# 1 

# Historical Concentrations of Perm ethrin and Malath ion in Surface

Water and Bed Sediments thro ughout the United States

Robert K. D. Peterson, Ph.D.

Joseph Old Elk

Jerome J. Schleier III, M.S.

Department of Land Resources and Environmental Sciences

Montana State University

334 Leon Johnson Hall

Bozeman, MT 59717-3120

bpeterson@montana.edu

406-994-7927

# 2 Introduction

On January 7, 2009, the Sixth Circuit vaca ted the U.S. Environmental Protection

Agency’s 2007 rule exempting certa in pesticide applications that are compliant with the Federal

Insecticide, Fungicide, and R odenticide Act (FIFRA) from th e permitting requirements of the

Clean Water Act (CWA). According to the rulin g, the dischargers of pe sticide pollutants are

subject to the National Pollutant Discharge Elimination System (N PDES) permitting program

under the CWA. As a result of the ruling, anyone w ho applies a pesticide in, over, or near waters

of the U.S. will need a permit issued under the CWA. The pe rmit requirements will affect more

than 900,000 private and 350,000 commercial and governme nt applicators in the United States.

The permit requirements will apply to mosqu ito and disease vector control districts

throughout the U.S. But, what is the likelihood that insecticides used for adult mosquito

management would be present in water in concen trations that would excee d U.S. EPA levels of

concern? In the past few years, numerous human-health and ecological risk assessments,

including aquatic assessments, have been conduc ted on insecticides used for adult mosquito

management. These risk assessments have conclu ded that the risks from these insecticides are

negligible (see list of journal ar ticles and reports belo w). However, another approach would be

to examine the aquatic concentrations of insectic ides from all uses to assess the historical

frequency and amounts of those that are used fo r adult mosquitoes. This would provide an

evaluation of the potential for mosquito adulticides, which are used at much lower rates than

agricultural and residential uses, to be detected in waters of the U.S.

In this report, we use the U.S. Geological Survey National Water-Quality Assessment

(NAWQA) Program ( http://infotrek.er.usgs.gov/apex/f?p=136:1:0::NO ) to determine the

historical concentrations for malathion and perm ethrin in surface water and bed sediments in the

U.S. from all residential and agricultural uses. Malathion and permethrin are the only mosquito

adulticides that are measur ed as part of NAWQA.

Methods

The data used in this report came from the USGS National Water-Quality Assessment

(NAWQA) Program Data Warehouse Surface Wa ter/Bed Sediment data located at

http://infotrek.er.usgs.gov/nawq a_queries/swmaster/index.jsp . Under the database parameter

group of ‘Organics, pesticide’ the query groups of interest were:

63326 – Malaoxon solids recove rable dry weight, μg/kg

61652 – Malaoxon Water filtered recoverable, μg/L

39531 – Malathion bed sediment recoverable dry weight, μg/kg

63327 – Malathion solids rec overable dry weight, μg/kg

39533 – Malathion suspended sediment recoverable, μg/L

# 3 39532 – Malathion water filtered recoverable micrograms per liter, μg/L

39530 – Malathion water unfiltered recoverable, μg/L

49349 – cis-Permethrin bed sediment smaller than 2 millimeters wet sieved (native water)

field recoverable dry-weight, μg/kg

63365 – cis-Permethrin solids recoverable dry weight, μg/kg

82687 – cis-Permethrin water filtered (0.7 mi cron glass fiber filter) recoverable, μg/L

49350 – trans-Permethrin bed sediment smalle r than 2 millimeters we t sieved (native

water) field recoverable dry-weight, μg/kg

63366 – trans-Permethrin solids recoverable dry weight, μg/kg

Malaoxon’s values were included as mala thion values. Only “39531” malathion bed

sediment was used for malathion bottom sediment readings. Both the cis and trans isomers of

permethrin were counted togeth er and only “49349” and “49350” ci s- and trans-permethrin bed

sediment were used in determining permethrin bottom sediment readings. Also, because the

readings represent both scales in microgram per kilogram and microgram per liter the

concentrations are expresse d in parts per billion (ppb).

Concentrations below the Minimum Repor ting Level (MRL) or Laboratory Reporting

Levels (LRLs) were treated as a single value of non-detect (ND). Estimat ed concentrations (E)

were valued higher than ND because they re present a confirmed detection but an unknown

concentration. They were ranked according to incr easing value, but it is not possible to confirm

the true concentration so they should only be us ed as a possible indication of detection rather

than an actual concentration. Ranked highest were the confirmed concentrations listed in order of

increasing value. Also, to give a more accurate repr esentation of the data we decided to include a

90 th 

# percentile value in addition to the median and peak values.

Values were listed according to their NA WQA Study Unit Identification (SUID’s) (Fig.

1). They represent a series of interconnected drainage areas except for NSQN which is the

National Stream Quality Accounting Network (NASQAN). Only the CHEY, CORE, HPGW,

and POTO study units produced no readings of permethrin and malathion. The COOK and

NROK study units contained no concentrations above the level of detection for either pesticide.

The only verifiable concentration for malathi on in bottom sediment was found in the WHMI

study unit, but because there were only three r eadings it was listed twice as both the peak and

90 th 

# percentile values.

Sampling frequency was determined by taking th e number of readings for a drainage area

and dividing it by the number of months between the beginning and end dates of the sampling

range, excluding any significantly long period where readings were absent.

# 4 Figure 1. Study units of the U.S. Geological Su rvey National Water-Quality Assessment

Program ( http://water.usgs.gov/nawqa/map/cyc2_browse.gif ).

Results and Discussion

The values in Table 1 represent detections/ non-detections for all isomers and degradates

of malathion and permethrin over all residentia l and agricultural uses. The drainages sampled

span the U.S. and each drainage has numerous sampling locations. Many of the locations began

sampling in the early 1990’s and sampling freque ncy was at least once per month. There are

approximately 29,000 samples in which malathion and permethrin were sampled.

The results clearly reveal the infrequency of detections of the two insecticide active

ingredients and their degradates (Table 1). Out of the thousands of surface water samples,

permethrin was only detected tw ice at peak levels above the U.S. EPA level of concern for

aquatic invertebrates ( Daphnia magna , 0.055 ppb) (see highlighted cells). The two values were

well below levels of concern for aquatic vertebrate s. At least 90% of the readings were below

the reporting limit (i.e., the limit of detection) for permethrin.

# 5 Malathion was detected more frequently in surface water. Ten samples were above

USEPA levels of concern for aquatic invertebrates ( D. magna , 0.5 ppb) (see highlighted cells).

However, all 90 th 

# percentile values for malathion were well below levels of concern.

For bottom sediment samples, malathion was only measured in a few locations and was

above the detection limit once. For permethri n, except for one location, all measurements were

below the limit of detection at the 90 th 

# percentile of total samples. Permethrin was detected seven

times at peak levels above levels of concern. The data for bottom sediments should be

interpreted cautiously because th e concentrations in ppb are not necessarily bioavailable as they

are often absorbed strongly to colloids.

Overall, the NAWQA data suggest that (1) permethrin and mala thion from all uses rarely

occur in surface water at levels that exceed U.S. EPA levels of concern, (2) because of greatly

lower use rates for mosquitocide applications compared to agricultural and residential uses, the

contributions to water from permethrin and malathion mosquito applications would be

negligible, and (3) if measure d, naled, resmethrin, and sumithri n would most likely never be

found above limits of detection because of use patterns and rates.

Selected Relevant Literature

Currier, M., M. McNeill, D. Campbell, N. Newt on, J.S. Marr, E. Perry, S.W. Berg, D.B. Barr,

G.E. Luber, S.M. Kieszak, H.S. Rogers, S.C. Backer, M.G. Belson, C. Rubin, E. AzzizBaumgartner, and Z.H. Duprey. 2005. Human e xposure to mosquito-control pesticides---

Mississippi, North Carolina, and Virg inia, 2002 and 2003. MMWR Morbidity and

Mortality Weekly Report 54: 529-532.

Davis, R.S., R.K.D. Peterson, and P.A. Macedo. 2007. An ecological risk assessment for

insecticides used in adult mosquito mana gement. Integrated Environmental Assessment

and Management 3: 373-382.

Duprey, Z., S. Rivers, G. Luber, A. Becker, C. Blackmore, D. Barr, G. Weerasekera, S. Kieszak,

W.D. Flanders, and C. Rubin. 2008. Commun ity aerial mosquito control and naled

exposure. Journal of the American Mo squito Control Association 24: 42-46.

Karpati, A.M., M.C. Perrin, T. Matte, J. Lei ghton, J. Schwartz, and R.G. Barr. 2004. Pesticide

spraying for West Nile virus control and em ergency department asthma visits in New

York City, 2000. Environmental He alth Perspectives 112: 1183-1187.

Macedo, P.A., R.K.D. Peterson, and R.S. Davi s. 2007. Risk assessments for exposure of

deployed military personnel to insecticides and personal protective measures used for

disease-vector management. Journal of Toxi cology and Environmental Health, Part A 70:

1758–1771.

Macedo, P. A., J. J. Schleier II I, M. Reed, K. Kelley, G. W. G oodman, D. A. Brown, and R. K.

D. Peterson. 2010. Evaluation of efficacy and human health risk of aerial ultra-low

volume applications of pyrethrins and piper onyl butoxide for adult mosquito management

# 6 in response to West Nile viru s activity in Sacramento County, California. Journal of the

American Mosquito Control Association 26:57-66.

NYCDOH (New York City Department of Heal th). 2005. Adult mosquito control programs:

environmental impact statement (EIS). New York, NY, USA.

O'Sullivan, B.C.Y., J. Lafleur, K. Fridal, S. Ho rmozdi, S. Schwartz, M. Belt, and M. Finkel.

2005. The effect of pesticide spraying on the ra te and severity of ED asthma. American

Journal of Emergency Medicine 23: 463-467.

Peterson, R.K.D., P.A. Macedo, and R.S. Davis. 2006. A human-health risk assessment for West

Nile virus and insecticides used in mo squito management. Environmental Health

Perspectives 114: 366-372.

Schleier III, J.J., R.S. Davis, L.M. Ba rber, P.A. Macedo, and R.K.D. Peterson. 2009a. A

probabilistic risk assessment for deployed m ilitary personnel after th e implementation of

the “Leishmaniasis Control Program” at Ta llil Air Base, Iraq. Journal of Medical

Entomology 46: 693-702.

Schleier III, J. J., R. S. Davis, L. M. Shama, P. A. Macedo, and R. K. D. Peterson. 2008. Equine

risk assessment for insecticides used in adult mosquito management. Human and

Ecological Risk Assessment 14:392-407.

Schleier III, J.J., P.A. Macedo, R.S. Davis, L.M. Shama, and R.K.D. Peterson. 2009b. A twodimensional probabilistic acute human-health risk assessment of insecticide exposure

after adult mosquito management. Stocha stic Environmental Research and Risk

Assessment 23: 555-563.

Schleier III, J.J., R.K.D. Peterson, P.A. Macedo, and D.A. Brown. 2008. Environmental

concentrations, fate, and risk assessment of pyrethrins and pi peronyl butoxide after aerial

ultralow-volume applications for adu lt mosquito management. Environmental

Toxicology and Chemistry 27: 1063-1068.

Schleier III, J. J. and R. K. D. Peterson. 2010. Deposition and air concentr ations of permethrin

and naled used for adult mosquito ma nagement. Archives of Environmental

Contamination and Toxicology 58:105-111.

Suffolk County (Suffolk County Department of Public Works and Department of Health

Services). 2006. Draft generi c environmental impact statement. Suffolk County, NY.

USEPA (U.S. Environmental Protection Agency ). 2006a. Reregistration Eligibility Decision

(RED) for Permethrin. PDF Case No. 2510, U.S. Environmental Protection Agency,

Washington D.C.

USEPA (U.S. Environmental Protection Agency ). 2006b. Reregistration Eligibility Decision

(RED) for Malathion. Case No. 0248. Washington D.C. 1-101.SUID Drainagename #oflocations #ofreadings SamplingfrequencyTimespan median 90thpercentile peak median 90thpercentile peak median 90thpercentile peak median 90thpercentile peakACAD Acadian‐PontchartrainDrainages56 646 4/month 05/14/98‐06/10/09ND ND ND ND ND 0.0251 ND ND ND ND 0.0117E 0.144ACFB Apalachicola‐Chattahoochee‐FlintRiverBasins145 1138 5/month 08/11/92‐08/05/09ND ND ND ND ND 0.0156 na na na ND ND 0.14ALBE Albemarle‐PamlicoDrainages104 821 3/month 05/08/92‐10/14/09ND ND ND ND ND 0.012 na na na ND ND 0.067ALMN Allegheny‐MonongahelaRiverBasins 19 100 2/month 06/19/96‐08/29/00ND ND 18 ND ND ND na na na ND ND NDCAZB CentralArizonaBasins17 128 1/month 02/07/96‐10/14/09ND ND 8.6 ND ND ND na na na ND 0.015 0.27CCYKCentralColumbiaPlateau(CCPT)‐YakimaRiverBasin(YAKI)146 1022 4/month 11/18/91‐09/23/09ND 7.6 26 ND ND 0.01 na na na ND ND 0.235CNBR CentralNebraskaBasins25 678 3/month 05/01/92‐08/06/09ND ND ND ND ND ND na na na ND ND 0.054CONN Connecticut,Housatonic,andThamesRiverBasins86 487 2/month 10/19/92‐04/23/09ND ND ND ND ND 0.003E na na na ND ND 4.3COOK CookInletBasin 10 37 1/month 05/27/98‐07/05/01ND ND ND ND ND ND na na na ND ND NDDELR DelawareRiverBasin 95 724 5/month 07/13/98‐10/14/09ND ND ND ND ND ND na na na ND ND 0.055EIWAEasternIowaBasins25 821 4/month 09/18/95‐08/10/09ND ND ND ND ND ND na na na ND ND 0.126GAFL Georgia‐FloridaCoastalPlainDrainages97 710 3/month 08/11/92‐07/29/09ND ND ND ND ND ND na na na ND ND 0.226GRSL GreatSaltLakeBasins 66 345 2/month 08/03/98‐08/07/09ND ND ND ND ND ND na na na ND 0.0086E 0.245HDSN HudsonRiverBasin 73 669 3/month 08/23/93‐03/09/09ND ND ND ND ND ND na na na ND ND 0.445KANAKansasRiverBasin 17 81 5/month 08/21/96‐12/15/97ND ND 7.9 ND ND ND na na na ND ND 0.005ELERI LakeErie‐LakeSt.ClairDrainages 16 663 3/month 03/06/92‐08/06/09ND ND ND ND ND ND na na na ND ND 0.0258LINJ LongIsland‐NewJerseyCoastalDrainages60 410 2/month 01/22/96‐07/27/09ND ND ND ND ND ND na na na ND ND 0.026LIRB LowerIllinoisRiverBasin 19 412 2/month 05/16/96‐08/11/09ND ND ND ND ND ND na na na ND ND 0.0879LSUS LowerSusquehannaRiverBasin 163 497 5/month 09/14/92‐09/26/00ND ND ND ND ND ND na na na ND ND 0.129MISE MississippiEmbayment16 657 3/month 08/22/95‐08/13/09ND ND ND ND ND ND na na na ND 0.0285 1.75MOBL MobileRiverBasin 49 499 3/month 08/11/98‐07/14/09ND ND ND ND ND ND na na na ND ND 9.58NECB NewEnglandCoastalBasins39 247 2/month 09/14/98‐09/13/07ND ND 12 ND ND ND na na na ND ND 0.0254NROK NorthernRockiesIntermontaneBasins14 67 2/month 06/18/98‐08/30/00ND ND ND ND ND ND na na na ND ND NDNSQN NationalStreamQualityAccountingNetwork(NASQAN)51 4015 23/month 10/05/95‐08/13/09na na na ND ND 0.11 na na na ND ND 1.16NVBR NevadaBasinandRange 25 460 2/month 09/14/92‐07/31/09ND ND ND ND ND 0.0356 na na na ND 0.0045E 0.38OAHU Oahu 15 74 2/month 08/26/98‐06/20/01ND ND 15.1 ND ND ND na na na ND 0.0158 0.184OZRK OzarkPlateaus 52 347 1/month 08/18/92‐06/30/09ND ND ND ND ND 0.001E na na na ND ND NDPODL PotomacRiverBasin(POTO)&DelmarvaPeninsula(DLMV) 139 1059 5/month 06/01/92‐08/11/09ND ND ND ND ND ND na na na ND ND 0.41PUGT PugetSoundDrainages 50 427 3/month 09/18/95‐09/19/07ND ND ND ND ND ND na na na ND ND 0.868REDN RedRiveroftheNorthBasin 60 324 3/month 08/04/92‐08/31/00ND ND ND ND ND ND na na na ND ND 0.0195RIOG RioGrandeValley 23 254 1/month 09/22/92‐09/18/07ND ND ND ND ND ND ND ND ND ND ND 0.0497SACR SacramentoRiverBasin 19 369 2/month 10/11/95‐06/24/09ND ND ND ND ND ND ND ND ND ND 0.0132 0.634SANASantaAnaBasin 28 253 2/month 09/14/98‐08/10/09ND ND ND ND ND ND na na na ND 0.0044E 1.35SANJ SanJoaquin‐TulareRiverBasins57 1649 8/month 04/15/92‐07/23/09ND ND 16 ND ND 0.146 na na na ND 0.0047E 1.14SANTSanteeRiverBasin&CoastalDrainages 34 460 2/month 08/07/95‐06/02/09ND ND ND ND ND ND na na na ND 0.008E 0.216SCTX South‐CentralTexas17 251 1/month 08/07/95‐09/16/09ND ND ND ND ND ND na na na ND ND 0.107Table1.SurfacewaterandbedsedimentconcentrationsofpermethrinandmalathionfromstudyunitsitesintheU.S.GeologicalSurveyNationalWater‐QualityAssessmentProgram.Permethrin(ppb)BottomSediment SurfaceWater BottomSediment SurfaceWaterMalathion(ppb)SCTXSouthCentralTexas75/month08/07/9509/ 6/09NNNNNNnananaNN0. 07SOFL SouthernFloridaDrainages12 332 2/month 09/05/95‐09/19/07ND ND ND ND ND ND na na na ND ND 0.0837SPLT SouthPlatteRiverBasin 54 612 3/month 09/10/92‐08/10/09ND ND ND ND ND 0.022 na na na ND ND 0.16TENN TennesseeRiverBasin(UTEN<EN)99 838 5/month 07/25/95‐08/05/09ND ND ND ND ND ND na na na ND ND 4.84TRIN TrinityRiverBasin 30 602 3/month 08/04/92‐08/05/09ND ND ND ND ND 0.002E na na na ND 0.00253E0.182UCOL UpperColoradoRiverBasin 18 153 1/month 10/05/95‐8/24/06ND ND ND ND ND 0.00295Ena na na ND ND 0.0256UIRB UpperIllinoisRiverBasin 11 350 2/month 04/11/96‐09/08/09ND ND ND ND ND ND na na na ND ND 0.111UMIS UpperMississippiRiverBasin 44 535 3/month 07/11/95‐07/08/09ND ND ND ND ND ND na na na ND ND 0.0396USNK UpperSnakeRiverBasin 62 489 2/month 08/18/92‐07/23/09ND ND ND ND ND ND na na na ND ND 0.02WHMI White,Great(WHIT)&LittleMiami(MIAM)RiverBasins 98 1629 7/month 10/03/91‐08/12/09ND ND ND ND ND 0.011 ND 0.2 0.2 ND ND 0.67WILL WillametteBasin 67 821 4/month 08/22/92‐08/05/09ND ND ND ND ND 0.019 na na na ND ND 0.79WMIC WesternLakeMichiganDrainages 70 629 3/month 08/24/92‐08/11/09ND ND ND ND ND 0.005 na na na ND ND 0.187YELL YellowstoneRiverBasin 23 249 2/month 02/22/96‐07/09/09ND ND ND ND ND ND na na na ND ND 0.025na‐Notavailable(nomeasurements)ND‐Nondetect(belowthereportinglimit)E‐EstimatedconcentrationforaknownreadingND<E<Truereadings