United State*
Environmental Protection Agency
Office of Water &
Office of Research and
Development
Office of Science and Technology
Health and Ecological Criteria Div.
Washington, D.C. 2046O
EPA-822-R-93-O12
September 1993 •
Sediment  Quality Criteria
for the Protection  of
Benthic Organisms:
FLUORANTHENE
                              Printed on Recycled Paper

-------

-------
                                  CONTENTS
Foreword	    ii
Acknowledgments	    iv
Tables	      vi
Figures	     vii

Introduction	     1-1
Partitioning	........	     2-1
Toxicity of Fluoranthene: Water Exposures	     3-1
Toxicity of Fluoranthene (Actual and Predicted): Sediment Exposures ....     4-1
Criteria Derivation for Fluoranthene	   5-1
Criteria Statement	     6-1
References	-.	     7-1
Appendix A:  Summary of Acute Values for Fluoranthene for Freshwater and
            Saltwater Species 	; .	    A-l
Appendix B:  Summary  of Data from Sediment Spiking Experiments with
            Fluoranthene	     .  B-l

-------
                                       FOREWORD
        Under the Clean Water Act (CWA) the U.S. Environmental Protection Agency (U.S.
 EPA) and the States develop programs for protecting the chemical, physical,  and biological
 integrity of the nation's waters.   Section 304(a)(l) directs the Administrator to develop and
 publish "criteria" reflecting the latest scientific knowledge on: (1) the kind and extent of effects
 on human health and welfare, including effects on plankton, fish, shellfish, and wildlife, which
 may be expected from the presence of pollutants in any body of water, including ground water,
 (2) the concentration and dispersal of pollutants, or their byproducts, through biological, physical
 and chemical processes, and  (3)  the effects of pollutants on biological community diversity,
 productivity, and stability. Section 304(a)(2) directs the Administrator to develop and publish
 information on, among other things, the factors necessary for the protection and propagation of
 shellfish, fish, and wildlife for classes and categories of receiving waters.

       To meet this objective, U.S. EPA has periodically issued ambient water quality criteria
 (WQC) guidance beginning with the publication of "Water Quality Criteria 1972" (NAS/NAE,
 1973).   All  criteria  guidance through late  1986 was  summarized in an U.S. EPA document
 entitled "Quality Criteria for Water, 1986" (U.S. EPA, 1987). Additional WQC documents that
 update criteria for selected chemicals and provide new criteria for other pollutants have also been
 published. In addition to the development of WQC and to continue to comply with the mandate
 of the CWA, U.S. EPA has conducted efforts to develop and publish sediment quality criteria
 (SQC) for some of the 65 toxic pollutants or toxic pollutant categories. Section 104 of the CWA
 authorizes the administrator to conduct and promote research into the causes, effects,  extent,
 prevention, reduction and elimination of pollution, and to publish relevant information. Section
 104(n)(l) in particular provides for study of the effects of pollution, including sedimentation in
 estuaries, on aquatic life, wildlife, and recreation.  U.S. EPA's efforts with respect to sediment
 criteria are also authorized under CWA Section 304(a).

       Toxic contaminants in  bottom sediments of the nations's lakes, rivers, wetlands, and
 coastal waters create the potential for continued environmental degradation even where water
 column contaminant levels meet established WQC. In addition, contaminated sediments can lead
 to water quality impacts, even when direct discharges to the receiving water have ceased. EPA
 intends SQC be used to assess the extent of sediment contamination, to aid in  implementing
 measures to limit or prevent additional contamination, and to identify and implement appropriate
 remediation activities when needed.

       The criteria presented in this document are the U.S. EPA's best recommendation of the
 concentrations of a substance  that may be present in  sediment while still protecting benthic
 organisms from the effects of that substance.  These criteria are applicable to a variety of
freshwater and marine sediments because  they  are based  on the biologically  available
 concentration of the  substance in  sediments.  These criteria do not protect  against additive,
synergistic or antagonistic effects  of contaminants or bioaccumulative effects to aquatic life'
wildlife or human health.                                                             '
                                          11

-------
       The  criteria derivation methods outlined in this document are proposed to provide
protection of benthic organisms from biological impacts from chemicals present in sediments.
Guidelines and guidance are being developed by U.S. EPA to assist in the application of criteria
presented in this document, in the development of sediment quality standards, and in other
water-related programs of this Agency.

       These  criteria are being issued in support of  U.S.  EPA'S regulations  and policy
initiatives.  This document is Agency guidance only. It does not establish or affect legal rights
or obligations. It does not establish a binding norm and is not finally determinative of the issues
addressed.   Agency decisions in any particular case will be made by applying the law and
regulations on the basis of the specific facts.
                                          111

-------
 Principal Author

       David J. Hansen

 Coauthors

       Walter J. Beny



       Dominic M. Di Toro


       Paul R. Paquin



       Laurie D. De Rosa



       Frank E. Stancil, Jr.

       Christopher S. Zaiba

Technical and Clerical Support

      Heinz P.  Kollig

      Glen B. Thursby



      Maria R.   Paruta



      BettyAnne Rogers
                              ACKNOWLEDGEMENTS
  U.S. EPA, Environmental Research Laboratory,
  Narragansett, RI
 Science Applications International Corporation,
 Narragansett, RI

 Manhattan College, Bronx, NY;
 HydroQual, Inc., Mahwah, NJ

 HydroQual, Inc.,
 Mahwah, NJ

 HydroQual, Inc.,
 Mahwah, NJ


 U.S. EPA, Environmental Research Laboratory, Athens, GA

 U.S. EPA Headquarters, Office of Water, Washington, DC
U.S. EPA, Environmental Research Laboratory, Athens, GA

Science Applications International Corporation,
Narragansett, RI


NCSC Senior Environmental Employment Program
Narragansett, RI

Science Applications International Corporation,
Narragansett, RI
                                       IV

-------
      Persons who have made significant contributions to the development of the approach and
supporting science used in the derivation of sediment criteria for nonionic organic contaminants
are as follows:
      Herbert E. Allen
      Gerald T. Ankley
University of Delaware, Newark, DE

U.S. EPA, Environmental Research Laboratory,
Duluth, MN
      Christina E. Cowan        Battelle, Richland, WA
      Dominic M. Di Tore


      David J. Hansen


      Paul R. Paquin

      Spyros P. Pavlou

      Richard C.  Swartz


      Nelson A. Thomas
HydroQual, Inc., Mahwah, NJ;
Manhattan College, Bronx, NY

U.S. EPA, Environmental Research Laboratory,
Narragansett, RI

HydroQual, Inc., Mahwah, NJ

Ebasco Environmental, Bellevue, WA

U.S. EPA, Environmental Research Laboratory,
Newport,OR

U.S. EPA, Environmental Research Laboratory,
Duluth, MN
      Christopher S. Zarba       U.S. EPA Headquarters, Office of Water, Washington, DC

-------
  Table 2-1

  Table 2-2.


  Table 3-1.


  Table 3-2.



 Table 3-3.
                           TABLES
              i
  Fluoranthene measured and estimated Log10KoW values.
 Table 4-1.

 Table 4-2.


 Table 5-1.

 Table 5-2.


Table 5-3.

Appendix A.

Appendix B.
  Summary  of logioKow values for fluoranthene measured by the U.S. EPA
  Environmental Research Laboratory, Athens, GA.                         '

  Chronic sensitivity of freshwater and saltwater organisms to fluoranthene
  Test specific data.

  Summary of freshwater and saltwater acute and  chronic values, acute-chronic
  ratios, and derivation of final acute values, final  acute-chronic ratios and final
  chronic values for fluoranthene.

  Results of approximate randomization test for the equality of freshwater and
  saltwater FAV distributions for fluoranthene and approximate randomization test
  for the equality of bentbic and combined benthic and water column (WOC) FAV
  distributions.

  Summary of tests with fluoranthene-spiked sediment.

  Water-only and sediment LCSOs used to test the applicability of the equilibrium
 partitioning theory for fluoranthene.

 Sediment quality criteria for fluoranthene.

 Analysis  of variance for derivation of sediment quality criteria confidence limits
 for fluoranthene.

 Sediment quality criteria confidence limits for fluoranthene.

- Summary of acute values for fluoranthene for freshwater and saltwater species.

- Summary of data from sediment  spiking experiments with fluoranthene.  Data
  from these experiments were used to calculate K^ values (Figure 2-1) and to
  compare mortalities of amphipods with pore water toxic units (Figure 4-1) and
 predicted sediment toxic units (Figure 4-2).
                                         VI

-------
                                      FIGURES
                         ;
Figure 1-1.   Chemical structure and physical-chemical properties of fluoranthene.

Figure 2-1.   Organic  carbon-normalized  sorption  isotherm  for fluoranthene (top) and
             probability plot of KQC (bottom) from sediment toxicity tests conducted by Swartz
             et al., (1990) and DeWitt et al., (1992).  The line in the top panel represents the
             relationship predicted with a log KQC of 5.00, that is C^oc = KOC • Cd.

Figure 3-1.   Genus mean acute values from water only acute  toxicity tests using freshwater
             species vs. percentage rank of their sensitivity.  Symbols representing benthic
             species are solid, those representing water column species are open.  Asterisks
             indicate greater than values. A = adult, J — juvenile, N = nymph,  X  =
             unspecified life stage.

Figure 3-2.   Genus mean acute values from water only acute toxicity tests using saltwater
             species vs. percentage rank of their sensitivity.  Symbols representing benthic
             species are solid, those representing water column species are open.  Asterisks
             indicate greater than values.  E = embryo, J = juvenile.

Figure 3-3.   Effect of UV light on toxicity of fluoranthene to the mysid, Mysidopsis bahia.
             Labels refer to  light source (Vita-light and UVA-340 are  artificial UV light
             sources).   UV  measurements  (in  fiW/cm2) were made  with a  Macam
             Photometries model UV-103 radiometer which read UV-A at 365 ± 36 nm. and
             UV-B at 310 ± 34 nm. The UV-A irradiances were 57.5 for Vita-lights at 16
             cm above the water, 252 for UVA-240 at 45 cm, 473 for UVA-340 at 26 cm, and
             1,725 for sunlight.  The curve was  similar whether the data were plotted against
             UV-A or UV-B.  (From Thursby, 1992)

Figure 3-4.   Probability distribution of FAV difference statistics to compare water-only data
             from freshwater vs. saltwater (upper panel) and benthic vs. WQC (lower panel)
             data.

Figure 4-1.   Percent mortality of amphipods in sediments spiked with acenaphthene or
             phenanthrene (Swartz, 1991a), endrin (Nebeker et al., 1989; Schuytema et al.,
             1989), or fluoranthene (Swartz et al., 1990; De Witt et al., 1992), and midge in
             sediments spiked with dieldrin (Hoke,  1992) or  kepone (Adams et al.,  1985)
             relative  to pore water toxic  units.   Pore water  toxic units are ratios  of
             concentrations of chemicals measured in individual treatments divided by  the
             water-only LC50 value from water-only tests.   (See Appendix B  in this SQC
             document, Appendix B in the endrin, dieldrin, acenaphthene, and phenanthrene
             SQC documents, and original references for raw data.)
                                          VII

-------
  Figure 4-2.
 Figure 5-1.
 Figure 5-2.
Figure 5-3.
  Percent mortality of amphipods in sediments spiked  with acenaphthene  or
  phenanthrena (Swartz,  1991a),  dieldrin (Hoke and Ankley,  1991)-  endrin
  (Nebeker et al., 1989; Schuytema et al., 1989) or fluoranthene (Swartz et al.,
  1990; De Witt et al., 1992) and midge in dieldrin spiked sediments (Hoke  1992)
  relative to "predicted sediment toxic units." Predicted sediment toxic units are
  the ratios of measured treatment concentrations for each chemical in sediments
  0*g/goc) divided by the predicted LC50 0*g/goc) in sediments (K^ x Water-only
  LC50 Otg/L)  x 1 Kgoc/^OOOgoc).   (See Appendix B  in  this  document and
  Appendix B in the dieldrin,  endrin, acenaphthene,  and phenanthrene SQC
  documents for raw data).

  Comparison between SQC concentrations and 95% confidence intervals  effect
  concentrations from benthic organisms exposed to fluoranthene-spiked sediments
  and sediment  concentrations predicted  to be chronically safe in fresh water
  sediments.   Concentrations predicted to be chronically safe (Predicted Genus
 Mean Chronic Values, PGMCV) are derived from the Genus Mean Acute Values
  (GMAV) from water-only 96-hour lethality tests, Acute Chronic Ratios (ACR)
 and Koc values. PGMCV = (GMAV  -f- ACR)KoC. Symbols for PGMCVs are
 A for arthropods, O for fishes and D for other invertebrates.  Solid symbols are
 benthic genera; open symbols water column genera. Arrows indicate greater than
 values.  Error bars around sediment  LC50 values indicate  observed range of
 JLC-jUs.

 Comparison  between SQC concentrations and 95% confidence intervals effect
 concentrations from benthic organisms exposed to fluoranthene-spiked sediments
 and sediment concentrations  predicted  to be chronically  safe in  salt water
 sediments. . Concentrations predicted  to be chronically safe (Predicted Genus
 ^f^^^C ValueS} PGMCy) a*6 derfved from the Genus Mean Acute Values
 (GMAV) from water-only 96-hour lethality tests, Acute Chronic Ratios (ACR)
 and Koc values. PGMCV = (GMAV + ACR)!^.  Symbols for PGMCVs are
 A for arthropods, O for fishes and D for other invertebrates.  Solid symbols are
 benthic genera; open symbols water column genera.  Arrows indicate greater than
 values.   Error bars around sediment LC50 values indicate observed ranee of
 LCSOs.

 Probability distribution of concentrations  of fluoranthene in sediments from
 streams, lakes and estuaries in the United States  from 1986 to 1990, from the
 STORET (U.S. EPA, 1989b) database, compared to the fluoranthene SQC values
 of 62 jtg/g in  freshwater sediments  having TOC =  10%  and  6.2 ug/g in
freshwater sediments having TOC =  1% and compared  to  SQC values for
saltwater sediments of 30 /*g/g when TOC = 10% and 3.0 /*g/g when TOC=1 %
The upper dashed line on each figure represents  the SQC value when TOC =
 10%, the lower dashed line represents the SQC when TOC  = 1 %.
                                        Vlll

-------
Figure 5-4.   Probability distribution of concentrations of fluoranthene in  sediments from
             coastal and estuarine sites from 1984 to 1989 as measured by the National Status
             and Trends Program (NOAA, 1991).  The horizontal line is the saltwater SQC
             value of 300 jtg/goc-
                                  DTSfTTATMHR

      This report has been reviewed by the Health and-Ecological Criteria Division, Office of
Science and Technology, U.S. Environmental Protection Agency, and approved for publication.
Mention  of trade  names or  commercial products  does not constitute  endorsement or
recommendation for use.
                             AVAILABILITY NOTICE

      This document is available to the public through the National Technical Information
Service (NTIS), 5285 Port Royal Road,  Springfield, VA 22161.  NTIS Accession Number
XXXX-XXXXXX.
                                        IX

-------

-------
                                     SECTION 1


                                  INTRODUCTION


1.1 GENERAL INFORMATION:
                                    \

       Under the Clean Water Act (CWA) the U.S. Environmental Protection Agency (U.S.


EPA) is responsible for protecting the chemical, physical and biological integrity of the nation's


waters.  In keeping with this responsibility, the U.S.  EPA published ambient water quality


criteria (WQC) in 1980  for 64 of the 65 toxic pollutants or pollutant categories designated as


toxic in the CWA. Additional water quality documents that update criteria for selected consent


decree chemicals and new criteria have been published since 1980. These WQC are numerical


concentration limits that are the U.S. EPA's best estimate of concentrations protective of human


health and the presence  and uses of aquatic life. While these WQC play an important role in


assuring a healthy aquatic environment, they alone are not sufficient to ensure the protection of


environmental or human health.


       Toxic pollutants in bottom sediments of the nation's lakes, rivers, wetlands, estuaries and


marine coastal waters create the potential for continued  environmental degradation even where
                                            i

water-column concentrations comply  with  established WQC.    In  addition, contaminated


sediments can be a significant pollutant source that may cause water quality degradation to


persist, even when other pollutant sources are stopped. The absence of defensible sediment


quality criteria (SQC) makes it difficult to accurately assess the extent of the ecological  risks


of contaminated sediments and to identify, jdoritize  and implement appropriate clean up


                                           1-1

-------
 activities and source controls.  As a result of the need for a procedure to assist  regulatory
                           :
 agencies in making decisions concerning contaminated sediment problems, a U.S. EPA Office

 of Science and Technology, Health and Ecological Criteria Division (OST/HEC) research team

 was established to review alternative approaches (Chapman, 1987).  All of the  approaches

 reviewed had both strengths and weaknesses and no single approach was found to be  applicable

 for SQC derivation in all situations (U.S. EPA, 1989a).  The equilibrium partitioning  (EqP)

 approach was selected for nonionic organic chemicals because it presented the greatest promise

 for generating defensible national numerical chemical-specific SQC applicable across a broad

 range of sediment types. The three principal observations  that underlie the EqP method  of

 establishing SQC are:

        1.     The concentrations of nonionic organic chemicals in sediments, expressed on an

              organic carbon basis, and in pore waters correlate to observed biological effects

              on sediment dwelling organisms across a range of sediments.

       2.     Partitioning models  can relate sediment concentrations for nonionic  organic

              chemicals on an organic carbon basis to freely dissolved concentrations in pore

              water.

       3.     The distribution  of  sensitivities of benthic and  water column organisms to

              chemicals are similar; thus, the currently established WQC final chronic values

              (FCV) can be used to define the acceptable effects concentration of a chemical

             freely-dissolved in pore water.

       The EqP approach, therefore, assumes that: (1) the partitioning of the chemical between

sediment organic carbon and interstitial water is at equilibrium; (2) the concentration in either


                                         1-2

-------
phase can be predicted using appropriate partition coefficients and the measured concentration
                           ?
in the other phase; (3) organisms receive equivalent exposure from water-only exposures or from

any equilibrated phase: either from pore water,via respiration, sediment via ingestion, sediment-

integument exchange, or from a mixture of exposure routes; (4) for nonionic chemicals, effect

concentrations in sediments on an organic carbon basis can be predicted using the organic carbon

partition coefficient (Koc) and effects concentrations in water; (5) the FCV concentration is an

appropriate effects concentration for freely-dissolved chemical in interstitial water; and (6) the

SQC 0*g/goc) derived as the product of the KQC and FCV is protective of benthic organisms.

SQC concentrations presented in this document are expressed as peg chemical/g sediment organic

carbon and not on an interstitial water basis because:  (1) pore water is difficult to adequately

sample; and (2) significant amounts  of the dissolved chemical may be associated with dissolved

organic carbon; thus,  total chemical  concentrations  in interstitial water  may  overestimate

exposure.

        The .data that support the EqP approach for deriving  SQC for nonionic organic

chemicals are reviewed by Di Toro et al. (1991) and U.S. EPA, (1993a). Data supporting these

observations  for fluoranthene are presented in this document.

       SQC  generated using the EqP  method are suitable for use in providing guidance to

regulatory agencies because they are:

       1. numerical values;

       2. chemical specific;

       3. applicable to most sediments;

       4. predictive of biological effects; and


                                          1-3

-------
         5.  protective of benthic organisms.
                            t
  As is the case with WQC, the SQC reflect the use of available scientific data to: (1) assess the

  likelihood of significant environmental effects to benthic organisms from chemicals in sediments;

  and (2) to derive regulatory requirements which will protect against these effects.

        It should be emphasized that these criteria are intended to protect benthic organisms from

  the effects of chemicals associated with sediments.  SQC are intended to apply to sediments

 permanently inundated with water, intertidal sediment and sediments inundated periodically for

 durations sufficient to permit development  of benthic assemblages.   They do not apply to

 occasionally inundated soils containing terrestrial organisms.  These criteria do not address the

 question of possible contamination of upper trophic level organisms or the synergistic, additive

 or antagonistic effects of multiple chemicals.  SQC addressing these issues may result in values

 lower or higher than those presented in  this  document.  The SQC presented in this  document

 represent the U.S. EPA's best recommendation at this time of the concentration of a chemical

 in sediment that will not adversely affect  most benthic organisms.  SQC values may be adjusted

 to account for future data or site specific considerations.

       SQC values may also need to be  adjusted because of site specific considerations. For

 example, spill situations, in which the chemical equilibrium between water and sediments has

 not yet been reached, a sediment chemical concentration that is less than the SQC may pose risks

 to benthic organisms. This is because for spills, disequilibrium concentrations in interstitial and

 overlying water may be proportionally higher relative to sediment concentrations.  Research has

 shown that the source or "quality" of total organic carbon  (TOG) in the sediment does not

greatly affect  chemical binding  (DeWitt  et al., 1992).  However, the physical form of the

                                          1-4

-------
chemical in the sediment may have an effect.  At some sites concentrations in excess of the SQC
                          ;
may not pose risks to benthic organisms, because the compound may be a component of a

particulate, such as coal or soot,  or exceed solubility such as undissolved oil.  In these

situations, the national SQC would be  overly protective of benthic organisms and should not be

used unless modified using the procedures outlined in the "Guidelines for Deriving Site-specific

Sediment Quality Criteria for the Protection of Benthic Organisms" (U.S. EPA, 1993b).  The

SQC may be underprotective where the toxicity of other chemicals are additive with the SQC

chemical or species of unusual sensitivity occur at the site.

       This document presents the  theoretical basis and the supporting data relevant to the

derivation of the SQC for fluoranthene.  An understanding of the "Guidelines for Deriving

Numerical National Water Quality Criteria for the Protection of Aquatic Organisms and Their

Uses" (Stephan et al., 1985),  response to public  comment (U.S. EPA, 1985) and "Technical

Basis  for Deriving Sediment Quality Criteria for Nonionic Organic Contaminants for the

Protection of Benthic Organisms by Using Equilibrium Partitioning " (U.S. EPA, 1993a) is

necessary  in order to understand the following text, tables and calculations.  Guidance for the

acceptable use of SQC values is contained in "Guide for the Use and Application of Sediment

Quality Criteria for Nonionic Organic  Chemicals" (U.S. EPA, 1993c).



1.2 GENERAL INFORMATION:  FLUORANTHENE

    Fluoranthene is a member of the polycyclic aromatic hydrocarbon (PAH) group of organic

compounds.  Some sources of fluoranthene are crude oil, coal tar and motor oil (Verschueren,

1983). Fluoranthene is also produced  naturally by plants, algae and bacteria (Suedel, 1989).


                                         1-5

-------
Some PAHs are of environmental concern because they are known to be carcinogens and/or
                          t
mutagens (Brookes, 1977). With an increase in fossil fuel consumption in the United States, an

increase in emissions of PAHs to the environment can be expected over the next several decades,

(Eadieetal., 1982).

    Fluoranthene has a three  ring structure and exists as pale yellow plates or needles

(Figure 1-1).   It has a solubility in water of 0.26 mg/L at 25°C and is a  solid at room

temperature (melting point of 111°C) (Verschueren,  1983).  Two significant processes which

can influence the fate  of fluoranthene in the sediment are sorption and biodegradation (U.S.

EPA, 1980). Sorption of fluoranthene onto solids in the water column and subsequent settling,

as well as partitioning onto  organics in the sediment,  can significantly affect fluoranthene

transport.  Bioaccumulation is a short-term process in which PAHs with 4 rings or less are

metabolized and long-term partitioning into biota is  not considered a significant fate process

(U.S. EPA, 1980). Other processes found to have little or no effect on the fate of fluoranthene

in the sediment are oxidation, hydrolysis and volatilization (U.S. EPA, 1980).

     In the absence of ultraviolet (UV) light the acute toxicity of fluoranthene ranges from 36

to >212 /tg/L for freshwater and 52 to >20,000 /tg/L for saltwater organisms (Appendix A).

Differences between fluoranthene concentrations causing acute lethality and chronic toxicity in

the absence of UV light in invertebrates are small; acute-chronic ratios (ACR) range from 3.385

to 3,404 for two species.  The ACR for one species of fish is much larger (14.09).  Sunlight

photoactivates fluoranthene to increase its toxicity to up to over an order of magnitude greater

than non-UV activated chemical (Appendix A). Although fluoranthene bioaccumulates hi aquatic

biota, the associated  health or ecological risks are unknown.


                                          1-6

-------
             MOLECULAR FORMULA
             MOLECULAR WEIGHT
             DENSITY
             MELTING POINT
             PHYSICAL FORM
             VAPOR PRESSURE
 C16H10
 202.26
 1.252 g/cc (25°C)
Pale yellow plates or needles
     5.0xlO
-------
 1.3 OVERVIEW OF DOCUMENT:




       Section 1 provides a brief review  of the EqP methodology, and a summary of the



 physical-chemical properties and aquatic toxicity of fluoranthene.  Section 2 reviews a variety



 of methods and data useful in deriving partition coefficients for fluoranthene and includes the



 KQC recommended for use in the derivation of the fluoranthene SQC.  Section 3 reviews aquatic



 toxicity data contained in the fluoranthene WQC document (U.S. EPA, 1980) and new data that



 were used to  derive the FCV used in  this document to derive the SQC concentration.  In



 addition, the comparative sensitivity of  benthic and water column species is examined as  the



justification for the use of the FCV for  fluoranthene in the derivation of the SQC.  Section 4



 reviews data  on the toxicity  of  fluoranthene in  sediments, the need  for organic  carbon



 normalization of fluoranthene sediment concentrations and the accuracy of the EqP prediction



 of sediment toxicity using KQC and an effect concentration in water.   Data from Sections 2, 3




and 4 are used in Section 5 as the  basis  for the derivation of the SQC for fluoranthene and its



uncertainty. The SQC for fluoranthene is then compared to STORET (U.S. EPA, 1989b) and



National Status and Trends (NOAA, 1991) data on fluoranthene's environmental occurrence in



sediments.  Section 6 concludes with the criteria statement for fluoranthene. The references



used in this document are listed in  Section 7.
                                         1-8

-------
                                     SECTION 2



                                  PARTITIONING




2.1 DESCRIPTION OF THE EQUILIBRIUM PARTITIONING METHODOLOGY:



       Sediment quality criteria (SQC) are the numerical concentrations of individual chemicals




which are intended to be predictive of biological effects, protective of the presence of benthic



organisms and applicable to the range of natural sediments from lakes,  streams, estuaries and



near coastal marine waters. As a consequence, they can be used in much the same way as water



quality criteria (WQC); ie., the concentration of a chemical which is protective of the intended




use such as aquatic life protection. For non-ionic organic chemicals, SQC are expressed as fig




chemical/g organic  carbon and apply to sediments having ^ 0.2% organic carbon by dry




weight. A brief overview  follows of the concepts which underlie the equilibrium partitioning




(EqP) methodology for deriving SQC. The methodology is discussed in detail in the "Technical




Basis  for Deriving  Sediment Quality  Criteria  for Nonionic  Organic  Contaminants for the



Protection  of Benthic Organisms by Using Equilibrium Partitioning"  (U.S.  EPA, 1993a),



hereafter referred to as the SQC Technical Basis Document.



       Bioavailability of a chemical at a particular sediment concentration often differs from one




sediment type to another. Therefore, a method is necessary for determining a SQC based on the




bioavailable chemical  fraction  in a  sediment.     For nonionic organic  chemicals, the



concentration-response  relationship for the biological effect  of concern can  most often be



correlated with the  interstitial water (i.e., pore water) concentration 0*g chemical/liter pore



water) and not to the sediment chemical concentration (jig chemical/g sediment) (Di Toro et al.,
                                         2-1

-------
  1991).  From a purely practical point of view, this correlation suggests that if it were possible
                           s
  to measure the pore water  chemical  concentration,  or predict it from  the  total sediment

  concentration and the relevant sediment properties, then that concentration could be used to

  quantify the exposure concentration for an organism.  Thus, knowledge of the partitioning of

  chemicals between the solid  and liquid phases in a sediment is a necessary component for

 establishing SQC. It is for this reason that the methodology described below is  called the

 equilibrium partitioning (EqP) method.

       It is shown in the SQC Technical Basis Document (U.S. EPA, 1993a) that the final acute

 values (FAVs) in the WQC documents are appropriate for benthic species for a wide range of

 chemicals.  (The data showing this for fluoranthene are presented in Section 3).  Thus, a SQC

 can be established using  the  final chronic value (FCV) derived using the WQC Guidelines

 (Stephan et al.,  1985) as the  acceptable effect concentration in pore or overlying water (see

 Section 5), and the partition coefficient can be used to relate the pore water concentration to the

 sediment concentration via the partitioning equation. This acceptable concentration in sediment

 is the SQC.


       The calculation is as follows:  Let FCV Otg/L) be the acceptable concentration in water

for the chemical  of interest; then compute the SQC using the partition coefficient, (Kp;

^fcgicdtmmt).  between sediment and water:

              SQC = KP  FCV                                                   (2_D

This is the  fundamental equation used  to generate the SQC.  Its  utility depends  upon the

existence of a methodology for quantifying the partition coefficient, KP.

       Organic carbon appears to be the dominant sorption phase for nonionic organic chemicals



                                          2-2

-------
in naturally occurring sediments and thus controls the bioavailability of these compounds in

                                                                /
sediments.  Evidence for this can be found in numerous toxicity tests, bioaccumulation studies


and chemical analyses of pore water and sediments (Di Toro et al.,  1991).  The evidence for


fluoranthene is discussed in this section and section 4.  The organic carbon binding of a chemical


in sediment is a function of that chemical's organic carbon partition coefficient (Koc) and the


weight fraction of organic carbon in the sediment (foe).  The relationship is as follows:
       It follows  that:


                                                                             (2-3)
where SQCoc is the sediment quality criterion on a sediment organic carbon basis.


      KQC is not usually measured  directly (although it can be done, see section  2.3).


Fortunately, KQC is closely related to the octanol-water partition coefficient (Kow) (equation 2-5)


which has been measured for many compounds, and can be measured very accurately. The next


section reviews the available information on the KoWfor fluoranthene.




2.2  DETERMINATION OF KQW FOR FLUORANTHENE:


    Several approaches  have  been used to determine KQW for the derivation of  SQC, as


discussed in the SQC Technical Basis Document. At the U.S. EPA, Environmental Research


Laboratory at Athens, GA (ERL,A) three methods were selected for measurement and two for


estimation of KQW. The measurement methods were shake-centrifugation (SC), generator column
                                         2-3

-------
 (GCol) and slow-stir-flask (SSF) and the estimation methods were SPARC (SPARC Performs
                          T
 Automated Reasoning in Chemistry; Karickhoff et al.,  1989) and CLOGP (Chou and Jurs,

 1979).  Data were also extracted from the literature.  The SC method is a standard procedure

 in the Organization for Economic Cooperation and Development (OECD) guidelines for testing

 chemicals, therefore it has regulatory precedence.
 TABLE 2-1.  FLUORANTHENE MEASURED AND ESTIMATED LOG10KoW VALUES.
METHOD
Measured
Estimated
Estimated
Estimated
Estimated
Estimated
Estimated
Estimated
LOG10KoW
5.15
4.90
4.95
4.95
5.21
5.22
5.29
5.33
REFERENCE
DeBruijnetaL, 1989
Mabey et al., 1982
CLOGP1
GEMSb
SPARC0
Yalkowsky et al., 1983
Mackay et al., 1980
Callahan et al., 1979
•CLOGP is an algorithm that is included in the database QSAR located at the U.S. EPA,
Environmental Research Lab., Duluth, MN (Chou and Jurs, 1979).
"GEMS is the Graphical Exposure Modeling System  for the U.S. EPA.   It is an interactive
computer system located on the VAX Cluster in the  National Computer Center in Research
Triangle Park, North Carolina, under management of  EPA's Office of Toxic Substances.  PC
GEMS is the version for personal computers.
CSPARC is from SPARC Performs Automated Reasoning in Chemistry,  (Karickhoff et al.,
1989).
   • In the examination  of the literature data for fluoranthene, only one primary reference was

found listing a  measured logioKoW.  This value was 5.15 (Table 2-1).  Several primary

references were found for estimated log10KoW values in the literature ranging from 4.90 to 5.33

(Table 2-1). Although the range of reported values for fluoranthene is significantly lower than

                                       2-4

-------
the range of values for some other compounds, it is relatively large, and we were not able to



determine from studying the primary articles that any value was more likely to be accurate than



any other. KQW values for SPARC and CLOGP are also included in Table 2-1.  SPARC is a



computer expert system under development at EKL, A, and the University of Georgia, at Athens.



The CLOGP algorithm is  included  in the database QSAR located at EPA's Environmental




Research Laboratory (ERL,D) at Duluth, Minnesota.  For more information on SPARC and



CLOGP see U.S. EPA (1993a). The SPARC estimated log10KoW value for fiuoranthene is 5.21.



The CLOGP program estimate of the log10KoW value for fiuoranthene using structure activity




relationships is 4.95.



      We had little confidence in the available measured or estimated values for KOW, therefore




the SCj GCol, SSF methods were used to provide additional data from which to define KQW for



fiuoranthene (Table 2-2). The SC method yielded a log10KoW = 5.00 (n=3), the GCol method




yielded a log10KoW =  5.39 (n=4),  and the SSF method yielded a log10KoW  = 5.09 (n=6).



Comparison of the results from the SC, GCol, SSF and SPARC KQW determination methods for



the five chemicals for which SQC are currently being developed (acenaphthene, dieldrin, endrin,




fiuoranthene and phenanthrene) indicate that the SSF method provides the best estimate of KQW



(U.S. EPA, 1993a). The SSF method had less variability, less experimental bias (Bias is defined




as the mean difference between the best-fit estimate of KQW using all four methods and the



estimates from each method.) and was generally in the range of the SC, GCol, and SPARC




methods (U.S.  EPA, 1993a).  Therefore, the SSF value of 5.09 is the value for log10KoW



recommended for SQC derivation. This value agrees with the SPARC estimated value and the




average of the values measured by the three methods under carefully controlled conditions at
                                         2-5

-------
 ERL,A. This KQW is the logarithm of the mean of six KQW measurements made by SSF. The
                         !
 logs of the KOW values measured by SSF range from 4.98 to 5.23.
 TABLE 2-2. SUMMARY OF LOG10KoW VALUES FOR FLUORANTHENE MEASURED BY
 THE U.S. EPA ENVIRONMENTAL RESEARCH LABORATORY, ATHENS, GA.
SHAKE-
CENTR1FUGATION
rso
4.99
5.00
5.01
5.00s
GENERATOR
COLUMN
fGCoD
5.19
5.35
5.47
5.48
5.39*
SLOW-STIR
FLASK
4.98
5.02
5.02
5.10
5.14
5.23
5.09a
             "Logic of mean of measured values.



2.3 DERIVATION OF KOC FROM ADSORPTION STUDIES:

      Two types of experimental measurement of the K^ are available. The first type involves

experiments which were designed to measure the partition coefficient in particle suspensions.

The second type of measurement is from sediment toxicity tests in which measurements of

sediment fluoranthene, sediment organic carbon (OC) and non-dissolved organic carbon (DOC)

associated fluoranthene dissolved in pore water were used  to compute KQC-
2.3.1  KOC FROM PARTICLE SUSPENSION STUDIES:

      Laboratory studies to characterize  adsorption are generally conducted using particle

suspensions.  The high concentrations of solids and turbulent conditions necessary to keep the
                                      2-6

-------
mixture in suspension make data interpretation difficult as a result of a particle interaction effect.
This effect suppresses the partition coefficient relative to that observed for undisturbed sediments
(Di Toro, 1985; Mackay and Powers, 1987).
       Based on  analysis  of an extensive body of  experimental data for a wide range  of
compound types and experimental conditions, the particle interaction model (Di Toro, 1985)
yields the following relationship for estimating KP:
                                  oe
                                                                                (2-4)
                          1 + mf , oc KOC / ux
where m is the particle concentration in the suspension (kg/L), and u* = 1.4, an empirical
constant.  In this expression the KOC is given by:
              logioKoc = 0.00028 +  0.983 log10KoW                               (2-5)
       Experimental data demonstrating the effect of particle suspensions was not found for
fluoranthene during a comprehensive literature search for partitioning information. Nonetheless
the above discussion highlights the need to consider particle interaction effects when interpreting
partitioning data in particle suspension studies.
       In the absence of particle effects, KQC is related to KQW via Equation 2-5.  For
 log10KoW = 5.09 (See section 2.2), this expression results in an estimate of logtoKoc = 5.00.
2.3.2 KOC FROM SEDIMENT TOXICITY TESTS:
       Measurements of KOC are available from sediment toxicity tests using fluoranthene
(Swartz et al., 1990, DeWitt et al., 1992).  The tests from Swartz et al. (1990) used three

                                          2-7

-------
  saltwater sediments with a range of. organic carbon contents of 0.2 to 0.5 percent.  The tests
                            }
  from DeWitt et al. (1992) used a marine sediment amended with five types of organic matter

  yielding sediments with organic caibon contents of 0.3 to 0.43 percent. (Table 4-1; Appendix

  B.)  Fluoranthene concentrations were measured in the sediment and pore waters providing the

  data necessary to calculate the partition coefficient for an undisturbed bedded sediment. Swartz

  et al. (1990) measured total pore water concentrations and DeWitt et al. (1992) measured total

  and freely dissolved pore water concentrations.  The relationship of total to free pore water in

  the DeWitt et al. (1992) analysis was applied to the total pore water data in Swartz et al. (1990)

 to estimate free pore water in that study. Also an adjustment was made to pore water to account

 for 28% loss due to filtration during experimental measurements (Swartz, 1992).

        The upper panel of Figure  2-1 is a plot of the  organic carbon-normalized sorption

 isotherm for fluoranthene,  where the sediment fiuoranthene concentration, G*g/gOC) is plotted

 versus free (dissolved) pore water concentration, fttg/L).  The data used to make this plot are

 included in Appendix B.  One of the amended sediments for the DeWitt analysis was omitted

 because the author believed that elevated dissolved organic carbon may have interfered with the

 method used to determine free interstitial water fiuoranthene concentrations.  The line of unity

 slope corresponding to  the log10Koc =  5.00 derived from SSF is compared to the data.  A

probability plot of the observed experimental logl^Koc values is shown in the lower panel of

Figure 2-1.  The log10KoC values are approximately normally distributed with a mean of log10KoC

 - 5.05 and a standard error of the mean of 0.071. This value agrees with the log10BQjC of 5.00,

which was computed from the SSF determined (Section 2.2) fluoranthene log10KoW of 5.09 using

Equation 2-5.
                                          2-8

-------
       100000
10000
  O

  jg
    g
  o°
  ZQ

  81
  Q
  CO
           10
              =  I  I  I I I III!
                                 I I III!    I  I I I I lilt   I  III I LKI
                                                          I I Ig
                                                LEGEND
                                   — Swortz et al., 1990

                                   - De  Witt et al.,  1992
                      11 mi
                              i i i MHI   i  in inn
                                                      i i MIII   i  i  i i mi
             0.1
                           10
     100
        1000
     10000
                 PORE  WATER CONCENTRATION (ug/L)
oc = KQC • Cd.
                                     2-9

-------
2.4 SUMMARY OF DERIVATION OF KQC FOR FLUORANTBDENE:
                          r
       The KQC selected to calculate the SQC for fluoranthene is based on the regression of

logioKoc to logioKoW (Equation 2-5), using the fluoranthene logioKoW of 5.09 recently measured

by ERL, A.  This approach, rather than the use of the KQC from the toxicity tests, was adopted

because the regression equation is based on the most robust data set available that spans a broad

range of chemicals and particle types, thus encompassing a wide range of KQW and foc.  The

regression equation yields a log10Koc of 5.00. This value is in agreement with the log10Koc of

5.05 measured in the sediment toxicity tests.
                                        2-10

-------
                                    SECTION 3

               TOXICITY OF FLUORANTHENE: WATER EXPOSURES

3.1 TOXICITY OF FLUORANTHENE IN WATER: DERIVATION OF FLUORANTHENE
    WATER QUALITY CRITERIA:

      The equilibrium partitioning (EqP) method for the derivation of sediment quality criteria

(SQC) uses the fluoranthene water quality criterion (WQC) final chronic value (FCV) and

partition  coefficients (K<>c)  to  estimate the  maximum concentrations of nonionic organic

chemicals in sediments, expressed on an organic carbon basis, that will not cause adverse effects

to benthic organisms.  For this document, life stages of species classed as benthic are either

species that live in the sediment (infauna) or  on the sediment surface (epibenthic) and obtain

their food from either the sediment or water column (U.S. EPA, 1989c). In this section (1) the

FCV from the fluoranthene WQC document (U.S. EPA, 1980) is revised using new aquatic

toxicity test data; and (2) the use of this FCV is justified as the effects concentration for SQC

derivation.  Tests conducted in the dark or under normal laboratory lighting are discussed in

Sections 3.2 and 3.3. The phototoxicity of fluoranthene is discussed in Section 3.4.

   3.2 ACUTE TOXICITY - WATER EXPOSURES:

      Twenty standard acute toxicity tests with fluoranthene have been conducted under normal

laboratory lighting on 13 freshwater species from 12 genera (Appendix A). Overall genus mean

acute values (GMAVs) range from 36  to > 211.7 /tg/L. The acute values for three species

tested, Lumbriculus  variegatus.  Physella virgata. and Ophiogomphus sp., were all  > 178.5

/tg/L. The acute values for the 4 most sensitive species differed by only a factor of 3; 32 to 95
                                        3-1

-------
 /*g/L.  Nine tests on benthic life-stages of nine species from eight genera are contained in this
                          t
 database (Figure 3-1; Appendix A). Benthic organisms were similar to water column species

 in sensitivity to fluoranthene; GMAVs range from 61.1 to > 178.5 fig/L.  One infaunal species,

 the annelid L variegatus. had an LC50 of > 178.5 /tg/L. The final acute value (FAV) derived

 from the overall GMAVs (Stephan et al., 1985) for freshwater organisms is 33.58 ng/L (Table

 3-2).

       Fifteen acute tests have been conducted on 8 saltwater species from 8 genera (Appendix

 A).  Overall GMAVs range from 51.54 to > 20,000 jtg/L, with crustaceans the most sensitive.

 There are results from 6 tests on benthic life-stages of 6 species from 6 genera (Figure 3-2;

 Appendix A).  Benthic organisms were among  both the most sensitive and  most resistant

 saltwater genera to fluoranthene. The most sensitive benthic species is the mysid, Mvsidopsis

 bahia, with an average flow-through 96 hour LC50 of 51.54 /tg/L based on two tests with

 measured concentrations. Other benthic species for which there  are data are only slightly less

 sensitive while others are resistant to fluoranthene and had GMAVs ranging from 66.93 to >

 20,000 (ig/L.  The FAV derived from the overall  GMAVs (Stephan et al., 1985) for saltwater

 organisms is  16.13 jig/L (Table 3-2).



 3.3 CHRONIC TOXECITY - WATER EXPOSURES:

       Chronic toxicity tests have  been conducted  with  fluoranthene using  a freshwater

 cladoceran, (Daphnia magna) and fathead minnows (Pimepheles promelas) and a saltwater mysid

Mi. frahia (Table 3-1). I), magna and M- bahia were tested in life-cycle exposures.  P. promelas

 were exposed in an early life-stage toxicity test.
                                          3-2

-------
  1000,-
             A Arthropods
             D Other Invertebrates

             O Rshes
a
o>

UJ
                                                                         Snail
                                                              PhysoOO
                                                                Snail
   100
UJ
UJ
O
               Lepomls *(J)
                  Sunflsh
                 Paltoperia *00
                    Stonefly
                                                  Plmephales • (JA)
                                                          3W
                                                                             .,.,.      Mlnnov
                                                                              
-------
  100000
   10000
•3s
in

1
tu
     1000
111
O
100
       10
                   A Arthropods
                   D Other Invertebrates
                   O Fishes
                                                                        Arbacia *(E)
                                                                        Sea Urchin
                                                                Mulinia (J)
                                                                Coot Clam i
                                                                               Cyprinodon *{J)
                                                                                Sheepshead
                                                                                  Minnow
         Mysldopsis
            Mysid
(J)
                                         Neanthes (J)
                                            Annelid
                   Palaemonetes (J)
                     Grass Shrimp
                                                           Menidia (J)
                                                            Silverside
                               Ampelisca (J)
                                 Amphipod
                                                            _L
                          20               40               60               80


                             PERCENTAGE RANK OF SALTWATER GENERA
                                                                                       100
 Figure 3-2.   Genus mean acute values from water only acute toxicity tests using saltwater
               species vs. percentage rank of their sensitivity. Symbols representing  bentbic
               species are solid, those representing water column species are open.  Asterisks
               indicate greater than values.  E = embryo, J = juvenile.
                                           3-4

-------
•






g
1
Q
8
§
H
O
<
E
C|
S
|
i
SB
CO

t*
S

!>§
B°
MO
CO H
X ft
MH
"^
uS
MOT
pj CQ
•
ro
1
CQ
8
m
!D
1
C 0
0) O
O» '


sj III 1 1 1 1 1 "I '
n
•

oss e ZB!SB as z
H*** S***0* • w «
. . 4. . • • o j» * o
.., row c^o WHO ONO H
a n ro win M n ef> H roHH J
° Q '.. '
*' •< W w
m a w £
H £3 E *i
^ S «!« •: g • 1 2 | -
tj>M,HroH w nroeo '
a. g .' d« N M^IH B a!
1 E B « 1 ?
Sw* SE H •*aj^lpl'l
eooea Sd H* ?e»Hd°
|HH gj* H H ' • «
, ' w ' w
^ ". „ H 1 ro S
2«5ro -Co ?oo


^^
»3 ^ ^ -~ *^ ~
c£ k3 f£ rt *^ i-3 rt
S H 35 5 H 5
SB * 68 te * * M

m w
o iJ wo w <-i y
3 H 3 M M w »->
a s
'• -" -3-3 -I *
si B| ii ^ ^i 5
§1 11 J J §1 |l -ol
•S£ *« -H-H -H-H "O£ A9 -H-H
«0 *J E 0 O • m *S ti-1 5.5
o3 Si fa ^i "3 £A| ^fl







g
U
U
•5
1
H
OS
1
o
? •
J 0
a
0 >i
H -H
l-l rH
•w. U
J & 8
s § *
* iH 98
3 8 M
M M . i-l

£2 s .-2g
o " rt/o^ °
8
-------
        n, magna exposed to fluoranthene for 21 days were not affected in 10.6 /tg/L or less.
                           t
  There was a reduction, relative to controls,  of 23.1% in growth at 2L2 /tg/L and 36.9% in

  survival at 43.5 /tg/L. P. r>romelas exposed to fluoranthene for 28 days in an early life-stage

  toxicity test were not affected in 10.4 /tg/L or less.  There was a reduction of 67% in survival

  and a 50.2% reduction in growth relative to controls in 21.7 /tg/L.  In the 96 hour acute lethality

  test, 25% of the P. promelas died in 211.7 /tg/1, saturation for fluoranthene (Brooke,  1991).

  The concentration of 211.7 /tg/1 was used as the acute value for P. promelas because this value

 approximated an LC50 and greater concentrations could not be tested in this measured flow-

 through test.

        Saltwater M. bjhja were tested in two life-cycle toxicity tests.  In the first, they were

 exposed to fluoranthene for 28 days (EG&G, 1978). There was no effect on survival or

 reproduction (growth was  not measured) after 28  days of exposure to  fluoranthene at

 concentrations <.12 /tg/L. At a fluoranthene concentration of 21 /tg/L survival and reproduction

 were reduced by 26.7 and 91.7%, respectively, relative  to the controls.  At the highest

 concentration of fluoranthene, 43 /tg/L, all M. bjhia died.  In the second test, M- bahia were

 exposed to fluoranthene for 31 days (Champlin and Poucher, 1991b). Effect concentrations were

 similar to the first test. M- bahia were not affected at fluoranthene concentrations <. 11.1  /tg/L.

 Survival was reduced 30%, growth 12% and reproduction 100%  relative to controls, in 18.8

/tg/L, the highest concentration tested.

       The difference between acute and chronic sensitivity to fluoranthene, in tests where UV

activation did not occur, varied minimally between species (Table 3-2). Three species  mean

acute-chronic ratios (ACR) are available; 3.385 for D. magna.  3.404 for M. bahia and 14.09
                                         3-6

-------
  a\
                                       «N
                                       t-
                                                  PI
                                                  o\

to
•+

in
                                s

                                                                   05


                                                                   
                                                                w o N
                                                                O-H  •
                                                                in u o

                                                                dot »
                                                                il *J
                                                               -H-H -H

                                                               (b h b<
              ro

              "
                                                                              in
,

H
23
                   S
                2
                                                                            rt-*
                                                                            a. N t-


                                                                            <«> O c\
                                                                            tH-H •
                                                                             • 4JM
Fr
                                                                            i^ *-» w
                                                                            fl) i a

                                                                            ill
Fina

Fina

Fina
                           3-7

-------
  for E promelas. The final acute chronic ratio final (ACR) is the geometric mean of these three
  values (5.455).
         The FCVs (Table 3-2) are used as the effect concentrations for calculating the SQC for
 protection of freshwater and saltwater benthic species.  The FCV for freshwater organisms of
 6.16 ftg/L is the quotient of the FAV of 33.6 pg/L and the final ACR of 5.45. Similarly, the
 FCV for saltwater organisms of 2.96 jtg/L is the quotient of the FAV of 16.1 /tg/L and the final
 ACR.
 3.4 PHOTOTOXrCTTY OF FLUORANTHENE:
       Under laboratory conditions many PAHs are predicted to be not acutely toxic at or below
 their solubility in water (Veith et aL,  1983).  Under ultra-violet light (UV), however, the
 toxicity of some PAHs can increase by several orders of magnitude. This effect has been shown
 to be a result of photoactivation rather than photodegradation of the parent compound to more
 toxic metabolites.  With some PAHs, toxicity occurs  by activation  by UV light of chemical
 present on or within an organism. Bluegills (Lepomis macrochims^  exposed to anthracene in
 sunlight in outdoor artificial streams died; L. macrochirus in the same stream, but downstream
 in the shade survived.  L. macrochirus exposed in the shade died within 24 hours when placed
 into clean water and brought into the sunlight. Likewise, D. magna were much more sensitive
 to anthracene in the presence of sunlight than when exposed under laboratory light, with toxicity
proportional to UV intensity  (Allred and Giesy,  1985).   UV-A wavelengths (UVA) were
implicated as responsible for most of the photoinduced toxicity.
       The mechanism by which UV light activates PAHs is the same as  that for electron
                                        3-8

-------
 excitation of plant pigments during photosynthesis by visible light.  This process of excitation
                           ;
 of PAH electrons and the probable consequence of that excitation are reviewed by Newsted and

 Giesy (1987).  Briefly, if a compound absorbs light, then electrons can be elevated to higher

 energy states to form the excited singlet state.  If the excited electrons return immediately to

 their ground state then the extra energy is lost harmlessly through fluorescence.  However, if

 the electrons pass through a triplet state, then the energy can be transferred to other molecules

 (thought to be oxygen in the case of PAHs).  Singlet oxygen formed in this process is capable

 of denaturing biomolecules. Singlet oxygen is very reactive with water and unless organisms,

 PAH,  and sunlight  are present simultaneously,  photoactivation  does not enhance toxicity.

 Therefore, benthic organisms which remain buried or organisms in the shade can survive PAH

 concentrations which would be lethal if they emerged from the sediment or shade into sunlight.

PAHs  are concentrated in  the non-polar environments of cells, such as the phospholipids of

membranes. Singlet oxygen in tissues is longer lived, thus greatly increasing the likelihood that

it  would denature biomolecules.   This also explains why membrane damage is one of the

probable mechanisms for this type of toxicity (Kagan et al., 1987) and why organisms exposed

to PAHs out of direct sunlight die when placed in the sun in PAH-free water.

       Fluoranthene has exhibited photoinduced toxicity during standardized toxicity tests with

a variety of organisms (Appendix A). Although, the toxicity of fluoranthene appears to increase

with increases in intensity  of UVA at low UV intensities (Figure 3-3), the acute toxicity of

fluoranthene to saltwater organisms is similar under commercially available UV lights and

sunlight (Figure 3-3; Appendix A).  This is important since conducting acute and particularly

chronic toxicity tests outside hi sunlight would be extremely difficult and expensive.  The
                                          3-9

-------
























§


,ca
*c
cts
.,fN
CO
"co
CL
0
I







•8

In
?
0
o
O
— ^ — i 	
:> o
•> to
:
:
£ !
=• L
c P
^3 •
CO |
:
|

*
E \
O :
co !
E °1
I 31
§ W :
O > )
CO ^f

©  :
-J ^ :
i — J
CO A /
^^^^ ^v (*
^> 	

	 1 	 1 	 1 	 I
o o o o c
^f CO CM T—
CD
CM


CD
. CD
CO
"*""


CD
. CD
CM



CD
- o
CO




0
- CD
^"



CD
D
                                o

                                      V.
                                      'v.

                                      •O


                                      1

         3
^ <; ^ •« ^ ^ ^




  ™ *^. > «H Tf H
         ti •!
         CTJ *fH

(1/Brf) 09O1
                 3-10

-------
magnitude of increase in fluoranthene's toxicity following UV activation can be great. The ratio
                          j
of LCSOs from acute tests conducted in the dark or under cool-white fluorescent light {"dark")

to LCSOs for the same species exposed in the same laboratory using either UV lights or sunlight

ranges from 2 to 5,000 (Appendix A).  This enhanced toxicity also can occur with relatively

short exposures to UV light.  Kagan et aL, (1985) observed that 1,000 /tg/L of fluoranthene,

pyrene or anthracene was not toxic to five aquatic species in 30 minute exposures. Exposures

to these PAHs for 30 minutes followed by 30 to 60 minutes exposures to UV resulted in LCSOs

from 4 to 360  /tg/L.  Data from chronic tests conducted in both the "dark" and under UV light

are available for two freshwater species, D. magna and P. promelas. and one saltwater species,

M. bahia.  The chronic values decreased by factors of 33 for D. magna. 5.8 for P. promelas.

and 2.1 for M. bahia in the presence of UV light (Table 3-2).  The magnitude of increase in

acute toxicity under UV light was greater than the magnitude of increase in chronic toxicity.

under UV light, and so the acute-chronic ratios under UV light are somewhat lower (Table 3-2).

       There are not enough acute toxicity data from tests using UV light to calculate final acute

and chronic values for  freshwater and saltwater aquatic life.  However, if existing freshwater

and saltwater UV data are combined, the magnitude of the possible decrease in the FCV for

organisms in photic zones can be approximated. The FAVuv derived using overall GMAVs

from all UV and sunlight tests (Appendix A) is 0.5067 /&g/L.  This value is approximately 66

times lower than the "dark"  freshwater FAV, and approximately 32 times lower than the "dark"

saltwater FAV.

       The difference between acute and chronic sensitivity to fluoranthene, in tests under UV

light, varied minimally between species (Table 3-2).  Three species mean ACR are available;
                                         3-11

-------
  1.05 for I>. daphnia, 1.492 for M- bahia and 4.72 for P. promelas.  The final ACR under UV
                           j
  light is the geometric mean of these three values (1.948). The estimated FCVuv for freshwater

  and saltwater organisms combined of 0.2601 is the quotient of the FAVuv of 0.5067 and the

  final ACR.


       At first glance it might seem that photoinduced increases in toxicity are not relevant to

 benthic organisms and that SQC should not be derived using data from UV toxicity tests. This

 may not be true and for this reason SQC  in this document may be under protective in some

 instances.   There are  many  examples of  specific  benthic organisms  where exposure to

 fluoranthene (and  other PAHs)  and sunlight can co-occur.  For example, fiddler crabs which

 typically occupy burrows within the sediment, could accumulate fluoranthene from that sediment,

 and when they come out onto the surface of the sediment at low tide during daylight hours could

 be affected by PAHs in their tissues. Most freshwater insects that inhabit sediment during early

 developmental stages could also be affected by photo-induced PAHs in their tissues when they

 mature and emerge from water during daylight as adults.  The importance of PAH's transferred

 from  benthic species  in aquatic food  chains to aquatic  predators which may be exposed to

 sunlight is unknown.  Rooted aquatic plants also could be directly  affected  by fluoranthene

 contaminated sediment if they were to accumulate fluoranthene and translocate it to their leaves.

 Plants may be a source of photoactivated PAHs to herbivores.

       At this time, U.S. EPA does not recommend a SQC value that considers fluoranthene

toxicity data from  UV tests.  This is partly because data are insufficient to calculate a FCV.

More importantly,  there is an absence of data demonstrating a causal linkage between exposure

of sediment-associated fluoranthene and increased risks  of UV enhanced effects on benthic
                                        3-12

-------
organisms or organisms coupled to benthic organisms via food chains. EPA. encourages research

efforts on these topics.

3.5 APPLICABILITY OF THE WATER QUALITY CRITERION AS THE EFFECTS
   CONCENTRATION FOR DERIVATION OF THE FLUORANTHENE SEDIMENT
   QUALITY CRITERION:

       The use of the FCV  (the chronic effects-based WQC concentration) as the effects

concentration for calculation of the EqP-based SQC assumes  that  benthic (infaunal and

epibenthic) species, taken as a group, have sensitivities similar to all benthic and water column

species tested to derive the WQC concentration.  Data supporting the reasonableness of this

assumption over all chemicals for which there are published or draft WQC documents are

presented in Di Toro et al. (1991), and the SQC Technical Basis Document U.S. EPA (1993a).

The conclusion of similarity of sensitivity is supported by comparisons between (1) acute values

for the most sensitive benthic and acute values for the most sensitive water column species for

all chemicals;  (2) acute values for all benthic species and acute values for all species in the

WQC documents across all chemicals after standardizing the LC50 values; (3) FAVs calculated

for benthic species alone and FAVs calculated for all species in the WQC documents; and (4)

individual chemical comparisons of benthic species vs. all species.  Only in this last comparison

are fluoranthene-specific comparisons in sensitivity of benthic and all (benthic and water-column)

species conducted. The following paragraphs examine the data on the similarity of sensitivity

of benthic and all species for fluoranthene.

       For fluoranthene, benthic species account for 8 out of 12 genera  tested in freshwater,

and 6 out of 8 genera tested in saltwater (Figures 3-1, 3-2). An initial test of the difference

between the freshwater and saltwater FAVs for all species (water column and benthic) exposed
                                         3-13

-------
 to fluoranthene was performed using the Approximate Randomization method (Noreen, 1989).
                           i
 The Approximate Randomization method tests the significance level of a test statistic when

 compared to a distribution of statistics generated from many random subsamples.  The test

 statistic in this case is the difference between the freshwater FAV, computed from the freshwater

 (combined water column and benthic) species LC50 values, and the saltwater FAV, computed

 from the saltwater (combined water column and benthic) species LC50 values (Table 3-1).  In

 the Approximate Randomization method, the freshwater LC50 values and the saltwater LC50

 values are combined into one data set.  The data set is shuffled, then separated back so that

 randomly generated "freshwater"  and "saltwater" FAVs can be computed.  The LC50 values

 are separated back such that the number of LC50 values used to calculate the sample FAVs are

 the same as the number used to calculate the original FAVs.  These two FAVs are subtracted

 and the difference used as the sample statistic. This is done many times so that the sample

 statistics make up a distribution that is representative of the population of FAV differences

 (Figure 3-4).   The test statistic is compared  to  this distribution to  determine it's level  of

 significance.  The null hypothesis is that the  LC50 values that comprise the  saltwater and

freshwater data bases  are  not  different.   If this  is true,  the difference between the actual

freshwater and saltwater FAVs should be common to the majority of randomly generated FAV

differences. For fluoranthene, the test-statistic  falls at the 78 percentile of the generated FAV

differences. Since the probability is less than 95%, the hypothesis of no significant difference

in sensitivity for freshwater and saltwater species is accepted (Table 3-3).

       Since freshwater and saltwater species showed similar sensitivity, a test of difference in

sensitivity for benthic and all (benthic and water column species combined, hereafter referred
                                         3-14

-------
  LU
  O
fWW
so
6O
40
20
0
•20
-40
-60
-80
-100
I I I HUH
- FRE
-
-
^
-
-
I d
I cP
- o°
-O
i M Mini
                 I 11 Mill   I I I I I I III    I   I  I  I   I H  T    HIM I I I  I   Hill 11 I I

                  FRESHWATER VS SALTWATER                 !

                                                                    o-
                       I  I HIIIM	1	1  I  I  I   I	1	""ill I  i  mini i i
             0.1
                    10   20
60
80  90
99    99.9
  LLJ
  CCO
  UI-J
  H-o)
  It 3
    ~
  <
  u_
100


 80


 60


 40


 20


  0


-20


-4O


-6O


-80
         -100
                111 nun—i  i mini	1—i—r-rn—i—r

              -   BENTFBC VS WQC
                         o o'
             I  I IMIIII	1	1  I  I   I  I	I	mun i  i  IIHIIM i
             0.1
                    10   20
GO
80  90
99    99.9
                                 PROBABILITY
Figure 3-4.
  Probability distribution of FAV difference statistics to compare water-only data
  from freshwater vs. saltwater (upper panel) and benthic vs. WQC (lower panel)
  data.
                                    3-15

-------
             TABLE 3-3. RESULTS OF APPROXIMATE RANDOMIZATION TEST FOR
             THE EQUALITY OF THE FRESHWATER AND SALTWATER LC50
              DISTRIBUTIONS FOR FLUORANTHENE AND APPROXIMATE
              RANDOMIZATION TEST FOR THE EQUALITY OF BENTfflC AND
              COMBINED BENTfflC AND WATER COLUMN (WQC) LC50
                                 DISTRIBUTIONS.

             Compar-
             ison     Habitat or Water Type*  ARStatisticb    Probability0

             Fresh    Fresh (12)   Salt (8)          17~4            78~
             vsSalt

             Benthic   Benthic (14) WQC (20)        3.64           74
             vs Water
             Column  +
             Benthic (WQC)
             'Values in parentheses are the number of LC50 values used in the comparison.
             bAR statistic = FAV difference between original compared groups.
             "Probability that the theoretical AR statistic .<_ than the observed AR statistic
             given that the samples came from the same population.
       Since freshwater and saltwater species showed similar sensitivity, a test of difference in

sensitivity for benthic and all (benthic and water column species combined, hereafter referred

to as "WQC") organisms combining freshwater and saltwater species using the Approximate

Randomization method was performed.  The test statistic in this case is the difference between

the WQC FAV, computed from the WQC LC50 values, and the benthic FAV, computed from

the benthic organism LCio values.  This is slightly different then the previous test for saltwater

and freshwater species.  The difference is that  saltwater and freshwater species represent two

separate groups.  In this test the benthic organisms are a subset of the WQC organisms set. In

the Approximate Randomization method for this test, the number of data points coinciding with

                                      3-16

-------
the number of benthic organisms are selected from the WQC data set.  A "benthic" FAV is



computed.  The original WQC FAV and the  "benthic" FAV are then used to compute the



difference statistic. This is done many times and the distribution that results is representative



of the population of FAV difference statistics.  The test statistic is compared to this distribution



to determine  its  level of  significance. The probability distribution of the computed FAV



differences are shown in the bottom panel of Figure 3-4. The test statistic for this analysis falls



at the 74 percentile and the hypothesis of no difference.in sensitivity is accepted (Table 3-3).



This analysis suggests that the FCV for fluoranthene based on data from all tested species is an



appropriate effects concentration for benthic organisms.
                                          3-17

-------

-------
                                     SECTION 4

           TOxicrrY OF FLUORANTHENE (ACTUAL AND PREDICTED):
                              SEDIMENT EXPOSURES
4.1 TOXKTTY OF FLUORANTHENE IN

      The toxicity of fluoranthene spiked into sediments has been tested with three saltwater

amphipod species, and one .amphipod, one midge, one cladoceran, and two fish species from

freshwater.  Data from all species tested have been included in Table 4-1, but only data from

tests with benthic species have been included in Table 4-2 and Figures 4-1 and 4-2.  All

concentrations of fluoranthene in sediments or interstitial water where effects were observed in

benthic  species (Table 4-1) are  greater than SQC or FCV concentrations reported in this

document.  Details about exposure methodology are provided because,  unlike aquatic toxicity

tests, sediment testing methodologies have not been standardized. Generalizations across species

or sediments are limited because of the limited number of experiments. Therefore, insights into

relative sensitivities of aquatic species to  fluoranthene can only be obtained from results of

water-only tests (Section 3).  Data are available from many experiments using both field and

laboratory sediments contaminated with mixtures of PAHs and other compounds which include

fluoranthene. Data from these studies have not been included here because it is not possible to

determine the contribution of fluoranthene to the observed toxicity.

       Gendusa (1990) exposed fathead minnows, Pimephales promelas. and channel catfish,

Ictalurus punctatus. to fluoranthene-spiked  sediments with a total organic carbon content (TOC)
                                         4-1

-------
 tn
 0)
 u
o
 C*
                                               o  on oo     o on oo
 3 on on     3 on on
 cq HI H    co IH IH
 m
   •
 in
                                         in

                                         u>
                                                    f-
                                                    on
            cs

            rH
            on
                                                           O

                                                           H
                                                           in
                                                         t»
                                                           •
                                                         in
                                                                                                 in
                                                                                                 H
                                                                                           oo
                                                                                           oo
                             o
                             o
                             in
                                         o
                                         CO
                        o
                        in
                                                               oo
                                                               in
                       eo

                       r-
                                                          oo
                                                          vo
                                                                                 vo


                                                                                 m
                                                                                             o
                                                                                             00
                                                                                           in
                                                                                           in
                                                                                           en
                                                                                                                  V>
                             ro

                             N
                        tn

                        in
                                                               rn
                       t-

                       00
                                                                                 o

                                                                                 in
                                                                                                            on
                                                                                                      en
                                                                                                       •
                                                                                                      o
                                                                                                                              ro
                       P
            o

            8
            H
o
s
M
                                                o
                                                in
                                                U
                                                M
                                              o

                                              8
                                              H
           o

           8
           H
                                                                                                                                             o
                                                                                                                                             in
                                                                                           H
                                        O
                                        t-l

                                        sir

                                        CO*
                        O
                        T-l


                        SB

                        to*
           S3

           co
                                                                          CO
                                                        .0         O
                                                         H         H

                                                         s?         s7

                                                         CO         CO*
                      o         o
                      H         H

                      S3         S?

                      CO*         CO*
                                                                                                                                  to
                                                                                                                              o
                                                                                                                              01


                                                                                                                              S3

                                                                                                                              CO
vo


o
                                        in

                                        o
                                   \o
                                   i>
                                    •
                                   o
                                                                          o
                                                                          in
                                             vo
                                             •*

                                             o
                                                                                            o
                                                                                            in
a
"Sr
 p. 0)

-rtrH
JSrH
                                                   Q.C
                                                   •H r-l
                                                   Ar-l
                                                                   4-2

-------
            o
            «H
        I
        s
        CO
           £

ce
pt
I
-H
s
Sedi
Sou
Descri
I
rt
ta

I
O
a
                          u
                          o
                          it ot
                          COrt
                 4J
                 o
                                 CO
                                 w
                                 in
                                 A
                                   en
                                   a>
         o
         m
         oo
                 10
                 es
                 in
                          in
                PO

                A
                        4J
                        o
                        i!0
                        got
                        * o\
                        COH
                                        in
                        o

                        00
                                        d
                                        A
                        en

                        A
                                                o

                                                N
                                gat
                                * a\
                                Mrt
                             
                                                                  co
                                                                  -H-H
                                                                  h CO
                                                                                          in
                                                                ii
                                                                W"Q

                                                                gi
                                                                -H-H
                                                                Cd CO
                         -03
                         Ot-
                         Chf
Amphipod,
Corophium
pod,
hiu
C
                                             .
                                            9o
                                            O

                                            "•
                                                                             Ml
                                                                  '8
                                                          2
                                                         p, a
                                                          3
                                                          rt
                                                          §
ipod,
uBtorius
B
                                                                                             a
                                                                                           si-3
                                            4-3

-------































I
I
*•
H
I
TABLE
a
o
a
0
U
•3
Q)

«*0,q
M ?\ in **^»
s^s s


o .
§ S
5 5
||i
3§*
-2 C?
* °
co
a
M
S
fcl-S
IS!"
jgo1-
Uy
H"~*





Sediment
Source;
its Deacription
X
u
0}
o
« *3 d d d *•*
*> *) Q
O O O O   ^ ^ ^
C3 E a D x SB
w eo co w to oT
* f 0
• • i "I "I *!
o o o
& 5 5

c "c "o •§
*H *H -H *O
B« B"3 SB B* e*0 *°
"J^i "1,1 "* m^ mo w?
*!$ °!s °ls °J °'^ *«
|S |E |S |S |5S |1
M>§ «•§ «? «f «f« «•§
|| || || §«• §13 gg;
•H "rl »H -H »H -H -H "H -H -H O **3 -*3
tool ft, 01 ft.cn b co b 01 co Sco
3 o<
«"S ml J& oi .1 J J "
"SS-2 "8°^ "8 § 3 "8^3 "8^3 *8^ 3
^i3.« d SI oj ila'SJ ^3*3 "Sw"! J|S "3
"-< iH
o d
4J J^l
W JJ
4J jj
^2 ^J ^
Q s-I Q H

<•— » .-^.
TD • "co o
* oo ro •
VO rt '00
W — 0» —



0 0
co a\
o r-

to in
in u>
• •
O\ CO

0 0
in in
a a
0 0
rt rt
oT 01"
rt rt
PI CO
0 0*


i s
o o
IM I"*
O 4J O -H
,5, .^
~ jE1 «
*o o *o co
:fi !fi
C O V O O TJ
•H -H "Q -H -H -O
Cb CO <3 bi CO <(

oj mi
ir?*1^ *"*^
S S g ia o 3






















•d
a
I
^
«
D
*
g
•H
*J
S
U
Measured concen
lue
alue
ial water
al water
» B > 4J -H
_, > -H 4J
S 0 4J -H
^3 1^ CQ |i
• in y M n
H/5 ^^ i i !H
1*4 ±J Q)
S S § H "
• 1 s § s
» f» 1 *• p
4-4

-------
of 0.7%.  Sediments were spiked with fluoranthene dissolved in acetone which was added




directly to the sediment. After the acetone was allowed to evaporate for 15 minutes, crystalline



fluoranthene was stirred into the sediment, and overlying water was added. Animals were added



24 hours later.  I. punctatus were exposed for 96 hours, P. promelas were exposed for 96 hours




and 30 days.  Fluoranthene concentrations at the end of the sediment tests were much lower than




at the beginning of the tests, presumably because the sediments did not have time to equilibrate.




The 4-day LCSOs for I. punctatus and P. promelas and the 30-day LC50 for P. promelas were




3.683, 0.97 and 0.437 jtg/g dry wt. respectively, and 526.2, 131.0, and 62.46 jtg/g organic



carbon respectively.  These LCSOs are means of the LCSOs calculated on the basis of the initial




and final measurements of fluoranthene in the tests.



       Suedel et al., (1993) exposed the amphipod, Hyalella azteca. the midge, Chironomus




tentans, and the cladoceran, Daphnia magna. to three fluoranthene-spiked sediments of similar



TOC  content, 0.44 to 0.50%.  Sediments were spiked with fluoranthene dissolved in acetone.




Microliter quantities were added to the sediment surface and allowed to dry for two minutes,



then the sediments were  mixed by hand for 60 seconds before the  addition of test water.



Animals were added to the test beakers 18-24 hours later. LCSOs normalized to dry wt. differed



by a factor of  3.2 (2.3 to 7.4 jig/g) for H. azteca. a factor of 2.9 (3.0 to 8.7 /zg/g) for C.



tentans. and a factor of 3.6 (4.2 to 15.0 /tg/g) for D. magna. The organic carbon normalized




LCSOs for H. azteca differed by a factor of 3.0 (500 to 1,480 /ig/goc), a factor of 2.6 (682 to




1,740 g/goc) for C. tentans. and a factor of 3.4 (955 to 3,261 A*g/goc) f°r D- magna.  Organic



carbon normalization had  little effect because the TOC contents of the three sediments were so




similar.
                                          4-5

-------
        Swartz et al. (1990) exposed the amphipods Corophium spinicorne and Rhepoxvnius
                           t

 abronjus to three fluoranthene-spiked sediments with TOC contents of 0.18%, 0.31% and


 0.48 %. Sediments were prepared using the methods of Swartz et al. (1985) by mixing varying


 amounts of organically-rich fine sediment into sand with a low organic content. Fluoranthene,


 dissolved in acetone,  was added to sediment aliquots in rolling mill jars and rolled.   The


 sediments were allowed to equilibrate for approximately two weeks before sediment was added


 to test chambers.  The 10-day LCSO's for R. abronius increased with increasing organic carbon


 concentration when the fluoranthene concentration was expressed on a dry weight basis, but were


 not different when concentration was expressed on an organic carbon basis.  LCSO's normalized


 to dry weight differed by a factor of 3.1 (3.4 to 10.7 jtg/g) for R. abronius over a 2.7-fold range


 of TOC. The organic carbon normalized LCSO's for R. abronius differed by a factor of 1.2


 (1,890  to 2,230 jig/goc). Because less than 50% mortality of C. spinicorne resulted in the


 highest fluoranthene treatments in two of the three sediments used in this experiment, it was not


possible to make similar comparisons with this species.


       De Witt et al. (1989) exposed the saltwater amphipod E. estuarius to fluoranthene-spiked


sediments at five different salinities and R.. abronius and the freshwater amphipod IL azteca to


fluoranthene-spiked sediments at  single salinities (Table 4-1).  Sediments were spiked  with


fluoranthene dissolved in acetone and mixed on a rolling mill intermittently  over a 24 hour


period.  Overlying water was then added to the test chambers and allowed to equilibrate for 24


hours before the addition of test animals.  Fluoranthene toxicity to E. estuarius was not affected


by interstitial water  salinity.  Nominal LC50 values  (fluoranthene  was not measured at all


salinities) varied by a factor of 1.3 (range 13.8 to 17.5 pg/g) on a dry weight basis.  TOC was
                                          4-6

-------
not measured in these sediments.  The 10-day LC50 for R. abronius (5.1 /tg/g, dry wt) was
                         ;
similar to those reported by Swartz et al. (1990).

       De Witt et al. (1992) exposed R.  abronius to five fluoranthene-spiked sediments of

similar organic carbon content amended with organic carbon from five sources: Zostera marina

(eelgrass); fine grained material which had settled from the water column of Yaquina Bay, OR;

organic-rich sediment from a small slough in Alsea Bay, OR; feces of a suspension-feeding

oyster (Crassostrea gigas) and feces of a deposit-feeding shrimp  fCallianassa californiensis').

Sediments were spiked by shell coating fiuoranthene onto glass jars and rolling for 24 hours.

The sediments were then allowed to equilibrate for 5 weeks before use in the experiments. The

TOC content of the sediment varied from 3.1 to 4.0%. The authors concluded that the source

of organic carbon had little effect on the 10-day LC50 values which varied by a factor of 2.2

(range 8.65 to 19.1jtg/g) on a dry weight basis and by a factor of 2.0 (range 2,790 to 5,620

/tg/g on an organic carbon basis.

       Combining the results of Swartz et al., (1990) and De Witt et al. (1992) for R. abronius.

10-day LC50 values for fluoranthene varied by a factor of 5.6 (3.4 to 19.1 /tg/L) on a dry

weight basis and by a factor of 3.0 (1,890 to 5,620) on an organic carbon normalized basis

(Table 4-1).

       Overall, the need for organic  carbon normalization of the concentration of nonionic

organic chemicals in sediments is presented in the SQC Technical Basis document (U.S. EPA,

1993a).  The need for organic carbon normalization for fluoranthene is also supported by the

results  of  spiked-sediment  toxicity tests described above.   Although  it is important to

demonstrate that organic carbon normalization is necessary if SQC are to be derived using the
                                          4-7

-------An error occurred while trying to OCR this image.

-------





1
o
3
•u
0)
• • *^ *•*
-2 30-H
^p ii infi
M y w 2
K o,
o
4J
0 o en
-H in *^o
•a u o>5
« M a.
Oi
tn
'O Ol^j
4J § "*•
]|S g
rH ^f Si
* si"

8£
§4J tn
id o
ft*
tn
c
•H 14
rH 4J in
«5S
j>

rH
VlS
SH
a —»
£
O (3
J3 0
4J -H
•S
A *0
Q

-H
U
i ®
8§
us



••»**>*

4J 4J iJ JJ U

rt rt rt rt

^ •*> * in ro t»
H oi e» in r- oo
S tO O ^l \Q O
«» i" in * « in
H • • • .
OJ O O O O O
f4 en in to oi o
J> in W t» rt rt
a, i< ro o\ m in
oi n



ij
n c~ o ^ o vo
* * 01 rt 0
* in m ,»o in

en 01 en 9t en
%

o o o o o
SB SEI^ SB 3B 33
eo co* eo* to co

m
S
u S o c
a) a o s
*j y w 4j|
3 3 9 at
•5 *3 'Q "S *o «s g
O rH O rH O rH O
Of Q) Ql Q) Q. ffl « C ^
•HrH -HrH -rl rH ffl O O
•Sd -SrJ ^^ O1** en
ET*5 &*< Qi^ *O*H *O*i
0
0\
en
rt
TO
rt  en c 
-------














.





























5
(continue

M
1
«<«
I

8
u
?
M
O
J7



2*
f<~>
h
o o o
o ** *"
mst
B
>i 0 o
i-i u in
H «CJ
6) IS i^
S
>•
a

s§
* "o
fe.
I!
£ O
4J-H
JE *j
n
a
•
-*4
U
to
7?
O 2
• •
r-t i-l
a) «
JJ XI
o o
J JJ ^J
JJ 4J
•H CJ *H d


Q rt Q tH



t" C~
M N

0 0
o\ a\
t-T ri



o o
H in
** H
'j* fl



O \Q
in cs
H H

«*« 0
CO ^1
• •
0 0

 &
w en



i i







_i
al
cv
H






























T^ * •• »
w\ O\ O\ Oi
•H • •
ts «*> <**
W rt iH


(•> ro
rl rH




0000
r1 «-• ^ H
^ ^ ^ 5^
eo _co i
aj oj
•rt -^
I 1
i 3
o) a
3 S
•gl -gl 1
•S* 0 °'§ '
JS 0 3 0 J
Qj Q) Q. ffl i
c r* K r* 1
fa fa «
»!
abronius
S,
abronius
aj o

?1 -si
is II
HO -H C
II II
?a Is
f
«

•(
4
.
1
0













1
o
ft
* ,
J
9
U
a
•s
•^
en8
o
gj
o
^

^
rH
X
^^
g
Cn
«
..q
4
X
3
^^
Cn
a.

o
tn
•H^
SI" gs
u o . m
Sin o H *
o in
B is »j * *
0 % 0 O
» C 0 ^8 g
8 ^vo • ® 0
§WC .Qr-J M Ij
*8 rH « g 3
^"^ en »H n CQ
N I-H en u « «3
0 « rH^H 0 0
B0u ,*J B H
>i5 -H N |H . >
H W -H tJ S *° *0
J 0 O CO^ § 0
•B B M *
V4 ffi h O 3 3
°f ?,fc^^P
4-10

-------
sediments (>315 /tg/L). This result runs counter to previous observations that the pore water
                         !



chemical concentration shows strong correlation with toxicity.  De Witt et al. (1992) note that




this eelgrass amended sediment was the only sediment tested where the organic carbon originated




from fresh plant material.  Similarity of LCSOs on an organic carbon basis and dry weight basis




suggest that the pore water fluoranthene may not have been entirely bioavailable.  Free (not




associated with dissolved organic carbon, DOC) pore water fluoranthene concentration was




measured using a modification of the Landrum et al. (1984) reverse-phase separation method.




Free pore water fluoranthene concentrations were generally 60 to  90%  of the total pore water




concentrations. For the five sediments tested, LC50 values based  on free flouranthene in pore




water (LC50  = 8.09 to  > 179 /tg/L) were as variable as those based on total pore water




fluoranthene (9.38 to > 315 /*g/L).  The fact that the organic-carbon normalized LC50s may be




better predictors of toxicity than pore water concentrations was  also observed with dieldrin




(Hoke and Ankley, 1991). Partitioning to dissolved organic carbon was proposed to explain the




lack of similarity  of LC50 values based on total pore water dieldrin concentrations.  This




explanation is not applicable to results with fluoranthene because the total and free pore water




fluoranthene concentrations and LC50 values were simitar and  uniform across all sediment




types.




       A more detailed evaluation of the degree to which the response of benthic organisms can




be predicted from toxic units of substances in pore water can be made utilizing results from




toxicity tests  with  sediments  spiked  with other  substances, including acenanphthene  and




phenanthrene (Swartz, 1991a), endrin (Nebeker et al., 1989; Schuytema et al., 1989), dieldrin




(Hoke 1992), fluoranthene (Swartz et al.,  1990, DeWitt et al. 1992), or kepone (Adams et al.,
                                          4-11

-------
 1985) (Figure 4-1; Appendix B).  The data included in this analysis come from tests conducted
                          r                             '            i


 at EPA laboratories or from tests which utilized designs at least as rigorous as those conducted



 at the EPA laboratories.   Tests  with acenaphthene  and phenanthrene used two  saltwater



 amphipods QU. plumulosus and E.. estuarius') and marine sediments. Tests with fluoranthene used



 a saltwater amphipod QjL. abroniusl and marine sediments.  Freshwater sediments spiked with



 endrin were tested using the amphipod H. azteca: while kepone-spiked sediments were tested



 using  the midge, £.  tentans.  Figure 4-1 presents the percentage mortalities of the benthic



 species tested in individual treatments for each chemical versus "pore water toxic units" (PWTU)



 for all sediments tested.  PWTUs are the concentration of the chemical in pore water fyig/L)



 divided by the water  only LC50 fttg/L).   Theoretically, 50% mortality should occur at one



 interstitial water toxic unit. At concentrations below one PWTU there should be less than 50%



 mortality, and at concentrations above one PWTU there should be greater than 50% mortality.



 Figure 4-1 shows that at concentrations below one PWTU mortality was generally low, and



 increased sharply at approximately one PWTU. Therefore, this comparison supports the concept



 that interstitial water concentrations can be used to predict the response of an organism to a



 chemical that is not sediment specific.  This pore water normalization was not used to derive



 SQC in this document because of the complexation of nonionic organic chemicals with pore



 water DOC (Section 2) and the difficulties of adequately sampling pore waters.







4.3 TESTS  OF THE  EQUILIBRIUM PARTITIONING PREDICTION OF SEDIMENT

    TOXICITY:



       SQC derived using the EqP approach utilize partition coefficients and FCVs from WQC



documents to derive the SQC concentration for protection of benthic organisms. The partition




                                        4-12

-------
              Ld
   _ UJ H Q-
	 O 3C S LU Ij
UJ < Q- Q M C.

 I   I   I  I  I  I

n <> o o *
        1    I    1
                            1    1    1    1
I    I    I    I    I
   g      8
                                                                4
                                                                 8

                                                                I
                                    %
                             4-13

-------
coefficient (Koc) is used to normalize sediment concentrations and predict biologically available
                         r

concentrations across sediment types. The data required to test the organic carbon normalization


for fluoranthene in sediments are available for four benthic species.   Data from tests with water


column species were not included in this analysis. Testing of this component of SQC derivation


requires three elements: (1) a water-only effect concentration, such as a 10-day LC50 value in


/tg/L, (2) an identical sediment effect concentration on an organic carbon basis, such as a 10-day


LC50 value in /tg/goc, and (3)  a partition coefficient for the chemical, KQC in L/kgoc.  This


section presents evidence that the observed effect concentration in sediments (2) can be predicted


utilizing the water only effect concentration (1) and the partition coefficient (3).


       Predicted ten-day LC50 values from fluoranthene-spiked sediments tests with H. azteca


and £. tentans were calculated (Table 4-2) using the LogjoKoc value of 5.00 from Section 2 of


this document and the sediment LC50's in Suedel (1993). Ratios of actual to predicted LCSOs


for fluoranthene averaged 0.217 (range 0.111 to 0.330) for H.  azteca and 0.387 (range 0.214


to 0.545) for C. tentans. The ratio of actual to predicted LC50 for I. punctatus (Gendusa, 1990)


was 0.146.  Data on P.. promelas (Gendusa, 1990) and D. maena were not used for prediction


because they are not benthic organisms.


       Predicted ten-day LC50 values on a ftg/goc basis from fluoranthene-spiked sediment tests


with IL. abronius (Swartz et  al., 1990; De Witt et al., 1992) were calculated (Table 4-2) using


the value of KQC (105-00) from Section 2 of this document and the 10-day water-only EC50 values


in Swartz (1991a). Ratios of actual to predicted LCSOs for fluoranthene averaged 2.13 (range


1.36 to 4.04) for IL. abronius. The data from De Witt  et al (1989) can not be used  for


prediction because the TOC of the sediments was not measured.
                                          4-14

-------
       A more detailed evaluation of the accuracy and precision of the EqP prediction of the



response of benthic organisms can be made using the results of toxicity tests with amphipods



exposed to sediments spiked with acenaphthene, phenanthrene, dieldrin, endrin, or fiuoranthene.



The data included in this analysis came from tests conducted at EPA laboratories or from tests



which utilized designs at least as rigorous as those conducted at the EPA laboratories.  Data




from  the kepone experiments are not included because a measured KQW for kepone obtained



using the slow stir flask  method is not available.   Swartz (1991a) exposed the saltwater




amphipods  R  estuarius and L.. plumulosus to acenaphthene in  three marine sediments having




organic carbon contents ranging from  0.82 to  4.2%  and to  phenanthrene in three marine




sediments having  organic carbon contents ranging from 0.82 to 3.6%.  Swartz et al. (1990)



exposed the saltwater amphipod IL abronius to fiuoranthene in three marine sediments having




0.18,  0.31  and 0.48% organic carbon.  Hoke and Ankley (1991)  exposed the amphipod H.



azteca to three dieldrin-spiked freshwater sediments having 1.7, 3.0 and 8.5% organic carbon



and Hoke (1992)  exposed  the midge C. tentans to two freshwater dieldren-spiked sediments



having 2.0 and 1.5% organic carbon.  Nebeker et al. (1989) and Schuytema et al. (1989)




exposed H. azteca to three  endrin-spiked sediments having 3.0, 6.1 and 11.2% organic carbon.



Figure 4-2  presents the percentage mortalities of amphipods in individual treatments of each



chemical versus "predicted sediment toxic units"  (PSTU) for each sediment treatment.  PSTUs



are the concentration of the chemical in sediments 0*g/goc) divided by the  predicted LC50




Gig/goc)  in sediments  (the  product  of KQC  and the 10-day  water-only LC50).   In  this



normalization, 50% mortality should occur at one PSTU.  At concentrations below one PSTU



mortality was generally low, and increased sharply at one PSTU. The means of the LCSOs for
                                         4-15

-------
a






"•
-
-



E
-
~*



«t
i
—
—
—
-


E
-
-
-



_ Q. .2 fe 

"tm
oa











i i i i i
S §






1 ! 	 -
{ -
. i
i
i
i
1
i -
i :
°!
> 1 ~_
> t> ^

 <^ "~ -
V ^ ^st><<^ ^< z
l 0 ° %
t ""
1 0
1
1 1 1 1 1 if^l 1
898°


p



S.

•



* z

X
o
g
III
v- UJ
^^E
Q
111
CO
0
S
0
^ 0
d UJ
a.



5
d
                                                      8
                                                      S
                                                      PL,
                        %
                                4-16

-------
these tests calculated on a PSTU basis were 1.90 for acenaphthene, 1.16 for dieldrin, 0 .44 for
                           j
endrin, 0.80 for fluoranthene,  and 1.22  for phenanthrene.   The mean  value  for  the  five

chemicals is 0.99. This illustrates that the EqP method can account for the effects of different

sediment properties and properly predict the effects concentration in sediments using the effects

concentration from water only exposures.
                                           4-17

-------

-------
                                     SECTIONS



                 CRITERIA DERIVATION FOR FLUORANTHENE



 5.1 CRITERIA DERIVATION:








       The water quality criteria (WQC) Final Chronic Value (FCV), without an averaging



 period or return frequency (See section 3), is  used to calculate the sediment quality criteria




 (SQC) because it is probable that the concentration of contaminants in sediments are relatively




 stable over tune, thus exposure to sedentary benthic species should be chronic and relatively




 constant.  This is in contrast to the situation in the water column, where a rapid change in




 exposure  and exposures of limited durations can occur  due  to fluctuations  in effluent




 concentrations, dilutions in receiving waters or the free-swimming or planktonic nature of water



 column organisms. For some particular uses of the SQC it may be appropriate to use the areal



 extent and vertical stratification of contamination of a sediment at a site in much the same way



that averaging periods or mixing zones are used in WQC.




       The FCV is  the value that should protect 95%of the tested species included  in the



calculation of the WQC from chronic effects of the substance. The FCV is the quotient of the




Final Acute Value (FAV), and the final Acute  Chronic Ratio (ACR) for the substance. The



FAV is an estimate of the acute LC50 or EC50 concentration of the substance corresponding to



a cumulative probability of 0.05 for the genera from eight or more families for which acceptable



acute tests have been conducted on the substance.  The ACR is the mean ratio of acute to




chronic toxicity for three or more species exposed to the substance that meets minimum database




                                        5-1

-------
requirements.  For more information on the calculation of ACRs, FAVs, and FCVs see the
                         t

National Water Quality Criteria Guidelines (Stephan et al., 1985).  The FCV used in this


document differs from the FCV in the fluoranthene WQC document (U.S. EPA, 1980) because


it incorporates recent data not included in that document, and omits some data which does not


meet the data requirements established in the WQC Guidelines (Stephan et al., 1985).


       The equilibrium partitioning (EqP) method for calculating SQC is based on the following


procedure.  If FCV Otg/L) is the chronic concentration from the WQC for the chemical of


interest, then the SQC Otg/g sediment), is computed using the partition coefficient, KP (L/g


sediment), between sediment and pore water:


             SQC = KP FCV                                                 (5-1)


       Since organic carbon is the predominant sorption phase for nonionic organic chemicals


in naturally occurring sediments, (salinity, grainsize and other sediment parameters  have


inconsequential roles  in  sorption, see sections 2.1  and 4.3) the organic carbon partition


coefficient, (Koc) can be substituted for KP.  Therefore, on a sediment organic carbon basis, the


SQCoc G*g/goc)} is:

             SQCoc = KOC FCV                                              (5-2)


Since (Koc) is presumably independent of sediment type for non-ionic organic chemicals, so also


is SQCoc. Table 5-1 contains the calculation of the fluoranthene SQC.


       The organic carbon normalized SQC is applicable to sediments with an organic carbon


fraction of foe ^  0.2%.  For sediments with f^ < 0.2%, organic carbon normalization and


SQC may not apply.
                                         5-2

-------
        TABLE 5-1. SEDIMENT QUALITY CRITERIA FOR FLUORANTHENE
Type of
Water Body
Fresh Water
Salt Water
Log10Kow
(L/kg)
5.09
5.09
Logi^
(L/kg)
5.00
5.00
FCV
6.16
2.96
(Mg/goc)
620"
300b
            = (105'00 L/kgoc)«(10-3 kgoc/gocW6.16 fig fluoranthene/L) = 620 fig
fluoranthene/goc
             =  (105-00 L/kgocXlO'3 kgoc/goc)»(2.96 fig fluoranthene/L) = 300  fig
fluoranthene/goc
       Since organic carbon is the factor controlling the bioavailability of nonionic organic

compounds in sediments, SQC have been developed on an organic carbon basis, not on a dry

weight basis.  When the chemical concentrations in sediments  are reported as  dry weight

concentration and  organic  carbon data are available,  it is best to  convert the  sediment

concentration to fig chemical/gram organic carbon. These concentrations can  then be directly

compared to  the SQC  value.   This facilitates  comparisons between  the  SQC and  field

concentrations  relative  to identification of hot  spots and  the  degree to which  sediment

concentrations do or  do not exceed SQC values.  The conversion from dry weight to organic

carbon normalized  concentration can be done using the following  formula:

       Hg Chemical/goc  = fig Chemical/gDRY WT  + (% TOC 4- 100)

                       = fig Chemical/gDRYWT  • 100 * % TOC

       For example,  a freshwater sediment with a concentration  of 6.00 fig chemical/gDRYWT

and 0.5 % TOC has  an organic carbon-normalized concentration of 1,200 fig/goc (6.00 ftg/gDRrwT


                                         5-3

-------
 • 100 H- 0.5 =  1,200 /tg/goc) which exceeds the SQC of 620 /ig/goc-  Another freshwater
                          i

 sediment with the same concentration of fiuoranthene (6.00 Mg/gnRvwr) but a TOC concentration


 of 5.0% would have an organic carbon normalized concentration of 120 /ng/gbc (6.00 /tg/gDRY


 vr • 100 -s- 5.0 = 120 Atg/goc), which is below the SQC for fluoranthene.


       In situations where TOC values for particular sediments are not available, a range of


 TOC values may be used in a "worst case" or "best case" analysis. In this case, the organic


 carbon-normalized SQC values (SQCoc) may be  "converted" to dry weight-normalized SQC


 values (SQCDRYWr.).  This "conversion" must be done for each level of TOC of interest:


              SQCDRYWT =  SQCoc Otg/goc) • (% TOC -s- 100)


 where SQCDRYVrr is the dry weight normalized SQC value. For example, the SQC value for


 freshwater sediments with 1 % organic carbon is 6.2 /tg/g:


              SQCDRYWT. = 620 jig/a*, •  1% TOC  * 100 = 6.2 /*g/gDRYWT


 This method is used in the analysis of the STORET data in section 5.4.


 5.2  UNCERTAINTY ANALYSIS:


    Some of the uncertainty in the calculation of the fluoranthene SQC can be estimated from


the degree to  which the EqP model, which  is the basis for the criteria, can rationalize  the


available sediment toxicity data. The EqP model asserts that (1) the bioavailability of nonionic


organic chemicals from sediments is  equal on an organic carbon basis, and (2) that the effects


concentration in sediment (^g/gocD can be estimated from the product of the effects concentration


from water only exposures  G-ig/L) and the partition coefficient KQC (L/kg).  The uncertainty


associated with the SQC can be obtained from a quantitative estimate of the degree to which the


available data support these assertions.
                                         5-4

-------
    The data used in the uncertainty analysis are from the water-only and sediment toxicity tests
                          ;

that have been conducted to fulfill the minimum database requirements for the development of


SQC (See Section 4.3 and Technical Basis Document, U.S. EPA, 1993a). These freshwater and


saltwater tests span a range of chemicals and organisms; they include both water-only and


sediment exposures and they are replicated within each chemical-organism-exposure  media


treatment.  These data were analyzed using an analysis of variance (ANOVA) to estimate the


uncertainty (i.e.  the variance) associated with varying the exposure media and that associated


with experimental error. If the EqP model were perfect, then there would be only experimental


error.  Therefore, the uncertainty associated with the use of EqP is the variance associated with


varying exposure media.


    The data used in the uncertainty analysis are illustrated in Figure 4-2.   The data for


fluoranthene are summarized in Appendix B. LC50s for sediment and water-only tests were


computed from these data.  The EqP model can be used to normalize the data in order to put


it on a common basis.  The LCSOs from water-only exposures (LC50W; /tig/L) are related to the


organic carbon-normalized LCSOs from  sediment exposures  (LC50s>0c;  /*g/goc)  via the


partitioning equation:
             T f^n    — TT  T /"^n                                        /c o\
             i-A^JVg QC — X^Q^J-A^JU^r                                      1j—j 1





The EqP model asserts that the toxicity of sediments expressed on an organic carbon basis equals


the toxicity in water  tests multiplied by the KQC.  Therefore, both LC50S(OC and KoC*LC50w


are estimates of the true LC50OC for each chemical-organism pair.   In this analysis, the




                                          5-5

-------
 uncertainty of KQC is not treated separately. Any error associated with KQC will be reflected in
                            :                                        -  i

 the uncertainty attributed to varying the exposure media.


     In order to perform an analysis of variance, a model of the random variations is required.


 As discussed above, experiments that seek to validate equation 5-3 are subject to various sources


 of random variations.  A number of chemicals and organisms have been tested.  Each chemical -


  organism pair was tested in water-only exposures and in different sediments.  Let or represent


 the random variation due to this source. Also, each experiment is replicated. Let G represent


 the random variation due to this source. If the model were perfect, there would be no random


 variations other than that due to experimental error which is reflected in the replications. Hence


 o; represents the uncertainty due to the approximations inherent in  the model and G represents


 the experimental error. Let (erj2 and (o-e)2 be the variances of these random variables. Let i


 index a specific chemical-organism pair.  Let j index the exposure media, water-only, or the


 individual sediments.  Let k index the replication  of the experiment.  Then the equation that


 describes this relationship:


             ln(LC50i>i)fc)  = ft  + ay + €ij)k                                      (5-4)


 where ln(LC50)iJifc, are either InCLCSOw) or ln(LC50s,oc) corresponding to a water-only  or


 sediment exposure, and 0, are the population of ln(LC50) for the chemical-organism pair i. The


 error structure  is assumed to be lognormal which corresponds to assuming that the errors are


proportional to  the means, e.g. 20%, rather  than absolute quantities,  e.g. 1 /ig/goc.  The


 statistical problem is to estimate n-a (oj2, and (
-------
        TABLE 5-2: ANALYSIS OF VARIANCE FOR DERIVATION OF
        SEDIMENT QUALITY CRITERIA CONFIDENCE LIMITS FOR
                                FLUORANTHENE.
Source of Uncertainty
Exposure media
Replication
Sediment Quality Criteria
Parameter Value
0*g/goc)
aa 0.39
ae 0.21
aSQc a 0.39
The last line of Table 5-2 is the uncertainty associated with  the SQC; i.e.,  the variance

associated with the exposure media variability.

   The confidence limits for the SQC are computed using this estimate of uncertainty. For the

95% confidence interval limits, the significance level is 1.96 for normally distributed errors.

Hence:

                          = ln(SQCoc) + 1.96
-------
                 TABLE 5-3. SEDIMENT QUALITY CRITERIA
                      CONFIDENCE LIMITS FOR FLUORANTHENE

                                      Sediment Quality Criteria
                                    95% Confidence Limits
                 Type of       SQCOC
                 Water Body    A*g/goc       Lower      Upper
                 Freshwater    620         290        1300

                 Saltwater      300         140         640



5.3    COMPARISON OF FLUORANTHENE SQC CONCENTRATIONS TO SEDIMENT
       CONCENTRATIONS THAT ARE TOXIC OR PREDICTED TO BE CHRONICALLY
       ACCEPTABLE:

       Insight  into  the  magnitude of protection afforded  to  benthic  species  by SQC

concentrations and 95% confidence intervals can be inferred using effect concentrations from

toxicity tests with benthic species exposed to sediments spiked with fluoranthene and sediment

concentrations predicted to be  chronically safe to organisms tested in water-only exposures

(Figures 5-1 and 5-2). This is because effect concentrations in sediments can be predicted from

water-only toxicity data and KQC values (See Section 4).  Chronically acceptable concentrations

are extrapolated from genus mean acute values (GMAV) from water-only, 96-hour lethality tests

using acute-chronic ratios (ACR).  Therefore, it may be reasonable to combine these two

predictive procedures  to estimate,  for fluoranthene,  chronically acceptable  sediment

concentrations (Predicted Genus Mean Chronic Value, PGMCV) from GMAVs (Appendix A),

ACRs (Table 3-2) and the KQC (Table 5-1):

            PGMCV = (GMAV + ACR)«Koc.                               (5-7)

      In Figures 5-1 and 5-2 each PGMCV for fishes, arthropods or other invertebrates tested

                                       5-8

-------
      O
     s
     1
     N^
     UJ
     O
     O
     <
     UJ
     to
     O
     LU
     Q
     UJ
           106
            105
104
     0    103
            102
         Water-only tests: (96HR LC5Q -*• ACR) KQC

         A Arthropods
         D Other Invertebrates
         O Fishes
 ACR = 5.45

 Sediment Tests: 10 d LC50

 if Q. tentgns = 1235 ng/goc
   range 3 tests = 682 to 1 740
® H.gztecg = 974(ig/goc
   range 3 tests = 500 to 1 480
53 I. punctatus = 526 ng/goc (4d)
                           T    T
                          O   O
                                              T    t
                                             t
                                             A
 T
O
                                            • • upper:

                                            -SQC:
                                              lower: 290(ig/goc
                          20
                                     60
                                      80
100
                     PERCENTAGE RANK OF FRESHWATER GENERA
Figure 5-1.   Comparison between SQC concentrations and 95% confidence intervals, effect
             concentrations from benthic organisms exposed to fluoianthene-spiked sediments
             and sediment concentrations predicted  to be chronically safe  in fresh water
             sediments.  Concentrations predicted to be  chronically safe (Predicted Genus
             Mean Chronic Values, PGMCV) are derived from the Genus Mean Acute Values
             (GMAV) from water-only 96-hour lethality tests, Acute Chronic Ratios (ACR)
             and KQC values. PGMCV = (GMAV ^- ACR)!^. Symbols for PGMCVs are
             A for arthropods,  O for fishes and D for other invertebrates.  Solid symbols are
             benthic genera; open symbols water column genera. Arrows indicate greater than
             values.  Error bars around sediment LC50  values indicate observed range of
             LCSOs.
                                        5-9

-------
          o
         I
         UJ
O

O
G:
31


1
        CO

        LLJ
        CD
        Q

        o
        Q
        UJ
              105
              ,04
              102|
Water-only tests: (96HR LC50•*- ACR) KQC

A Arthropods
D Other Invertebrates
O Rshes
   log, nKoc^ 5.00                   •
   ACR = 5.45

   Sediment Tests: 10 d LC50
   •^ C.. splnlcorne « 2830 ng/gog
   ® R. qbronlus = 2960 ng/g^ .
       range 8 tests = 1890 to 5620
                                              upper: 640^^00
                                                      lower:
                           20         40         60         80         100

                        PERCENTAGE RANK OF SALTWATER GENERA
Figure 5-2.   Comparison between SQC concentrations and 95% confidence intervals, effect
             concentrations from benthic organisms exposed to fluoranthene-spiked sediments
             and sediment concentrations predicted  to  be chronically  safe in salt water
             sediments.  Concentrations predicted to be chronically safe (Predicted Genus
             Mean Chronic Values, PGMCV) are derived from the Genus Mean Acute Values
             (GMAV) from water-only 96-hour lethality tests, Acute Chronic Ratios (ACR)
             and KQC values. PGMCV = (GMAV -J-  ACR)Koc.  Symbols for PGMCVs are
             A for arthropods, O for fishes and D for other invertebrates.  Solid symbols are
             benthic genera; open symbols water column genera. Arrows indicate greater than
             values.  Error bars around sediment LC50 values indicate observed ranee of
             LC50s.
                                       5-10

-------
in water is plotted against the percentage rank of its sensitivity. Results from toxicity tests with
                          ;

benthic organisms exposed to sediments spiked with fluoranthene (Table 4-1) are placed in the


PGMCV rank appropriate to the test-specific effect concentration.  For example, the 10-day


JLC50 for H. azteca (974 /ig/goc) is placed between the PGMCV of 660 jtg/goc for the catfish


(Ictalurus) and the PGMCV of 1,121 /Jg/goc for the amphipod (Gammarus).  Therefore,


sediment  test LC50  or other effect concentrations  are intermingled in this figure with


concentrations predicted to be chronically  safe.  Care  should  be taken by the  reader in


interpreting these data with dissimilar endpoints. The following discussion of SQC, organism


sensitivities and PGMCVs is not intended to provide accurate predictions of the responses of taxa


or communities of benthic organisms relative to specific concentrations of fluoranthene in


sediments in the field.  It is, however, intended to guide  scientists and managers through the


complexity of available data relative to potential risks to benthic taxa posed by  sediments


contaminated with fluoranthene.


       The freshwater SQC for fluoranthene  (620 /*g/g0c) is less than any of the PGMCVs and


all but one of the LC50 values from spiked sediment toxicity tests. The PGMCVs for 8 of 12


freshwater genera are greater than the upper 95 % confidence interval of the SQC (1300 ftg/goc)-


The PGMCV for the catfish Ictalurus (660 pg/goc), the amphipod Gammarus (1,121 /tg/goc),


the cladoceran Daphnia (1,247 /tg/goc) and the hydrpid Hydra (1,285 /ig/goc) are below the SQC


upper  95% confidence interval.   This illustrates why the  slope  of the species sensitivity


distribution is important. It also suggests that if the extrapolation from water only acute lethality


tests to chronically acceptable  sediment concentrations is accurate, these or similarly sensitive


genera may be chronically impacted by sediment concentrations marginally above the SQC and
                                         5-11

-------
possibly less than the 95% upper confidence interval.  For fluoranthene, the PGMCVs of



freshwater organisms range over less than one order of magnitude from the most sensitive to the



most tolerant genus.  However, many of the LC50 values for the less sensitive species are



"greater than" values, presumably because actual LC50 values would exceed saturation. Chronic



effect concentrations may, however,  occur  at concentrations below saturation. A sediment



concentration five times the SQC would include the PGMCVs of five of the eight benthic genera



tested including stoneflies, amphipods, hydroids,  catfish, and snails.  Tolerant benthic genera



such as the annelid Lumbriculus. and the dragonfly Ophiogomphus might be expected to not be



chronically impacted in sediments with fluoranthene concentrations five times the SQC. We



speculate that sediment concentrations far in excess of this may be unlikely to chronically impact



benthic genera that tolerate chronic water-only exposures up to fluoranthene's water solubility.




      The saltwater SQC for flouranthene (300 ftg/goc) and the upper confidence limits are less



than any of the PGMCVs for saltwater genera.  For fluoranthene,  PGMCVs from the most



sensitive to the most tolerant saltwater genus range over two orders of magnitude. As with the



freshwater data, many of the values for less sensitive species are "greater than" values dictated




by fluoranthene's water solubility. A sediment concentration five times the SQC would include



the PGMCVs of all three benthic arthropod genera tested. Less sensitive benthic genera include



molluscs, polychaetes and fish, some of which might not be expected to be chronically impacted



in sediments with fluoranthene concentrations _>. 1,OOOX the SQC.




      The above extrapolation using the PGMCV approach for fluoranthene may be reasonable



given (1) the accuracy of the equilibrium partioning prediction using KQC and water-only LC50




values as demonstrated by the ratio of the actual and predicted LC50 value (Predicted Sediment
                                         5-12

-------
Toxic Units, PSTU; Table 4-2) and (2) the measured toxicity of fluoranthene-spiked sediments
                         i

to benthic taxa when compared to PGMCV predictions of their relative sensitivities.  If water


only LC50 and KQC values perfectly predict actual sediment toxicity then the ratio of the actual


to the predicted LC50 values (PSTU) would be 1.0. PSTU values for fluoranthene averaged


0.217 for Hvalella azteca. 0.387 for C. tentans. 0.146 for I. punctatus and 2.13 for Rhepoxynius


abronius; overall mean 0.80. Ten-day LC50 values for H. azteca and C. tentans were greater


than the SQC (620 MS/goc) but less than the upper 95%- confidence limit (1,300 jig/goc)-  The


measured LC50 for I. punctatus (526 /Kg/goc) and the PGMCV (660 /*g/g0c) for catfish are the


lowest values on Figure 5-1 as might be expected,  because this catfish was the most acutely


sensitive species tested in water-only exposures  (Figure 3-1).   However,  the fact that the


PGMCV, which estimates the safe concentration is less than the 96 hour LC50 value for this fish


suggests that one or both of these values may be suspect.





5.4  COMPARISON OF FLUORANTHENE SQC TO STORET AND NATIONAL STATUS

       AND TRENDS DATA FOR SEDIMENT FLUORANTHENE:


       A STORET (U.S. EPA,  1989b) data retrieval was performed to obtain a preliminary


assessment of the concentrations of fluoranthene in the sediments of the nation's water bodies.


Log probability plots of fluoranthene concentrations on a dry weight basis in sediments are


shown in Figure 5-3. Fluoranthene is found at varying concentrations in sediments from rivers,


lakes and near coastal water bodies in the United States.  Median concentrations are between 0.1


/tg/g to 0.3 /Kg/g in the three water bodies.  There  is significant variability with fluoranthene


concentrations in sediments ranging over seven orders of magnitude within the country.


       The SQC for fluoranthene can be compared to existing concentrations of fluoranthene in



                                        5-13

-------
w
       ,
        o
Figure 5-3.
•10 3 = STREAM ,
i"
« 2L
10 1 ^_
10 °-r '
10 ~1i-
10 "Z~r
10 "a5
- r *u
10 ~*l. <«««**
mr =
1Q "«1_i , •.....!
ai 1
10 4 __,_,„,,„„, ,
10 ^S-L^
!
10 2 ^ 	
10 1 k-
» °j.
« -';.
10 ^r
i
10 -«r
10 ^F
0.1 1
10 4g . .,mll| , ,
w 3 = ESTUARY
10 '••„ ..
10 !•• -
« °r
10 "1i-

10 *-T
10 ^r < «
10 ^J.
K) "C~ I 1 Illllll 	 1 	 L
0.1 1
TOTAL SAMPLES: 786
MEASURED SAMPLES: 254


^<«««Jic<^<«^
.-/

	
10 20 60

TOTAL SAMPLES: 57*
MEASURED SAMPLES: 28


*<«*^

^gp
jl^*
c < ««< «
I ' I ml 	 1 .il..
10 20 60

TOTAL SAMPLES: 88 '
MEASURED SAMPLES: 32


^^t«««
^^^^^^
^^
«« «««


10 20 60
•* — r Turn i r T- -^|iTn 1 1 i i •
e
® 1
-~^*-1
" ^**^~~ -
0^1 1
i
i

i
1 I..,,,,, , I,,,,,, , . =
80 90 99 99.9


1
V -• m ~*
m++i* ^
-
1
1


'BO 90 99 99.9

I 	 TH 1 1 1 i i — i — limn i i |
jj
T
_-.•
:««<^*^" 1
T

r

i 	 ||,, , | , , , i,,.,.. , , =
80 90 99 99.9
                                   PROBABILITY
       Probability distribution of concentrations of fluoranthene in sediments from
       streams, lakes and estuaries in the United States from 1986 to 1990, from the
       STORET (U.S. EPA, 1989b) database, compared to the fluoranthene SQC values
       of 62 jig/g in freshwater sediments having TOC =  10%  and 6.2 /tg/g in
       freshwater  sediments having TOC = 1% and compared to  SQC values for
       saltwater sediments of 30 /*g/g when TOC = 10 % and 3.0 /*g/g when TOC=1 %.
       The upper dashed line on each figure represents the SQC value when TOC =
       10%, the lower dashed line represents the SQC when TOC =  1%.
                                 5-14

-------
 sediments of natural water systems in the United States as contained in the STORET database




 (U.S. EPA, 1989b).  These data are generally reported on a dry weight basis, rather than an



 organic carbon normalized basis.  Therefore, SQC values corresponding to  sediment organic




 carbon levels of 1 to 10% are compared to fluoranthene's distribution in sediments as examples



 only. For fresh water sediments, SQC values are 6.2 /*g/g dry weight in sediments having 1 %




 organic carbon and 62 pg/g dry weight in sediments having  10% organic carbon; for marine



 sediments SQC are 3.0 /*g/g dry weight and 30 /ig/g dry weight,  respectively.  Figure 5-3



 presents the  comparisons of these  SQC  to probability distributions of observed sediment



 fluoranthene levels for streams and lakes (fresh water systems, shown on the upper panels) and




 estuaries (marine systems,  lower panel). For streams (n = 786) the SQC of 6.2 jcg/g dry weight




 for 1 % organic carbon fresh water sediments is exceeded for 2% of the data and the SQC of 62




 jttg/g dry weight, for fresh water sediments having 10% TOG is exceeded by less than 1% of




 the data. For lakes (n = 57) the SQC for 1 % organic carbon fresh water sediments is exceeded



 by about 5% of the data,  but the SQC for 10% organic carbon fresh water sediments is not



 exceeded by any of the sample data.  In estuaries, the data (n = 88) indicate that the criteria of



 3.0 jtg/g dry weight for salt water sediments having 1 % organic carbon is exceeded by less than




 2% of the data and the criteria of 30 pg/g dry weight for salt water sediments  having  10%



 organic carbon is not exceeded by the post 1986 samples.




      The fluoranthene distribution in Figure 5-3 includes data from some samples in which



 the fluoranthene concentration was below the detection limit.  These data are indicated on the



plot as "less than" symbols (<), and plotted at the reported  detection limits.  Because these



values represent upper bounds and not measured values the percentage of samples  in which the
                                         5-15

-------
 SQC values are actually exceeded may be less than the percentage reported.
                           i

       A second database developed as part of the National Status and Trends Program (NOAA,


 1991) is also available  for  assessing  contaminant  levels in  marine sediments that are


 representative of areas away from sources of contamination. The probability distribution for


 these data, which  can be directly expressed on an organic carbon basis,  is compared to the


 saltwater SQC for fluoranthene (300 /tg/goc) on Figure 5-4. Data presented are from sediments


 with 0.2 to 16.2 percent organic carbon.  The median organic carbon normalized fluoranthene


 concentration (about 7.0 jig/goc) is two orders of magnitude below the SQC of 300 Atg/goc-  Less


 than 1% of the measured values (n=797) are greater than the SQC for fluoranthene. Hence,


 these results are consistent with the preceding comparison of the marine SQC to STORET data.


       Regional differences in fluoranthene concentrations may affect the  above conclusions


 concerning expected criteria exceedences. This analysis also does not consider other factors


 such as the type of samples collected (i.e., whether samples were from surficial grab samples


 or vertical core profiles), or the relative frequencies and intensities of sampling in different study


 areas.   It is presented  as  an  aid in assessing the range of reported fluoranthene sediment


 concentrations and the extent to which they may exceed the SQC.





5.5 LIMITATIONS TO THE  APPLICABILITY OF SEDIMENT QUALITY CRITERIA:


       Rarely,  if  ever,  are contaminants  found alone  in  naturally occurring sediments.


 Obviously, the fact that the concentration of a particular contaminant does not exceed the SQC


does not mean that other chemicals, for which there are no SQC available,  are not present in


concentrations sufficient to cause harmful effects. Furthermore, even if SQC were available for
                                         5-16

-------
nun i i iiiiiicj i nun11 i inn111 i  mini i i mm; i i
                        8  z
                       i
                       o
mini i mini I i  mini i i mum i  miiitt lOimiii
                           o
                           flO
                           2
                         •
                         m

                         i
                         £
                                  •2 -a §3
                                  ill
                            111
                            a S *c3
                            III
                                  |I*
                                  |!|

                                  lit!
                                  £511
(OO
                                  8
                                  §>
                                  S
               1N3WIQ3S
                5-17

-------
all of the contaminants in a particular sediment, there might be additive or synergistic effects
                         t                                           ;
that the criteria do not address.  In this sense the SQC represent "best case" criteria.

       The concerns about mixtures of contaminants are particularly important with the PAHs,

which almost invariably occur as complex mixtures. Some guidance on interpretations of PAH

concentrations is possible given the presence of SQC for fluoranthene and other individual

PAHs.  This is because much is known about the toxicity and structure-activity relationships of

the so-called narcosis chemicals, a group of nonionic organic chemicals to which the PAHs

belong.  The toxicity of the narcosis  chemicals is  additive  (Broderius and Kahl, 1985). The

toxicity of these chemicals increases with increasing  KQW (Veith et al., 1983) and their

bioavailability in sediments decreases as a function of its KQW Therefore, the toxicities of many

PAHs in sediments are likely to be similar. This explains  why SQC values for fluoranthene


(fresh: 620 jig/goc, salt: 300 jig/goc), acenaphthene (fresh:  130 /ng/goc, salt: 230 A*g/goc) and

phenanthrene  (fresh:  180 fig/goo  salt:  240 ftg/goc)  differ  little and why it is theoretically

possible to develop an SQC for total  PAHs.  EPA is currently conducting research aimed at

development of SQC for combined PAHs.

       It is theoretically possible that antagonistic reactions between chemicals could reduce the

toxicity of a  given chemical such that it  might not cause unacceptable effects on benthic

organisms at concentrations above the SQC when it occurs with the antagonistic chemical.

However, antagonism has rarely been demonstrated. What should be much more common are

instances where toxic effects occur at concentrations  below  the SQC because of the additivity

of toxicity of many common contaminants (Alabaster  and Lloyd, 1982), e.g; heavy metals and

PAHs,  and instances where other toxic compounds for which no SQC exist occur along with
                                         5-18

-------
SQC chemicals.




       Care must be used in application of EqP-based SQC in disequilibrium conditions. In



some instances site-specific SQC may be required to address this condition. EqP-based SQC



assume that nonionic organic chemicals are in equilibrium with the sediment and IW and are



associated with sediment primarily through adsorption into sediment organic carbon.  In order




for these assumptions to be valid, the chemical must be dissolved in IW and partitioned into



sediment organic carbon.  The chemical must, therefore, be associated with the sediment for a



sufficient length of time for equilibrium to be reached. In sediments where particles like cinder,




soot, or  oil droplets contain PAHs, disequilibrium exists and criteria are over protective. In




liquid chemical spill situations disequilibrium concentrations in interstitial and overlying water




may be proportionately higher relative to sediment concentrations. In this case criteria may be



underprotective.




       In very dynamic areas,  with highly  erosional or depositional bedded  sediments,



equilibrium may not be attained with contaminants. However, even high KQW nonionic organic



compounds come to equilibrium in clean sediment in a period of days,  weeks or months.



Equilibrium times are shorter  for mixtures of two sediments each previously at equilibrium.



This is particularly relevant in tidal situations where large volumes of sediments are eroded and




deposited, yet near equilibrium conditions may predominate over large areas. Except for spills



and paniculate chemical, near  equilibrium is the rule and disequilibrium  is uncommon.  In



instances where it is suspected that EqP does not apply for a particular sediment because of




disequilibrium discussed above, site-specific methodologies may be applied (U.S. EPA,  1993b).



       Finally, it should be remembered that in some situations the phototoxicty of fluoranthene
                                        5-19

-------
may be important.  The current SQC for fluoranthene does not take phototoxic effects into



account.
                                        5-20

-------
                                      SECTION 6



                               CRITERIA








       The procedures described in the "Technical Basis for Deriving Sediment Quality Criteria




for Nonionic Organic  Contaminants for the  Protection of  Benthic  Organisms by  Using




Equilibrium  Partitioning" (U.S.  EPA, 1993a) indicate that  benthic  organisms  should be




acceptably protected in freshwater sediments containing <_ 620 /tg fluoranthene/g organic carbon




and saltwater sediments containing <_ 300 /tg fluoranthene/g organic carbon, except possibly



where a locally important species is very sensitive or sediment organic carbon is < 0.2%.




       Confidence limits of 290 to 1300 jig/goc for freshwater sediments and 140 to 640 ftg/goc




for saltwater sediments are provided as an estimate of the uncertainty associated with the degree



to which the observed concentration in sediment (/tg/goc)* which may be toxic, can be predicted



using the  organic carbon partition coefficient (Koc) and the water-only effects concentration.



Confidence limits  do not incorporate uncertainty associated with water quality criteria.  An



understanding of the theoretical basis of the equilibrium partitioning methodology, uncertainty,




the partitioning and toxicity of fluoranthene, and sound judgement are required in the regulatory



use of SQC and their confidence limits.




       These concentrations represent the U.S. EPA's best judgement at this time of the levels




of fluoranthene in sediments that would be protective of benthic species. It is the philosophy of



the Agency and the EPA Science Advisory Board that the use of sediment quality criteria (SQCs)



as stand-alone, pass-fail criteria is not recommended for all applications and should frequently
                                          6-1

-------
trigger additional studies at sites under investigation. The upper confidence limit should be
                          .*

interpreted as a concentration above which impacts  on benthic  species should be expected.


Conversely, the lower confidence limit should be interpreted as a concentration below which


impacts on benthic species should be unlikely.
                                           6-2

-------
                                     SECTION 7
                                    REFERENCES

 Adams, W.J., R.A. Kimerle and R.C. Mosher. 1985.  Aquatic safety assessment of chemicals
       sorbed to sediments.   In:  Aquatic Toxicology and  Hazard Assessment:  Seventh
       Symposium. Eds: R.D. Cardwell, R. Purdy and R.C. Banner. Amer. Soc. Testing and
       Materials, Philadelphia; PA. STP 854.  pp. 429-453.

 Alabaster, J.S. and R. Lloyd. 1982.  Water Quality Criteria for freshwater fish.  Chapter 11.
       Mixtures of Toxicants.  London, Butterworth Scientific.

.AUred, P.M and J.P. Giesy. 1985.  Solar radiation-induced toxicity of anthracene to Daphnia
       pulex.  Environ. Toxicol. Chem. 4:219-226.

 Birge, W.J., J.A. Black, S.T. Ballard and W.E. McDonnell. 1982. Acute toxicity testing with
       freshwater fish.  Final Report Task U. and DDL U.S. EPA.  Contract No. 68-01-6201.

 Bowling, J.W.,  G.J. Leversee, P.P. Landrum and J.P. Giesy.  1983.   Acute mortality of
       anthracene-contaminated fish exposed to sunlight. Aquatic Toxicol. 3:79-90,

 Broderius, S. and M. Kahl. 1985.  Acute toxicity of organic chemical mixtures to the fathead
       minnow.  Aquatic Toxicol. 6:307-322.

 Brooke, L. 1991. Memorandum to  Walter Berry.  Summary of results of acute and chronic
       exposures of fiuoranthene without and with ultraviolet (UV) light to various freshwater
       organisms.  Decembers. 5pp.

Brooke, L. 1992. Letter to Walter J.  Berry documenting result of Daphnia magna chronic test
       with fiuoranthene under normal laboratory light.  April 2.  2pp

Brookes, P. 1977.  Mutagenicity of polycyclic aromatic hydrocarbons.  Mutation Res. 39*257-
       284.

Buccafusco, R.J., S.J. Elis and G.A.  LeBlanc. 1981. Acute toxicity of priority pollutants to
       bluegill (Lepomis macrochirusl. Bull. Environ. Contain. Toxicol.  26:446-452.

Callahan, M.A.,  M.W. Slimak, N.W.  Gabel, I.P. May, C.F. Fowler, J.R. Freed, P. Jennings,
       R.L. Durfee, F.C.  Whitmore, B. Maestri, W.R. Mabey, B.R. Holt, and C. Gould.

                                        7-1

-------
       1979.   Water-related environmental fate  of 129 priority pollutants.   Volume n:
       Halogenated aliphatic hydrocarbons, halogenated ethers, monocyclic aromatics, phthalate
       esters, polycyclic aromatic hydrocarbons, nitrosamines, and miscellaneous compounds.
       U.S.  EPA,  Office  of Water Planning and Standards, Office of Water and Waste
       Management, Washington, DC, EPA-440/4-79-029b.

Champlin, D.M. and S. L. Poucher. 1991a.  Acute toxicity of fluoranthene to various marine
       organisms. Memorandum to D.J. Hansen.  U.S. EPA.  Narragansett, RI.

Champlin, D.M. and S. L. Poucher. 1991b.  Chronic toxicity of fluoranthene to the mysid,
       Mysidopsis bahia.  Memorandum to D.J. Hansen. U.S. EPA. Narragansett, RI.

Champlin, D.M. and S. L. Poucher.  1992a.  Acute toxicity of fluoranthene to saltwater animals
       (UV lights).  Memomandum to Brian Melzian.  September 11. 9pp.

Champlin, D.M. and S. L. Poucher.  1992b.  Flow-through chronic toxicity of fluoranthene
       under UV light to Mysidopsis bahia. Memorandum to D.J.  Hansen.  September 1. 3pp.

Chapman, G. A. 1987. Establishing sediment criteria for chemicals-regulatory perspective.  In:
       Fate and Effects of Sediment-Bound Chemicals in Aquatic Systems.  Editors: K.L.
       Dickson, A.W. Maki and W.A. Brungs.  Pergamon Press, New York. pp. 355-376.

Chou, J.T. and P.C. Jurs.   1979. Computer-assisted computation of partition coefficients from
       molecular structures using fragment constants.  J. Chem. Inf. Comput. Sci. 19(3): 172-
       178.

De Bruijn, J., F. Busser, W.  Seinen, and J. Hermens.  1989.  Determination of octanol/water
       partition coefficients for hydrophobic organic chemicals and with the "slow-stirring"
       method.  Environ. Toxicol. Chem. 8:499-512.

De Witt, T.H,  R.C. Swartz, and J.O. Lamberson.  1989.   Measuring the acute toxicity of
       estuarine sediments. Environ. Toxicol.  Chem.  8:1035-1048.

De Witt, T.H., R.J. Ozretich, R.C. Swartz, J.O. Lamberson, D.W. Shults, G.R. Ditsworth,
       J.K.P. Jones, L. Hoselton, and L.M. Smith. 1992. The effect of organic matter quality
       on the toxicity and partitioning of sediment-associated fluoranthene to the infaunal marine
       amphipod, Rhepoxynius abronius. Environmental Toxicology and Chemistry 11:197-208.

Di Toro, D.M., 1985.  A particle interaction model of reversible organic chemical sorption.
       Chemosphere. 14(10): 1503-1538.

Di Toro,  D.M., C. Zarba,  D.J. Hansen, R.C.  Swartz, C.E.  Cowan,  H.E.  Allen, N.A.
       Thomas, P.R. Paquin, and W.J. Berry. 1991.  Technical basis for establishing sediment
       quality  criteria  for  nonionic  organic chemicals  using  equilibrium  partitioning.

                                        7-2

-------
       Environmental Toxiciology and Chemistry.  10:(12)1541-1583.
                         i        '
Eadie, B.J., P.P. Landrum, W. Faust. 1982.  Polycyclic aromatic hydrocarbons hi sediments,
       pore water and the amphipod Pontoporeia hoyi from Lake Michigan.  Chemosphere
       ll(9):847-858.

EG&G, Bionomics.  1978.   Preliminary Research Report.   Acute and chronic toxicity  of
       fluoranthene to mysid shrimp (Mysidopsis bahia^. Submitted to U. S. EPA. Contract No.
       68-01-4646.

Gendusa, A.C.  1990.  Toxicity of chromium and fluoranthene from aqueous and sediment
       sources to selected freshwater fish.  Ph.D. Thesis, University of North Texas. U.M.I.
       300 N. Zeeb Rd., Ann Arbor, MI 48106. 138 pp.

Heitmuller,  P.T., T.A. Hollister and P.R. Panish. 1981.   Acute toxicity of 54 industrial
       chemicals to  sheepshead minnows (Cyprinodon variegatus).  Bull. Environ. Contain.
       Toxicol. 27:596-604.

Hoke, R. 1992. Results of the third dieldrin sediment-spiking experiment.  Memorandum to D.
       Hansen, D. Di Toro, and G. Ankley.  December 2.  5 pp.

Hoke,  R. and G.T.  Ankley.  1991.  Results of dieldrin sediment spiking study conducted in
       support of USEPA development of sediment quality criteria.  Memorandum to D. Hansen
       and D. Di Toro.  June 18, 1991.  9 pp.

Home, J,D. and B.R. Oblad.  1983.  Aquatic toxicity studies of six priority pollutants.  Final
       Report Task H. U.S.  EPA. Contract No. 68-01-6201.

Kagan, J., E.D. Kagan, I.S. Kagan, P.A. Kagan, and S. Quigley. 1985.  The phototoxicity
       of  Non-carcinogenic  polycyclic  aromatic  hydrocarbons  in aquatic  organisms."
       Chemosphere. 14(11/12): 1829-1834.

Kagan, J., A. Stokes, H. Gong, and R.W. Tuveson.  1987.  Light-dependent cytotoxicity of
       fluoranthene: Oxygen-dependent membrane damage. Chemosphere 16(10-12):2417-2422.

Karickhoff, S.W., L.A. Carreira, C. Melton, V.K. McDaniel, A.N. Vellino, and D.E. Nute.
       1989.  Computer prediction of chemical reactivity - The ultimate SAR.  U.S. EPA,
       Environmental Research Laboratory, Athens, GA, Environmental Research Brief;
       EPA/600/M-89/017.

Landrum, P.P., S.R. Nihart, B.J. Eadie and W.S. Gardner.  1984. Reverse-phase separation
       method for determining pollutant binding to Aldrich humic acid and dissolved organic
       carbon in natural waters.  Environ. Sci. Technol.  18:187-192.
                                        7-3

-------
 Landrum, P.P., S.R. Nihart, B.J. Eadie, and L.R. Herche. 1987.  Reduction in bioavailability
       of organic contaminants to the amphipod Pontoporeia hoyi by dissolved organic matter
       of sediment interstitial water.  Environ. ToxicoL Chem. 6:11-20.

 LeBlanc, G.A. 1980. Acute toxicity of priority pollutants to water flea rPaphnia magma). Bull.
       Environ. Contam. Toxicol. 24:684-691.

 Mabey, W.R., J.H. Smith, R.T. Podoll, H.L. Johnson, T. Mill, T.W. Chou, J. Gates, I.W.
       Partridge, H. Jaber, and D.  Vandenberg.  1982. Aquatic fate process data for organic
       priority pollutants.  U.S. EPA, Office of Water Regulations and Standards, Washington,
       DC, Final Report, EPA-440/4-81-041.

 Mackay, D., A. Bobra, and W.Y. Shui. 1980.  Relationships between aqueous solubility and
       octanol-water partition coefficients.  Chemosphere 9:701-711.

 Mackay, D. and B. Powers. 1987.  Sorption of Hydrophobic Chemicals From Water: A
       Hypothesis for the Mechanism of the Particle Concentration Effect.   Chemosphere
       16(4):745-747.

 National Academy of Sciences/National Academy of Engineering. 1973. Water Quality Criteria
       1972.  EPA.R3.73.033. 594pp.

 Nebeker, A.V., G.S. Schuytema, W.L.  Griffis, J.A. Barbitta, and L.A. Carey. 1989.  Effect
       of sediment organic carbon on survival of Hyalella azteca exposed to DDT and endrin.
       Environ. Toxicol. Chem. 8(8):705-718.

 Newsted, J.L and J.P. Giesy.  1987. Predictive models  for photoinduced acute toxicity of
       polycyclic aromatic hydrocarbons to Daphnia magma.  Strauss (Cladocera, Crustacea).
       Environ. Toxicol. Chem. 6:445-461.

 NOAA. 1991. National Status and Trends Program - Second summary of data on chemical
       contaminants in sediments  from the National  Status  and  Trends Program.  NOAA
       Technical Memorandum NOS OMA 59.  NOAA Office of Oceanography and Marine
       Assessment, Rockville, MD. 29 pp  + appendices.

 Noreen, E.W. 1989. Computer intensive methods for testing hypotheses: An introduction.
       John Wiley and Sons Inc., New York, N.Y.

 Oris, J.T., R.W. Winner, and M.V. Moore.  1991.   A four-day survival and reproduction
       toxicity test for Ceriodaphnia dubia.  Environ. Toxicol. Chem. 10:217-224.

Rossi,  S.S. and J.M. Neff.  1978.  Toxicity of polynuclear aromatic hydrocarbons  to the
       polycheate Neanthes arenaceodentata. Mar. Pollut. bull. 9:220-223.
                                        7-4

-------
Schuytema, G.A., A.V. Nebeker, W.L. Griffis, and C.E. MiUer. 1989.  Effects of freezing
       on toxicity of sediments contaminated with DDT and endrin.  Environ. Toxicol. and
       Chem. 8(10):883-891.

Stephan, C.E., D.I. Mount, D.J. Hansen, LH. Gentile, G.A. Chapman, and W.A. Brangs.
       1985.  Guidelines for deriving numerical national water quality criteria for the protection
       of aquatic organisms and their uses.   PB85-227049.   National Technical Information
       Service, Springfield, VA. 98 pp.

Suedel, B.C., J.H. Rodgers, Jr., and P.A. Clifford.  1993. Bioavaflability of fluoranthene in
       freshwater sediment toxicity tests.  Environ. Toxicol. and Chem.  12(1): 155-165.

Swartz, R.C., G.R.  Ditsworth, D.W. Schults, and J.O.-Lamberson.  1985. Sediment toxicity
       to a marine infaunal amphipod: Cadmium and its interaction with sewage sludge. Mar.
       Envir. Res. 18:133-153.

Swartz, R.C., D.W. Schults, T.H. DeWitt,  G.R. Ditsworth, and J.O.  Lamberson. 1990.
       Toxicity of fluoranthene in sediment to marine  amphipods:  A test of the equilibrium
       partitioning approach to sediment quality criteria. Environ. Toxicol. Chem. 9(8): 1071-
       1080.

Swartz, R.C.  1991.  Acenaphthene and phenanthrene  files. Memorandum to David J. Hansen,
       June 26, 1991.  160 "pp.

Swartz, R.C.  1991.  Fluoranthene experimental design: Final. Unpublished manuscript.  10pp.
       December 31, 1991.

Swartz, R.C.   1992.   Conference call on  Figure  2-1  fluoranthene  SQC document.   See
       memorandum from D.J. Hansen to W.J. Berry.  July 28.  1 p.

Thursby, G.B.  1992.  Saltwater section of fluoranthene document.  Memorandum to Sherry
       Poucher.  December 12, 1991.  25pp.

U.S. Environmental Protection Agency. 1978. In-depth studies on health and environmental
       impacts of selected water pollutants.  U.S. EPA. Contract No. 68-01-4646.

U.S. Environmental Protection Agency. 1980. Ambient water quality criteria for fluoranthene.
       Office of Water Regulations and Standards, Criteria and Standards Division. U.S. EPA,
       Washington, D.C. EPA 440/5-80-049.

U.S. Environmental Protection Agency. 1985. Appendix B - Response to public comments on
       "Guidelines for deriving numerical national water quality criteria for the protection of
       aquatic organisms and their uses." July 19,  1985.  Fed. Regist. 50:30793-30796.
                                        7-5

-------
 U.S. Environmental Protection Agency. 1987.  Quality Criteria for Water, 1986. EPA 440/5-
       86-001.  May 1, 1987. U.S. Government Printing Office No. 955-002-000008. 406pp.

 U.S. Environmental Protection Agency. 1989a.  Sediment classification methods compendium.
       Watershed Protection Division,  U.S. EPA. 280 pp.

 U.S. Environmental Protection Agency. 1989b. Handbook: Water Quality Control Information
       System, STORET. Washington, D.C., 20406.

 U.S. Environmental Protection Agency. 1989c.  Briefing Report to the EPA Science Advisory
       Board on the Equilibrium Partitioning Approach to Generating Sediment Quality Criteria.
       Office of Water Regulations and Standards, Criteria and Standards Division, 132 pp.

 U.S. Environmental Protection Agency. 1993a. Technical Basis for Deriving Sediment Quality
       Criteria for Nonionic Organic Contaminants for the Protection of Benthic Organisms by
       Using Equilibrium Partitioning.  (In review).

.U.S. Environmental Protection Agency.   1993b.   Guidelines  for Deriving  Site-Specific
       Sediment Quality Criteria for the Protection of Benthic Organisms. (In review).

 U.S. Environmental Protection Agency. 1993c. Guide for the Use and Application of Sediment
       Quality Criteria for Nonionic Organic Chemicals.  (In Review).

 Verschueren, K. 1983.  Handbook of Environmental Data on Organic Chemicals, Second
       Edition.  Van Nostrand Reinhold Company, New York.  1310 pp.

 Veith, G.D., D.J. Call, andL.T. Brooke. 1983.  Structure-toxicity relationships for the fathead
       minnow, Pimephales promelas: narcotic industrial chemicals.  Can. J. Fish. Aquat. Sci.
       40:743-748.

 Yalkowsky, S.H., S.C. Valvani, and D. Mackay. 1983.  Estimation of the aqueous solubility
       of some aromatic compounds. Residue Rev. 85:43-55.
                                       7-6

-------





CO
K
&
V
•Jq
j3 5
^®
°
CO
c
M
C3
rflo
s w
EG l l
CJ
%
Oi
co

o
^in
S"
uw
1 g
^ |— |
|¥| r .
P rf
g S
8^
h
1
•", g
rij 1^1
wS
M§
3 E-!
M co

S
3
S

COMMON/SCI .
«*> ro
s S
H H
H
_? en »
•O en -a
^ rH 0 nJ
HHHH^^H > H cn H 3
encncnenoencn • en H en 5
ssss-oss-rss * s „
S ° S
JS .8 .8 JS m 8 8 ® ""I" S <»
1 1 ! 1 i 1 1 .2 1 s 1 1
SSSSSSSSSSS'J
., (
..qvovoininoines o ^
O) • • co • r» co r co i ivo° i
^* H rt H
A A
^gvoininoino ,>o
en -Z ' "* • ** ' & c* t i <*  > >
Q P 0 & Q g [>
H H H H Q. H H Q. ° Q, B. «
^'fe&'&.COfn&.COCOCOCOCO

MWHHMHM&&SSH

.
^"*^!>§SSg§|gc1ll
•rj \H m ffl 8 -H -H >§ >S ..§ .S .S
I i 1 1 2 - - §i ' |i si ai 'g
S So^S^n 2 * nivi fc i^ MTJCQ
ID nJ-OO-go 43 rH rHiDrdonjajnjardoa
22 SS-^S ^ "8 ^« -•'« ^« oc °c og oa ^S
il if 11 If 11 11 '«> ** *•§ ^1 51 41
^a ^li ii ii 5g] sH.gH 53 cisl nS si 11






H
en
en
^4
Brooke, :

H
H
VO

H

\o

VO
•
VO
H
tH
A

VO
VO
rH
H
A


g

Q
ft.

H


si;

CD
H
S
(U
H
B
Amphipod,
Gammarus pseudold

-------

















































•a
CO
x A. - continu
Appendi:







CO
rv
P
fe
B
i
a
tg
3 £j

K S
M £f)

Q

3j
B
M

O
^ w
^ ^
£ D3
W H

CU
CO
<.o

te\ U
rj M
J5

« o
II
O K
U ^

1
* §
g H
fe|
3^
M CO


1
0
CO
8
ro
CO
en
rH

«*
"O
(d
rH
JQ
0
•d
§
CD
I
O

""•«•. in
en ro
=3. H



^>. in
tn ro
a, H


o

"*•• in
en ro
a. rt



^ 0

g in
"*• po
H


&



CO*

M
M



id
•H
(C
-.rH
rH Q)
>»H P
Q) O
G jj
OrH
•U Q)
CO PJ









H
CD
0*
rH
Brooke,

in

CO
r-
rH
A

in
CO
r^
H
A

in
*
CO
r-
H
A

in

CO
c*
H
A

a


Q
E

H
53



a
CQ
09
Dragonf:
Ophioeroi









H
en
en
H
Brooke,

r-

en
o
rH
A

«>
en
o
H
A

c**
•
en
o
H
A

r.

en
0
H
A

a

^
£}
EH"
fa

H
B



a
m
CO
Dragonf:
Ophiocroi
ro
CO
en
' H

*.
'O
«J
rH
.Q
O
•O
1





1




1





1



O

t*.
00
H


s



Q
CO*

*
*



m
to
•H
g
3 a
SI
Rainbow
Oncorhvi









H
en
en
H
Brooke,

in

o
en
A


in
o
en
A


in
•
o
en
A


in
*
0
en
A


s


Q
E

*
„



CO
m
-H
3 co
0 3
iJ-B
I-!
Rainbow
Oncorhvi









H
en
en
H
Brooke,

o

,
r-



o
,
j^



o
c-




o
f^
r*
'
c*»



g

^
5
H
fa

*
rj



m
m
-rl
3 co
0 j2
jj cj
fH
Rainbow
Oncorhvi








o
en
en
rH
Gendusa,






i



i





(



H

- *
r**



a



a
CO

*
^



minnow,
Les promelas
Fathead
Pimepha]
ro
CO
en
H

^
•o

H
H

A

^
•
H
H

•

t-

^_l
rH

A

a


o


*
1-3



minnow
Les promelas
Fathead
Pimepha]









H
en
en
H
Brooke,

CM
CM

CM
rH


es
•
CM



eM
CM
CM
rH


eM
CM

CM
H


a

^
^
B

S:
•o



minnow,
.es promelas
Fathead
Pimepha]









H
en
en
H
Brooke,



i




i







1



vo

vo
H
rH
A

a


Q
EH
fa

*
^



•/
macrochirus
Bluegil]
Lepomis
rH
CO
en
H
*•
•
i-H
id

u
0)

8a
co r-
3a

-------







FENCES
K
K
8
ll
wo
5
03
D
gy
u

gj'co
f*4 | |
•JH •*
u
S>
ft
CO

8s
W C-4
||
O
§
g



00
t~
en
H
'-' ! a 
\ ft X o
Co co g S
* i S
i
p
. g D D
Q Q
co co*







a a t6
H CNJ H
*o en *o a\ ~ "O en
B en B en B en
(0 t-4 (B H (d rH
G ,- G •> G ~ *
*ri H -H h -H ^| en
i-id) rH 0) rH CD H
tG O JC O .G O ft
Uft U ft U ft W
S <»
cT
H it
0 CO
r^
C^ CN
•» 1 1
H
H *


0 ' '


CO
o in
^i

S D D &
Q EI Q Q
co co co" co*
CO
r-
cn
""*
^
£Q
U
•*H
a e
H O
•d en G
Sen O
rH -H
PQ
G -
rH d) O
PK rj
TO 3
J3 O O
in
H
nn
<*
in
•
1 rH
in .•
^
in
•
' rH
in


CO _
"! «
o
CO

S S
a Q
CK &








-BO :£ O J2 O
U ft U ft U ft
S »
c! H
CO VO
in •
1 • H
o

CO VO
in
i ' H
o


VO CO . VO
t^ in
H
M O

& JgJ p"l
> P ni
D •• co
co b co*







ri
•d en
B en
(0 rH

TO 3
•B O
rj p,
CO
en
VO
VO
m
en
•
VO
VO
m

a
VO
VO


m
VO
VO

D
Q
co







•O en
G en
B rH
•HU
r* Q
CJ ft
in
•H
in
•
cs

H
in

(\i
rH


in
CJ
H

D
Q
m.
CO







to
•O en
§3
-H V?
O. rl
go
TO 3
•G O
O ft
in
in
H
in
in

H

in
in

rH
OJ


in
in
H

0
£
co"
                                                                                                                                                            f)
                                                                                                                                                            •k
p
b
   co
                       H
                                H
                                          W
                                                                                W
                                                                                         H
                                                                                                   n
                                                                                                            H
                                                                                                                      w
                                                                                                                                                  H
                          CQ
                      •Od)
                      -H  £
                      rHU
                       0)  C
                       C   5
T3T3
-H-H
 ta  tn
sis bahia
Mysid
Mvsi
Mysid,
Mvsidopsis bahia
ia
s
sid,
idops
ita
hipod,
elisca
Grass shrimp,
Palaemonetes pucrio

-------










































rrt
Appendix A. - continue*





CO
i
1
In
3 E
m o
0


1
O
rt "w
jcj CQ
u
g
CO
• 0
om
§u
w

^x
1 g
*2j 1^1
M £.«
s g
o
§
i
H


**, tj*
I3J |.|

68
Ht*c
l^j




COMMON/SCI. NflME





(d  B
-H rl -H rl -H
rH 0) rH O rH
60 .C 0 J3
P. OP| Of
nJ °
<„ O
OJ 0
* en «M o*

A

A °
•V. O
cn o
a. ro cj
H C<1 O
A
H) °
•»>. o
Cn o
sj. ro N
*"* °* w
A
•~i °
a a a §
o
c^
A


p p &

& 3 0
eo co" co*




•^ *^ 1^
*^ i* iS


rl rl H




American lobster
Homarus americanus
American lobster
Homarus americanus
Sea urchin,
Arbacia punctulata


I


tf nJ
H H t
y\ "d cn »O c
7\ C Q\ C C
- B •> B
H -H fc -H
U rH 0) rH
3 pB O r*
1. UP. U C
en
CO ,
ro



cn
CO 1
•
ro

en
CO
ro

en o
o
o
03
A


& \=>

£ P
•>. «.
CO CO




IS &J"


W rj




Sea urchin,
Arbacia punctulata
Sheepshead minnow,
Cvprinodon varieqatus

<
i
• t

« *,
-i U I
n (U c
r\
r-uui-;iitii, j
Heitmullei
o
o
»
°l
A

0
o
o
o
A
O
O
o
o
OJ
A
O
o
o
o
VO
in
A

D

Q
CO




IS
w


l"2




Sheepshead minnow,
Cvprinodon varieqatus

a
*»
j\
-t

?
* 1!
Uf[dureqo
•C'n irocr
CO
CO
in
rH


CO
CO
in
H
CO
*
CO
in
rH

CO
CO
in
f_l




D

g
co




w


hD




Sheepshead minnow
Cvprinodon varieqatus





id
n -d t
2 Sc
H . (d T
k" -S
1) rH
3 JH
3 P
1. U C

W
H



r>
rH


^i
H

OJ
H





D

CO
CO




u


IK




Sheepshead minnow
Cvprinodon varieqatus





id
n *d c
n Be
H (Of
H* -H
2 3
3 f-i
3 (3 ;
3 J3
1. U C
VO
«
VO
rH
• VD


VO
VO
r^
VO
VO

VO
H
VO

VO
VO
. H
VO




&

Q
CO




EB


1—




Inland silverside,
Menidia bervllina





id
r> i D)
k (d
3 C! g
^ i i
II rH
0 rH
HO (d
o
^ Jj ^^ ._J
a) ID n. E
id 4J R 53
> g < J3
H £ ;> o
id 5
rH II ~- II
11 * % &
O ' T3
3 3 ^ §
H B .• 1- m
B fe " g S
J f) m-^ ®

^ & &^ H
" 0) ^ in d
1 H JZ ,, „ U
^ „ 51 d> -d
"Lifestage: A = adult, 0
but habitat known.
•Habitat : I = inf auna, I
•Method: FT' = flow-throu
S = static
UV = ultravioli
D = dark (UVB
SL = Sunllight
•"Concentration : M = cheir

-------



















o
If)
u
H
O
o
in
u

<1)
JJ
1
•a
9
u
-rt
JJ
1
O
m
0)
-rt
0
0)
&
m
0)
1
a)
4J
!
§
u
-rt
4J
0)
Q
0)
&

rf
*3
s
IH
O
Geometric mean
to
i
O)
.>
M
, habitats and lifestages within the genus.
M

-------

-------
CQ a,
D
* If

3:

CQ 5
|Jg
IV1 *|^|
H ~" ;
05 :
« co
O< EH
X rH
g
ffj
CO TJ
H H

g H ' 1
05 H
& E-,
< u
o

*
p j
g *
fej co .
Is
If
CO r/}

^ H
P5 9
w £

«i
PM
MO .
rfl™
c_I O H
*$ M 5 '
Q fc
"**" ri
u
co s3
ll

B i
CO G §
t«Hi H
< Q
H W
• £-1 CQ
CQ ri|
. *1 i"\
rH O t*
H O Q
§g5



CQ
K!
U
a
a!
N
9









o^
"^



82
'"*

^
W EH «
m |S Q *5
r H H p
3 ci **•*
g§


Oj •
a 3
Ho'eJ
SEDIMEN
CONCENTRATI
DRY WT. OR
U
M
K|
Pj *^
r? *-*
tr
y




Q

E"*
CQ
fa
EH
«23 "*S|*» CO
H W H
SOU
W p! CJ
Q t> W
H O Pi
CQ CQ CO


: : :
rH rH rH
id J N
eninoco' oco- oco
••••CO "'CO ••
OHCOVOrH COVDrH COVD


0 O O
in • • in • o
in o • o o in • o o •
• • N o o • r- o -in
NOTjtHrH NCOrH ON


^ «. «•
O5 DJ P4
O O O

^ *. *.
^i CD ^n CQ ^t tQ
fl3 J3 (d £3 flj ,3
CQ -H CQ -H CQ -H
C 03 CH 09 CH
«J>3 rt?3 nJ?
C X-H C X-H c X
-HOC -HOC -HO
&p o d o o . ao
(1) rl & 0) rl & 0)
(dJnX) (d J2 XI n5 xl
jn3(3 t«S«i >«a



















en
en
•*'



o
in
o



r>
N
CO




O
vo
CO
H



0

0
vo









tn
3
abroni


••
•
ns

jj
0)
jj
4J
-H N
!Z en
ss








cn co
• •
in in



«# in
CO CO
o o



r~ en
VO CO
H CO
rH




o o
H •*
en in
cn •
*4* ^1



f^
c*~ •
• H
rH tn



o

«
o

- 3
•S-g
RJ ?
0) X-
0} O
o
ns a)
as-


-.
.
IS

4J
0)
JJ
JJ
•H N
B= cn
Q "^








o en
O H
.in in



co in
»* co
o o



co r^
H en
H M




0 O
cn vo
H VO
N CO
H •
• vo
in H



o r»

0 H
rH VO



•e

oT
o
m
- 3
n o c*
3 

	
d

jj
0)
-j
jj
-H N
S: cn
(U cn








CO CO
tn N
in in



H 0
CO CO
o o



CO
O H
<3> O
CO




O 0
»*l N
in H
rH in
VD ^t<
• in



r-

• rH
VD cn



«•«
^
(*
o
n
- 3
m U C 09
3 RJ > 3
H 
-------

-------