Passive-Sampler-Based Bioavailability Assessment of PCB Congeners Associated with Aroclor-Containing Paint Chips in the Presence of Sediment.

This is the first investigation of the bioavailability of PCBs associated with paint chips (PC) dispersed in sediment. Bioavailability of PCB-containing PC in sediment was measured using ex situ polyethylene passive samplers (PS) and compared to that of PCBs from field-collected sediments. PC were mixed in freshwater sediment from a relatively uncontaminated site with no known PCB contamination sources and from a contaminated site with non-paint PCB sources. PC < 0.045 mm generated concentrations in the PS over one order of magnitude higher than coarser chips. The bioavailable fraction was represented by the polymer-sediment accumulation factor (PSAF), defined as the ratio of the PCB concentrations in the PS and organic carbon normalized sediment. The PSAF was similar for both field sediments. The PSAFs for the field sediments were ~ 50-60 and ~ 5 times higher than for the relatively uncontaminated sediment amended with PC for the size fractions 0.25-0.3 mm and < 0.045 mm, respectively. These results indicate much lower bioavailability for PCBs associated with PC compared to PCBs associated with field-collected sediment. Such information is essential for risk assessment and remediation decision-making for sites where contamination from non-paint PCBs sources is co-located with PCB PC.

Leaching Rate of Polychlorinated Biphenyls (PCBs) from Marine Paint Chips.

Polychlorinated biphenyls (PCBs) were added to certain marine vessel bottom paints as a plasticizer to improve the adhesion and durability of the paint. The most common PCB formulation used to amend such paints was Aroclor 1254. Fugitive Aroclor-containing paint chips generated from vessel maintenance and repair operations represent a potential source of PCB contamination to sediments. Limited published studies indicate that Aroclor-containing paint is largely inert and exhibits low PCB leaching into water; however, the rate and degree of leaching of PCBs from paint chips have not been directly studied. This laboratory-based study evaluated the rate and extent of leaching of PCBs from paint chips into freshwater. The results of this investigation demonstrate that the rate of PCB dissolution from paint chips decreased rapidly and exponentially over time. Based on this study, it is estimated that the rate of leaching of PCBs from paint chips would cease after approximately 3 years of exposure to water. When all leachable PCBs were exhausted, it is estimated that less than 1% of the mass of PCBs in the paint chips was amenable to dissolution. The results of this experiment suggest that Aroclor-containing paint chips found in sediments are likely short-term sources of dissolved-phase PCB to pore or surface waters and that the majority of the PCBs in paint chips remain in the paint matrix and unavailable for partitioning into water.

Forensic identification and quantification of oil sands-based bitumen released into a complex sediment environment.

On or about July 25, 2010, approximately 843,000 gal of condensate diluted bitumen (dilbit, a heavy oil) was released into the Kalamazoo River near Marshall, Michigan. As the discharged Line 6B oil migrated downstream the lighter diluent volatilized, formed visible oil droplets/flakes in the water column, became denser than water and/or became aggregated with sediment and migrated to the underlying bottom sediments. Accurate identification and determination of the amount of Line 6B oil present in the sediment was a primary requirement for remediation and allocation of liability. Based on a multi-tiered application of advanced hydrocarbon fingerprinting methodology, key chemical characteristics of the spilled oil were identified that allow for distinguishing heavy oil-related contamination from the complex river sediment background hydrocarbon contamination. It was determined that among the characteristics evaluated, concentration ratios of selected tri-aromatic steranes and triterpanes were most efficient parameters for identification and quantification of the spilled oil in the environment. This quantification approach was successfully applied and validated with field sample results and is consistent with the well-established environmental stability of these petroleum biomarkers and modern hydrocarbon fingerprinting methodology.

Chemical Preservation of Semi-volatile Polycyclic Aromatic Hydrocarbon Compounds at Ambient Temperature: A Sediment Sample Holding Time Study.

Site investigations require the collection and analysis of representative environmental samples to delineate impacts, risks, and remediation options. When environmental samples are collected, concentrations of semi-volatile polycyclic aromatic hydrocarbons (PAHs) begin to change due to several processes, such as evaporation, adsorption, precipitation, photo, and microbial degradation. Preservation techniques are used to minimize these changes between collection and analysis. The most common techniques are refrigeration, freezing, and acidification. In the mid 1970 s, regulatory agencies developed a holding time limit of 14 days for PAHs in soil/sediment samples stored at < 6 °C. The technical basis for this limit is not well defined yet failing to meet this limit may force resampling. This study examined the effectiveness of preservatives at maintaining PAH concentrations in sediment samples to 60 days. Sediment samples were collected at three sites that were impacted with petrogenic and pyrogenic PAHs. Chemically preserved (sodium azide, NaN3) and unpreserved samples were analyzed at defined time intervals from 0 to 60 days. Statistical analysis indicated acceptable preservation of PAHs in the sediment samples preserved with sodium azide for 60 days when maintained at either ambient laboratory temperature or 4 ± 2 °C, and for up to 21 days with no preservative when maintained at 4 ± 2 °C.

Experimental Evaluation of Preservation Techniques for Benzene, Toluene, Ethylbenzene, and Total Xylenes in Water Samples.

An experiment was designed to address the validity of the prescribed maximum allowable holding-time limit of 14 days when acidified at < 2 pH and maintained at 4°C to prevent significant loss of benzene, toluene, ethyl benzene, and xylenes (BTEX) in preserved water samples. Preservation methods prescribed by the United State Environmental Protection Agency were used as well as adaptions of that procedure to determine stability between 3 and 21 days. Water samples preserved at 4°C and pH of < 2 with hydrochloric acid did not result in unacceptable (> 15%) BTEX losses during the study as defined by procedures and statistical methods described by the American Society for Testing and Materials International. In addition, water samples preserved only with acid (pH < 2) at ambient temperatures (20-27°C) also provided acceptable results during the 21-day study. These results have demonstrated the acceptability of BTEX data derived from water samples exceeding the standard holding-time and/or temperature limits.

Laboratory and field verification of a method to estimate the extent of petroleum biodegradation in soil.

We describe a new and rapid quantitative approach to assess the extent of aerobic biodegradation of volatile and semivolatile hydrocarbons in crude oil, using Shushufindi oil from Ecuador as an example. Volatile hydrocarbon biodegradation was both rapid and complete-100% of the benzene, toluene, xylenes (BTEX) and 98% of the gasoline-range organics (GRO) were biodegraded in less than 2 days. Severe biodegradation of the semivolatile hydrocarbons occurred in the inoculated samples with 67% and 87% loss of the diesel-range hydrocarbons (DRO) in 3 and 20 weeks, respectively. One-hundred percent of the naphthalene, fluorene, and phenanthrene, and 46% of the chrysene in the oil were biodegraded within 3 weeks. Percent depletion estimates based on C(30) 17α,21ß(H)-hopane (hopane) underestimated the diesel-range organics (DRO) and USEPA 16 priority pollutant PAH losses in the most severely biodegraded samples. The C(28) 20S-triaromatic steroid (TAS) was found to yield more accurate depletion estimates, and a new hopane stability ratio (HSR = hopane/(hopane + TAS)) was developed to monitor hopane degradation in field samples. Oil degradation within field soil samples impacted with Shushufindi crude oil was 83% and 98% for DRO and PAH, respectively. The gas chromatograms and percent depletion estimates indicated that similar levels of petroleum degradation occurred in both the field and laboratory samples, but hopane degradation was substantially less in the field samples. We conclude that cometabolism of hopane may be a factor during rapid biodegradation of petroleum in the laboratory and may not occur to a great extent during biodegradation in the field. We recommend that the hopane stability ratio be monitored in future field studies. If hopane degradation is observed, then the TAS percent depletion estimate should be computed to correct for any bias that may result in petroleum depletion estimates based on hopane.