United States
                     Environmental Protection
                     Agency
 Environmental Monitoring and
 Support Laboratory
 Cincinnati OH 45268
                     Research and Development
 EPA/600/S4-85/052 Dec. 1985
&EPA          Project Summary
                     Standardization  of  EPA
                     Method  8610

                     T. F. Cole, A. Riggin, and S. V. Lucas
                      U.S. EPA Method 8610, "Total Aro-
                     matics by Ultraviolet Absorption" was
                     evaluated in conjunction with U.S. EPA
                     Method 3560, "Reverse Phase Cartridge
                     Extraction" for the separation and qual-
                     itative determination of the presence or
                     absence  of visible  or ultraviolet ab-
                     sorbing organic compounds listed in
                     Appendix VIII of the Resource Conser-
                     vation and Recovery Act (RCRA). A data
                     base of the visible and ultraviolet (UV)
                     spectral data for these compounds was
                     developed and used to estimate detec-
                     tion limits of Appendix VIII organic
                     compounds which absorb UV or visible
                     light in the region 220 to 700 nm. The
                     reverse phase cartridge extraction pro-
                     cedure of Method 3560 was evaluated
                     for its ability to separate polar and non-
                     polar  subsets of 21  Method 8610 ana-
                     lytes by the use of methanol and hex-
                     ane eluents. The extraction procedure
                     was found to be unsuitable for group
                     separation in its present form, and
                     needs further study in order to evaluate
                     the behavior of individual analytes such
                     as acids,  bases, and polynuclear aro-
                     matic compounds. The spectrophoto-
                     metric determinative technique of
                     Method 8610 was found to be very sen-
                     sitive for  a majority of the compounds
                     in the range of 220 to 400 nm, but re-
                     quires further evaluation with a variety
                     of groundwater samples  in order to
                     study  the matrix effects of groundwa-
                    ter on the sensitivity of the method.
                      This Project Summary  was devel-
                     oped by EPA's Environmental Monitor-
                     ing and Support Laboratory, Cincinnati,
                    OH, to announce key findings of the
                    research  project that is fully docu-
                    mented in a separate report of the same
                    title (see Project Report ordering infor-
                    mation at back).
 Introduction

   The Environmental Protection
 Agency (EPA) has proposed an amend-
 ment (October 1,1984 Federal Register)
 to its hazardous waste regulations
 under the Resource Conservation and
 Recovery Act (RCRA) consisting of a hi-
 erarchical analysis procedure for
 groundwater testing. The proposed hi-
• erarchical  procedure would allow haz-
 ardous waste  facility  operators to
 quickly screen groundwater samples for
 compounds of concern using relatively
 inexpensive methods,  thus reducing
 their overall testing burden for  regu-
 lated pollutants witho'ut jeopardizing
 environmental protection.
   One of  the proposed  methods in-
 cluded in the hierarchical analysis pro-
 tocol is Method 8610, "Total Aromatics
 by Ultraviolet Absorption." When used
 in conjunction  with Method 3560,
 "Reverse Phase Cartridge Extraction,"
 Method 8610 is intended to enable oper-
 ators of hazardous waste facilities to
 cost effectively  monitor groundwater
 beneath their facilities for a large num-
 ber of regulated  compounds and  make
 decisions for advanced testing.
   In an effort to evaluate the usefulness
 of Methods 3560 and 8610, EPA con-
 tracted Battelle's Columbus Laborato-
 ries,  under Contract Number 68-03-
 1760, to conduct a research program to:
 (1) generate a data base of ultraviolet
 and visible spectral data for Method
 8610 analytes;  (2) evaluate Method
 3560 for the collection and separation of
 polar and nonpolar Method 8610 ana-
 lytes; and (3) evaluate Method 8610 for
 the analysis of  total aromatic com-
 pounds.

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      Evaluation of Method 8610
        The work completed under the evalu-
      ation of U.S. EPA Method 8610 was con-
      ducted in three segments: (1) acquisi-
      tion of reference spectral  data on both
      polar and  nonpolar aromatic com-
      pounds and the development of a data
      base of this information; (2) the devel-
      opment of a subset of Method 8610 ana-
      lytes for verification of the literature in-
      formation and for estimated detection
      limit (EDL) evaluation; and (3)  determi-
      nations of  UV/visible spectra  of com-
      mercially available method analytes for
      which no literature data was available.

      Development of the UV and
      Visible Spectral Database
        A data base of physical properties and
      spectral data of the 90 polar and 39 non-
      polar organic analytes listed in Method
      8610 was created using Lotus 1,2,3 soft-
      ware  and an IBM personal computer.
      The spectral information has been  pre-
      sented in 10 nm windows to aid in the
      potential development of further refine-
      ments to the method. Files for  this data
      base were stored on 5-1/4" floppy disks.
      Except for polychlorinated biphenyls
      (PCBs), physical and spectral  data for
      analytes which consisted  of a  group of
      isomers  were searched as individual
      isomers. Since PCBs include 208 indi-
      vidual isomers, the  literature search
      was directed only towards the thirteen
      common commercial formulations
      (Aroclors).  Of the  90 polar compounds
      listed in Method 8610, at  least two dif-
      ferent literature sources of spectral data
      were found for 70 compounds, and one
      literature reference was  found for 11
      compounds.  No spectral information
      was available for the remaining nine
      compounds. For the 39 nonpolar ana-
      lytes, at least two different  literature
      sources of spectral data were found for
      each compound (except PCBs).

      Evaluation of Detection Limits
        Methanol solutions containing 0, 2.5,
      5, 25 and 50 ppm of benzene were used
      to assess the signal to noise and detec-
      tion limit capabilities of both the Gary 14
      and the Gary 17D scanning spectropho-
      tometers. For  the Gary  14, an absor-
      bance reading of 0.05 to 0.1 absorbjnce
      units was  necessary to distinguish  a
      positive response from the  normal
      background noise level  (about 0.01 au)
      of this instrument. Similar data ob-
      tained on the  Gary 17D indicated  that
      an absorbance reading of 0.005 is read-
      ily discernable from the background ab-
sorbance of the  reagent blank and is
well above the noise level of this instru-
ment. Thus, a scanning spectrophoto-
meter with performance characteristics
equal to  or  better  than the Gary 17D
would be required to meet the proposed
decision  level of 0.005 au in  Method
8610.
  EDLs were computed using 0.005 au
as the detection limit value and by mak-
ing several assumptions with respect to
the method and compounds under con-
sideration: (1) a 100 mL aqueous sam-
ple, (2) a Method 3560 elution volume of
5.0 ml of methanol  or hexane and anal-
ysis without further  concentration,
(3) quantitative recovery in a single
5.0 mL eluate, and (4) use of an average
molecular weight of 200 g/mole. EDLs
estimated for these conditions versus
molar absorptivities are presented  in
Table 1.

Evaluation of Method 3560
  The reverse phase cartridge extrac-
tion  procedure of  Method 3560 was
evaluated with a subset of compounds
chosen from the Method 8610 analyte
list. The extraction procedure was eval-
uated for elution solvent order and for
effectiveness of the reverse phase car-
tridge cleanup and  equilibration
scheme. The subset compounds from
Method  8610 were evaluated for their
elution characteristics  and  percent re-
coveries with a modified solvent elution
scheme.

Column Cleanup Evaluation
  UV spectra of methanol washes of
6-mL C18 columns (Baker-10 SPE)
showed that the cleanup procedure
prior to the use of  the GIS columns  as
supplied by the manufacturer is essen-
tial. Since Method 3560 specifies the
generation of both  methanol and hex-
ane elutes, the proper cleanup steps are
5 mL of  hexane  followed by 5 mL  of
methanol and, finally, 10 mL of reagent
water to prepare the  column for the
aqueous sample. One problem with 1
original Method 3560 procedure v\
the use of hexane as the first eluti
solvent after column extraction 01
100 mL aqueous sample. Since hexa
is a much stronger reverse phase s
vent than methanol,  a second eluti
with methanol  would be superfluo
and no polarity separation could
achieved. Furthermore, since hexane
not miscible with water, the  residi
water on the column packing could p
vent efficient elution of the  colunr
These expected problems were inde
observed when the specified  hexar
methanol order was used. Therefoi
the order was reversed to the corre
one (methanol/hexane) for all the spi
recovery experiments performed.

Evaluation of Solvent Elution
of Selected Compounds
  Selected compounds  were individ
ally spiked directly onto pre-clean<
cartridges using 10 (jil of methanol. Tl
columns were then serially eluted wi
5 mL each of reagent water, methani
hexane, and a second hexane elutio
and the UV spectrum of each 5 mL el
ate was recorded. The second hexat
elution was used to determine  wheth
complete elution from the column w;
achieved. The compounds were spikt
directly onto the columns  rather the
into a  100 mL water sample  to sep
rately examine elution characteristics <
the 5 nonpolar and 15 polar compounc
tested. The results of this elution evali
ation are presented in Table 2. Thes
results suggest a number of conclt
sions  regarding the application (
Method 3560 to Method 8610 analytei
  •  The extraction/elution procedui
    used is not capable of group separ;
    tion into polar and  nonpolar con
    pounds,  as  evidenced  by  the fai
    that all  five of the  nonpolar con
    pounds of Table 2 were at least pa
    tially present  in the methane
Table 1.   Estimated Detection Limits of Method 8610 Compounds Based on Molar Absorpth
         ities
Absorptivity
Range (e)
W2 - W3
W3 - W4
W4 - W5
Unavailable
EDL, ng/L of
Groundwaterlal
500
50
5
Number of
Compounds In
the Given Flange
Polar
4
37
39
W
Nonpolo
9
6
23
1
MEDLs are based on average molecular weight of 200, a concentration factor of 20, and a minimur
 absorption of 0.005 au for detection.

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Table 2.  Recovery by Solvent Elution of Selected Polar and Nonpolar Aromatic Compounds Spiked Onto Reverse Phase Cartridges

                                                   Percent Recovered in Given Elution Solvent
         Compound
Amount Spiked,
    \igper
   Cartridge
                                              Reagent
                                            Water Rinse
               Methanol
                Eluent
First Hexane
   Eluent
        Second
        Hexane
        Eluent
                   Total
              Percent Recovery
Rep 1   Rep 2  Rep 1  Rep 2  Rep 1  Rep 2  Rep 1  Rep 2  Rep 1  Rep 2  Average
Nonpolar Aromatic Compounds

Benzene                          368
Dibenzo(a,j)acridine                   9.2
1,3-Dichlorobenzene                2,580
Fluoranthene                        10
Methoxychlor                        27

Polar Aromatic Compounds
                 la)
                              21
                              11
                              62
                              57
                              74
                     21
                     11
                     62
                     51
                     74
 18
  4
 15
 50
 40
15
 5
30
54
43
10
13
 49
 15
 77
115
114
MDash (-) indicates compound not detected in given fraction or replicate.
">'0n/y one replicate for aniline.
>c>The hexane fractions were inadvertantly not collected, partially explaining the relatively low average recovery shown.
 49
 16
 92
111
117
 49
 16
 84
113
116
Acetophenone
Aniline
Butylbenzylphthalate
3,3 ' -dichlorobenzidine
<2,4-Dichlorophenoxy)acetic acid
2,4-Dimethylphenol
2,4-Dinitrophenol
2,6-Dinitrotoluene
1,2-Diphenylhydrazine
Methylparathion
1,4-Naphthoquinone
Pyridine
Strychnine
Thioacetamide
2,4,6-Trichlorophenol
20
10
23
11
26
28
20
20
25
35
23
40
20
7.4
88
-
8
-
-
19
-
-
13
-
-
-
-
-
83
-
-

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     T. F. Cole, A. Riggin, and S. V. Lucas are with Battelle, Columbus Laboratories.
       Columbus, OH 43201 -2693.
     FredK. Kawahara is the EPA Project Officer (see below).
     The complete report, entitled "Standardization of EPA Method 8610," (Order No.
       PB 85-247 013; Cost: $ 16.95, subject to change) will be available only from:
            National Technical Information Service
            5285 Port Royal Road
            Springfield, VA 22161
            Telephone: 703-487-4650
     The EPA Project Officer can be contacted at:
            Environmental Monitoring and Support Laboratory
            U.S. Environmental Protection Agency
            Cincinnati, OH 45268
United States
Environmental Protection
Agency
Center for Environmental Research
Information
Cincinnati OH 45268
Official Business
Penalty for Private Use $300
EPA/600/S4-85/052
                                               OOOQ329

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