Chemical Processes Observed

As a result of dissolution of the limestone by the partly neutralized acid wastes, calcium concentrations more than doubled in the near-deep monitoring well 10 months after injection started in 1963.67 In early 1966, however, they dropped to background levels (about 200 mg/L), possibly in response to biochemical decomposition of the waste. In September 1968, after about 300 million gallons of the acidic, unneutralized waste had been injected, the calcium concentration began to increase again. An abrupt increase in calcium to 2700 mg/L accompanied by a decrease in pH to 4.75 in January 1969 led to the decision to plug the near-deep monitoring well.

In an attempt to find out how fast the waste was reacting with limestone, a 3-h backflushing experiment, in which waste was allowed to flow back out of the injection well, yielded some unexpected results. The increase in pH of the neutralized waste could not be fully accounted for by the solution of limestone as determined from the calcium content of the backflushed liquid; the additional neutralization apparently resulted from reactions between nitric acid and alcohols and ketones in the original waste induced by increased pressure in the injection zone compared to surface conditions.41

The lack of nitrates (which were present at levels of 545 to 1140 mg/L in the waste) in the near-deep monitoring well, combined with the presence of nitrogen gas, indicated that degradation by denitrifying bacteria had taken place.67 Backflushing shortly before injecting unneutralized wastes confirmed denitrification. Nitrate concentrations decreased rapidly as the backflushed waste was replaced by formation water. Similar backflushing experiments conducted after unneutralized wastes were injected, however, provided no evidence of denitrification, indicating that microbial activity was suppressed in the portion of the zone containing unneutralized wastes.

Elkan and Horvath170 performed a microbiological analysis of samples taken from the north and south deep monitoring wells in December 1974, about 6 months after the dilute waste front had reached the south well. Both denitrifying and methanogenic bacteria were observed. The lower numbers and species diversity of organisms observed in the south monitoring well compared with those in the north well indicated suppression of microbial activity by the dilute wastes.

Between September 1973 and March 1977 bicarbonate concentrations increased from 282 mg/L to 636 mg/L and dissolved organic carbon increased from 9 mg/L to 47 mg/L. These increases were accompanied by an increase in the dissolved-gas concentration and a distinctive odor like that of the injected wastes. The pH, however, remained unchanged. During the same period, dissolved methane increased from 24 mg/L to 70 mg/L, indicating increased activity by methanogenic bacteria. The observation of denitrification in the near-deep monitoring well and methanogenesis in the more distant south monitoring well fit the redox-zone biodegradation model.

Significant observations made at this site are:

1. Organic contaminants (as measured by dissolved organic carbon) continue to move through the aquifer even when acidity has been neutralized.

2. Even neutralized wastes can suppress microbial populations.

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