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Research about Palos Verdes Shelf

Source-linked reports with geographic coverage including Palos Verdes Shelf.

5 recordsLinked to original sources
USGS2018

DDT and related compounds in pore water of shallow sediments on the Palos Verdes Shelf, California, USA

For nearly two and a half decades following World War II, production wastes from the world's largest manufacturer of technical DDT (1-chloro-4-[2,2,2-trichloro-1-(4-chlorophenyl)ethyl]benzene) were discharged into sewers of Los Angeles County. Following treatment, the wastes were released via a submarine outfall system to nearshore coastal waters where a portion accumulated in shallow sediments of the Palos Verdes Shelf (PVS). An investigation of the pore-water geochemistry of DDT-related compounds (DDX) was undertaken in an effort to understand factors controlling the rate of reductive dechlorination (RDC) of the major DDT degradate, 4,4′-DDE (1-chloro-4-[2,2-dichloro-1-(4-chlorophenyl)ethenyl]benzene). Equilibrium matrix-solid phase microextraction (matrix-SPMEeq) combined with automated thermal desorption-gas chromatography/mass spectrometry (TDGC/MS) was used to determine freely dissolved concentrations of ten DDX analytes in sediment cores collected from three locations on the PVS (stations 3C, 6C, 8C, which are 7 km, 2 km, and 0 km, respectively, downcurrent from the outfall system). Pore-water concentrations (pM) of the principal DDX compounds involved in RDC were: 3C-DDE: 6.0–24, DDMU (1-chloro-4-[2-chloro-1-(4-chlorophenyl)ethenyl]benzene): 11–160, DDNU (1-chloro-4-[1-(4-chlorophenyl)ethenyl]benzene): 1.8–68; 6C-DDE: 5.6–170, DDMU: 5.6–177, DDNU: 1.7–87; 8CDDE: 27–212, DDMU: 31–403, DDNU: 5.5–89. Variations in the spatial distribution of DDX analytes in pore water reflect several factors including proximity to the outfalls, RDC reaction rates, and natural variability in sedimentation and post-depositional transport processes. A comparison of pore-water data produced using matrix-SPME eq /TD-GC/MS and whole-core squeezing/solvent extraction/liquid injection-GC/MS indicates that the majority of the DDE in the upper sediment column (≤about 10 cm) is associated with dissolved/colloidal organic matter. Below that depth, freely-dissolved DDE predominates. The principal organic geochemical phase controlling sorption of DDE in PVS sediments are residual hydrocarbons, the vast majority of which originated from petroleum refinery wastes. Organic carbon-normalized sediment-water distribution coefficients (KOC) were calculated from solid-phase and pore-water concentrations of DDX and organic carbon. Log K OC values (L/kg) were relatively invariant across the shelf and with depth in the sediment column. Shelf-wide compound-specific coefficients (log K OC ) were: DDE: 7.5 ± 0.11, DDMU: 6.92 ± 0.13, DDNU: 6.37 ± 0.19. The spatial uniformity of K OC means that biological exposure and availability of the DDX compounds can, in principle, be estimated from solid-phase chemical measurements.

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USGS2017

Final data report for factors controlling DDE dechlorination rates on the Palos Verdes Shelf: A field and laboratory investigation

This data report provides a compilation of information developed over the last 6+ years by a multi-disciplinary, multi-institutional research team. The overall goal of this work has been to identify the biological, chemical, and physical factors that control rates of reductive dechlorination of DDE and DDMU in sediments of the Palos Verdes Shelf (PVS). More specific questions and objectives are delineated in the Scope of Work (section 12.1., Appendix 1). The study was composed of two parts: 1) field characterization studies, and 2) laboratory microcosm experiments. The goal of the field characterization studies was to define the conditions under which reductive dechlorination of DDE (and DDMU) is occurring in PVS sediments. This involved two separate cruises (2009, 2010) during which sediment cores, bottom water and other real-time field measurements (e.g., conductivity, temperature, depth of the water column) were acquired. The sediment cores were distributed among research team members for detailed chemical (R. Eganhouse, B. Orem, M. Reinhard), microbiological (A. Spormann), and physical (B. Edwards) analysis as well as for laboratory microcosm experiments (M. Reinhard). A team of collaborating USGS scientists generously contributed valuable information pertaining to geochronology (P. Swarzenski), the character of sedimentary geosorbent phases (P. Hackley), mineralogy (D. Webster), and grain-size characteristics (C. Sherwood) of PVS sediment samples. Together, this information will serve as framework for a conceptual model of natural degradation processes in the DDT-contaminated sediments on the PVS. These findings will enable the USEPA to gain a better understanding of the controls on reductive dechlorination and how dechlorination rates vary spatially and temporally. This, in turn, should facilitate decision making concerning the progress of natural attenuation and when monitoring at the site can be terminated. Toward that end, a brief Synthesis Report, summarizing and interpreting the acquired data, is being prepared and will be released in the coming year.

Palos Verdes Shelf↗
USGS2017

Final synthesis report for factors controlling DDE dechlorination rates on the palos verdes shelf: A field and laboratory investigation

This project was organized into separate field and laboratory studies aimed at answering “18 questions” in the original Scope of Work (cf., section 2 of this report, Background, for explanation). Because of some early results, certain questions became irrelevant and were, therefore, not pursued. In other cases, there simply was not enough time to complete the originally planned studies. On the other hand, additional work, not identified in any of the original “18 questions”, was carried out for purposes of addressing specific issues of concern to the USEPA (United States Environmental Protection Agency). Examples of the latter include: 1) the analysis of an expanded list of sediment cores for DDX (DDX refers to the ten DDT-related compounds of interest in this study; cf., Eganhouse et al., [1]) and selected PCB congeners to facilitate estimation of site-specific reductive dechlorination (RDC) and total loss rates, 2) analysis of gravity and box cores for trace elements to allow stratigraphic alignment, and 3) determination of the extent of mineralization of p,p’-DDE (1-chloro-2-[2,2-dichloro-1-(4- chlorophenyl)ethyl]benzene) in microcosm experiments. In this Executive Summary, we offer a brief recapitulation of what was learned about the factors controlling reductive dechlorination of p,p’-DDE in Palos Verdes Shelf (PVS) sediments using the “18 questions” as a structural guide. The summary is written in narrative form, but references to specific sections (corresponding to the “18 questions”) are identified parenthetically in the text so that the reader can explore the expanded answers that appear later in the report.

Palos Verdes Shelf↗
USGS2011

Palos Verdes Shelf oceanographic study; data report for observations December 2007–April 2008

Beginning in 1997, the Environmental Protection Agency (EPA) defined a contaminated section of the Palos Verdes Shelf region in southern California as a Superfund Site, initiating a continuing investigation of this area. The investigation involved the EPA, the U.S. Geological Survey (USGS), Science Applications International Corporation (SAIC), Los Angeles County Sanitation Districts (LACSD) data, and other allied agencies. In mid-2007, the Palos Verdes Shelf project team identified the need for additional data on the sediment properties and oceanographic conditions at the Palos Verdes Superfund Site and deployed seven bottom platforms, three subsurface moorings, and three surface moorings on the shelf. This additional data was needed to support ongoing modeling and feasibility studies and to improve our ability to model the fate of the effluent-affected deposit over time. It provided more detail on the spatial variability and magnitude of resuspension of the deposit during multiple storms that are expected to transit the region during a winter season. The operation began in early December 2007 and ended in early April 2008. The goal was to measure the sediment response (threshold of resuspension, suspended-sediment concentrations, and suspended-sediment transport rates) to bed stresses associated with waves and currents. Other objectives included determining the structure of the bottom boundary layer (BBL) relating nearbed currents with those measured at 10 m above bottom (mab) and comparing those with the long-term data from the LACSD Acoustic Doppler Current Profiler (ADCP) deployments for nearbed current speed and direction. Low-profile tripods with high-frequency ADCPs co-located with two of the large tripods were selected for this goal. This report describes the data obtained during the field program, the instruments and data-processing procedures used, and the archive that contains the data sets that have passed our quality-assurance procedures.

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USGS2000

Diagenetic fate of organic contaminants on the Palos Verdes Shelf, California

Municipal wastes discharged through deepwater submarine outfalls since 1937 have contaminated sediments of the Palos Verdes Shelf. A site approximately 6–8 km downcurrent from the outfall system was chosen for a study of the diagenetic fate of organic contaminants in the waste-impacted sediments. Concentrations of three classes of hydrophobic organic contaminants (DDT+metabolites, polychlorinated biphenyls (PCBs), and the long-chain alkylbenzenes) were determined in sediment cores collected at the study site in 1981 and 1992. Differences between the composition of effluent from the major source of DDT (Montrose Chemical) and that found in sediments suggests that parent DDT was transformed by hydrolytic dehydrochlorination during the earliest stages of diagenesis. As a result, p , p ′-DDE is the dominant DDT metabolite found in shelf sediments, comprising 60–70% of ΣDDT. The p , p -DDE/ p , p ′-DDMU concentration ratio decreases with increasing sub-bottom depth in sediment cores, indicating that reductive dechlorination of p , p ′-DDE is occurring. Approximately 9–23% of the DDE inventory in the sediments may have been converted to DDMU since DDT discharges began ca. 1953. At most, this is less than half of the decline in p , p ′-DDE inventory that has been observed at the study site for the period 1981–1995. Most of the observed decrease is attributable to remobilization by processes such as sediment mixing coupled to resuspension, contaminant desorption, and current advection. Existing field data suggest that the in situ rate of DDE transformation is 10 2 –10 3 times slower than rates determined in recent laboratory microcosm experiments (Quensen, J.F., Mueller, S.A., Jain, M.K., Tiedje, J.M., 1998. Reductive dechlorination of DDE to DDMU in marine sediment microcosms. Science, 280, 722–724.). This explains why the DDT composition (i.e. o , p ′-, p , p ′-isomers of DDE, DDD, DDT) of sediments from this site have not changed significantly since at least 1972. Congener-specific PCB compositions in shelf sediments are highly uniform and show no evidence of diagenetic transformation. Apparently, the agents/factors responsible for reductive dechlorination of DDE are not also effecting alteration of the PCBs. Two types of long-chain alkylbenzenes were found in the contaminated sediments. Comparison of chain length and isomer distributions of the linear alkylbenzenes in wastewater effluent and surficial sediment samples indicate that these compounds undergo biodegradation during sedimentation. Further degradation of the linear alkylbenzenes occurs after burial despite relatively invariant isomer compositions. The branched alkylbenzenes are much more persistent than the linear alkylbenzenes, presumably due to extensive branching of the alkyl side chain. Based on these results, p , p ′-DDE, PCBs, and selected branched alkylbenzenes are sufficiently persistent for use in molecular stratigraphy. The linear alkylbenzenes may also provide information on depositional processes. However, their application as quantitative molecular tracers should be approached with caution.

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