Acid rain, dissolved aluminum and chemical weathering at the

Hubbard Brook Experimental Forest, New Hampshire

N~YF M. JOHNSON. CHARLEST. DRIS~OLL. JOHN S. EATOU. GENI- E. LIKEYS and

Wn LlAhl H. M~Do\~I-I I
Earth Sciences Department. Dartmouth College. Hanover. NH 03755. U.S.A.
Civil Engineering Department. Syracuse I ni\ersit). Syracuse. NY 12310. II S A.
Dlvlsion of Biological Sciences. SectIon of Ecology and S!stematics.
Cornell Cni\ersit\. Ith.xa. NY 14850. Ll.S.A

Abstract- Contemporary acid ram in the Hubbard Brook eco\ystcm has Induced a series of geochcmi-
cal responses. Neutralization is accompllshed in essentially a 2-step process. Initially. hydrogen ion
acidity is neutralized by the dissolution of rextiLe alumma primarilly found in the soil zone. In the
Hubbard Brook area this reactive alumina has solul.ion propertIe\ much like natural glbbaite. Alumin-
um-rich surface waters with a pH of 4.7 5.2 are typical of this neutrali7atlon stage. In a second step.
both hydrogen ion acidity and aluminum acidity art: neutrallxd by the chemical Meathering of prtmary
silicate minerals. i.e. by the alkali and alkaline earths contained in the bedrock and glacial till of the
watershed. The chemical weathering reaction is much slouer than the alumina disbolution reactjon. so
that the aluminum acidity stage (pH 4.7 5.2) may persist for suhslantlal periods. Tqpicdlly. howcber. in
the Hubbard Brook area the aluminum acidity has heen neutralized and a pH > 5.2 is obtained before
surface waters reach .a third-over stream channel. Bt:cat~scof rhe rrlati\elg low pHs throughout the soil
zone and in the streamwater. carbonic acid reaction? are csscntially absent at the present time In the
Hubbard Brook system. Water pathlength (or residence time) In the soil Lnne is the crucial factor in the
state of acid rain ncutrali7ation. aluminum chemistr! and chemical weathering. As measured bj the
losses of alkali and alkaline earths from the ecosystem. chemical weathering rate in the Hllhhard Brook
area at the present time is not especially high relative 10 other areas.

INTRODUCTION tinuously monitored by the 1J.S. Forest Service.

UNDI:R most natural geological conditions chemical
weathering is done in a mildly acid or neutral en-
vironment. At the present time, however, large areas
of the earths surface are subject to a substantial flux
of strong acids from atmospheric sources. i.e. acid
rain (LIKENS er al., 1979). To the extent that these
atmospheric pollutants represent an abnormal ad-
dition of acid to the landscape, they may induce
changes in the normal pattern of chemical weathering.
Previous work has shown that the acid rain phenom-
enon has apparently caused high aluminum concen-
trations to appear in low order streams of the north-
eastern United States (JOHNSON. 1979: DRISWLL.
1980) and in Scandanavia (GJESSIN<; et (I/., 1976). In
these environments AI( appears to play an im-
portant intermediate role in the neutralization of acid
rain (JOHNSON, 1979; DRISCOLL. 1980). The intent of
this paper is to elaborate on the interactions between
acid rain. aluminum solubility and chemical weather-
ing as observed at the Hubbard Brook Experimental
Forest. New Hampshire.
EXPERIMENTAL SETTING
The Hubbard Brook Valley is located in central
New Hampshire and is the site of a 3076 hectare ex-
perimental watershed (Fig. 1). Since 1956 the amount
of precipitation and stream discharge have been con-
Chemical analyses of stream water and precipitation
have been sampled weekly since 1963. The combi-
nation of hydrologic data and chemical data has pro-
vided a relatively complete. long-term picture of
chemical and nutrient budgets for this area (LIKENSet
(I/.. 19771. The earliest report of acid rain in the
lJnited States was based on the chemical evidence
from the Hubbard Brook Valley (Lr~r:us (I al.. 1972).
The Hubbard Brook watershed lies in a belt of high
grade metamorphic rocks and granites. Underlying
the Hubbard Brook watershed is a pelitic schist of
sillimanite grade (Littleton Fornation) which is exten-
sively intruded by a quart7 monzonite (Kinsman For-
mation). The bedrock mineralogy consists predomi-
nantly of silicate minerals with minor amounts of
sulfides present and no carbonates.
The area has been heavily scoured by glaciers
which left the watershed area about 14.OOOyr ago
(DAVIS and FORD. 1981). Bedrock has been heavily
glaciated and no vestige of pre-glacial weathering ac-
tivity is obvious. A mantle of till overlies the entire
landscape with only local buttresses or cliffs of bed-
rock protruding through the till generally near ridge
crests. The till varies widely in thickness and tends to
be thinnest on the ridge crests. In the monitored
watersheds (Fig. I ) it averages some 3 m in thickness,
and is composed of fragments of locally derived gra-
1422 NOYEM. JOHNSON
et al.
 Acid rain dissolved aluminum and chemical weathering
Table 1 for April). Some 540, of annual streamflow occurs
Soil chemistry of Hubbard Brook watershed.
Source: Whittaker, et al. (1979) and IL Pierce
cpers. COllXll.)
Horizon pH range cEc (meg/lOO gm)
01 3.3 - 4.5 97
01 3.2 - 4.0 118
Ai 3.7 - 4.5 5.8
81 4.0 - 5.1 21-47
B3 4.3 - 5.1 13
c 5.0 - 6.0 3-5
nites and high grade pelitic schists. Because glacial till
covers most of the landscape surface, it is the till
which is most exposed to chemical weathering rather
than the underlying bedrock. Till also plays an impor-
tant role in the hydrology of the watershed by provid-
ing a water tight barrier between surface waters and
bedrock. Bedrock which is covered by more than a
meter of till is virtually unweathered, showing at
times a perfectly preserved, glassy glacial polish on its
surface.
The soils of the Hubbard Brook Experimental For-
est are mostly well-drained spodosols (haplorthods) of
sandy texture formed on the glacial till (LIKENSer al.,
1977). A distinguishing feature of all spodosols is a
conspicuous organic layer, the A0 horizon, which
forms the top unit of the soil zone. The soil is very
porous, especially the A, horizon which may have a
pore volume of S&95; (HOYLE,1973). The soil sur-
face has a very rough microtopography (pit and
mound) caused by the uprooting of trees by wind. Soil
depths are highly variable but average about OSm
(LIKENSer ui., 1977). Some bulk chemical properties of
a Hubbard Brook soil are listed in Table 1. Pedogenic
minerals found in these soils are kaolinite, vermiculite
and amorphous alumina.
The Hubbard Brook area received an average of
130cm of precipitation each year, of which 627;
(80cm) leaves the watersheds as streamflow. Precipi-
tation is uniformly distributed throughout the year,
with about ill precipitation events each year on the
average. or about two precipitation events per week.
Each winter a continuous snowpack develops to a
depth of about 1.5 m. The soils stay unfrozen all year
long, except for occasional episodes in early winter
when the snowpack is thin or absent. Unfrozen soil is
attributed to the insulating effect of the thick snow
cover and the presence of the humus layer of the soil
(HnKr et al., 1962). Frost free soil implies that the
mechanisms of water transport in the soil zone are
constant throughout the year.
Streamflow in the Hubbard Brook watershed fluc-
tuates widely in the course of the year. Lowest
streamflow occurs during the summer months (mean
runoff of 1.5cm~unit-area for August) while highest
stream flows are associated with the melting of the
winter-snowpack (mean runoff of 22.2 cm/unit-area
1423
during March. April and May, with more than 30,,
occurring in April alone. In the Hubbard Brook
watersheds overland flow is negligible due to the
rapid infiltration of water in the interfluve areas. The
upper reaches of the watersheds are often dry during
summer, but streamflow in the lower reaches is peren-
nial. There is no deep groundwater input to stream
flow, but there is also no measurable Loss of stream or
soil water to a deep ~roundwater reservoir (LIKENS er
CT/..1977). Water percolates through the soil column
but is restrained from deep seepage by a relatively
impermeable soil f&pan, the till or relatively
unjointed bedrock.
Soil water and stream water are linked by means of
a network of subsurface passages embedded in the
soil zone called interRow channels (WHIPKEY. 1965).
Interflow channels act as drainage conduits between
soil water and stream. The operation of interflow
drainage enables the soil to become, in effect, an
extension of the stream channel, and vice versa. Inter-
flow channels may be considered a special kind of an
ephemeral, perched water table situated within the
soil zone and directly feeding into the nearest stream
channel. During wet periods the channel network
expands by incorporating stream bank areas, head-
water drainages and interflow channels into the sys-
tem of surface flow. During dry periods, the stream
network contracts by abandoning the headward
extension of channels. stream banks and interflow
passages.
The water storage capacity for the soils typically
found at Hubbard Brook is some 25-38 cm (HOYLE,
1973). Given the input of 130cm of precipitation per
year, a mean residence time for soil water of It&i6
weeks is thus implied. However. from season-to-sea-
son and from point-to-point within the watershed,
water residence time is much more variable than the
mean conditions cited above would suggest.
When viewed from a given point on the stream, the
mean residence time of the water at that point is a
function of stream discharge. On dry, low flow days
water moves slowly through the surrounding soils
before entering the stream. i.e. mean residence time of
the water in the local system is relatively long. On
days when high discharges obtain, water moves
rapidly through the surrounding soils on its way to
the channel, i.e. mean residence time is relatively
short.
When the stream channel network is viewed as a
whole on a given day, water residence time becomes a
function of position within the system. That is, waters
in the head-water channels have had a pathlength in
the soil-channel system which is shorter than those
waters occupying the channel further downstream.
On the average the mean pathlength of the water
within the channel on a given day will become longer
at increasing distances downstream. Longer path-
length in this case may be interpreted as longer resi-
dence time within the soil -channel system.
1424 NOYI?M. JOHNSONet al.

Table 2 located adjacent to gauged watersheds (Fig. 1). An

contparison of the mean coxpsition of "acid rain"
ungauged watershed was chosen because the gauging
and strsaawaterin the Hubbard BroOk Eq%?rfmtntal weir itself, being composed of cement in an otherwise
Forest during 1963-1974. Data from Table 7. Likens
" &., 1977.
lime-free environment, can alter the chemistry of
waters downstream from the weir.
Direct Precigitbtion str;Bilmwatsr
Water samples were collected at 9 regular sites
SC +
.0739+.003 II&l .0126~.OQlS uq/l along Falls Brook (Fig. 1) at monthly intervals over a
NH* -222.01 .04t.01
ca*+ .1??.02 1.65t.06
3-yr period, February 1975 through February 1978.
Na+ .12%.01 .88-r.O2 The chemistry of these 330 water samples provides
.OS~.Ol .38*.01
g++ .07+.02 .2.?t.01 the long-term data for this study. In addition, four
Al+++ ___ .23+.01 other synoptic sample suites were collected to
SO,-- 2.87f.11 6.232.11
NOa- 1.432.11 1.93t.31 specifically examine the chemistry of aluminum, fluor-
cl- .51*.09 .54f.O2 ide and dissolved organic carbon. One of these
SiOn __- 4.43
PS 4.13 4.90 sample suites (17 October 1978) was taken under
nearly-dry, drought conditions. The other three (6
March 1979, 3 April 1979 and 4 May 1979) were
taken during various stages of the annua) spring
In summary then, the mean residence time of water flood.
within our study watershed is a function of both pos- In its upper reaches (sites I-III, Fig. 1) the channel
ition along the channet and the amount uf water flow- area and saturated banks of Falls Brook expand and
ing through the system on the day concerned. contract with season and with ambient hydroIogic
conditions. Surface water appears and disappears irre-
Water chemistry gularly in the channel as a function of microrelief,
The Hubbard Brook Experimental Forest has been permeability and saturation state of the channel itself.
monitored for precipitation chemistry since 1963, the Kn downstream reaches (sites III-VIII, Fig. 1) stream-
longest record of this kind in existence (TabIe 2). The flow was observed to be perennial during the course
ambient acidity is primarily due to strong acids, not- of this study.
ably HzS04 and HN03. This chemistry differs from
the usual geochemical characterization of rain water
in which acidity is controlled by carbonic acid (GAR- ANALYTICAL TECHNIQUES AND
RELSand MACKENZIE,1971, p. 106). COMPUTATIONAL PROCEDURES
Stream water chemistry in six south-facing (Fig. 1) All sampling procedures and routine chemical analyses
watersheds also has been monitored at Hubbard were simibu to those described in the Hubbard Brook Eco-
Brook (Table 2). Stream water samptes were collected system Study (LIKENSet ab, 1977). Aluminum fractionation,
fluoride fractionation and carbon fraction measurements
weekly at a fixed point on each of six six streams just were made to supplement this study. Chemical equilibrium
above the gauging station. Like the precipitation calculations were made utilizing the data collected.
chemistry, the dominant anions in streamwater are
Aluminumfiactionation methods
sulfate and nitrate. Unlike precipitation, however, the
Aluminum was determined by the ferron--orthophenan-
hydrogen ion ~n~ntration is lower by almost an
throiine method (RAINWA~ and THATCHER,1960; SMITI+
order of magnitude. and HEM, 1972). which utilizes 8-hydroxy-quino~~ne com-
Although the chemistry of stream water at Hub- plexes with mononuclear aluminum ions. Iron also
bard Brook is relatively constant (LIKENSet al., 1967), complexes with hydroxy quinolinc. and interferes with this
there are some significant variations in chemistry as a method. However, iron levels in Falls Brook are generally
low (< 10 pg/l) and iron interference was corrected for by
function of discharge. At a fixed point along a stream preparing a standard iron interference curve and measor-
in the Hubbard Brook system, three major responses ing the iron concentration in the sample. The catculated
can be distinguish~; those that are diluted by iron interference was generally less than I,, of the
increasing stream discharge, those that are concen- aluminum content of the sample.
trated by increasing stream discharge, and those that Three separate aluminum measurements were made on a
given sample to determine aluminum speciation. Total
are unchanged by increasing stream discharge-(Jorrr+ aluminum was determined by measuring the aluminum in
SON et al., 1969). These chemical changes can be an acid-digested sample. Total monomeric aluminum was
explained variously in terms of reaction kinetics taken as the aluminum measured without the aeid-diges-
(LANGBEINand DAWDY, 1964) or on the basis of a tion procedure (TURNER, 1968; Smrm, 197t; OKURA cr ui..
1962). Organicahy complexed ah.uninum was determined
simple mixing model (JOHNSONet al., 1969; HALL, by passing a sample through a cation exchange column
1970). and analyzing the effluent for monomeric aluminum. In
this procedure the free and labile inorganic aluminum
Falls Brook complexes are absorbed on the column while organically
To assess the geochemiczd e&ts of acid rain, the complexed aluminum passes through (DRISCOLL,1980).
With thqse three aluminum measurements, estimates of
water ch~istry of a first through fifth order stream three aluminum fractions can be obtained. Organ~~liy
network (Falls Brook) was monitored over a 3-yr complexed (non-labile) aluminum is taken directly as the
period. Falls Brook is not gauged, however, it is monomeric aluminum which passes through the cation
 Acid rain dissolved aluminum and chemical weathering 1425

Table 3

Equilibrium Relationships Used in This Study

Equation Equilibrium Constant Reference

(Hydroxide Ligands)
Al+' + Hz0 = Al(OH)+' + MC ; KON,= 1.03 x 10-5 May et al, 1979
A1+3 + 2H20 = Al(OH,; + 2H* : KOH,, = 7.36 x lo-" ibid.
Alc3 + 4H20 = AltOK); + 4H+ ; KOH'c = 6.93 x 1O-'3 ibid.

(Fluoride Liqands)
A1'3 + F- = AlF*' ; KF, = 1.05 x 107 Burrows, 1977
AIf C 2F- = AlFf ; KF? = 5.77 x 10 ibid.
Al+3 f 3F- = AlF, i XT:.= 1.07 x 101' ibid.
Ali f 4F- = AlF, ; mi, = 5.37 x 10'9 ibid.
Ait3 + 5F- = AIFs-2 ; Wg = 8.33 x IO'" ibid.
Alc3 + hF- = A1F6-3 ; WC. = 7.49 x IO*0 ibid.

(Sulfate Liyands)
Alt3 + SOi* = ALSO; ; KS, = 1.63 x 10' ibid.
Rlt3 + 2'3,* = Al(SO,,); ; KS2= 1.29 x 105 ibid.

(Aluminum trihydroxide)
A1(OH)s + 3H+ = 3A1+3 4 3H20
Synthetic Gibbsite i KS0= 1.29 x 108 May et al., 1979
Natural Gibbsite : f$O = 5.89 x IO* ibid.
Microcrystalline Gibbsite : KS0 = 2.24 x lO* Hem and Robertson, 1967
Amorphous Aluminum trihydroxide i KS0 = 6.31 x lOi stonm and Morgan, 1970

(Alunlnum Silicates)
iAizSizOs(OH)r + 3H+ =
A1+3 + iiuSiOki 'iHz0
taoiinitf : KS0 = 2.05 x 10' ibid.
Halloysite ; KSO=4.37x155 Heinet al., 1972

(Variable Composition Silicates1

[Al(W) sl,_xlSiOzlx + (3-3x)HC =
(l-x)Al*'+ xHkSiO* + (3-5x)li20* -1.7 + 1.56 PH
amorphous Ideal Aluminosilicate i KS0 = 10 *ace*, 1978
Reversible Non-ideal -5.49 + i.59 PH
AluminosilIcatr ; KS0= 10 Paces, 1978

(sasxc Aluminum Sulfate)

--LP.
AlOHSOo = AlC3 + OH- + SO: = 5.89 x 10 "an Brcemdir,1'376
' %O -
*where x = 1.24 - 0.135 PH

exchange column. Inorganic (labile) monomeric aluminum Carbon fractionation methods

is obtained from the difference between total monomeric
aluminum and organically complexed (non-labile) mono-
meric aluminum; this fraction would include free (aquo)
aluminum and soluble aluminum hydroxide, fluoride and
sulfate complexes. Acid soluble aluminum is obtained from
the difference between total aluminum and total mono-
meric aluminum; this fraction would include those forms
that require acid digestion such as colloidal aluminum,
polymeric aluminum and strongly bound alumina-organic
complexes.
Fluoride fractionation methods
We used a fluoride ion selective electrode (ORION, 1976)
to measure fluoride. Two separate fluoride measurements
were made in this study, free fluoride and total fluoride
(ORION, 1976). Free fluoride was determined by direct
measurement with the electrode. Total fluoride was deter-
mined by using a total ionic strength adjustor and buffer
(TISAB) solution. This solution contained sodium chloride,
glacial acetic acid and cyclohexylene dinitrilo tetraacetic
acid adjusted to a pH between 5.0 and 5.5. The addition of
this reagent to water samples, provides a constant back-
ground ionic strength, decomplexes fluoride and adjusts
solution pIi, so that toal fluoride can be measured by
electrode (ORION, 1976). Bound fluoride was taken as the
difference between the measured total fluoride and free
fluoride.
Dissolved organic carbon (DOC) was measured using a
persulfate oxidation (MENZEL and VACCARO,1965) fol-
lowed by syringe stripping of CO, (STANTON, 1973). An
infrared analyzer or gas partitioner was used to measure
the CO,. Phenolics were measured using a modified Folin-
Ciocalteau reagent (KLOSTER,1974) and a tannic acid stan-
dard. Dissolved organic carbon was separated into molecu-
lar weight fractions using Amicon ultrafiltration and the
following fiiters: UM2 (loo0 NW cutoff), PM10
(10,000 MW cutoff), and KM100 (100,000 MW cutoff). Fil-
ters were operated in accordance with the manufacturers
instructions. To remove leachable organics, filters were
rinsed with 600 ml of high purity deionized water before
use.
7hermodynamic equilibrium calculations
Aluminum speciation was calculated by assuming dis-
solved species were in chemicaf equilibrium. The resulting
aluminum activity was used to calculate the state of satura-
tion of various minerals. Monomeric inorganic aluminum
may exist in solution as free (aquo) aluminum, or as sol-
uble hydroxide, fluoride and sulfate complexes. The
thermodynamic equilibrium relationships (Table 3) for sol-
uble and solid phase aluminum forms were selected from
what we consider to be the best values in the literature.
Aquo aluminum activity was calculated with measured
inorganic monomeric aluminum, pH, free-fluoride and sul-
1426 NOYE M. hmso~ et al.

Table 4

Em&ions for Calculatinri Various AluisinumFom

Aluminum Sulfate Complexes

Al-S& = {Al+] ISO;*lKS~Yz/Y, + tA1+~~SO;2~2KszY~/Y~ (Eqn. 4)

AluminumBoundFluoride

F-Al = iAlf3){F-)KF~/Y~ + 2fAl+3~~~-)2KF~/Yt + 3tAlC3jfF-1%F~ +

4{Al+)tF-~*KFti/Y> + S{Al ~{f->%FwB +
6~Al+~~F-1%F~/Y3 (Eqn. 5)

AluminumAcidity

A1acid

= the hydrogen ion activity (moles/L)

IF- 1 = the free fluoride activity (mler/l)
tSOul = the sulfate concentfation (moles/l)
(Al inorganic) is the labile nwnamric aluminumCOncentratiOn
(moles/l)
YI,Yz,Yz = the mew activity coefficient of mnavalent,
divalent, and trivalent species, resp%Ctivcly
KOXn,KF,,KSn=aluminumhydroxide, fluoride and suLfate ligand
equilibrium constants - see Table 3 for values.

fate measurements as well as tbermodyrtamic equilibrium
constants (eqn 1, Table 4). [A~thou~ sulfate was not
measured in its free form sulfate complexes in low ionic
strength waters are minor and can be negiected (DIU~LZ,
19gQ.J Using this value for aquo aluminum activity, we
could then calculate the theoretically coexisting solubie
aluminum hydroxide compfexes (eqn 2, Table 41, soluble
aluminum fluoride complexes (eqn 3, Table 4), soluble
aluminum sulfate complexes (eqn 4, Table 4) aluminum
bound fluoride (cqn 5, Table 4) and aiuminum acidity (eqn
6, Table 4). Aluminum acidity is the capacity of aqueous
aiurn~~um to neutralize hydroxyl ion. Recause aiumjnum
which is chelated with natural organic m&on wit1 not
readiiy hydroiyze over the pM range observed in solutions
in this study (D~WXXLL, X98Q,this ahrminum component
was not included in the aIumiaum acidity calculation.
Solid-phase eq~~b~~ calcutations were also made to
compare our mesured solution ~rn~~t~o~ with that pre-
dicted by known minerals. Ibis ~rn~i~ was made by
cakuiating mirreral ~~b~urn i&ices (P~crr~, 197g).
Minerat disequiIibrfum indices (I,) are computed by taking
the logarithm of the ratio of the mineral activity product
(Q,,)to the equilibrium constant (I&) (eqn 7).
A d~~~ibrium index greater than zero iadica%s that
the system is oversaturated with respect to the specific min-
eral. Values less than zero denote undersat~ation and
values of zero r&ect equilibrium with respect to the miner-
al of interest.
Ion activity coeticient values were computed by means
of the Debye-Htickef approximation (STUMMand MOR-
GAN, 1970).
RESULTS
The average chemical composition of Fails Brook
for the 36.month interval between February 1975 and
February 1978 is shown in Table 5. Distinct changes
in chemical composition were evident aiong the
length of Fails Brook frabie 5). Water in the upper
ma&es of Falls Brook (sites I-TIT, Table 5) was more
acid, ri&er in ~~~~ and d~~sh~ in alkali and
alkahne earth cations compared to the lower reac&~
of Falls Brook. Ammonium and nitrate, concen-
trations decreased significantly in a downstream di-
rection while silica and polyphenol levels increased.
ionized carbonic acid content was variable but rela-
tively low; bicarbonate alkalinity was essentially non-
existent. In contrast to these widely fiuctuating spe-
cies, sulfate and chloride were notably constant in
concentration along Falls Brook.
 Table 5

'wan Chemistry of falls Brook as a Function of

Stream Order and Elevation

Unless Otherwise Specified all Units are ms/l

Fi+ + POti
stream ++ ++ ++
NH*
Site Elev. Order Ca Na K+ (W/j.) (W/l) 2Al so,-- NOj- a- %Koo3- tug/e) SiO2 *polyphenol
w

I 81&l 1 .87f.04 .37f.03 .21f.01 .lO?.Ol 18.3k.6 38'10 .71+.03 6.Ot.l 2.0f.5 .36t-.03 . 23t.04 3.1t.6 2.2C.l .15*.01

II 770 2 1.24i.04 .%3t.07 . 28t.01 .16+.01 11.5f.9 lSt3 .32+.03 5.5i.l 2.1+.4 .39t.02 .09t.02 3.oi.4 5.2k.4 .2O-c.O3

III 755 2 1.325.05 I.03t.05 .29+.02 .16+.01 S.1i.6 ll-t2 .21?.01 5.3f.1 1.9i.3 .39f.01 .lO+.Ol 2.95.3 6.1f.3 .25*.02

I" 715 2 1.55t.04 .96*.03 .32t.01 .17t.01 6.4+.4 11+2 .20?.02 5.5k.l 1.9r.3 .40f.02 .13?.02 3.6+.4 5.5t.2 .21c.o2

v 664 3 i.65t.04 1.05t.03 .34f.01 .17'.01 2.9f.3 11+2 :15?."1 5.Sk.l 1.72.3 .37?r.O2 .12+.01 3.4C.5 5.8t.2 .25t.03

'j; 597 3 1.652.05 1.04-t.03 .35?.0! .2Of.01 3.5+.3 11'2 .19t.01 5.8f.l 1.5f.2 .41?.02 .09+.01 3.1f.3 6.4f.2 .32-e.O2

"II 539 4 1.68?.04 1.05t.03 .37?.01 .21f.01 3.1f.3 lo+1 . 18k.01 5.9f.l 1.3+.2 .40+.01 .09+.01 3.1+.4 6.3f.2 .37-f.O2

VIII 445 4 1.58f.03 1.03f.03 .37f.01 .23?.01 2.6t.3 11t1 .16f.01 5.et.1 1.2t.2 .40t.01 .07+.01 3.6+.4 6.4t.2 .34?.03

IX 415 5 1.70f.05 .87t.06 .45+.01 .27t.02 2.1k.3 *t1 .15t.01 5.7t.1 l.Of.2 .42f.01 . 12-f.02 3.6k.4 6.2f.2 .41+.05

'Based on 37 consecutive monthly samples for the period February 1975 through February 1978.
Error Expressed as standard deviation of the mean.

'Total aluminum

'Includes ionized carbonic acid and alkalinity

*For the period 30 Sept. 75 throuqh 23 Sept. 76

1428 NOYEM. JOHNSON
et al.

These long-term data (Table 5) portray an overall
picture of a rapidly and systematically evolving
aqueous system; one whose chemistry adjusts step-
by-step to the various processes operating within the
Falls Brook watershed. The most conspicuous chemi-
cal changes are those involving dissolved aluminum.
As reported previously (JO~INSON, 1979), the long-term
data showed that the total aluminum dissolved in
Falls Brook varied as a function of pH and/or pos-
ition within the watershed. It was presumed, there-
fore, that a relatively soluble aluminum mineral,
probably Al(OH),, was present in the watershed and
was largely responsible for neutralizing the acid rain
incident on the watershed (JOHNSON,1979).
To explore these possibilities further, the aluminum
chemistry of the Falls Brook system was subsequently
studied using the analytic methods developed by
DRISCOLL(1980) and summarized above. The results
of these analyses are tabulated in Table 6.
We use the data for 6 March 1979 to illustrate
certain spatial trends in the aluminum chemistry of
Falls Brook (Fig. 2). As exemplified by the 6 March
1979 data (Table 6, Fig. 2). the upper reaches of Falls
Brook contained more inorganic monomeric
aluminum than the lower reaches. On the other hand
just the opposite trend was true for the organically
complexed aluminum (Fig. 2). The combined effect of
these trends was that the proportion of organically
complexed aluminum in Falls Brook streamwater in-
creased steadily in the downstream direction (Fig. 2).
The fluoride chemistry of Falls Brook also changed
markedly in a downstream direction (Table 6. Fig. 2).
Total fluoride levels were relatively low at the high
elevation sites but increased steadily downstream to

Dissolved Aluminum Species for balls Brook on Four Selected Days.

Unless otherwise specified units are micrograms/liter. Al is total
(acid digestible) aluminum, Al is total monomeric alumin&, Al is
organically complexed aluminum? LXX is dissolved organic carbon: B
is polyphenol. Of the calculated values ~1 is aluminum complexed
with hydroxyl, Al is aluminum complexed WL,Ph fluoride, Al is alu-
minum complexed wfth sulfate, Al+++ is free (aqua) alumin&

4 May 1979

MEASURED DATA

soI,-2 LXX m
SITE pH (mq/l) F- Air Ala Al (v/l) (my/l)
0

I 4.76 5.3 .OS 566 497 51 2.56 .16

II 4.82 5.1 1.1 417 368 115 2.05 .15
III 4.92 4.7 3.1 354 267 115 2.45 .22
I 5.00 4.6 8.0 249 189 106 2.37 .27
v 5.30 4.8 42 217 175 125 2.50 .26
I 5.11 4.9 21 290 222 152 3.45 .40
VII 5.10 5.0 2-i 322 256 184 3.88 .44
VIII 5.15 4.9 25 304 237 189 3.61 39
IX 4.99 5.6 11 380 299 203 4.26 :53

3 April 1979

I 4.70 5.3 .05 556 471 0 2.33 .26

II 4.82 5.1 1.1 438 221 13 1.75 .18
III 5.04 4.7 3.7 159 103 32 2.63 .31
I" 4.98 4.6 12 169 108 18 2.15 .24
" 5.30 4.8 50 113 061 18 2.93 .27
"I 5.19 4.9 30 207 122 65 3.16 .28
VII 5.37 5.0 65 141 a4 47 2.71 .32
"III 5.38 4.9 61 141 84 65 2.96 .28
IX 5.31 5.6 51 155 98 56 3.36 .32

6 March 1979
I 4.75 5.3 .05 650 605 18 -- _-
II 4.80 5.1 0.7 524 465 61 -- _-
III 4.84 4.7 2.0 387 320 113 -- _-
IV 4.94 4.6 9.1 273 225 104 -- __
" 5.20 4.8 28 235 182 92 -- __
VI 5.04 4.9 14 320 251 125 -- -_
VII 5.03 5.0 1.9 320 249 142 -- __
VIII 5.11 4.9 19 294 227 128 -- __
IX 5.03 5.6 11 320 244 128 -- __

17 October 1978l

III 5.30 6.0 9.2 156 107 61 2.72 .21

I" 5.13 6.1 11.5 156 112 41 2.16 .26
V 5.61 6.9 58 110 71 56 2-40 .21
VI 5.79 7.4 51 135 96 73 3.14 .38
VII 6.04 7.6 61 144 84 78 3.44 .54
VIII 6.29 7.1 62 110 66 54 2.84 .36
IX 6.29 7.0 54 151 92 88 4.05 .64

1
Sites I and II dry on this date.
 'Acid
rain dissolved aluminum and chemical weathering 1429

4 May 1979

CALCULATED DATA

Air-Ala Ala-Al0 ZAl ZAlc TAl LA1 Al+++

SITE h Li t?FS
bY 446 202.6 49.8 15.8 268.2 177.8
51 253 115.1 49.0 7.0 171.1 81.9
87 152 bl .7 57.3 2.4 121.4 30.7
60 83 24.3 49.0 0.7 74.0 9.0
42 50 7.1 42.0 0.1 49.2 0.8
67 71 12.2 55.6 0.2 68.0 3.0
66 72 10.8 58.2 0.2 69.2 2.7
67 48 7.7 38.5 0.1 46.3 1.6
81 96 L'1.3 55.7 0.8 87.8 0.2

3 April 1979
R5 471 190.2 57.4 18.2 265.9 205.0
217 2OR 93.7 41.9 5.7 141.3 66.7
57 71 '14.4 24.8 0.9 60.1 10.9
bi 90 18.7 63.3 0.6 82.6 7.4
52 43 4.0 37.6 <.I 42.4 0.5
85 87 8.6 46.7 0.1 35.4 1.5
57 37 3.4 33.0 <.i 36.6 0.3
57 19 2.1 16.7 <.l 18.8 0.2
57 42 4.8 36.6 c.1 41.4 0.5

6 March 1979

45 587 261.7 66.6 21.1 349.4 237.7

59 404 189.2 57.9 12.2 259.4 144.6
67 207 Vi.0 64.5 4.3 151.8 55.1
48 12i 27.3 80.2 1.0 108.5 12.6
53 90 15.0 72.2 0.2 87.4 2.5
69 126 27.1 89.6 0.7 117.4 8.6
71 107 16.8 84.2 0.5 101.5 5.5
67 99 19.5 74.4 0.4 94.3 4.7
76 lifi 30.0 75.1 0.9 106.0 3.9

17 October 197El'

49 46 24.8 18.1 0.3 43.2 2.802

44 71 22.5 42.9 0.5 65.3 5.050
33 15 4.2 10.7 <.? 14.9 0.121
39 13 6.8 6.1 <.I 12.9 0.085
60 7 5.3 1.7 C.1 7.0 0.017
44 12 11.3 0.7 <.I 12.0 a.007
59 4 3.8 0.2 c.1 4.0 0.002

I
Sites 'Iand II dry on this date.

site V, from which point they stayed relatively con- A detailed analysis of aluminum chemistry together
stant. At the higher elevation sites (I--.111)free fluoride with the analysis of major cations and anions enabled
levels were extremely low with most of the fluoride us to compute the ionic strength of each water sample
being in a bound form (Table 6, Fig. 2). As total fluor- collected. On the average for Falls Brook water, the
ide levels increased in the downstream direction, free ionic strength value would be 2.8 x lo-; SD.
fluoride levels also increased. in downstream waters 0.2 x 10T4 which for this study represents average
free fluoride comprised a significant fraction of total activity coefficient values of 0.98, 0.93 and 0.84 for
fluoride. [In an aqueous system such as Falls Brook monovalent, divalent and trivalent ions, respectively.
bound-~uoride would be almost entirely complexed
with alumjnum as other potential fluoride complexes DISCUSSION OF RESULTS
would be quantitatively insignificant (DRISCOLL,
1980). The fact that total fluoride increased in a Aluminum chemistry
downstream direction. i.e. with increasing pathlength Substantial changes in the amount and kind of dis-
within the system, would suggest that the ftuoride is solved aluminum were observed in Falls Brook from
derived from the till and bedrock of the watershed site-to-site (Table 6). The data from 6 March 1979
rather than from an atmospheric source.] illustrate some of these changes (Fig. 3). On 6 March
A comparison of measured bound-fluoride (utiliz- 1979 a high discharge (spring flood) condition was
ing ion electrode methods) with calculated bound- present, so that the mean residence time of stream-
fluoride (eqn. 5. Table 2) provides an independent water site-by-site was relatively short when compared
check of the analytic methods and the chemical equi- to the dry condition of the preceding summer, specifi-
librium model. The mean measured bound-fluoride cally the data from 17 October 1978 (Table 6). How-
value of Falls Brook was 0.045 mg/f; SD. 0.011, while ever, many of the chemical trends observed in the 6
the mean caiculated aluminum-bound tluoride value March 1979 date (Fig. 3) also apply to the 17 October
was 0.059 mg/l; SD. 0.016. 1978 data. Generally, the inorganic monomeric
1430 NOVEM. JOHNSONet at.

For example a comparison of Fafis Brook

aluminum chemistry with various phases of
ahuninum trihydroxide is shown in Fig. 4. This com-
parison shows that the free (aquo) aluminum activity
of Falls Brook is generally oversaturated with respect
to synthetic gibbsite but undersaturated with respect
to natural gibbsite, microcrystalline gibbsite and
amorphous aluminum trihydroxide. The natural gibb-
site phase (MAY et al., 1979) comes closest to de-
scribing our observed data. Similar results have been
reported in surface waters of the Adirondack region
of New York (DRISCOLL,1980).
Aluminum trihydroxide, however, is not the only
aluminum compound which is compatible with the
Falls Brook data. A theoretical model for a variable
composition aluminosilicate mineral (PACES, 1978)
also describes the Falls Brook data rather well (Fig.
5). The PA&~ (1978) model has been advocated by
-c TOTAL FUHllOL
Kramer (1980) as a likely factor in the chemistry of
+ FREE FLLA?i?IOE
acidified waters generally. Although the Falls Brook
data and the PACES(1978) model generally conform,
the data fit is somewhat removed from the proposed
theoretical values (Fig. 5, Table 7). When viewed in
the context of the Pa& (1978) mode!, the Falls Brook
system is more similar to other naturaf waters (which
drain granitic rocks) than it is to the theoretical ideal
(see Fig. 5).

Fig. 2. Observed aluminum, hydrogen ion and fluoride

concentrations in Falls Brook during 6 March 1979. Total
aluminum (Al,), total monomeric aluminum (Al=) and or-
ganic monomeric aluminum (Al,) were measured directly
(see text).

al~jnurn in Falls Brook was a mixture of free aqua

ahrminum, aluminum hydr0kk complexes,
aluminum &_toride complexes and to a lesser extent
aluminum sulfate complexes (Tabie 6, Fig. 3).
By assessing various inorganic aluminum com-
plexes, it has been possible to evaluate the free @quo)
aluminum activity and compare these values to the
theoretical solubility of various mineral phases utiliz-
ing disequilibrium indices (Table 7). Several minerals
which might control aqueous aluminum concen-
trations were investigated. These included three
ahtminum trihydroxide phases, (i) micaocrystalhne
gibbsite (HEMand ROBW~N, 1967), (ii) natural gibb-
site, and (iii) synthetic gibbsite (MAY et al., 1979); two
constant composition solid suhrtions (1: 1 layered)
aluminosilicate minerals, (if haiioysite (HEM et af.,
1973) and (ii) kaolinite (Srt.r~~ and MCX~GAN, 1970);
two variable composition solid solution duminosili-
cate minerals, (i) amorphous idcal aluminos&ate and
Elewotton (meters)
(ii) reversible non-ideal ahminosilicate (PA&, 1978); downslreom direction -)
and a single phase of basic aluminum sulfate (VAN
Bw, 1973). The amounts of dissolved aluminum Fig. 3. Species of dissolved aluminum in Falls Brook dur-
ing 6 March 1979. Organically complexed aluminum has
observed in the Falls Brook system could be been measured directly; free (apuo) aluminum, aluminum
explained by any of these minerals with the possible hydroxide, fluoride and sulfate complexes have been calcu-
excention of basic atuminum sulfate (Table 71. lated using eons (t), (21,(3) and (4) (Table 3).
 Acid rain dissolved aluminum and chemical weathering 1431

Table 7

Mea" disequilibrium index (I 1

for Falls Brook streamwater
(Table 6) with respect to vagious aluminum minerals. I
values of zero indicate equilibrium; positive values foe
1 indicate oversaturation; negative values, undersatura-
t&n. Errorexpressed at the 95% confidence interval (2~)
about the mea" of 34 samoles (Table 6).

Mineral I
r

Microcrystalline gibbsite -0.69 f 0.71

Natural gibbsite -0.1, t 0.71
Synthetic gibbsite 0.55 t 0.71
Halloysite -1.08 t 0.69
Kaolinite 1.26 f 0.69
Basic aluminum sulfate 2.74 t 1.69
Anwrphous alumnosilicate (ideal) -1.24 c 0.37
Reversible alumnosilicate (non-Ideal) -0.59 t 0.41

The comparisons above show that the present evi-
dence is insufficient to isolate uniquely any single
mineral which controls the aluminum chemistry of
the Falls Brook system. The evidence suggests, how-
ever, that such a mineral does exist within the Falls
Brook system. For the present at least the natural
gibbsite phase of MAY et al. (1979) provides the best
model for explaining the aluminum chemistry of Falls
Brook streamwater.
Organic compounds
Strong correlations have been observed between
dissolved organic carbon and organic monomeric
aluminum concentrations in Falls Brook (Fig. 6).
Similar relationships have been observed in surface
waters of the Adirondack mountains (DRISCOLL,
1980). The dissolved organic carbon in Falls Brook
seems to vary from season-to-season with respect to
its ability to complex aluminum (Fig. 6). Using ultra-
filtration techniques we found that most of the orga-
nically complexed aluminum is associated with the
103-lo4 mol. wt fraction of the dissolved organic car-
bon. This finding agrees with that reported by BENES
er al. (1976) who analysed the dissolved organic car-
bon and aluminum in a small Norwegian brook.
Our data (Table 6) show further that polyphenols
comprise a relatively constant 19% (r = 0.896) of the
total dissolved organic carbon in Falls Brook stream-
water. It would seem then that organically complexed
aluminum, dissolved organic carbons and polyphe-
nols in the Falls Brook system are related to each
other in some unknown way.
Neutralization of acid rain
As previously reported (JOHNSON,1979; DRISCOLL.
1980), dissolved aluminum plays an import role in the
neutralization of acid rain over the Northeast. Dis-
solved aluminum, however, is by itself an acid, being
able to neutralize hydroxyl ion. In this section we will
examine this aspect of aluminum in streamwater.
The acidity of precipitation at Hubbard Brook
averages 120 p-equiv/l of hydrogen ions after compen-
sation for the concentrating effects of evapotranspor-
tation (LIKENS et a/., 1977). The acidity in rain is

4.5 5.0 55 6.0 6.5

PH
Fig. 4. Comparison of Falls Brook data (Table 6) with various theoretical solubility models for AI(O
Free (aquo) aluminum and hydrogen ion activities were determined on four separate days encompassing
both drought and flood conditions (see text).
1432 NOYEM. JOHNSONet al.

Reversible Non-ideal

v October 17, 1978 -

a March 17, 1978
o April 3, 1979
0 May 4, 1979

PH

Fig. 5. A comparison of the Falls Brook data (Table 6) with variable aluminosilicate solid solution
models proposed by PAEES(1978).

{Al+ 1-{ILSiO.JX
(H+)3-3X
1 where x = 1.24-0.135pH

Feldspar and granite solution lines represent best fit of data reported by BUSENBERG
and CLEMENC%
(1976)and FOUILLACet al. (1976), respectively.

almost entirely hydrogen ion acidity; aluminum and precipitation is largely converted into aluminum
other forms of acidity in precipitation are negligible acidity by the time the precipitation makes its first
(GALLOWAYet al., 1976). In the Falls Brook appearance as stream water (site I, Tables 5 and 6). In
watershed the hydrogen ion acidity of the ambient the Hubbard Brook area, MULDER(1980) has shown
that the humus layer and the B2 horizons provide
most of the aluminum to acid waters percolating
down through the soil. CRONAN et al. (1978) have
.20-
reported similar soil-dissolved aluminum relation-
ships for the alpine regions of New Hampshire.
_ .I& 0 17
In areas of New Hampshire where acid rain has
=! 0 4
had no contact with the soil, surface waters may con-
P
- .l6- tain little alumina in solution and have a pH
E approaching that of acid rain itself (UNKLES, 1980;
2
5 .l4- WIENSKIand UNKLES,1980). In Fig. 7 we show chemi-
* cal data from a stream draining the summit areas of
Mt Cube, which lies some 30 km to the SW of the
; .l2- Hubbard Brook area. Where water was in contact
0
= with only metamorphic boulders (> 800 m, Fig. 7), it
8 .lO- had a low pH and relatively low aluminum content.
% Immediately after penetrating into a thin soil
=
.g .06- (~800 m, Fig. 7), however, it approached saturation
0 with an aluminum phase comparable to that found in
H the Falls Brook watershed (lower panel, Fig. 7). After
O ..x- the initial reaction with alumina, neutralization of
0 0
a
acidity proceeded in a downstream direction in a
/ 0 fashion resembling Falls Brook (upper panel, Fig. 7).
Although limited in scope, these studies pinpoint the
I I soil zone as the main site for aluminum acquisition by
3 4 acid waters. Aluminum was not dissolved to any large
Dissolved Orqanic Carbon I mq/l) extent from surfaces of high-grade metamorphic
Fig. 6. Relation&p between organically complexed rocks.
aluminum and dissolved organic carbon in Falls Brook After the initial and rapid pH changes due to the
waters on two dates. dissolution of reactive alumina, further neutralization
 Acid rain dissolved aluminum and chemical weathering 1433

. ti+
o TOTAL
ALUMINUM

700 600 500

Elevation (meters)
dorvnstrcom -

Fig. 7. Dissolved aluminum and acidity of stream waters draining the summit area of Mt Cube, New
Hampshire, on 4 April 1980. On this date snowmeh was flowing over and through a boulder field of
metamorphic rocks (cross-hatched area) before soaking into soil and later reappearing as streamflow.
Levels of aluminum saturation are calculated on the basis of pH and a theoretical solubility product for
AI of 10m9. Aluminum hydroxide complexes were also included in the calculated saturation value.
but fluoride and organic complexes were not considered. Data from WIENSKIand UNKLES(1980).

occurs more slowly as alkali and alkaline earth aluminum mineral may control the aluminum content
cations are introduced into the system. The ultimate of pH of much of the present-day acidified surface
source of these basic cations in the Hubbard Brook waters of the Northeastern U.S. The reactive
area is the chemical weathering of silicate minerals. In aluminum trihydroxide (or aluminosilicate) phase is
the short-term, however, these cations may come from most obvious in the soils of the region (MULDER,
the ambient biologic system and organic materials of 1980; UNKLES, 1980; WIENSKI and UNKLES, 1980;
the soil. Our data show that the dissolution of cal- CRONAN et al., 1978). To a large extent,this soil
cium, sodium, magnesium, and potassium from the aluminum is acting as a powerful buffer of surface
Falls Brook watershed is slow compared to the in- water acidity over the Northeastern U.S. The ultimate
itial neutralization by aluminum dissolution. Conse- sink for both hydrogen ion and aluminum acidity,
quently, we view the overall neutralization of acid however, is the chemical weathering of primary
rain at Falls Brook as a 2-step process. As the first aluminosilicates.
step. hydrogen ion acidity of the incoming precipi-
tation is transformed into a mixture of hydrogen ion Acid-base interactions
and aluminum acidity for some time before it is In this section we will quantitatively assess the re-
finally neutralized in a second step by chemical lations between hydrogen ion acidity, aluminum
weathering products, mainly calcium and sodium. acidity and basic cations in the Falls Brook system.
Steamwaters appear to be continuously in equilib- We show in Fig. 8 how on 6 March 1979 the total
rium with a reactive aluminum mineral, so that this acids within Falls Brook were neutralized by strong
1434
160-
140-
F Basic Cat Ions
Elevation (meters)
downstream dlrectlon-
Fig. 8. Changes in the acidity and basic cation concen-
tration of Falls Brook on 6 March 1979. Total base neutra-
lizing capacity (or acidity) is considered to be comprised of
hydrogen ion and aluminum acidity. Hydrogen ion acidity
is thus the difference between total base neutralizing ca-
pacity and aluminum base neutralizing capacity. The
chemistry for the summit area (850 m) is assumed to be the
same as the incident precipitation on the Hubbard Brook
area during the week preceding 6 March 1979.
basic cations. The overall state of neutralization on
this date was obviously a function of location within
the system. The long-term data (Table 5) show that
these trends are typical for the Falls Brook system.
We show in Fig. 9 a different view of the acid-base
balance for Falls Brook on 6 March 1979. The
amount of hydrogen ion and aluminum acidity neu-
tralized was balanced against the basic cations dis-
solved at successive sites along Falls Brook. To make
the balance as complete as possible changes in anion
(Cl-, NO;, SO:-) concentration were ineluded in
this analysis. The cumulative acid-base balance of
Falls Brook (Fig. 9) shows that the stream was signifi-
cantly more acid than it should be, considering the
amount of basic cations that have been added to it. It
would seem then that the closed-system premise used
in this acid-base analysis (Fig. 9) does not really hold,
and that an additional source of acidity is available to
the Falls Brook system. A likely source for this extra
acidity in the organic acids produced by internal bio-
logical reactions, such as nit&cation (LKENSet al.,
1977). Given the low pH throughout the soil (Table 1)
and the stream (Table 5), carbonic acid 6 probably
not a significant factor in the Falls Brook system.
Although Figs 8 and 9 represent the acid-base
NOYTM. JOHNSONet al.
try for just a single day, similar trends were observed
?
throughout the study period (Tables 5 and 6).
Acid-base reaction rates
Our data show that hydrogen ion/aluminum
acidity and basic cation concentrations in the Falls
Brook watershed vary as a function of position within
the watershed (Tables 5 and 6, Figs 8 and 9). As dis-
cussed earlier, the residence time or pathlength of the
water moving through the watershed is also a func-
tion of position. We can therefore assess the kinetics
of the acid-base reactions by relating water chemistry
to water residence time.
When stream position is transposed into drainage
area, the acid-base curves shown in Fig. 8 are seen to
be hyperbolic in form (Fig. 10). That is, the plot of
chemical concentration versus reciprocal drainage
area is essentially linear (Fig. 10). As oriented in Fig.
10, the slope of a regression line has units of Ap-
equiv/Acm (i.e. Ap-equiv cm-3/Acm- ) which rep-
resents the chemical change taking place during a unit
!l pathlength of water passage through the system. The
intercept of a regression line represents the chemica!
state of very long pathlength water within the system.
Both Figs 8 and 10 clearly show that the most exten-
sive chemical changes taking place occur in the head-
waters, i.e. the low-order stream segments of the
&ions
acid cations(H:Al)
+O : 1
80 700 cjoo 500 400
E&v&on h-hers)
downstream directton ----
Fig. 9. An acidity balance for the Falls Brook system on 6
March 1979. The neutralization of acidity (hydrogen ion
and aluminum) is balanced against the release of basic
cations at successive sites in the Falls Brook watershed.
The cumulative curve indicates that more basic cations are
released than can be accounted for by the neutralization of
chemis- aluminum and hydrogen ion acidity.
 Acid rain dissolved aluminum and chemical weathering
6 MARCH 1979
. Bases
o Acids
t
3-YEAR AVERAGES
. Bases
I 1
2 3
~e~i~~~~~ Drainage Area (ha)-'
Fig. 10. Distribution of total strong bases (Ca, Na,
K, Mg) and total acidity (Hf, A&-t)) within the Falls
Brook drainage area on 6 March 1979 (upper panel); dis-
tribution of strong bases (Ca*, Na+, K+, Mg+) over the
long-term (Table 5) is similarly represented in lower panel.
The correspondence in slopes between the long-term data
(bases, lower panel) and that for a single day (bases, upper
panel) indicates that this parameter is a chemical charac-
teristic of the watershed as a whole. Over the long-term
(Table 5) silica and basic cations show a common, hyper-
bolic distribution with respect to drainage area (lower
panel) which suggests that they are derived from a com-
mon source, i.e. the weathering of silicate minerals within
the watershed itself.
For watersheds in the northeastern U.S. drainage
area is proportional to mean annual discharge (LEO-
POLD et al., 1964, p. 251), so that discharge values
could be used in the abscissa of Fig. 10 instead of
drainage area. If discharge values are used, the slope
of a regression line then has units of A@equiv/A time
(i.e. Ap-equiv cme3/Atime cnY3) which represents the
amount of chemical change taking place per unit of
water residence time.
In either case, however, the acid-base reactions tak-
ing place within the Falls Brook watershed are evi-
dently systematic and reproducible from year-to-year.
The fact that the regression line for the basic cations
on a long-term basis (Fig. 10, lower panel) is virtually
the same as that for a single day (Fig. 10, upper panel)
argues for the generality of the chemical reactions
involved, which in this case describes the amount of
chemical weathering within the system.
Rate of chemical weathering
In the lower panel of Fig. 10 we show that both
basic cations and silica are a~umulated in Falls
Brook streamwater as a function of water pathlength
1435
(or residence time), conforming essentially to a hyper-
bolic pattern. Both constituents are byproducts of
chemical weathering and their synchronized appear-
ance in Falls Brook streamwater testifies to the exist-
ence and extent of chemical weathering activity within
the system.
The rate of chemical weathering over a given area
may be assessed by the rate at which alkali and alka-
line earth ions are extracted from the area, i.e. the
ionic denudation rate. In this discussion we will cali-
brate ionic denudation in terms of the base cation
equivalents which leave a unit area of watershed dur-
ing a year (m-equiv/m2-yr). The regression analysis
portrayed in Fig. IO (lower panel) suggests that the
concentration of basic cations in Falls Brook water
approaches 130 p-equiv/l for water of long pathlength
(when corrected for the flux of basic cations from the
atmosphere). In the Hubbard Brook area runoff aver-
ages 80 cm, or 800 l/m2 of watershed. The product of
mean runoff and mean basic-cation concentration
yields a value of 100 m-equivjm for annual cationic
denudation rate. This compares favorably with the
120 m-equiv/m value derived from cationic budgets
observed over an 1I-yr period (LIKENSef N/., 1977).
However, in addition to the basic cations which are
lost each year in streamflow (10@120m-equivm).
basic cations are also being stored within the
Hubbard Brook ecosystem by accreting biomass
(LIKENSet al., 1977: BORMANNand LIKENS.1979). A
more accurate index of ambient ionic denudation for
the Hubbard Brook area would include this amount
(80 m-equiv/m2) and the ionic denudation value thus
becomes 18~2~m-equiv/m~. This value is close to
the regional average for the Northeast
(22Om-equiv/mz) or the average for the North
American continent (380 m-equiv;m). On a compara-
tive basis at least, the Hubbard Brook area would
appear to be quite average or even below average in
its ionic denudation and implicitly in its chemical
weathering rate. This relatively normal ionic denuda-
tion is occurring despite the well-known flux of acid
rain over the Hubbard Brook area. Whether or not
the acid rain phenomenon has increased or decreased
chemical weathering rate in the Hubbard Brook area
is not really known. We do not have adequate histori-
cal information to compare with our present-day in-
formation.
We have shown previously (Fig. 10) that the rate at
which total acidity is neutralized in the Falls Brook
system closely follows the rate at which silicate miner-
als are weathered. Furthermore, the place where these
reactions occur is mostly in first and second-order
drainages (Table 5, Fig. 10). Evidently, the kinetics of
contemporary chemical weathering in the Falls Brook
system are such that most of the reaction has
occurred in the time it takes for average rainfall (or
snowmelt) to reach a third-order stream channel. As
noted previously (JOHNSON,1979), it is stream order,
not stream eievation, which correlates with the state
of streamwater chemistry in the Hubbard Brook areas
1436 NOYEM. JOHNSONet al.
as a whole. Stream order is closely related to water
pathlength (or residence time) within the watershed.
Stream order is thus a useful parameter in the charac-
terization of stream water chemistry in a hydrolygic
system such as Hubbard Brook.
SUMMARY AND CONCLUSIONS
Evidence from the Falls Brook watershed system
suggests that the neutralization of acid rain is ac-
complished by a 2-step chemical reaction. Initially,
strong acids in precipitation are rapidly but incomple-
tely neutralized by the dissolution of a reactive
aluminum phase in the soil zone. The resulting sol-
ution is one depleted in hydrogen ion but enriched in
aluminum. Total acidity, including both hydrogen ion
and aluminum acidity, is then slowly neutralized by
basic cations which are released by the decomposition
of silicate minerals. The rate at which acid rain (and
secondary aluminum acidity) is neutralized is ultima-
tely set by the rate at which silicate minerals are de-
composed under ambient conditions. At the present
time most of the neutralization and weathering
tions are accomplished within first and second
drainage basins.
The results described above for Falls Brook are not
unique to the Hubbard Brook area of New Hamp-
shire. Data from the Adirondack region of New York
(DRISCOLL, 1980) parallel that from Falls Brook. It
appears then that over much of the forested, hardrock
landscape of the Northeastern U.S., the processes of
acid rain neutralization follow that at Falls Brook.
Reactive alumina from the soils of the Northeastern
U.S. is acting as a buffer for the acidity of present day
surface waters in the region. Surface waters with a
high aluminum content tend to be located in low
order drainage basins, where the residence time of
water is relatively short. Where acid rainwater
had no contact with alumina or calcite, the pH of
surface water may approach that of incoming
rain.
Acknowledgements-We are indebted to R. REYNOLD$W.
GRAUSTEIN,E. CLEAVES,A. FEDERER,J. KRAMERand F. H.
BORMANNfor many of the conceptual constructs in this
work. The direct support of D. Buso, V. LEVASSEUR,R.
MOORE,W. BERRYMAN, A. JOHNSON,H. HOOPERand es-
pecially W. MARTIN, was indispensable to the successful
completion of this study, a fact which we gratefully ac-
knowledge.
This is a contribution to the Hubbard Brook Ecosystem
Study. Financial support was provided by the National
Science Foundation. The Hubbard Brook Experimental
Forest is operated by the USDA Forest Service, Broomall,
Pennsylvania.
REFERENCES
BENESP., GJE~SINGE. T. and STEINNERE. (1976) Interac-
tions between humus and trace etements in fresh water.
Water Res. 10, 711-716.
BORMANNF. H. and LIKENSG. E. (1979) Pattern and Pro-
cess in a Forested Ecosystem 253 pp. Springer.
BUSENBERG E. and CLEMENCY C. V. (1976) The dissolution
kinetics of feldspars at 25C and 1atm COZ partial
pressure. Geochim. Cosmochim. Acta 40, 41-49.
CRONANC. S., RE~NERS W. A., REYNOLDS R. C. and LANG
G. E. (1978)
, I
Forest floor leaching: contributions from
mineral, organic and carbonic acids in New Hampshire
subalpine forests. Science 200, 309-311.
DAVISM. B. and FORD M. S. (1981) Sediment focusing m
Mirror Lake, New Hampshire. Limnol. Oceunoyr. (in
press).
DRISCOLLC. T. (1980) Chemical characterization of some
dilute acidified lakes and streams in the Adirondack
Region of New York State. Ph.D. Thesis, Cornell Univ.
FOUILLACC., MICHARDG. and SARAZING. (1976) Acqui-
sition of solute by river Truyere waters. Proc. lnf. Symp.
on Water-Rock Interaction, Czechoslovakia. 1974 (eds J.
Cadek and T. PaEes), pp. 64-69.
GALLOWAYJ. N., LIKENSG. E. and EDGERTONE. S. (1976)
Acid precipitation in the northeastern United States: pH
and acidity. Science 194, 722-724.
GARREL~R. M. and MACKENZIEF. T. (1971) Evolution qf
Sedimentary Rocks 397 pp. Norton.
GJESSING E. T., HENRIKSENA., JOHANNESSEN M. and
WRIGHT R. F. (1976) Effects of acid precipitation on
freshwater chemistry. Impact of Acid Precipitation on
Forest and Freshwater Ecosystems in Norway (ed. F. H.
Braekke). SNSF-project, Oslo.
reac- HALL F. R. (1970) Dissolved solute-discharge relationships:
order mixing models, Water Resour. Res. 6, W-850.
HART G. E., LEONARDR. E. and PIERCER. S. (1962) Leaf
fall, humus depth and soil frost in a northern hardwood
forest. Res. Note 131, 3 pp. Forest Service, USDA.
HEM J. D. (1968) Aluminum species in water, in trace in-
organics in water. Advances in Chemistry 73, 98-l 14.
HEMJ. D. and ROWUSON C. E. (1967) Form and stability
of aluminium hydroxide complexes in dilute solution.
U.S. Geol. Surv. Water Supply Pap. 1827-A.
HEMJ. D., ROBERTSON C. E., LMD C. J. and POLZERW. L.
(1973) Chemical interactions of aluminum with aqueous
silica at 25C U.S. Geol. Suru. Water Suppl. Pap. 1827-E
57 PP.
HOYLEM. C. (1973) Nature and properties of some forest
soils in the White Mounttains of New Hampshire. Rex
Pap. NE-260, 18 pp.
JOHNSONN. M. (1979) Acid rain: neutralization within the
has Hubbard Brook ecosystem and regional implications.
Science 204, 497-499.
JOHNZ%IN N. M., LIKENSG., BORMANNF. H., FISHERD. W.
acid
and PIERCER. S. (1969) A working model for the vari-
ation in stream water chemistry at the Hubbard Brook
Exnerimental Forest, New Hamushire. Water Resour.
Re;. 5, 1353-1363.
KLOSTERM. 8. (1974) Determination of tannin and lignin.
J. Am. Water Works Assoc. 64, 44-46.
KRAMERJ. R. (1980) Aluminum chemistry in acid surface
waters. Program, 10th conf. Int. Assoc. Water Pollut.
Res., 19-20 June 1980, McMaster Univ., Hamilton.
LANGBEINW. B. and DAWDY D. R. (1964) Occurrence of
dissolved solids in surface waters in the United States,
U.S. Geol. Surv. ProJ Pap. 501-D, pp. 115-117.
LEOPOLDL. B., WOLMANM. G. and MILLERJ. P. (f964)
Fluviaf Processes in Geomorphobgy. Freeman.
LIKENSG. E., BORMANNF. H., JOHNSONN. M. and PIERCE
R. S. (1967) The calcium, magnesium, potassium and
sodium budgets for a small forested ecosystem. Ecology
_.
48, 772-785.
LIKENSG. E., B~RMANNF. H. and JOHN~N N. M. (1972)
Acid rain. Environment 14, 33-40.
LIKENSG. E., BORMANNF. H., PIEEKE R. S., EATON J. S.
and JOHNSONN. M. (1977) Biogeochemistry of a Forested
Ecosystem. Springer.
LIKENSG. E., WRIGHTR. F., GALLOWAYJ. N. and BUTLER
T. J. (1979) Acid rain. Sci. Am. 241, 43-50.
 Acid rain dissolved aluminum and chemicai weathering 1437

MAY H. M., HELMKE and JACKSONM. L. (1979a) Determi- aluminum hydroxide complexes in dilute aqueous sol-
nation of mononuclear dissolved aluminum in near-neu- utions, CS GPO/. Surr. Watrr Supply Pup. 1827-D.
tral waters. Chem. Geol. 24, 259-269. STAINTONM. P. (1973) A syringe gas-stripping procedure
MAY H. M., HELMKEP. A. and JACKSONM. L. (1979b) for gas-chromatographic determination of dissolved in-
Gibbsite solubility and thermodynamic properties of organic and organic carbon in freshwater and carbonate
hydroxy-aluminum ions in aqueous solution at 25 C. in sediments. J. Fish. Ret BOCW~ CIm 30, 1441
~e~~,~i~~. C~s~~oc~jrn. .4cfa 43, 861-868. 1445.
MEKZEL D. W. and VACCARCI R. F. (1964) The measure-
ment of dissolved organic and particulate carbon in sea-
water. Limnol. Oceanogr. 9, 138142. TURNER R. C. (1968) Three forms of alummum m aqueous
MULDER J. (1980) Aluminum chemistry of soil and soil systems determined by 8-quinolrnolete extraction
seeps in the Hubbard Brook ecosystem, unpublished methods, Gun. J. Chrm. 41, 2521-2527.
report, held by Department of Ecology and Systematics. L'NKLES T. E. (1980) Acid rain neutralization in the Beaver
Cornell Univ. Brook Watershed. Mt. Mousilauke. New Hampshire.
OKURA T.. GUTO K. and YOTSUYANAGIT. (1962) Forms of unpublished report. held by Earth Sciences Department.
aluminum determination by an S-quinolinolete extrac- Dartmouth College.
tion method. nnul. Clzent. 34, 581-582. VAN BKEEMANN. (1973) Dissolved uluminum tn acid sulfate
Orion. Instruction Munttul (1976) Fluoride Electrodes. soulsand m acrd mane waters. Soil .SI,; S~K -1~1.Proi, 37.
Orion Research. Inc.. Cambridge, 694-697.
PA?ES T. (1978) Reversible control of aqueous aluminum WHIPKEY R. Z. (1965) Subsurface stormflow from forested
and silica during the irreversible evolution of natural slopes. Bulf. lnr. Assoc. Sci. Hi&-o/. IO, 74 X5.
waters. G~o~~irn, C~~.~~~(~c~;~~. Acfu 42, 1487~1393. WHIITTA~ER R. f-l.. LIKENS G. E.. BORMANN F. H.. E,%To>
RAINWATER F. H. and THATCHER L. L. (1960) Methods of J. S. and SICCA?I~AT. G. 119791 The Hubbard Brook.
collection and analysis of water samples. U.S. Groi. Suw. Ecosystem Study: forest nutrient cycling and clement
Water Suppl}~ Pup. 1454. behavtor. Ecoloyy 60, 203 220.
SMITH R. W. (1971) Relatrons among equilibrium and non- WIENSKI E. and UNKLES T. E. (I9801 The nrutralizatton of
equilibrium aqueous species of aluminum hydroxide acid rain in a stream segment of Mt. Cube. New Hamp-
complexes. Adr. Chem. Ser. 106, 2X&279. shire. unpublished report. held by Earth Sciences
SMITH R. W. and HEM J. D. (1972) Effect of aging on Department. Dartmouth College.