United States
                   Environmental Protection
                   Agency
National Exposure
Research Laboratory
Research Triangle Park, NC 27711
                   Research and Development
EPA/600/SR-96/098     August 1996
                   Project  Summary
v>EPA
                   Evaluation  and  Selection  of
                   Analytical  Methods  for  Lawn-
                   Applied  Pesticides
                   Marcia G. Nishioka, Marielle C. Brinkman, and Hazel M. Burkholder
                    The  work described in this report
                   summarizes four different surveys that
                   were conducted. The first two surveys
                   were conducted to identify  the lawn
                   pesticides, including herbicides, insec-
                   ticides, and fungicides, used in the Co-
                   lumbus, Ohio area by professional lawn
                   care companies and home owners, re-
                   spectively. The  third survey was con-
                   ducted  to identify  through  literature
                   publications  available  methods  for
                   analysis of 12  different  lawn-applied
                   pesticides that  were identified in the
                   first two surveys. The fourth survey, a
                   literature search, was conducted to
                   identify the major soil metabolites of
                   four herbicide acids. Data from the two
                   literature searches have been ab-
                   stracted  and  compiled  into  separate
                   databases  using Borland's  Paradox
                   (DOS) software.
                    Methods  reported in  the  literature
                   may not be appropriate for anticipated
                   EPA pesticide studies in track-in and
                   intra-home redistribution. Published
                   methods are not specific to the  matri-
                   ces of interest here (house  dust,
                   entryway soil, and polyurethane foam
                   collected carpet  and turf  surface-
                   dislodgeables).  Potential interferences
                   and co-extracted species such as hu-
                   mic acids, aliphatic fatty  acids, lipids,
                   phenols, PAH  and  other  combustion
                   source-derived  species  are  not ad-
                   dressed.
                    This Project Summary was developed
                   by  EPA's National Exposure Research
                   Laboratory, Research Triangle Park, NC,
                   to  announce  key findings of the re-
                   search project that is fully documented
                   in a separate report of the same title
 (see Project Report ordering informa-
 tion at back).

 Introduction
  Various pesticides have been identified
 in house dust and indoor air. In at least
 one case, the presence in the home of
 several  pesticides (e.g.  chlorpyrifos,
 diazinon, o-phenylphenol) was clearly due
 to indoor use of whole room foggers and
 sprays. The  presence of other pesticides
 appeared to  be due to infiltration and mi-
 gration into  the home of pesticides that
 were  originally  applied  to foundations,
 walkways, and gardens (e.g. permethrin,
 chlordane, heptachlor). Infiltration through
 foundation cracks  probably explains the
 presence of chlordane  indoors in  many
 older homes and may be similar to radon
 infiltration. However, for pesticides such
 as permethrin, which are applied at sites
 distant from the foundation, track-in of con-
 taminated soil on shoes may explain the
 presence of these outdoor-applied  pesti-
 cides in the home.
  House dust may be  a more complex
 matrix than soil or plant material, as other
 human and  combustion source-derived
 pollutants will be encountered (e.g. fatty
 acids, lipids, phenols, PAH,  carpet addi-
 tives). The ease in applying standard soil
 analysis methods to house dust samples
 for outdoor applied pesticides will be com-
 promised further by pesticide levels that
 are expected to be significantly lower due
 to the dilution that occurs during any migra-
 tion process. Therefore, methods suitable
 for outdoor levels are unlikely to be suit-
 able for lower indoor levels in a specific
 matrix like house dust.

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Conclusions
  The primary lawn-care pesticides ap-
plied in the Columbus area are preemer-
gence and  post-emergence  herbicides.
The most frequently used preemergence
herbicides are  the  dinitro-aniline  deriva-
tives pendimethalin, benfluralin, and triflu-
ralin. The latter two are often combined in
a  mixture  for  application  (trade  name
Team).
  The most frequently  used  post-emer-
gence herbicides are the acid  herbicides,
dicamba, 2,4-dichlorophenoxyacetic acid
(2,4-D),  mecoprop (or MCPP),  and 2-me-
thyl-4-chloro-phenoxyacetic acid (MCPA).
Dicamba, 2,4-D, and mecoprop are fre-
quently  combined  for  application  (trade
name Trimec, among others). Recent con-
cern over possible adverse health effects
from 2,4-D exposure has prompted sev-
eral of the larger lawn-care companies to
replace the 2,4-D with MCPA in the Trimec
or Trimec-equivalent formulations.
  Applications  of insecticides  and fungi-
cides  vary widely in  Columbus. These ap-
plications depend on the particular com-
pany and the general weather patterns. At
least  one company  routinely  applies  an
insecticide  with herbicides.  Mild winters
and/or cool, wet weather increase the use
of fungicides and insecticides. Other com-
panies report that they have  not applied
fungicides in several years.
  A previous study of pesticides in  house
dust  stated that  house dust extracts
caused  significant  problems for "in con-
trol" GC quantification. Because problems
of this nature were not identified in  analy-
ses of soil  samples, we have  to assume
that soil and house  dust are distinctly dif-
ferent in composition and that the  com-
plexity of house dust extracts  requires
more rigorous analytical  methods, espe-
cially cleanup steps. Methods that  have
been reported in the literature cannot be
recommended  for anticipated  pesticide
studies in track-in and intra-home redistri-
bution because they do not address the
matrices of interest,  do not provide  suffi-
cient cleanup steps,  and,  thus,  do not
have the requisite sensitivity. Published
methods generally address the less  com-
plex matrices of soil and water.
  From  the  standpoint of analysis meth-
odology alone, the published  methods 1)
allude to difficulties  in dealing  with co-
extracted humic acids without providing
solutions, 2)  provide little or no  sample
cleanup,  3) detail excessive artifact forma-
tion  during derivatization  steps, 4) obtain
low  recovery of analytes from  clay-like
soils, 5) provide insufficient detection lim-
its,  and/or 6) rely  on relatively high-cost
GC/MS  analyses rather  than  lower-cost
GC selective  detector analyses.
  Appropriate  trace  analysis  methods
need to  be  developed for  the herbicide
acids, the dinitro-aniline  herbicides  and
moderately polar insecticides/fungicides,
and  glyphosate in  house dust, entry-way
soil,  and dislodgeable residues. These
methods need to address cleanup of co-
extracted humic acids,  fatty acids, lipids,
and  other neutral  co-extracted organics.
Target detection limits  of 10-100 ppb in
dust and soil are anticipated for studies of
the migration of lawn-applied  pesticides.
Extraction methods developed for dust and
soil need to  be compatible  with the PUF
polymeric structure, so that only  a simple
scaling  factor is  needed  to  adapt dust
methods to  PUF-collected  surface-
dislodgeables. Proposed analysis  meth-
ods for  dust and  soil  are detailed  in this
report.
  The literature survey  of herbicide acid
soil metabolites indicated that major me-
tabolites are either acidic or phenolic spe-
cies. For the chlorophenoxy herbicide ac-
ids  (2,4-D,  mecoprop,  and  MCPA) the
dominant metabolite  is  the  phenol  that
results after cleavage  of the alkanoic side
chain (e.g. 2,4-dichlorophenol from  2,4-
D).  Because of the  similarity in polarity
between herbicide and  metabolite, both
species  may be  analyzed using  a  single
method.  This approach  is routinely used
in studies of glyphosate, where both  par-
ent  and  its  metabolite,  aminomethyl-
phosphonic acid, are monitored.

Recommendations
  We recommend that the analysis meth-
ods proposed  in  this report be evaluated
for application to the respective pesticide
classes  with regard to  recovery, precision,
and accuracy in the three matrices of in-
terest. The analysis  methods should  be
evaluated for detection and quantification
at trace  (10-100 ppb) levels in house dust,
high clay content entry-way soil, and PUF-
collected surface dislodgeables.
  This report was submitted in partial ful-
fillment  of Contract  No.  68-DO-007  by
Battelle  Columbus Operations under spon-
sorship  of the U.S. Environmental Protec-
tion Agency.

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   Marcia Nishioka,  Marielle  Brinkman, and Hazel Burkholder are with Battelle,
     Columbus, OH 43201
   Robert G. Lewis is the EPA Project Officer (see below).
   The complete report, entitled "Evaluation and Selection of Analytical Methods for
     Lawn-Applied Pesticides," (Order No. PB96-199559; Cost: $25.00, 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:
           National Exposure Research Laboratory
           U. S. Environmental Protection Agency
           Research Triangle Park, NC 27711
United States
Environmental Protection Agency
National Risk Management Research (G-72)
Cincinnati, OH 45268

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