Abiotic Degradation Rates for Carbon Tetrachloride: and Chloroform: Progress in FY 2008

Amonette, James E. ; Jeffers, Peter M. ; Qafoku, Odeta ; Russell, Colleen K. ; Wietsma, Thomas W. ; Truex, Michael J.

关键词: AR FACILITIES;    CARBON TETRACHLORIDE;    CHLOROFORM;    HYDROLYSIS;    GROUND WATER;    TEMPERATURE DEPENDENCE;    MINERALS;    CATALYTIC EFFECTS;    CHEMICAL REACTION KINETICS;    HANFORD RESERVATION;    BIODEGRADATION carbon tetrachloride;    hydrolysis;    kinetics;    abiotic degradation;    rates;    heterogeneous;    sediment;    Environmental Molecular Sciences Laboratory;   

DOI  :  10.2172/1006330
RP-ID  :  PNNL-18020
PID  :  OSTI ID: 1006330
Others  :  Other: 25679a
Others  :  16898
Others  :  830403000
Others  :  TRN: US1101244

美国|英语

来源: SciTech Connect

【 摘 要 】

This is a letter report summarizing work performed in FY2008 to determine the rates of carbon tetrachloride hydrolysis at temperatures close to actual groundwater temperatures. The report describes the project, the methodology, and the results obtained since the project's inception in FY2006. Measurements of hydrolysis rates in homogeneous solution have been completed for temperaturs of 70 C through 40 C, with additional data available at 30 C and 20 C. These results show no difference between the rates in deionized H2O and in filter-sterilized Hanford-Site groundwater. Moreover, the rates measured are 2-3 times slower than predicted from the open literature. Measurements of rates involving sterile suspensions of Hanford-Site sediment in Hanford-Site groundwater, however, show faster hydrolysis at temperatures below 40 C. Extrapolation of the current data available suggests a six-fold increase in rate would be expected at groundwater temperature of 16 C due to the presence of the sediment. This result translates into a 78-year half-life, rather than the 470-680 year half-life that would be predicted from rate determinations in homogeneous solution. The hydrolysis rate data at 20 C, in contrast to those at higher temperatures, are preliminary and have low statistical power. While significant (p < 0.05) differences between the heterogeneous and homogeneous systems are seen at 30 C, the results at 20 C are not statistically significant at this level due to limited data and the very slow nature of the reaction. More time is needed to collect data at these low temperatures to improve the statistical power of our observation. Given the critical need for hydrolysis rate data at temperatures relevant to groundwater systems, we have three recommendations for future work. First, we recommend a continuation of the sampling and analysis of the remaining long-term sealed-ampule experiments described in this report. These are primarily 20 C and 30 C experiments. The data at 20°C, which are most germane to the groundwater environment, will likely take two more years before they are complete. Second, due to the importance of heterogeneous effects, we recommend the continuation of sampling and analysis for a similar set of experiments looking at hydrolysis rates of CT and CF in contact with individual minerals (montmorillonite, kaolinite, albite, and muscovite) or Hanford-Site sediment, and, for CF, in homogeneous solutions. These experiments were set up under a separate project funded by a congressional earmark (EM-22) for which funding expired at the end of FY08. Third, we strongly recommend development of a 13C/12C isotope ratio mass spectrometry (IRMS) approach for determination of hydrolysis rates at groundwater temperatures and relevant CT and CF concentrations. The technique is sensitive enough that we expect to be able to shorten the time required for a rate-constant determination by 20-fold. Thus, a 5-year experiment conducted by the sealed-ampule approach could be shortened to 3 months by the IRMS approach. This sensitivity also would allow the IRMS technique to be used to follow hydrolysis rates at concentrations found in groundwater plumes at Hanford.