Dissolved organic carbon (DOC) leached from the forest floor is an imp
ortant source of acidity In forest soils. The study of DOC and its aci
dic properties has been particularly difficult because of uncertaintie
s about the use of isolated fractions of DOG. To evaluate the acidic p
roperties of soluble organic substances in time forest floor we collec
ted and examined leachates from a spruce-fir Spodosol in east-central
Maine. Filtered, lyophilized, bulk leachates and DOC fractions were an
alyzed by potentiometric titration in constant ionic media (0.01 M KCl
) to determine the charge density, exchange acidity, and apparent acid
ity constants (pK(a)) of each organic material. Based on the titration
data, hydrophilic acids had the greatest content of acidic functional
groups (e.g., carboxylic acid groups). Bulk leachates, hydrophobic ac
ids, and hydrophilic acids had mean (+/- SE) exchange acidities of 0.1
31 +/- 0.002, 0.127 +/- 0.002, and 0.198 +/- 0.003 mu eq mu mol(-1) C,
respectively, and pK(a)s of 3.71 +/- 0.05, 4.10 +/- 0.03, and 3.70 +/
- 0.03. From the titration of bulk leachates, we calculated organic an
ions contributions of 267 to 858 mu eq L(-1). An organic charge contri
bution model was also used to evaluate the titration data, along with
DOC fractionation percentages and total DOC in the forest floor leacha
tes. The acidic properties calculated from this model and those of the
bulk leachate samples agreed closely (r(2) = 0.93), suggesting that a
cidic properties of DOC were not altered by isolation procedures. Fore
st floor organic anion contribution to zero-tension lysimeter solution
s was also estimated by three methods (a charge contribution model, an
ion deficit calculations, and chemical equilibrium model simulations)
that yielded similar results. For the best estimation of organic anion
s in soil solutions, empirically derived constants from large samples
of bulk leachates (isolation not needed) and use of a chemical equilib
rium model are recommended.