Natural attenuation of volatile organic compounds (VOCs) in the leachate plume of a municipal landfill: using alkylbenzenes as process probes.

More than 70 individual VOCs were identified in the leachate plume of a closed municipal landfill. Concentrations were low when compared with data published for other landfills, and total VOCs accounted for less than 0.1% of the total dissolved organic carbon. The VOC concentrations in the core of the anoxic leachate plume are variable, but in all cases they were found to be near or below detection limits within 200 m of the landfill. In contrast to the VOCs, the distributions of chloride ion, a conservative tracer, and nonvolatile dissolved organic carbon, indicate little dilution over the same distance. Thus, natural attenuation processes are effectively limiting migration of the VOC plume. The distribution of C2-3-benzenes, paired on the basis of their octanol-water partition coefficients and Henry's law constants, were systematically evaluated to assess the relative importance of volatilization, sorption, and biodegradation as attenuation mechanisms. Based on our data, biodegradation appears to be the process primarily responsible for the observed attenuation of VOCs at this site. We believe that the alkylbenzenes are powerful process probes that can and should be exploited in studies of natural attenuation in contaminated ground water systems.

Anthropogenic organic contaminants in the effluent of a combined sewer overflow: impact on Boston Harbor.

Effluent from a large combined sewer overflow (CSO) in Boston and receiving waters near the CSO outfall were sampled during dry and wet weather conditions. Surficial sediments were also collected from the vicinity of the CSO and at nearby sites. The samples were analyzed for a variety of organic constituents including organic carbon and nitrogen, linear alkylbenzenes (LABs), coprostanol and polychlorinated biphenyls (PCBs). As judged by the presence of waste-specific markers (LABs, coprostanol), the CSO effluent contains sewage under both dry and wet weather conditions. When rainfall occurs, the concentration of suspended solids and all organic constituents in the particulate phase increase, ultimately approaching those characteristic of untreated sewage. The concentrations of LABs and PCBs in the effluent are strongly correlated, indicating that PCBs in the CSO are derived from sewage inputs. During heavy rainfall, the vast majority (> 90%) of the hydrophobic organic substances are associated with suspended particulate matter, whereas during dry weather, a significant fraction resides in the operationally defined 'dissolved' phase. Estimates of the mass emission rates of CSO constituents show that > 70% of the suspended particles and > 90% of the particulate organic carbon, hydrocarbons and trace organics are discharged during wet weather. Particles in the receiving water appear to be strongly influenced by the CSO effluent during wet weather. Concentrations of PCBs in surficial sediments near the CSO are correlated with those of coprostanol and the LABs, indicating that these compounds are derived from similar sources. Based on the observed correlations, approximately 60-80% of the sedimentary PCBs originate from sewage. Comparison of sigma LAB/coprostanol ratios of effluent particles, surficial sediments and sewage sludges suggest that the vast majority of the marker compounds and the PCBs in sediments are not from the CSO, but are derived from one of two sewage treatment plants that discharged sludge into the harbor until 1991. The sludge-derived contaminants were probably carried by tidal currents into Dorchester Bay and deposited in shallow, quiescent embayments where sedimentation is favored. These results illustrate the potential importance of long-range transport of waste-derived contaminants in urban harbors and their rapid accumulation in localized depocenters.

Progression of natural attenuation processes at a crude-oil spill site: I. Geochemical evolution of the plume.

A 16-year study of a hydrocarbon plume shows that the extent of contaminant migration and compound-specific behavior have changed as redox reactions, most notably iron reduction, have progressed over time. Concentration changes at a small scale, determined from analysis of pore-water samples drained from aquifer cores, are compared with concentration changes at the plume scale, determined from analysis of water samples from an observation well network. The small-scale data show clearly that the hydrocarbon plume is growing slowly as sediment iron oxides are depleted. Contaminants, such as ortho-xylene that appeared not to be moving downgradient from the oil on the basis of observation well data, are migrating in thin layers as the aquifer evolves to methanogenic conditions. However, the plume-scale observation well data show that the downgradient extent of the Fe2+ and BTEX plume did not change between 1992 and 1995. Instead, depletion of the unstable Fe (III) oxides near the subsurface crude-oil source has caused the maximum dissolved iron concentration zone within the plume to spread at a rate of approximately 3 m/year. The zone of maximum concentrations of benzene, toluene, ethylbenzene and xylene (BTEX) has also spread within the anoxic plume. In monitoring the remediation of hydrocarbon-contaminated ground water by natural attenuation, subtle concentration changes in observation well data from the anoxic zone may be diagnostic of depletion of the intrinsic electron-accepting capacity of the aquifer. Recognition of these subtle patterns may allow early prediction of growth of the hydrocarbon plume.

Long-chain alkylbenzenes: their analytical chemistry, environmental occurrence and fate.

Since ca. 1950 long-chain alkylbenzenes have been produced industrially for the synthesis of alkylbenzenesulfonates, the anionic surfactants most commonly used in commercial detergents. Prior to 1965 the alkylbenzenes were generated by Frieldel-Crafts alkylation of benzene with tetrapropylene. This reaction produces a complex assemblage of phenylalkanes (TABs) having highly branched side chains. Due to their stability, the TABs proved to be environmentally troublesome and were ultimately replaced (during the mid-1960s) by the linear alkylbenzenes (LABs). The LABs consist of a mixture of secondary phenylalkanes with linear alkyl side chains ranging in length from C10 to C14. Because of their unique structures and composition, these compounds are easily identified and measured in complex environmental samples. The linear alkylbenzenes are also found in municipal wastewaters where their presence is thought to result from the use of domestic and industrial detergents. Because they are synthetic and unlikely to occur in other significant inputs to coastal marine waters, long-chain alkylbenzenes have obvious potential as waste-specific molecular tracers. The presence of long-chain alkylbenzenes in sediment trap particulates and marine sediments collected near a major waste outfall system in southern California indicates that these hydrocarbons can survive exposure to an oxygenated water column during sedimentation. Whereas changes in the isomer composition of the LABs with depth in the sediments are suggestive of microbial alteration, the vertical distribution of the TABs and LABs can be used as a geochronological tool to reconstruct waste depositional histories.