Annapolis Held Office
              Region III
    Environmental Protection
Monitoring of the Upper Chesapeake Bay
                for the
     Syrnetrical Trazine Herbicides
         Atrazine and Simazine
           J. J. Austin., Jr.
             R. C. Bubeck
             T. 0. Munson
           Presented at the
     12th Middle Atlantic Meeting
       American Chemical Society
Hunt Valley, Maryland, April 5-7, 197S

-------
        Annapolis Field Office
              Region III
    Environmental Protection Aycncv
Monitoring of the Upper Chesapeake Bay
                for the
     Symetrical Trazine Herbicides
         Atrazine and Sinazine
           J. J. Austin, Jr.
             R. C. Bubeck
             T. 0. Manson
           Presented at the
     12th Middle Atlantic Meeting
       American Chemical Society
Hunt Valley, Maryland, April 5-7, 1978

-------
        Annapolis Field Office
              Region III
    Environmental Protection Agency
Monitoring of the Upper Chesapeake Bay
                for the
     Symetrical Trazine Herbicides
         Atrazine and Simazine
           J. J. Austin, Jr.
             R. C. Bubeck
             T. 0. Munson
            Presented  at  the
      12th Middle Atlantic Meeting
        American Chemical Society
 Hunt Valley,  Maryland, April  5-7,  197S

-------
                             Introduction





     The reported decline and disappearance of rooted aquatic plants


                     fl 2")
in the Chesapeake Bay1 '  . has raised concern over the possbile role

                 fr

of herbicides in surface runoff.  To monitor the ambient level of



the most widely used*- ' and potentially more persistent^ ' symmetrical



trazine herbicide Atrazine (Aatrex) 2-chloro-4-ethylaminq-6-isopropylamino-



s-trazine and the similar herbicide Simazine (Princep) 2-chloro-4,



6-bis(ethylamino)-s-trazine in the waters of the upper Chesapeake Bay,



the Environmental Protection Agency's, Region III, Annapolis Field Office,



during the 1977 summer season collected surface water samples from



the upper bay and the Potomac River estuary.  Samples to measure

                         t

seasonal variations of the Susquehanna River were obtained from the



U.S. Geological Survey, Water Resource Division, Harrisburg, Pennsylvania.



Water and sediment samples were taken at the USGS Harrisburg station



together with discharge measurements.  Water samples were returned



to the  EPA,  Annapolis  Field Office for analysis.

-------
                                Method







     Samples were analyzed in accordance with the Method for Trazine




Pesticides in Industrial Effluents; Federal Register 38, No. 75,




Pt. II.




     With this method one liter samples were extracted with three




60 milliliter portions of methylene chloride.  Subsequently the




solvent is changed to hexane utilizing a Kerderna-Danish assembly




and the extract evaporated to one milliliter.  Qualitative and




quantitative analyses were then performed utilizing gas chromatography.




A maximum of fifty microliters was injected onto a one percent




Carbowax 20M column maintained at  160°C with a 60 ml/min helium flow.




A  Hall Detector operated  in  the nitrogen specific mode at an attenuation




of 1x10 was employed  for  maximum selectivity and sensitivity.




Under  these conditions  a  10  percent of  full scale response was




obtained with  50  microliters of sample  containing either  .03 ppb




Atrazine  or  .04  ppb  Simazine.




      Recovery  of spiked blanks averaged greater  than 97%  for both




herbicides.   Single  operator precision  was better than  +_ .02 ppb.

-------
                               Discussion




                                                     «,

     As the major source of fresh water to the upper Chesapeake Bay, the



Susquehanna River drains much of northeastern and central Pennsylvania



and parts of south central New York.   °     Because of its shallow



depth and great width, lateral mixing at Karrisburg, Pa. is poor.

                                                    *


The west bank at mile 69, Harrisburg, closely resembles the Juniata



River and Conodoquient Creek, which drain limestone terrains to the



west.  The center generally resembles the West Branch Susquehanna



River, while water samples near the east bank show the influence of



mine drainage from the river's eastern tributaries.      To measure



seasonal variations  of herbicide concentrations  in the surface run-



off,   ^   •* depth intergrated samples were taken from three stations



on both the east and west channels and composited for each channel.



Highest Atrazine concentrations were found in the west channel, which



drains the more agricultural region.  A peak concentration^ 1^  ' of



1.21 ppb Atrazine was  observed with the first runoff  after application.



Subsequent rainfalls removed less as field and crop cover increased.



However, with harvest  and the death of other cover, concentrations were



observed to  again  increase  with  increased flow.   Concentration of Atrazine



 in the east  channel^ "^  •*  were  generally half those  of the west channel



 and were observed  to follow the  same trends.


                                                  fFie 51
      The presence of Simazine  in the west channelv  6   closely



 followed that of Atrazine.   However, concentrations were usually less



 than a quarter of those of Atrazine.  A peak  Simazine concentration



 of 0.31 ppb was observed.   Concentrations of  Simazine in the  east

-------
/channel^  1^   ' were  again but  half those  observed  for  the west  channel,


with almost  all  late season  samples being below our  detection  limit


of  .04 ppb Simazine.


      (Fig 7)   During the summer  of 1977 drought conditions  existed


with  corresponding low flows.  When significant rainfall occurs close


to  time  of application, greater  losses have been shown in  field tests


conducted with these compounds.   ' '


      Extrapolating between analysis dates and using  the mean daily


 flows,  daily loadings were computed.  Transport of both Atrazine and


 Simazine^ •*-<* °>J) were observed  to decrease rapidly  after  applications,


 but greater field losses occurred after crops were harvested and fields


 bared.   The total load calculated over the study period from June 8


 until December 23, 1977, was about 2.7 metric ton of Atrazine and


 about 0.54 metric ton of Simazine.*-  ^  •*  Field test plot studies


 have shown that from 1-2% of the active herbicide is lost  in surface

                     f(•> 7~\
 runoff and erosion;  '   as much as 15% of the application has been


 reported lost as degradation products and active herbicide.


      Application of these herbicides at the recommended rate of 2-4


 pounds per acre results in an initial surface  soil concentration of 22 to


 44 ppm.  1°   •*  When  concentrations in  the water column are computed

                        v
 on the  assumption that  all herbicide once originated on the sediments


 being transported,  both Atrazine  and Simazine  are seen to peak after


 applications in or  near this  range.  The rapid decline is attributed to


 chemical $  microbiological  degradations  and  dilution  of the surface


 application in  the  soil column.   '    Once  in the  aquatic environment,


 Jiowever, the more alkaline  conditions  have  been shown to greatly retard


 any degradation.' '

-------
     Selected Bay and Potomac Estuary samples were filtered through .45


Micron Glass Fiber Filters before analysis.  From 80% to +100% of the


herbicides were found in the dissolved fraction.  For the sediment


load observed in the Susquehanna River, a partition of 20% of the


herbicide concentration on to the sediments would indicate a concentration

                                                    *
factor over the water column of 1000-6000.  Such concentrations could


result in increase local levels to rooted plants which act as natural


sediment traps.


     The dispersion of herbicides entering the upper Chesapeake Bay


from the Susquehanna River was monitored on a monthly basis from June


through August.  Surface water samples were collected along a longi-


tudinal axis at selected stations of the water quality monitoring


network of  the EPA AFO for the upper Chesapeake Bay.^ lg      The July


sampling was conducted by the Chesapeake Bay Institute, Baltimore,


Maryland, and  returned to the AFO for analysis.  Peak concentrations


of Atrazine range from 0.54 ppb to  0.78 ppb.^Flg   ^  Generally


concentrations were observed to decrease with distance from ±he start


of the estuary.  Concentrations of  Simazine          in the Chesapeake


 Bay,  like  the  Harrisburg, Pa. station, were generally less than


 a quarter  of those  observed  from Atrazine  and showed the same trends of


 dissipation with distance.   Peak concentrations range from 0.11 to


 0.22 ppb.


      In July and August  the  presence of  these herbicides was also


 monitored in the  Potomac River  estuary.   lg      Surface water samples


 were collected at  slack tide from selected stations  over the seventy


 river miles between Chain Bridge  and the Rt.  301 Nice Bridge..  The

-------
'August sampling1 lg     during a drought period of steady flow shows


 the same trend of decreasing concentration from the start of the estuary.


 Using salinity measurements the dilution due to tidal mixing was computed


 for the upper Bay and Potoamc River samples.  In general the excellent


 predictions obtained were within the uncertainty of the analytical

                                                     ft

 measurement, indicating tidal'mixing as the major1force dissipating


 concentrations of herbicide entering the estuary.


      In an area uneffected by salinity incursion, the July 18, 1977

               (Fig 16)
 Potomac River         samples show a distinctive peak in concentrations


 with respect to river mile, which is only partically explainable by


 the higher concentrations noted the week before as the remains of a


 runoff  event moving down river.


      Relative to the upper Bay and Susquehanna River, the concentration


 of Simazine in the Potomac is much higher compared to Atrazine.  In


 the upper Bay and Susquehanna River, concentrations of Simazine were


 but a quarter of those  observed for Atrazine.


       Future work will continue the monitoring of  the Susquehanna River


 through the 1978 application  season, and will concentrate on  the


 collection of large volumn  samples for  direct analysis of herbicides


 in suspended  sediments  and  algae.  Analysis of bottom sediment and plants


 will  also be  attempted.

-------
                              References
1.    Elser, H.J., Observations on the Decline of Milfoil ami Other
     Aquatic Plants in Maryland, 1962-1967, Annapolis, Mel., Department
     of Natural Resources, Ref. 67-12-1, pp. 1-14.

2.    Southwich, C.H. and Pine, F.W., Abundance of Submerged Vascular
     Vegetation in the Rhode River From 1966 to 1973, Chesapeake
     Science, Vol. 16, No. 1, June 1975, pp. 147-151.

3.    U.S. Environmental Protection Agency:  The Pollution Potential
     in Pesticide Manufacturing, EPA #TS-00-72-04 (1972).

4.    Goswami, K.P. and Green, R.E., Microbiological Degradation of the
     Herbicide Atrazine and It's 2-Hydroxy Analog in Submerged Soils,
     Environmental Science § Technology, Vol. 5, No. 5, May 1971,
     pp. 426-429.

5.    Ritter, W.F., Johnson, H.P., Lovely, W.G., and Molnau, M.,
     Atrazine, Propachlor, and Diazinon Residue on Small Agricultural
     Water Sheds Runoff Losses, Persistence and Movement, Environmental
     Science £ Technology, Vol. 8, No.  1, Jan. 1974, pp. 38-42.

6.   Correll, D.L., Pierce, J.W., and Wu,:T.L., Studies of the
     Transport of Atrazine and Alachlor from Minimum Till Corn
     Fields into Chesapeake Bay Tidal Waters, Proc. Northeastern Weed
     Science Society, Vol. 32, Jan. 1978.

7.   Hall, J.K., Pawlus, M., and Higgins, E.R., Losses of Atrazine in
     Runoff Water and Soil Sed., J. Envir. Qual., Vol. 1, pp 172-6, 1972.

8.   Herbicide Handbook of the Weed Science Society of America, Third
     Edition 1974.

9.   Nolfe, N.L., Zepp, R.G.,  Gordon, J.A., and Fricher, R.C., N.
     Nitrosamine Formation  from Atrazine,  Bulletin of Environmental
     Contamination  § Toxicology, Vol. 15,  No. 3,  1976, pp 342-347.

 10.  Junk, G.A.,  Richard, J.J., Suee, H.J., and Fritz, J.S., Journal
     of American Water  Works Association,  68  (4): 218-222 1976.

 11.  Anderson,  P.W., Variations in  the  Chemical Character of the
      Susquehanna River  at Harrisburg, Pennsylvania, Geological
      Survey Water-Supply  Paper 1779-3,  U.S. Government Patient
      Office, Washington,  D.C.,  1963.

-------
12.  Hall, J. X., end Hartv/ig, N. L., Atarsine Mobility in Tv;o Soils
     Under Conventions! Tillage, Journal of Environmental Quality.
     Vol. 'i, No. 1, 1975, pp. 63-67.

13.  Triplett, G. B., Conner, B. J., and Edwards, W. M., Transport of
     Atrasirie and Siinazine  in Runoff from Conventional and No Till
     Com. Journal of Environmental Quality. Vol. 7, No. 1, 1973,
     PP. 77-34.

1/4.  Kernney, P. C., Kgufiran, D. D., Herbicides Chemistry/'...Degradation
     and Mode of Action. Second Edition, Vol. 1, }/arcel Dekker, Inc.,
     New York, 1975, pp.  129-208.

15.  Hollister, T. A.,  Walsh, G. E., Differential Responses of Marina
     Phytoplanlrton to Herbicides; Oxygen Evaluation, Bulletin of
     Environmental Contamination and Toxicology. Vol. 9, No. 5, 1973,
     pp.  291-295.     .

-------
Susquehanna - River Basin




-------
        CHEMICAL  CHARACTER OF SrSQt-EHAKXA B1VER
B3
                                           EXPLANATION

                                                   1
                                            Sampling Station
                                          O     120
                                           .  Station Number

                                         DU
                         600   0  600 1200 1800 2400 FEET
                          i.i    i    i    i    i

FIGURE 1.—Location ot cheinlcnl  quality cross-section sampling stations.  Susquelianna
                          Kivcr nt llarrlsburs. Pa.
                                                                                       !

                                                                                       i •
                                                                                      4

-------







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-------

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                                          1977
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-------
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                                   1977
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  I
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       210
      1 75
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      1H5
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 T\

G1
                                            Susquehanna River at Harrisburg, Pa.

                                                           1977
'•+  Jyuie
 1S7«5      212751      237*5      262*5      -2S7.5.

      200-jQ      225cO      250.0    .  275 »0      300 o

-f-   July     v-f   August _   ,f September   -f- ...... October  .

         ."""       .....   •     '  "DTTE ..........
                                                                              312o5      337o5

                                                                                   325 e.O

                                                                                November  -f,
                                                                                                                0


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                                                                                                           362.5

                                                                                                     350.0'

                                                                                                      December -f '

                                                                                                              '

-------
SUSQUSIIANNA RIVER AT H.1RRISBUKG, PA.
Lab No.
77071315
77071316
77071317
77071318
77071319
77071320
77071321
77071322
77071323
77071324
77071325
77071326 .
77072701
77072702
77072703
77072704
77072705
77072705
77072707
77072708
77072709
77072710
Date
6-S-77

6-10-77

6-17-77

6-24-77 .

6-30-77

7-8-77

7-14-77

7-15-77

7-19-^77

7-21-77

7-26-77

Location
East
West
East
West
East
West
East
V/est
East
West
East
West
East
• V/est
East
V/est
East
West
East
Y/est
East
West
Atrazine
.16
.30
.19
.37
.18
.25
.27
.32
.64
1.21
.54
.18
.55
.96
.24
.44
.26
.27
.27
.62
.15
.24
Siraazine
115/1 T>Ob
<.02
.16
-<.02
.20
.03
.20
.06
' .22
.16
.25
.15
.05
.20
.28
.C6
- .16
.04
.15
.Co
.31
.04
.14

-------
SUSQUEHAHNA RIVER AT HARRISBURG,  PA.
Lao No. Date
77090101 8-4-77
77090102
77090103 8-12-77
77090104
77090105 8-25-77
770901O5
77101305 9-29-77
771013.07
77101303 • 9-30-77
77101309
77101310 10-3-77
77101311
77101312 10-7-77
77101313
77101314 10-11-77
77101315
77102703 10-17-77
77102704
77102705 10-18-77
771027C6
77102707 10-19-77
77102703
77102709 10-20-77
77102710
Location
East
West
Ease
West
East
West
East
Y/est
East
West
East
Y/est
East
Y/est
East
Y/est
East
West
East
Y/est
East
West
. East
West
Atrazine
US /I T>T3b
.13
.17
.10
.12
.08
.12
.09
.06
.07
.05
.06
.08
: .07
.06
.05
.11
.06
.05
.07
.09
.07
.07
.07
.04
Sircazine
ug/1 ppb
.06
.11
.04
.07
<04
.07
< .04
._ .04
<.04
<.04
^.04
.07
<.04
.05
<.04
.10
^.04
<.04
.<.04
<.04
<.04
<.04
<.04
^.04

-------
SUSQUEHANMA. RIVER AT IIARRISBURG, PA.
Lab Mo. Date
77111701 11-1-77
77111702
77111703 .11-7-77
77111704
77111705 11-8-77
77112201
77112202 11-10-77
77112203
77111801 11-11-77
77111802
77111803 11-14-77
77111804 '
77120701 . 11-16-77
77120702
77120703 11-18-77
77120704
77120705 11-23-77
771207C6
77120707 11-25-77
77120708
7712O709 12-2-77
77120710
77120711 12-4-77
77120712
Location
East
West
East
West
East
V/est
East
V/est
East .
V/est
East
V/est
East
V/est
East
\7est
East
•Y/est
East
West
East
V/est
East
V/est
Atrazine
.05
.09
.20
.07
.22
.30
.25
.35
.10
.28
.17
.16
.12
.12
.05
.11
<.03
<.03
<.03
.08
.07
- .15
.05
.12
Simazine
1)2/1 T3T>b
<.04.
.05
.16
<.04
.09
.08
<.04
.04
<.04
.05
^.04
<.04
<.04
. W-f.
<.04
<.04
<.04
<.04
<.04
.14
<.04
<.04
<.04
<.04

-------
SU3QUEKANNA. RIVER AT HARRIS3URG, PA.
Lab No^
77011001
77011002
77011003
77011004
77011005
77011005
77011007
77011003
Date Location
12-15-77 East
West
12-16-77 East
Y/est
12-20-77 East
West
12-23-77 . East
West
Atrazine
ue/i cub
<.03
.41
.03
.10
.05
.11
.03
. .03
Simazine
us/1 Dub
<.04
<.04
<.04
<.04
<.04
<.04
<.04
<.04

-------
TIM?
1500
1430
UOO
1310
1H5
1 400
1.400
1400
1330
1430
1330
1430
1515
1030
UOO
135?
1330
134S
1330
1030
1410
uin.
114.1
P/.OOOO
FLOJ     SEDlMFilTS
  CFS   •     PPM

 >?840CU     79 ib
           11*;p
           27.3;b
  94 iO
 .34,0
   4 6g
  11 .0
 131 iO"
 1?"!iO
 1?0.0
.  7?vO
  67. .0
  77iO
  1.5,0
11 9000 •»
 44 600 e
 ? 960 On
 74 600 v
202000.
Vzaoo,
1 ssooo.
 76600 »
 •'zrnoo
 76600.
 234HO,
 19500.
 14 700 e
                                            69   HARRISBUftG/P'i

                                     INSTANTANEOUS MFASUnntNTS

                            ...   '..  ..   ATKAZINF;
                            r:= = s = ssss=====:= = = = = = = = ==:=: = s:sss = ==7r=:r:
                      ppi?

                     OS 04
 n'1'04
.Qo04
 a. os
 Oi03
 0.03
 OiO
 OiO'
 0«06
 0 1 1 7
 0.25
 Oi2^
 Qi15
 nB07
 n«3b
 nil 7
 0.10
 0,1?
 n,&r
 0.24
 Oi31
WEST
  PPO

 0*09
 0.11
 0.10
 Oo06
 0.07
'• 0 ,05
 O',03
 0.10
 0»11
 Of 15
 0.11
 O.S3
 0 154
 0«42
 0.25
 OJ13
 0.50
 0.35
 Oc15
 OslA.
 0.74
LOAD
KG/DAY

 15.7  .
 ?4,3
 35c3 ,
 23.6
 35.3
 19.4
  8.7
  '5*5
  5.3
  4,5
  7*0
247.4
185.3
149 S7
 39-7
 22t4
 75*1
 46,3
 1U2
. 13*3
 26i7
 11 o7
 44,3
ATRA/SEO
    PPM  .

    0,82
    bo 65
  .  OJ30
  '  Oo52
 ' '  0,35
    0.43
    0,83
    ?.,27
    4.53
  13.75
    7,73
    '..62
    3,16
    2»71
    2.73
    1.59
    5..19
    4>00
    2.98
    8.85
  35.67.
  .11.14
  61.50
SSZ SSS1Z
EAST
  PPB

 OeO
 0.0
 0,0
 0.0
 0.0
 .0.0
 0.0
'0.0
 0.0
 0.0
 0,0
 0.04
 Oo06
 0.07
 o.ns
 OrO
 0.09
 0.06
 0.0
 0,05'
 0.17
 0.06
 0.10
                                                                 SIMAZINF

                                                               WEST      LOAD    SIHA/.3FO
                                                                 PPH      K6/0*Y
 0.0
 OiO
 0.0
 0,0 '
 0,0
 OtO
 0.0
 0.0
 P»C"4
 0 .04-
 0 60
 0*23
 0*17
 0,13
 0,07
 0*10
 0,1?
 0,14
 0*03
'0.13
 n.05
 Ot11
 0,52
 0.0
 0,0
 0.0
 0)0
 OoC..
 0.0
 0,0
 0,0
 1 ,V
 1.2
 0,0
66,8
54 ,1
46.1
26.9
11 ,2
20.6
17,6
 3,6
 5.2
 5,5
 4,1
11 .2
 0,0
 o.o -
 0,0
 0,0
 0,0
 oko
 0,0
 0.0
 1 »67
 5,00
 0.0
 1,03'
 0*92
 0.83
 O.R?
 0.79
 1 ,43
 3.46
 7.7-'.
 3.S6
15,50

-------
CHESAPEAKE BAY
Lab No,
77061441

77061440
77061438
77061439
77061437
77061433
77061434
77061435-
77061436
77061442
Station
20

19
14
18
5
T2
T4
T7
T10
A3
Date
6-14-77

6-14-77
6-14-77
6-14-77
6-14-77 '
• 6-14-77
6-14-77
6-14-77.
6-14-77
6-14-77
. Atrazine
xui/1 nnb
.66

.61
.75
.70
.41
.45
.44
.18
.10
.11
.11
.12
S imagine
xiar/1 Toob
' .18
.15
> .16
.27
.29
.12
.18
.20
.03
.04
.04
• .04
.04 .
Salinity
0/00
'••- •* - .17 .

•7-.''' .16 f
? •- C .17 -•
t.Vi .30 ':
*,*.~i 1.42 i.
•'-'••- 1.26 '
''?,?.'•' 2.90
$'-!.: 3.70
' :>» 4.40


-------
                             CHESAPEAKE BAY
Lab Mo.'
7/0/1501
77071502
77071503
77071504
77071505
77071506
77071507
77O71508
77071509
Station
20
19
18
5
T2
MA
T10
D2
Ml
Date
7-11-77
7-11-77
7-11-77
7-12-77
7-12-77
7-12-77
7-12-77
7-13-77
7-14-77
Atrazine
xis/1 TD-ob
.78
.63
.56
.34
.32
LA
.24
.12
.09
Sirrazine
us/1 T?nb
.22
.22
.21
.18
.11
LA"
.07
.05
.03
LA - Laboratory Accident

-------
                              CHESAPEAKE BAY
Lab No^ Station
77031809
77031311
77031832
77031813
77031815
77031819
77031825
77031607
77031623
20
18
5
T2
T4
T7
T10 •
A3
D2
Date
8-13-77
8-18-77
8-18-77
8-18-77
8-18-77
8-13-77
' 8-18-77
8-16-77
. 8-16-77
. Atrazine
ug/1 ppb
Total Dissolved
.19
.23 .24
.54
.36
.37 .29
.29
.18
.17
.16 .15
.14
Siinazine
ug/1 ppb
Total Dissolved
.09
.0-9, .15
.11
.10
.03 .11
.07
.06 !'
.05
.05 .05
.05
Salinity
n/oo



.42
2.02
4.92
7.20
9.22
9.64
77031635
F2
8-16-77
03
.02
                                                      11.30

-------
                                    STATIONS
Chain Bridge                                                0
Above Windy Run (opposite Georgetown Reservoir)             l.g
Key Bridge                                            ' "    3 35
Memorial Bridge     .      -                                  ^ 85
14th St. Bridge                                             59
Mains Point                                '                 76
Bellevue                      '  ..                           10^0
Hoodrow Wilson Bridge                       .               -J2 i
Rosier Bluff                                               13 6
Opposite Broad Creek       ..•' ,                            15 4
Fort Washington (Piscatav/ay)                               183
Dogue Creek - Marshall Hall                                22 0
Opposite Gunston  Cove                                      25 o
Chapman Point - Hallowing Point                            27 5
Indian Head                                                30 6
Deep Point - Freestone Point                               34 0
Possum Point                                               32 Q
Sandy Point'                  "                             42 Q
Smith Point  .                                        •    45 8
Maryland Point                     '                        52 4
Opposite Manjemoy Creek                                    58 4
Mathias Point                                              62 «
Rt.  301 Bridge                                             ,7 .
                                                           O/.'r

-------
POTOMAC INTENSIVE
Lab No.
77071801
77071805
77071803
77071810
77071812
77071314
77071817
77071818
77071819
77071820
77071821
77071322
77071823
Station
' P8
2
' 5
6
8
9
11
. ' 12 .
13
14
15
15A
16
Location,
Chain Bridge ' '
14th St. Br.
W W Bridge
Opp Broad Cr.
Dogue Cr, -
Marshall Hall
Chapman Point -
Hallov/ing Pt.
. Possum Point
Sandy Point
Smith Point
Maryland Point
Opp Nanjeinoy Cr.
Mathias Point
301 Bridge
Date,
7-18-77 .
7-18-77.
7-18-77 .
7-18-77
7-13-77
7-13-77
7-18-77
7-18-77 .
7-13-77
7-18-77
7-18-77
7-18-77
7-18-77
Atrazine
,' urr/1 ppb
,46
.53
.85
1.15
. . .84
.55
.24

.15

.06

.06
S imagine :
u/r/1 ,ppb
.34
.44
.58 '.
.78
.49
.33
.14

,03
•
.05

.07
Salinity
0/00







.63
.1.00
3.94
5.40
6.34
7.52

-------
                                            POTOMAC  INTENSIVE
                                                          Atrazine
Simazine
Lab No.
77082201
77032205
77082207
77082208
77082210
77082211
77082212
77082214
77082216
77082217
77082218
•
77082219
77082220
77082221
77082222
77082223
Station
P8
2
4
5
6
7
8 •
9
10B
11
12
13
14
15
15A
16
Location
Chain Bridge
14th St. Br.
Belle vue'
W W Bridge
Opp Broad Cr,
Ft. Washington
(Piscatav/ay)
Dogue Cr. -
Marshall Hall
Chapman Point -
Hallowing Pt.
Deep Point
Possum Point
Sandy Point
Smith Point
"Maryland Point
Opp Nanjemoy Cr,
Mathias Point
301 Bridge
Date-
8-22-77
8-22-77
8-22-77
8-22-77
8-22-77
8-22-77
8-22-77 .
8-22-77
8-22-77
8-22-77 .
8-22-77
8-22-77
8-22-77
8-22-77
8-22-77
8-22-77
ug/1 ppb
Total Dissolved
.38 .34
.34
.40
,42
.49 .44
.45
.48
.45

.39 .

.25
.13 ' ' '
. ;
,08
.08
ug/1 ppb
Total Dissolved
.33 .32
.39
.34 '
.36
.35 .33
.33
.33
.31

.19

.14
.05

.03
.04 ..
Salinity
0/00 _








.42
1.22
2.36
4.20
6.53
8.52
8.94
9.90
Spike recovery conducted with sample 77082210 yielded recovery of  36% and 78$  for Atrazine and
82$ and 73/5 for Simazine

-------
                 UNITED,~TATES ENVIRONMENTAL PROTECTION AGENCY
                       T  INAPOLIS FIELD OFFICE, REGION (

UBJECT:  Herbicide Partition Coefficients                      DATE: October 2,  1978
i
                     Ci f\
?ROM:     John Austin yr*v
         Chemist    (/

ro:       T. 0. Munson, Ph.D.
         Chief, Organic Analysis Unit


              A possible enriched microenvironment caused by suspended
         particles bearing higher concentrations of herbicides than the
         water column could expose rooted aquatic plants to higher and
         possible toxic concentrations, even though concentrations in the
         water column are very small.  The herbicides atrazine and simazine
         are slightly v/ater soluble  (atrazine 33 ppm; simazine 5 ppm) and
         exist mainly in the dissolved phase in environmental samples,
         although some small fraction is absorbed on suspended particles.
         Due to the low concentrations in the water column, accurate determination
         by difference can not be attained, as the amount absorbed is equal
         to or less than the analytical uncertainty.  In order to collect
         sufficient  suspended particles for direct analysis, a large volume
         •sample (60 1) v/as passed through a sharpies flow through centrifuge.
         Analysis was performed on filtered, unfiltered, and suspended
         fractions.

              The concentration factor for the suspended particles over the
         water column was 218 for atrazine and 542 for simazine.  The
         distribution  partition coefficients (Kj) for the absorbed to dissolved
         phases'were  221  for atrazine and 543 for simazine.  The suspended
         particles  were  found to  be  highly organic (volatile solids 40%).

               The distribution  between  solid and dissolved phases is dependent
         on  such  factors  as the amount  and composition of the solid, surface
         area,  pH of the  suspension  and  solution, and the amount and type
         of  organic matter  in the solid  and  in  the dissolved phases.  Reported
         Kd  values  for atrazine i^  soils  (1  to  16) become larger for high
          (ca. 74}  organic solids.    Kaolinite was found  riot to adsorb atrazine
          (Kd=0),  illite and montmorillonite  showed moderate absorption (Kd=4.3),
         while peat moss showed greater adsorption  (Kd=92).2  Studies of
          Chesapeake Bay sediment reported a  concentration factor of 23.3

          Coring, C.I.A.; and  Hamaker,  J.W., Chapter 2.IN:  Adsorption of  Organic
           Chemicals in the Soil Environment, Marcel  Dekker,  Inc., N.Y., 1972.
          2Talbert,  R.E.; Fletchall, D.H., Weeds Vol. 13, pp. 46-52, 1955.
          3Muby, L.; Ciba-Giegs, Inc., Personnel  Communication, June 1978.
 EPA Fo
-------
:  ',9/21/78
 1  t

   Station  £20   Havre de Grace

   Water Column

        Total  Atrazine                .28 yg/1
              Simazine                .15 yg/1

        Dissolved Atrazine            .27 yg/1
                  Simazine            .12 .yg/1

        Adsorbed Atrazine             .0004j^g/1
                 Simazine             .OOQ5jtlg/l

        Suspended Solids     .        6.4 mg/1
           pH                        7.5

   Suspended Particles

        Volatile solids               40%
        Atrazine                     61.9 ng/gm
        Simazine                     83.4 ng/gm

   Concentration factor over the v/ater column

        Atrazine                      218
        Simazine                      542

   Distribution partition coefficient (Kd)

        Atrazine                      221
        Simazine                      543

-------
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                                               '  '    1978
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                                                  DATE ~
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                                                 180

-------
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-------








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                                                1978
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           March :
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                                                       DATE
                                                                                            June

-------
                          UNITED SJ^TES ENVIRONMENTAL PROTECTIO^GENCY
                                 Wnapolis Field Office,  Region IIF&
StaSi
®
•«*«
  DATI£:  August 2/f, 197 S
SUBJECT:  Analysis of Spring Runoff Samples

  FROM:  John Austin  \IC\
        Chemist     //
                            'TV


i--~^'w
            TO:  T. 0. Munson, Ph.D._
                Chief, Organic Analysis Unit                                              .


                Samples were analyzed for organochlorine pesticides, organophosphorous
                pesticides, organic nitrogen herbicides and chlorinated phenoxy acid
                herbicides.  Analysis of chlorinated phenoxy acid herbicides was per-
                formed by the U.S. Geological Survey Central Laboratory, Atlanta, Georgia..
                The presence of Atrazine, Siraizine, 2,4-D, 2,4,5-T, Silvex, and PCB's
                were found in some or all of/the samples.  Compounds specifically analyzed
                for are tabulated with their detection limits.

                JAustinlad:3752:8/24/78        ,                                     '

                1 Enclosure                              •                         •
         EPA F°RM 132°-6 IREV. 3-76)

  SI

-------


Lab Ho. Date PCB's
Susquehanna River
at Conowingo, Mel.
73051501 5-15-78 .11
78051601 5-16-73 .08
78051704 5-17-78 .06
Potomac River
at Chain Bridge
78051819 .5-18-78 .13
James River
at #147 Bridge
Richmond, Va.
78051820 5-18-78 .13
N.R. = Not Run
Organophosphorous Pesticides
ug/1
Ethyl Parathion .14
Carbophenothion .39
Ethion .14
Malathipn .26
Mithyl Parathion .14
Ronnel .09 .
Diazianon .06








mm^mj^mmmis^^^mm^m
UfT/l
iHM2M
wmmm
2.4--D . Dichlorprop 2,4.5-T Silvex Atrssine


<,01 <,01 <,01 <.01
.03 <.01 .01- .02
N.R. N.R. N.R. N.R.


..04 'SOI .01 .01



.03 <.01 <.01 .01

. Organochlorine Pesticides

Aldrin
Chlordane
ODD
DDT
Endrin
Heptachlor
Heptachlor Epoxide
Lindane
Toxaphene
alpha -BHC
beta-BHC
Methoxychlor
Mirex
PCB
DDE


.10
1.08
.35


.92



.10


ug/1
.005
.05
.02
.04
.01
.001
.001
.003
.25
.002
.005
.10 • .
.03
.05
.02
ra«a
MS™
^1
Simazine


.05
.25
.09


.47



.06



















-------
Chlorinated Phenoxy Acid Herbicides
2,4-D
2,4,5-T
Silvex
Dichlorprop
                           .01
                           .01
                           .01
                           .01
                                                             Organic Nitrogen Herbicides
Linuron
Alachlor
Atrazine
Simazine
Propazine
Cyanazine
Cyprazine
Atraton
Prometon •
Ametryn
Prornetryn
Terbutryn
ug/1
 .48
 .11
 .03
 .05
 .06
 .10
 .10
 .10
 .10
 .10
 .10
 .10

-------
METROPOLITAN WASHINGTON SEWAGE TREATMENT PLANTS
                                      Atrazine  Simazine
Lab No.
77071201
77071202
77071203
77071204
77071205
77071206
77071207
77071208
77071209
77082557
Station
S-l
S-2
S-3
S-4
S-5
S-6
S-7
S-8
P-8

Location
Piscataway STP
Arlington STP
Blue Plains STP
Alexandria STP
Westgate STP
Hunting Cr STP
. Dogue Cr STP
Pohick Cr STP
Chain Bridge
Washington, DC
Treated Drinking
Date
7-11-77
7-11-77
7-11-77
7-11-77
7-11-77
7-11-77
7-11-77
7-11-77
7-11-77
8-25-77
yg/1 ppb
.75
-1.21
1.72
1.08
•26
.70
1 . 06
1.39
.92
.29
.30
yg/1 ppb
.38
.54
.55
.52
.28
.10
.19
.52
.49
.18
.19
         Wat er

-------