RESUMO
Sediments are ubiquitous in karst systems and play a critical role in the fate and transport of contaminants. Sorbed contaminants may be stored on immobile sediments or rapidly dispersed on mobile sediments. Sediments may also influence remediation by either enhancing or interfering with the process. To better understand the potential effects of sediments on remediation, we conducted physical and chemical characterizations of 11 sediment samples from 7 cave and spring deposits from karst regions of Tennessee, Virginia, and West Virginia. The samples were analyzed for particle-size distribution using sieves and laser diffraction particle analysis. The sediment size fraction <2 mm (sand, silt, and clay) was analyzed for slurry pH and specific conductivity (SC) using electrodes and for bulk total carbon, organic carbon, nitrogen and sulfur on an ElementarTM Vario MAX Cube CNS. The same <2 mm fraction was subjected to a pseudo-total extraction using aqua regia with subsequent solution analysis by inductively coupled plasma-optical emission spectrometry (ICP-OES). Most of the samples were dominated by the <2 mm size fraction. Their slurry pHs ranged from 6.8 to 8.4 and their SCs ranged from 45 to 206 µS/cm with the exception of two high SC samples (726 and 8500 µS/cm). The fraction of organic carbon (Foc) in the sediments ranged from <0.1 to 2%. The sample from a saltpeter cave historically used for gunpowder production contained the highest concentrations of N and S (~3 g/kg) but lower total C than some of the spring samples. The pseudo-total extractions were analyzed for Al, Ca, Fe, Mg, and Mn. Of those elements, Mg was the most consistent across the locations (2.0-6.1 g/kg), and Ca was the most variable (1.4-52 g/kg). Given the importance of particle size and elemental concentrations in chemical reactions and remediation, more data of this type are needed to predict contaminant fate and transport and to plan successful remediation projects.
RESUMO
Due to the complicated nature of karst aquifers, many groundwater treatment technologies are difficult to implement successfully. A particular challenge arises because sediments are ubiquitous and mobile in karst systems and may either facilitate contaminant transport or act as long-term substrates for storage via sorption. However, electrochemical remediation is a promising technology to be optimized for karst aquifers due to easy manipulation and control of groundwater chemistry as well as low cost, ability for in situ application, and performance under alternative power sources. This study investigates the effects of suspended karst sediments on the electrochemical remediation of groundwater via electro-Fenton (EF) mechanism. The EF mechanism relies on direct electrolysis (i.e., water electrolysis and ferrous iron release) and indirect, electrochemically-induced processes (i.e., Pd catalyzed H2O2 production). These processes can be optimized for H2O2 generation and support of its activation to hydroxyl radicals - a powerful oxidant capable of degrading and transforming a wide range of contaminants (e.g., chlorinated solvents). In this study, we tested sediments varying in concentrations of Fe, Mn and buffering capacities. When the sediments were introduced into the EF experiments, there were adverse effects on the H2O2 content: at steady state (120 min), Pd catalyzed formation of H2O2 decreased by 60%, 57%, and 75% in the presence of suspended sediment collected from three separate karst locations. Presented results imply that sediments' presence influences EF mechanism in electrochemical systems, but given the flexibility of the technology, it can be optimized in terms of electrode materials, current intensities and current regimes to address these challenges.