cm below the mineral soil surface in what was generally the Bh horizon; (2) three zero-tension lysimeters, two located directly below the O horizon and one 25 cm below the mineral soil surface. A buried soil bag experiment occupied a central corridor in each plot and was used to examine soil response to the treatments (David et al., 1990).

Table 1 Treatment schedule for the 1988 and 1989 field seasons
N

Treatment SO4 (eqha-lyear -l) SO4 (#eq 1-~ ) 1988 1989 1988 1989 1988 1989 NO3 (eq h a - l y e a r - l )

Code

NOs (#eq 1-~ ) 1988 1989

pH

i
1988 1989 0 0 0 2175 2175 7250 0 0 0 1865 1865 3730 6.59-7.00 2.66 2.36 2.36 2.66 2.14 6.03-6.95 2.73 2.43 2.43 2.73 2.43 .~

Control Low sulfur High sulfur Sulfur/nitrogen Low nitrogen High nitrogen 0 2175 4350 2175 0 0

C LS HS NS LN HN

3 3 3 3 3 3

0 1300 2600 1300 0 0

0 1800 3600 1800 0 0

0 0 0 1300 1300 4350

0 0 0 1800 1800 3600

0 1865 3730 1865 0 0

L.E. Rustad et al. /Agriculture, Ecosystems and Environment 47 (1993.) 117-134

121

Irrigation system
The irrigation system that delivered treatment solutions to the plots consisted of: ( 1 ) a water supply system; (2) a water storage system near the water supply; (3) a pump to transfer water from lower storage tanks to upper dosing and flushing tanks; (4) upper dosing and flushing tanks; (5) pressure regulators and partial circle spray nozzles at the four comers of each plot; (6) calcium carbonate neutralization beds (Fig. 1 ). The water supply system is based on a subsurface water interception system adjacent to Bear Brook. Water drains by gravity from this system into four 8000 1 storage tanks and is pumped upslope (about 60 vertical m) through PVC pipes (7.5 m in diameter) to six 4000 1 dosing tanks and six 1500 1 flushing tanks. The treatment acids are added to the dosing tanks when they are about 20% full, and mixing is achieved by the agitation of filling the tanks. Treatment solutions are delivered to the plots by gravity through a system of six polyethylene pipes (5 cm in diameter), each leading to one plot on each of three rows on the basis of treatment type. The ends of these pipes have check valves below the plot network to allow the lines to be drained through calcium carbonate neutralization beds. Solutions are applied to each plot through four 90 arc spray nodes located at the four comers of each plot. Pressure regulators, in line with each of the nozzles, ensure that each nozzle delivers solutions at the same rate. Sprinkler application uniformity was tested extensively before acid treatments began and evaluated using a coefficient of uniformity (Christiansen, 1942). The mean ( + SD) coefficient of uniformity for the plots was 67 _+6%, with a range from 57 to 74%. This compares with the mean coefficient of uniformity for ambient throughfall (tested on three of the plots), which was 75 ___10.7%, with a range of 63.1-83.9%. These evaluations indicated that the uniformity of application for the sprinklers was roughly similar to that of ambient throughfall.

Treatment applications
Prior to acid additions, 1.6 m m depth of untreated water was applied to the plots to wet the vegetation and soil surfaces. The plots were then irrigated with 4.3 m m of treatment solution. In the initial treatment season (1988), weekly treatment applications began on 25 July and continued until 10 October; in the second treatment season (1989), treatments began on 24 May

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L.E. Rustad et al. /Agriculture, Ecosystems and Environment 47 (1993) 117-134

and continued until 2 October (Table 1 ). Target loads and concentrations were decreased in 1989 to make the experiment more comparable with the adjacent whole watershed manipulation (Erickson et al., 1990). Treatment results from an additional two years of treatment (1990 and 1991 ) and a subsequent recovery period (1993) will be discussed in a later paper. The cumulative increase in hydrologic flux to the plots was 4.7 cm in 1988 and 9.6 cm in 1989 against a background throughfall hydrologic flux of about 90 cm year- 1.

Soil solution collections and analyses

This paper reports on soil solutions collected from the autumn of 1987 to May 1990. Soil solutions were collected on a 2-4 week schedule. Volumes were measured in the field, and samples were bulked by lysimeter type, plot, and depth for chemical analyses. Within 7 days of collection, pH and acid neutralization capacity (ANC) were measured and subsamples were filtered through a 0.4/~m filter for analysis of cations, anions, Si, and NHg, and through a 0.7 gm glass-fiber filter for dissolved organic carbon (DOC). Aliquots for cations, Si, and DOC were acidified prior to analysis, and anion aliquots were stored at 4 C. Table 2 lists the procedures for sample analysis. Standard quality assurance procedures were followed for all analyses as detailed in the citations in the Methods section (Table 2).

Statistical analyses
All data were tested for normality using a Kolomogorov test (Conover, 1980). Data that did not fit a normal distribution were transformed logaTable 2 Soil solution analytical methods Parameter pH ANC Base cations (Ca, Mg, K, Na) Aluminum Anions (SO4, NO3, C! ) Ammonium Si DOC Description Potentiometric Automated titration with Gran Plot Hame atomic absorption spectroscopy Furnace atomic absorption spectroscopy Ion chromatography Automated colorimetry Automated colorimetry Liberation of COe and IR determination Reference Hillman et al., 1985 HiUman et al., 1985 Hillman et al., 1985 Hillman et al., 1985 HiUman et al., 1985 Anonymous, 1986a Anonymous, 1986b American Public Health Association, 1981

L.E. Rustad et al. /Agriculture, Ecosystems and Environment 47 (I 993) I 17- 134

12 3

rithmically and retested for normality. In all cases, the logarithmic transformation was found to be adequate to approximate a normal distribution, and all subsequent statistical analyses were performed on the transformed data. Treatment effects were evaluated using analysis of variance. The Ryan-Einot-Gabriel-Welsch multiple F test was used to perform mean separations because it appears to be the most powerful step-down multiple-stage test in the literature (Ramsey, 1978), and it is also compatible with the overall ANOVA F test, in that it rejects the null hypothesis when the F test does so (Statistical Analysis Systems Institute (SAS), 1985 ). Differences between the two field seasons by lysimeter type, depth, and treatment were investigated by means of a standard t-test, and correlation analyses were used to evaluate relationships among soil solution parameters. All statistical analyses were performed using procedures of SAS ( 1985 ).
Results and discussion

Pretreatment soil solution chemistry

In the upper soil solutions (i.e. tension Bhs horizon, zero-tension O horizon), Ca 2+ was the dominant cation in solution and SO4 2- was the dominant anion on a charge equivalent basis (Table 3). Approximations of organic anions, based on DOC concentrations and electroneutrality deficits, suggested that DOC was also important in surface horizons. In the lower soil solutions (i.e. Bh horizon), the dominant cation in solution was Na +, and SO4 2- and C1- were the dominant anions. Although solutions collected from both lysimeter types showed similar chemical trends, clear differences existed between the tension and zero-tension lysimeters. Zero-tension lysimeter solutions were consistently more acidic and more highly colored, had higher SO2- and lower Si concentrations, and were generally more variable than tension lysimeter solutions (Table 3). These differences can be attributed to the fact that soil solutions collected by zerotension lysimeters consisted primarily of macropore flow which, after passing through organic horizons, had relatively brief contact with the mineral soil matrix. Soil solutions collected by tension lysimeters may consist of a greater proportion of micropore flow, which should have a longer time to equilibrate with the mineral soil (Swistock et al., 1990). Because the overall chemical trends observed in the zero-tension lysimeter solutions were similar to those in the tension lysimeter solutions, the remaining discussion is restricted to tension lysimeter solution results. In the pretreatment data, the within-treatment variability associated with differences among plots was generally as large, or larger, than the amongtreatment variability, which resulted in few significant pretreatment differ-

124

L.E. Rustad et al. /Agriculture, Ecosystems and Environment 47 (1993) 117-134

Table 3 Pretreatment soil solution chemistry for tension and zero-tension lysimeters. Coefficientsof variation given in parentheses. Sample numbers range from 40 to 107 Tension lysimeter solutions Zero-tensionlysimeter solutions
Upperdepth

H Ca Mg K Na NH4 AI Si SO4 NO3 CI ANC DOC

Lowerdepth

13 (392) 79 (37) 32 (35) 18 (70) 70 (33) 3 (190) 17 (68) 132 (28) 74 (31) 7 (180) 61 (74) 17 (113) 802 (66) 1 (99) 77 (27) 30 (20 10 (40) 91 (22) 2 (116) 5 (102) 112 (32) 101 (22) 8 (133) 62 (43) 24 (68) 249 (104)

40 (102) 200 (63) 99 (69) 53 (87) 57 (53) 5 (222) 25 (49) 94 (64) 272 (73) 9 (188) 58 (71) -22 (388) 2272 (78) 17 (104) 74 (36) 40 (31) 10 (92) 94 (25) 3 (351) 16 (69) 62 (31) 150 (32) 7 (235) 79 (36) -11 (234) 304 (205)

H Ca Mg K Na NH, AI Si SO4 NO3 CI ANC DOC

Units are #tool 1-1 for AI and Si, gmol C 1-1 for DOC, and geq 1-1 for all other parameters.

ences among the treatments. Differences observed among treatments after initiation of acid additions were, therefore, attributed to treatment effects.

Soil solution response to acid manipulations Overview of response Soil solution chemical properties showed clear and rapid responses to treatments. In the upper lysimeter solutions, concentrations of both SO 2- and NO~- increased relative to those in the control for all S and N treatments,

L.E. Rustad et al. / Agriculture, Ecosystems and Environment 47 (1993) 117-134

125

respectively (Table 4). As solutions passed through the upper 25 cm of the pedons, mean SO2- concentrations decreased significantly by 50-86% of initial values. Mean NO~- concentrations decreased significantly with depth in the LN and NS treatments (by 71-93% of initial values) but remained virtually constant with depth in the HN treatments. The decreasing concentrations of SO2- with depth may be attributed to the adsorption of SO2- by the soil exchange complex. This trend is consistent with the increase in soil-adsorbed SO2- observed in the upper solum using buried soil bags (David et al., 1990). The decreasing concentrations of NO~- with depth as observed in the LN and NS treatments reflect the importance of biological immobilization for NO~-. The constant NO~- with depth observed in the HN treatment, however, indicates that this high rate of NO~- input exceeds the capability of the soil/plant system to assimilate the added N. In 1988, SO42- concentrations were depressed in the HN treatment at both depths; in 1989, SO2- concentrations were depressed in the HN treatment only at the lower depth (Table 4; Figs. 2 (a) and 2 (b)). This trend is consistent with the hypothesis that high HNO3 loadings decrease soil solution pH and increase positive charge on oxide surfaces, thereby increasing soil anion exchange capacity and SO2- retention. The increase in positive surface charge may have been greater during the 1988 field season when treatment solution concentrations were 1.7 times greater than those applied in the 1989 field season (Table 1). A similar loss of soil solution SO2- and stream SO2(Nodvin et al., 1986, 1988; Fuller et al., 1987) in response to nitrificationinduced acidification was observed following two clearcutting experiments at the Hubbard Brook Experimental Forest, NH. Increased concentrations of strong acid anions in solution due to treatments were generally accompanied by elevated concentrations of H +, A1n4, and base cations (Table 4). Of these cations, Ca 2 and Mg2 showed the most consistent response to the treatments (Table 4; Fig. 2). They were also the cations most strongly correlated to the strong acid anions (Table 5). These results suggest that the mineral acidity in soil solutions associated with the treatments was neutralized primarily by cation exchange processes which were dominated by the exchange of H + for Ca 2 and Mg2. These results are consistent with those reported by David et al. ( 1991 ) and Fernandez and Rustad (1990) who showed that Ca 2 and Mg2 were the dominant counter-ions for experimental additions of SO2- and NO~-. They are also consistent with those of David et al. (1990), who showed significant increases in exchangeable Ca 2 and Mg2 in soil bags buried below the forest floor in the HS plots of the experiment reported here. They attributed this increase in exchangeable Ca 2+ and Mg2 to a release of these cations from the forest floor to soil solution during the initial stages of acidification with subsequent adsorption in the mineral soil below. Perhaps a more integrated approach to examining the ionic composition of

Table 4 Mean soil solution chemistry from tension lysimeters by treatment type t, treatment period ( 1988 vs. 1989 ), and depth (units are/zmol 1- ~ for A1 and Si,/anol C 1- t for DOC, ml for volume, and p,eq 1- ~for all other parameters) C LS HS LN HN NS

o~

Treatment effects 1988 1989 1988 1989 1988 1989 1988 1989 1988 1989 1988

1988 1989

1989

Upper depth

H
353 b 511 b

46 (81) (77)
192 b

41 (84) (52)
199 b

16

Ca
45"

13 (49) 67" (28) (40)

16

MG (20) 14 (66)
72 105

* (62) 30 (106)

Na

NH4

,~ ~.

AI
139 128

(15) 1 (32) 25 (47) (26)

1113 c

19 (72) 394b (68) 193b (49) 10 (53) 150 (36) 2 (197) 37 (72) (9) 110 (39) 1 (61) 80 (121) 126 (17)
39 a

(26) 277 b (32) 108b (40) 18 (118) 123 (37) 1 (32) 24 (26)
131

Si
777 ~

(22) 1 (2) 90 (121) 122 (21)

SO4 (94) 2ab (126)

98

(23)
996 ~

NO 3
80

(15) 78" (32) 2a (76)

36 (69) 237 b (36) 135b (54) 34 (63) 102 (35) 1 (38) 42 (75) 197 (55) 101 "b (65) 259 ~ (109) (64)
73 61

(26) 300abe (77) 161 a~ (142)

57

:~ ~.

C1

ANC

DOC

(29) -7 (102) 580 (61)

-14

CB-C^ 2

,~ .~.

Volume

(40) 1 (1568) 812 (62) 38 (89) 166 (55) 4-8

12 (23) 48" (23) 25 (24) 11 (50) 59 (24) 1 (75) 22 (30) 111 (23) 72a (21) 7*b (235) 29 (42) l (331) 833 (48) 31 (75) 159 (67) 17-21 (46) -57 (118) 1126 (69) -265 (147) 180 (66) 5-6 (86) 7ab (151) 77 (67) - 11 (164) 417 (52) -72 (98) 229 (46) 6-8 (14) -35 (88) 2002 (122) 36 (333) 118 (73) 3-5 (36) -26 (104) 525 (22) -260 (140) 183 (46) 5-6

23 (79) 109"b (60) 74 (51) 31 (104) 75 (46) 2 (119) 26 (76) 107 (15) 267 ~ (35) 1b (116) 36 (54) -16 (138) 574 (67) - 10 (385) 152 (70) 12-20

21 (66) 186"b (70) 104 (73) 11 (52) 117 (27) 1 (106) 27 (84) 89 (25) 395 c (68) 21 ab (136) 47 (37) -17 (106) 356 (47) -50 141 204 (30) 15-20

27 (68) 129ab (46) 70 (40) 18 (31) 87 (27) 3 (106) 33 (50) 137 (44) 69" (47) 158" (95) 44 (53) -23 (117) 1087 (105) 25 (425) 172 (48) 14-21

21 (86) 170ab (108) 80 (95) 12 (38) 80 (28) 4 (178) 23 (36) 128 (24) 74a (52) 254" (124) 37 (63) - 10 (145) 529 (24) -34 (150) 187 (47) 13-18

(455) 171 (55) 6-9

25 (43) 295 b (70) 76 (57) 11 (49) 94 (42) 4 (118) 44 (76) 97 (27) 292 "~ (109) 301 a (120) 44 (51) - 18 (75) 969 (135) - 121 (110) 150 (71) 9-18

Lower depth

H
70"

3 (65) (23)
3 0 ab 52 b

Ca

5"b (30) 47" (20)

8" (47) 75 ab (39)

6"b (37) 85 "b (57)

4 1 ab -..""

Mg
12

1 (114) 90" (30) 45" (25) (8)

121

Na (8)
1 1 3 1 1 1 1 1 1

1 (78) 59* (28) 25" (15) 8 (19) 88 (9)

44" (36) II (37) 97 (27)

3"b (36) 53 ab (24) 25" (21) 9 (33) 89 (15)

(20) 10 (57) 90 (25)
2

5 (105) 71 a (29) 34" (38) 7 (32) 106 (25)

(63) 6 (25) 112 (20)
1

1b (130) 79ab (20) 36"b (16) 8 (33) 97 (16)

29 (58) 362b (59) 167b (57) 21 (82) 145 (37)

17" (58) 167b (86) 89 (62) 13 (35) 131 (32)

2 (70) 86" (66) 36" (38) 6 (23) 105 (24)

(41) 8 (21) 105 (20)

1

NH4 (50) 4" (53)

133 84 98

AI

(22) 5" (39)

(57) 9 "b (83)

(65) 5a (46)
91

Si (20)
90 "b

~.

SO4t

(182) 92 b (104) 145 (38) 43 b (64)

852 b

(141) 9 (34) 78 (ll) 118"b (42)

7 8 ab

NO3
82

(23) 146" (31) 2" (59)

CI
18"

(9) 18" (174) 41 (30)

(113) 24 (77) 114 (40) 68b (51) 336 b (76) 46 (40)

- l0 b

~3

ANC (51) 211 (42)

204 26 10"h 3

(138) II (44) 82 (25) 195" (33) 7a (139) 60 (35) - 1"b (662)

DOC

(118) 8 (42) 104 (24) 107"b (12) 14" (171) 45 (49) 6ab (63) 250 (47) (26) 8a (122) 158 (29) (136)
273

CB-CA 2

(152) 257 (53) -58 b (116)

252

Volume (40) 19-23

(40) 246 (84) 6-9

(525) 298 (32) 8-9

(158) 8 (18) 68 (27) 127"b (9) 1" (77) 57 (33) l "b (528) 163 (14) - 9 "b (82) 295 (26) 21-24 (19) 157" (47) 5a (95) 59 (27) 5a (197) 193 (30) -3 (1080) 358 (52) 9 (16) -21 b (90) 306 (28) 21-22

(34) 3" (76) lO0 (13) 102"b (16) 59"b (99) 69 (34) 24" (44) 194 (71) 37 (29) 247 (31) 4

(80) I0 (87) lO1 (33) 106-b (15) 11" (112) 60 (38) 23': (41) 480 (92) 43" (59) 243 (45) 16-19

(61) 52 (45) -26 b (73) 296 (96) -253 (139) 256 (54) 6-7

(49) 17-22

(14) 121 ab (40) 48" (136) 58 (59) 9" (81) 149 (48) 6 (196) 338 (23) 9

(154) 61 (44) 2~ (208) 146 (20) - 1 8 "b (75) 330 (21) 22-23

*C, control; LS, low sulfur; HS, high sulfur; LN, low nitrogen; HN, high nitrogen; NS, nitrogen/sulfur.

2 C B - C ^ = ( C a + M g + K + N a ) - ( S O 4 + N O 3 + C1).

Asterisks in the treatment effects columns indicate that a significant treatment effect exists for the given year; means followed by no superscript or the same superscript(s) are not significantly different using the Ryan-Einot-Gabriel-Welsch multiple F test. 1988 means in italics are significantly different from the corresponding 1989 mean ( a = 0.05 for all analyses). Coefficients of variation are given in parentheses below the means. .-...i

128

L.E. Rustad et al. /Agriculture, Ecosystems and Environment 47 (1993) 117-134

Upper Soil Solutions

,a
k.

Lower Soil Solutions

2OOO

k~ r

r c.
r

-t

-/.

,,0 ~oa' ""

4-

.I-

250 -

loo0
r r O,

`*o

k~ V

L r f.

aoo

4oo.

.+,
,

z~ I a

J
+
'

,0o

~ 1,,

:~

~ ++

loo

o.

1JU188

1 NOV88

1 MIr89

1Ju189

1 Nov89

1MargO

t Ju188

1 Nov88

1 Mar89

t Ju189

1 NovB9

1 MlrS)O

Fig. 2. Temporal trends in mean concentrations of: (a) SO~- in upper tension lysimeter solutions; (b) SO 2- in lower tension lysimeter soil solutions; (c) NO~- in upper tension lysimeter solutions; (d) NO in lower tension lysimeter soil solutions; (e) Ca 2+ in upper tension lysimeter solutions; ( f ) Ca 2+ in lower tension lysimeter soil solutions; (g) Mg 2+ in upper tension lysimeter solutions; (h) Mg 2+ in lower tension lysimeter soil solutions; (i) K + in upper tension

L.E. Rustad et al. / Agriculture, Ecosystems and Environment 4 7 (1993) 117-134

129

U p p e r Soil Solutions
v ~q lso

Lower Soll Solutlons

I.

so

40

}"
4O ++ 2O lo +, , . , + ,+

I.

.
A

+
,+-

++
Q,

so

4-

.,e ,i

~ P-

.a

r m. 40 50

+.+
+' 4o + 2o lo + ' ' .4.-t-+ 4%

-~- ~

~"

.4 1so

r O. 1so I

L p.

120 -

120

!
o. o 1Jul88

4.4-'
SO

+
' + . , 4-+

40

1No 86

,
1Marll9 1J

IE9

,
1Nov89

,
1Marg0

--

1dulSII

1 Nov88

1MIr89

1Ju'le~

1Noves9

1M:'rg0

Fig. 2 (continued). lysimeter solutions; (j) K + in lower tension lysimeter soil solutions; (k) Na + in upper tension lysimeter solutions; (1) Na + in lower tension lysimeter soil solutions; ( m ) H + in upper tension lysimeter solutions; (n) H + in lower tension lysimeter soil solutions; (o) AI" + in upper tension lysimeter solutions; (p) AI"+ in lower tension lysimeter soil solutions. Treatment periods are indicated by arrows. The legend is as follows:., control; I, HN; *, Hs; [~, LN; , LS; ~ , NS.

130

L.E. Rustad et al. / Agriculture, Ecosystems and Environment 47 (1993) 117-134

Table 5 Pearson's correlation coefficients for SO4 and NO3 by treatment type Control 504 H Ca Mg K Na NH4 AI Si SO4
NO3

Sulfur treatments NO3 - 0.46 0.60 0.34 -0.01 0.28 0.15 - 0.40 - 0.06 - 0.06 0.11 0.20 -0.18 0.49 504 0.69 0.93 0.94 0.28 0.31 0.19 0.79 0.56 0.16 0.02 - 0.70 0.57 - 0.36 NO3 - 0.07 0.31 0.18 -0.01 0.05 0.11 - 0.06 0.27 0.17 0.20 0.03 0.10 - 0.11

Nitrogen treatments 504 - 0.24 - 0.32 - 0.35 -0.11 0.27 -0.23 - 0.14 0.03 -0.60 0.35 0.18 0.16 - 0.06 NO3 0.50 0.69 0.71 0.38 -0.10 0.27 0.50 0.15 - 0.60 0.27 - 0.49 0.05 - 0.11

CI ANC DOC Volume

- 0.41 0.21 - 0.08 0.20 0.54 0.03 - 0.38 - 0.16 - 0.06 0.06 0.27 -0.44 0.21

Correlation coefficients indicated in bold are significant at the 0.0001 level.

solutions is through the relative magnitude of mineral bases (CB; Na +, K , Mg 2+, Ca 2+ ) vs. mineral acids (CA; SO42- , NO~-, C1-). If CB-CA is positive, then net mineral base exists in solution, and/or an alternate anion is supporting hydrogen ion concentrations (e.g. organic ligands, HCO~- ). If CB- CA is negative, then mineral acids are supporting hydrogen ion (Baker et al., 1990). In control plots, CB-CA was positive both years, in upper and lower lysimeter solutions (Table 4), indicating the presence of net mineral base. In the HS and HN plots, CB-CA was driven negative at both depths, indicating the presence of net mineral acid due to the strong acid addition.

Temporal trends
Analysis of temporal trends in soil solution chemical response (Fig. 2) showed that both SO 2- and NO~- concentrations responded immediately to treatments and continued to increase throughout the treatment period (Figs. 2 ( a )-2 ( d ) ). Following the termination of treatments, excess SO~- retained by soils during treatment was released back to soil solutions. For the LS treatments, equilibrium with ambient SO2- deposition was apparently achieved within a few months. For the HS treatments, it appears that SO2- desorption was extensive enough to prevent a return to steady state conditions before the renewed initiation of treatments. In contrast, NO~- concentrations quickly returned to control levels because these soils have little to no capacity to adsorb this anion, and the limited retention in capillary soil solutions is quickly

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flushed from the pedon. Comparisons of the response of upper soil solutions with lower soil solutions for SO2- showed a smaller, more gradual increase in SO 2- concentrations at the lower depth, which is indicative of sulfate retention occurring in the solum above. Soil solution cation concentrations, particularly Ca 2+ and Mg 2+, closely paralleled anion concentrations in order to maintain electrical neutrality (Figs. 2 (e)-2 (p)).
1988 vs. 1989 Although soil solution chemical trends were similar in both the 1988 and 1989 field seasons, mean concentrations of most major soil solution constituents were lower in 1989 than in 1988 (Table 4; Fig. 2). This may be attributed to the following: (a) treatment concentrations were decreased by 1449% in 1989 (Table 1 ); (b) protonation of oxide surfaces may have occurred during the 1988 field season, resulting in a greater retention of SO 2- and NO~- and a reduced leaching of cations in the 1989 field season; and/or (c) the increased availability of NO~-, and to a lesser extent SO2-, in the latter half of the 1988 growing season may have stimulated biological activity and therefore increased net uptake of nutrients in the 1989 growing season. The fact that litterfall, a indicator of productivity, was greater in 1989 than in 1988 (K. Nadelhoffer, personal communication, 1990), supports this latter hypothesis. Variability in response Interpreting the response of soil solutions to experimental manipulations can be difficult given the inherent variability in forest soils and soil solutions (David and Gertner, 1987; David et al., 1990; Swistock et al., 1990), and the artificial variability induced by sampling techniques (Barbee and Brown, 1986; Litaor, 1988). In this study, soil solution variability was generally greater in the zero-tension lysimeters than in the tension lysimeters and in the upper lysimeters than in the lower lysimeters (Table 3). Of the individual soil solution constituents measured, variability was consistently highest for ANC, NO, and NH + and lowest for Na +, Cl-, and Si (Tables 3 and 4). Despite the high degree of variability associated with lysimeter solutions, treatment effects could be detected, and were generally consistent across the three plots per treatment as illustrated in Fig. 3 (a). An exception was NO~ concentrations in the HN treatment, in which two of the plots (A2 and C 1 ) showed a clear response to the treatments in both 1988 and 1989, whereas the third plot (B1) responded to the treatments in 1988 but showed little response in 1989 (Fig. 3(b)). Differences in response may be attributed to: non-uniformity of treatment solution application, macropore channeling of treatment solutions away from individual lysimeters, and differences in the physical, chemical, and biological properties of the soil surrounding the individual lysimeters.

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L.E. Rusted et el./Agriculture, Ecosystems and Environment 47 (1993) 117-134

High Sulfur Treatment a.

3000

.-I
O" -q

2250

'

1500

09 750

0h 1Jul88
1Nov88 ~A1 1Mar89 --P~ B6 ~ 1Jul89 C3

1Nov89

High Nitrogen Treatment

L

2000

b.

1500
0"

o~ 1 0 0 0

500

0 1Jul88 1Nov88 A2 1Mar89 -~B1 ~1Jul89 C2

1Nov89

Fig. 3. Temporaltrendsby plot in uppertension lysimeter soil solutions for (a) SO~- in the HS treatment and (b) NO~- in the HN treatment. Conclusions Results from a period of 1.5 years of strong acid additions under field conditions indicate that experimental manipulation with different levels of H2SO4 and HNO3 resulted in increased leaching of SO~- and NO3- accompanied by a increased loss of base cations and AI 3+ from the upper solum. Soil solution chemical composition responded rapidly to treatments, and solution concentrations remained elevated above control concentrations following the termination of treatments for 2-7 months, indicating that anions sorbed onto

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exchange sites during the treatment period were desorbed back into solution during recovery. The multiple-year nature of this study is intended to further evaluate the importance of soil processes with slower kinetics, including N cycling and the incorporation of S into organic soil pools. Likewise, the poorly understood long-term dynamics of recovery will be examined.

Acknowledgments
The authors would like to acknowledge the considerable contribution of Warren Hedstrom in the design and implementation of the irrigation system, the efforts of Betty Lee in preparation of the manuscript, and the support of the field and laboratory crews who helped make this research possible. This research was conducted through the support of the US Environmental Protection Agency. Although the research described in this article has been funded by the US Environmental Protection Agency, it has not been subject to the EPA's policy review and therefore does not necessarily reflect the views of the Agency.

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