CICEET Progress Report for the period 9/01/08 Through 2/15/09

Project Title: An in situ sediment porewater sampler for organic micropollutants based on solid phase microextraction (SPME) technology
Principal Investigator(s): Keith A. Maruya, Eddy Y. Zeng and Steven M. Bay
Project Start Date: 11/14/05

Figures

Figure 1a

Figure 1b

Figure 1c

Figure 2a

Figure 2b

Figure 3

Figure 4

Tables

Table 1

Table 2

Table 3

Table 4

Tasks to meet objectives
(1) Schedule and complete sample processing and analysis for Exp. 2B.
(2) Analyze relationships among solid phase, porewater, body burdens and SPME results for Exp 2B.
(3) Schedule and complete dry season in situ deployments at three sites ­ San Diego Bay, Tijuana River NERR and Duwamish River estuary (WA).
(4) Schedule and complete analysis of SPME samplers deployed in situ (dry season).
(5) Schedule and complete analysis of supporting field-collected media from two dry season sites.
(6) Schedule and initiate wet season in situ deployment at two sites ­ Tijuana River NERR and Ballona Creek estuary (CA).
(7) Collate most recent project information for preparation of 6 month progress report.

Progress on Tasks
With submission of this progress report, Tasks 1, 3, 6 and 7 have been completed. Tasks 2, 4 and 5 are 50% completed. Estimated completion of Tasks 2, 4 and 5 is 6/1/09.

Project Objectives for Next Reporting Period

Work Plan to Meet Objectives
(1) Complete data analysis for Exp. 2B
(2) Draft/submit manuscript on co-exposure experiments (Year 2 results).
(3) Complete analysis of SPME and supporting field-collected samples from dry season in situ deployments.
(4) Complete wet season in situ exposures of SPME samplers and collection of supporting field-collected media.
(5) Analyze retrieved SPME samplers exposed in situ (wet season).
(6) Process and analyze field collected media to support in situ assessment (wet season).
(7) Prepare and submit 6 month progress report.

Anticipated Success in Meeting Project Objectives
(1) Data analysis for Exp. 2B is 50% complete. Estimated completion date is 4/09.
(2) A manuscript detailing Year 2 results will be drafted upon completion of data analysis (commencing 5/09). Estimated submission date is 7/09.
(3) Analysis of SPME samplers deployed in situ during the dry season is 70% completed. Analysis of supporting field samples is 10% completed. Estimated completion date for all media is 8/09.
(4) Sampling plans for three wet season sites is 75% completed. Site selection and scheduling of wet season deployment will be accomplished by 3/09. Estimated completion date for wet season exposures/collection is 5/1/09.
(5) Analysis of wet season in situ SPME samplers will commence in 5/09. Estimated completion date is 07/09.
(6) Analysis of supporting field-collected samples will commence in 5/09. Estimated completion date is 09/09.
(7) Progress report to be submitted 9/1/09.

Overall Project Timeline Update
See Table 4.

Summary of Results
Year 2 bioaccumulation experiments ­ field-collected sediments (Exp. 2B). SPME samplers (7 and 100 mm PDMS) were co-exposed with bivalves (Macoma nasuta) and polychaetes (Nereis virens) to six different field-collected sediments without any fortification of target HOCs (e.g. PAH, PCBs and OC pesticides) in accordance with experimental conditions similar to those utilized previously for the spiked sediment co-exposure (Exp. 2A). Initial (day 0) characteristics of the test sediments were summarized in the previous progress report. Organic extracts of whole sediment, tissue by species, porewater isolated by centrifugation and SPME fibers sampled at the end of the experiment (day 28) were initially analyzed using GC-MS with electron ionization. Because many of the chlorinated analytes were not detectable using this technique, however, extracts (except SPME) were re-analyzed using electron capture negative ionization (ECNI) mass spectrometry, a more selective and sensitive method for halogenated compounds.

, except that flow-through instead of static seawater exchange was instituted. Characteristics of the six field-collected sediments, whose locations were chosen based on historical sediment quality "triad" data, are given in Table 2. These historical data indicated that mortality of estuarine amphipods at these locations ranged from a low of 15% to a high of 92%, and that concentrations of HOCs also varied widely, up to a factor of > 200 for total PCBs (Table 2).

Except for depressed DO levels in 2 of the 18 replicate aquaria that were short term in nature, water quality in all replicate aquaria was maintained within recommended guidelines. Survival for M. nasuta was 100% for all replicates across all treatments, and was greater than 87% for 5 of the 6 treatments for N. virens (Table 3). Survival of N. virens in the only sediment that had not been pre-characterized for HOC levels and or sediment toxicity (OCR) was 47%. DOC, TOC and soot or black carbon (BC) were measured using previously published protocols. Preliminary results show that TOC and BC ranged between 0.2 to 4.9% and 0.03 to 0.74%, respectively (Table 2). Sediment, SPME fibers, tissue and porewater isolated by centrifugation were extracted and analyzed by GC-ECD and GC-MS using research grade trace organics protocols. Results of these analyses are pending.

Year 3 in situ deployment. Both copper and stainless steel encased SPME samplers were deployed for short (48 h) and long term (21 d) exposures at four subtidal locations in San Diego Bay. Samplers were submerged just below the sediment-water interface attached to an in situ benthic chamber. Samplers with 7 µm PDMS were exposed for 48 h whereas those with 100 mm PDMS were deployed for the longer period. Preliminary data from analysis of SPME fibers indicated that very few detections were observed for the short term exposure (7 µm PDMS fibers). For the few confirmed detections, corresponding levels were at or below the fiber- and compound-specific method detection limits. In contrast, several PAH were consistently detected above the corresponding MDL for the 100 mm PDMS fibers. Summed preliminary concentrations for the four PAH detected (phenanthrene, anthracene, fluoranthene and pyrene) revealed a 16-fold difference in SPME measured porewater concentrations among the 4 stations (minimum: 3.6 ng/L for station "2243"; maximum: 58 ng/L for station "NS21).

Dissemination
Publications:
(1) Yang ZY, Maruya, Greenstein D, Tsukada, Zeng EY. 2008. Experimental verification of a model describing solid phase microextraction (SPME) of freely dissolved organic pollutants in sediment porewater. Chemosphere 72:1435-1440.

(2) Maruya KA, Zeng EY, Tsukada D, Bay SM. A passive sampler based on solid phase microextraction (SPME) for quantifying hydrophobic organic contaminants in sediment porewater. submitted to Environ Toxicol Chem

Workshops attended:
(1) SERDP/ESTCP Bioavailability Workshop, Aug 19-20, 2008, Annapolis MD.

Conferences:
(1) PI Maruya gave a presentation titled "Applications for passive sampling devices (PSDs) in impaired urban watersheds" at the SETAC Southern California Regional Chapter 2008 Annual Meeting, May 5-6, 2008, Dana Point, CA.

(2) PI Maruya gave a presentation titled "A SPME-based passive sampler for improving sediment quality assessment of hydrophobic organic contaminants (HOCs)" at the SETAC 5th World Congress, Aug 3-7, 2008, Sydney, Australia.

Manuals, Protocols:
None

Outreach Activities:
(1) Chaired session on passive sampling technology at the SETAC 5th World Congress, Sydney, Australia. Three co-Chairs from across the globe were recruited to maximize participation and information exchange on in situ applications of technologies like SPME. Over 30 abstracts were received and 18 platform and 9 poster presentations have been scheduled.

Contact with End Users:
One-on-one discussions with several potential end users occurred during the past reporting period. Included among these contacts were the following:
Bart Chadwick   Gunther Rosen, SPAWAR, San Diego, CA
Bruce Duncan, EPA Reg. X, Seattle, WA
Kirby Donnelly   Thomas McDonald, Texas A M
Peter Landrum, NOAA (ret.), Ann Arbor, MI

Drs. Chadwick and Rosen of SPAWAR included our SPME samplers in a field deployment in San Diego Bay as part of a multi-investigator study on the in situ bioavailability and toxicity of sediment-associated persistent organic compounds. Other participants in this study included G. Lotufo (USACE) and D. Reible (Univ. Texas), who are developing a similar in situ SPME sampler. In a separate but similar in situ evaluation, Drs. Donnelly, McDonald and Duncan solicited our participation in an assessment of the Lower Duwamish waterway in Washington state. We are also continuing dialogue with Dr. Landrum and his collaborators who are employing SPME to assess HOC bioavailability in freshwater sediments.

This project is also incorporated into the 2008-09 SCCWRP Research Plan that is formulated in collaboration with and approved by SCCWRP Member Agencies, who represent the major POTW dischargers and regulators in the Southern California coastal region.

Patent, Copyright, Invention Disclosure Activity:
None

Expenditures
A total of $500,306 has been encumbered by SCCWRP since project inception (11/14/05) through 06/30/08. Total expenditures to date include $367,519 invoiced to CICEET (100% of requested budget) and an additional $132, 787 of matching funds, representing ~95% of the estimated total budget. It is anticipated that remaining matching funds (~5% of total budget) will be sufficient to complete the project (Final Report submission).

End User Advisor Feedback
Name: Chris Beegan
Organization: State Water Resources Control Board, California
Location: Sacramento, CA
Phone number: 916 341 5577
E-mail: cbeegan@waterboards.ca.gov

1) At this stage, what are the potential applications for this research? Please discuss how you and others could potentially use the technology.
This technology would provide a direct measure of the bioavailability of sediment-associated organic pollutants, which could be incorporated into sediment quality objectives under development for the State of California. The primary drawback associated with bulk sediment chemistry, a widely used assessment tool, is that it provides no information on the bioavailable fraction. Staff at the State Water Board believe that developing sound and reproducible measurements of bioavailable contaminants is critical to the long term success of sediment quality management and restoration. Future applications of SPME could thus complement or potentially even replace bulk sediment chemistry in the multiple line of evidence (MLOE) approach recently adopted by the State for assessing sediment quality.

2) What, if anything, has changed about this project's potential applicability since the last reporting period (not applicable to the first Progress Report)?
Experimental results generated over the course of this project to date are most encouraging. It will be very interesting to see if the strong relationship between actual tissue residue with the levels measured on the SPME fibers demonstrated from the spiked sediment exposure (Exp. 2A) holds for field-collected sediments (Exp. 2B). It is also very encouraging to see that field trials in San Diego Bay have gone well to date, with 100% recovery of all samplers and measurable levels of PAHs.

3) Do you see any key challenges that the researchers may want to address or keep in mind?
The challenge of educating and convincing managers that bioavailability measures (such as those afforded by this technology) are valid and can support decision making is of primary importance. This was recently brought up at a DoD sponsored workshop on bioavailability in soils/sediments (see also Workshops attended). It was concluded that field level demonstrations and outreach activities are top priorities in accelerating and facilitating this technology transfer.

4) Does this report offer you enough information to adequately address the above questions?
Yes

5) Other feedback?
None