Characterization of legacy organic carbon in a culturally eutrophic lake : the role of the historic carbon deposition in the time course and extent of lake recovery

The time course of lake recovery after a reduction in external loading of nutrients is often controlled by conditions in the sediment. Remediation of eutrophication is hindered by the presence of legacy organic carbon deposits, that exert a demand on the terminal electron acceptors of the lake and contribute to problems such as internal nutrient recycling, absence of sediment macrofauna, and flux of toxic metal species into the water column. Being able to quantify the timing of a lake’s response requires determination of the magnitude and lability, i.e., the susceptibility to biodegradation, of the organic carbon within the legacy deposit. This characterization is problematic for organic carbon in sediments because of the presence of different fractions of carbon, which vary from highly labile to refractory. The lability of carbon under varied conditions was tested with a bioassay approach. It was found that the majority of the organic material found in the sediments is conditionally-labile, where mineralization potential is dependent on prevailing conditions. High labilities were noted under oxygenated conditions and a favorable temperature of 30 °C. Lability decreased when oxygen was removed, and was further reduced when the temperature was dropped to the hypolimnetic average of 8° C . These results indicate that reversible preservation mechanisms exist in the sediment, and are able to protect otherwise labile material from being mineralized under in situ conditions. The concept of an active sediment layer, a region in the sediments in which diagenetic reactions occur (with nothing occurring below it), was examined through three lines of evidence. Initially, porewater profiles of oxygen, nitrate, sulfate/total sulfide, ETSA (Electron Transport System Activity- the activity of oxygen, nitrate, iron/manganese, and sulfate), and methane were considered. It was found through examination of the porewater profiles that the edge of diagenesis occurred around 15-20 cm. Secondly, historical and contemporary TOC profiles were compared to find the point at which the profiles were coincident, indicating the depth at which no change has occurred over the (13 year) interval between core collections. This analysis suggested that no diagenesis has occurred in Onondaga Lake sediment below a depth of 15 cm. Finally, the time to 99% mineralization, the t99, was viewed by using a literature estimate of the kinetic rate constant for diagenesis. A t99 of 34 years, or approximately 30 cm of sediment depth, resulted for the slowly decaying carbon fraction. Based on these three lines of evidence , an active sediment layer of 15-20 cm is proposed for Onondaga Lake, corresponding to a time since deposition of 15-20 years. While a large legacy deposit of conditionally-labile organic material remains in the sediments of Onondaga Lake, it becomes clear that preservation, mechanisms that act to shield labile organic carbon from being degraded, protects this material from being mineralized and exerting a demand on the terminal electron acceptors of the lake. This has major implications for management of the lake, as it defines the time course of lake recovery following a reduction in nutrient loading.

Characterizing the effects of turbulence on sediment oxygen and sediment nitrate demand using flow-through reactors

Onondaga Lake has received the municipal effluent and industrial waste from the city of Syracuse for more than a century. Historically, 75 metric tons of mercury were discharged to the lake by chlor-alkali facilities. These legacy deposits of mercury now exist primarily in the lake sediments. Under anoxic conditions, methylmercury is produced in the sediments and can be released to the overlying water. Natural sedimentation processes are continuously burying the mercury deeper into the sediments. Eventually, the mercury will be buried to a depth where it no longer has an impact on the overlying water. In the interim, electron acceptor amendment systems can be installed to retard these chemical releases while the lake naturally recovers. Electron acceptor amendment systems are designed to meet the sediment oxygen demand in the sediment and maintain manageable hypolimnion oxygen concentrations. Historically, designs of these systems have been under designed resulting in failure. This stems from a mischaracterization of the sediment oxygen demand. Turbulence at the sediment water interface has been shown to impact sediment oxygen demand. The turbulence introduced by the electron amendment system can thus increase the sediment oxygen demand, resulting in system failure if turbulence is not factored into the design. Sediment cores were gathered and operated to steady state under several well characterized turbulence conditions. The relationship between sediment oxygen/nitrate demand and turbulence was then quantified and plotted. A maximum demand was exhibited at or above a fluid velocity of 2.0 mm•s-1. Below this velocity, demand decreased rapidly with fluid velocity as zero velocity was approached. Similar relationships were displayed by both oxygen and nitrate cores.