Project Number: 7298484 Project Title: Method development for Field Research Division: DPSE (now DART) Project Officer (PO): Donald D. Dollberg Other Personnel: Ronnee Andrews, Kate Gomez, Larry Jaycox, Charles Neumeister, Stephanie Pendergrass, Samuel. P. Tucker, PO Degree: Ph.D. PO Area of Expertise (scientific discipline): Inorganic Chemistry Project Start Date: 1995 Project End Date: continuing project (period referenced = 1996 to 2005) Total Budget over the Project Period: $1,308,722 Goal/Sub-Goal: Exposure Assessment Research Challenge/Issue: This project provides analytical chemistry method development support for projects in the research divisions (DSHEFS, DRDS, DBBS, DPSE, HELD, PRL and SRL) at NIOSH when existing methodology does not meet the needs of the project or when new or novel approaches to sampling and analysis of workplace contaminants are needed. This method development is provided to NIOSH researchers upon request (as resources permit) and is an integral part of the researcher's project for exposure assessment or control technology evaluation. In addition to internal personnel, additional method development support is available through a Comprehensive Analytical Support Contract(CASC) which is funded and managed under this project. The methods developed will be utilized for exposure monitoring of workers to chemicals in the workplace atmosphere or to compare whether control technology is effective in lowering worker exposure. Methods will be developed following established protocols as contained in the NIOSH Guidelines for Air Sampling and Analytical Method Development and Evaluation [Kennedy et al., 1995]. Activities: The general process of method development consists of literature review, sampling system selection/development, instrumental optimization, establishment of limits of detection and quantitation, and the measurement of analyte recovery and storage stability. Researchers in NIOSH will utilize the results from these newly developed sampling analytical methods to assess worker exposures. All methods development protocols are peer reviewed within the Branch to ensure that the best analytical approach is utilized. Analytical results and laboratory reports generated by the new method conform to established standard procedures in the DPSE (now DART) Quality Assurance Manual. Methods developed in this project will be user checked which involves reviewing the method and having audit samples analyzed by an external laboratory. This process will insure the applicability of the method before publishing in the NIOSH Manual of Analytical Methods (NMAM). The sample request and submission process is managed by a Contract officer, Lab Coordinator and Quality Assurance officer.
Once a method is developed then field samples collected by others in NIOSH (Industrial Hygienists or medical doctors in DSHEFS, DRDS, DBBS, DPSE, HELD, PRL and SRL) and then are analyzed by internal scientists or the Comprehensive Analytical Support Contract (CASC) lab. When possible, research for the method development will be submitted for publication. Outputs: There were 19 methods already in existence in 1996 which are useful for agriculture surveillance (See Appendix A, Table 1 which lists these methods) [NIOSH Manual of Analytical Methods, 1994]. Eleven more methods have been developed and issued (Table 2.) between 1996 and 2003 [NMAM 4th ed.; 2nd Supplement, 1998; 3rd supplement, 2003] NIOSH Published Analytical Methods 1) NMAM 5602: Chlorinated Organonitrogen Herbicides (Air Sampling) 2) NMAM 9200: Chlorinated Organonitrogen Herbicides (Hand Wash) 3) NMAM 9201: Chlorinated Organonitrogen Herbicides (Dermal Patch) 4) Method 9202: Captan and Thiophanate-methyl in hand rinse (HPLC) 5) Method 9205: Captan and Thiophanate-methyl in dermal patch (HPLC) 6) Method 5601: Organonitrogen Pesticides (GC/MS) These methods are detailed sampling and analytical procedures for measuring chlorinated organonitrogen herbicides or Captan and Thiophanate-methyl in air, hand rinse, and dermal patch samples. The methods expand the capability of researchers and practitioners to measure the exposure of farmers, farm workers, families, and others to these herbicides & fungicides in several exposure matrices. In particular, four of the methods address dermal exposure, an often important route of exposure to pesticides. Initial development of an HPLC method for captan (NMAM 5601) was followed by development of a confirmatory GC/MS method after phosmet interferences were detected in field samples. Accurate measurement and characterization of exposure leads to improved risk assessment. This method supported the Ag Health Study, Pesticide Exposure Among Farmer Applicators which found that the association between glove use and decreased atrazine exposure on days when atrazine was sprayed, however on days non-atrazine herbicides were sprayed, glove use was associated with increased atrazine exposure, suggesting the gloves were a possible source of atrazine exposure. Other Divisions Projects Supported by CEMB analytical personnel or CASC lab: IWSB 93/95-605: Herbicide Exposure Assessment Among Custom Applicators Methods developed for this project: 5602, 9200, 9201, Sequences (sample sets) run; 8010, 8741, 8481, 8419, 8426, no of samples = about 990. NIOSH Analytical Methods (to be issued pending external review) 7) Method 9204: Take-home pesticides patch; atrazine, metolachlor, chlorpyrifos, alachlor & acetochlor 8) Method 5605: atrazine, metolachlor, chlorpyrifos, alachlor & acetochlor 9) Method 9206: Glyphosphate wipes
10) Method 9207: Malathion 11) Method 9208: Captan 12) Method 9107: Coumaphos (wipes) & Chlorpyrophos CASC lab This method was developed to support HETA 02-0203 project; to monitor a tick eradication procedure, dipping cattle in dilute coumaphos. 13) Method 7606: Inorganic chloramines A CEMB researcher developed this method which can be used by Industrial Hygienists to monitor exposure to chloramines off-gassing from hog manure pits or poultry manure on ranches. Hines CJ, Deddens JA, Tucker SP, Hornung RW (2001): Distributions and Determinants of Pre-Emergent Herbicide Exposures Among Custom Applicators. Annals Occup Hyg 45:227-239. [cited 9 times] This paper describes the results of air, hand wash, and dermal patch sampling of custom applicators exposed to the herbicides alachlor, atrazine, 2,4-D 2ethylhexyl ester, and metolachlor. Tucker SP, Reynolds JM, Wickman DC, Hines CJ, Perkins JB (2001): Development of Sampling and Analytical Methods for Concerted Determination of Commonly Used Chloroacetanilide, Chlorotriazine and 2,4-D Herbicides in Hand Wash, Dermal Patch and Air Samples. Appl Occ Environ Hyg 16:698-707. This paper describes the development of air, hand wash, and dermal patch sampling and analytical methods for the chloroacetanilide, chlorotriazine and 2,4D herbicides and documents the performance and evaluation of the methods. A Sampling and Analytical Method for the Simultaneous Determination of Multiple Organonitrogen Pesticides in Air - E. R. Kennedy, J. Lin, J. M. Reynolds and J. B. Perkins [1997] AM IND HYG ASSOC J 58 (10): 720-725 OCT 1997. Other Divisions Projects Supported by CEMB analytical personnel or CASC lab: Herbicide Exposure Assessment Among Custom Applicators; IWSB 93/95-605 Three analytical methods were developed for this project: 5602, 9200, 9201. Five samples sequences were run which totaled about 990 samples. Intermediate Outcomes: • Table 1 (attached) lists commercial companies and organizations that cite NIOSH methods or provide a link to NMAM on their website. This indicates that our methods are considered a positive reason to select their services and is an indicator of our influence. • Jirachaiyabhas, V., Visuthismajarn, P., and Robson, M.G. Exposure assessment of traditional and IPM farmers on using pesticides: A case study at Bang Rieng Sub District, Khuan Nieng District, Songkhla Province
Songklanakarin J. Sci. Technol., 2004, 26(Suppl. 1) : 161-170
This paper describes surveillance of pesticide application and used NMAM 5600 as the analytical method.
•
The paper “Distributions and Determinants of Pre-Emergent Herbicide Exposures Among Custom Applicators. Annals Occup Hyg 45:227-239.” won the NIOSH Alice Hamilton Award for Excellence in Occupational Safety and Health in 2002 in the Human Studies Category. NA
End Outcomes:
External Factors: Seven of the methods mentioned above have not been issued due to the requirement for external review. There are in all 14 agriculture-related methods that will not be issued until this external review occurs. If this process could be improved then these methods could become available for use outside NIOSH. The root causes for delay are not known to this writer (whether recruiting reviewers is a limiting factor or other cause). Future Directions: We continue to support field research, providing analytical lab service internally or via the CAS Contract. This may include comparing newer sampling media or technique with existing ones, evaluating new methods, sampling devices, novel detectors, or other equipment, or extending the analytical range lower as this becomes feasible. References: Kennedy ER, Fiscbach TJ, Song RG, Eller PM, Shulman SA. “Guidelines for Air Sampling and Analytical Method Development and Evaluation” [May 1995] USDHHS/PHS/CDC/NIOSH/DPSE, Publication #95-117. [cited 9 times] NIOSH Manual of Analytical Methods (NMAM®), 4th ed. DHHS (NIOSH) Publication 94-113 (August, 1994), 1st Supplement Publication 96-135, 2nd Supplement Publication 98-119, 3rd Supplement 2003-154, Schlecht, P.C. & O'Connor, P.F. (pfo1@cdc.gov), Eds.
Table 1. Intermediate Outcome Evidence of the impact of NIOSH (NMAM) Methods Company/Organization Website Note AIHA marketplace http://www.aiha.org/webapps/co Links to NIOSH mmerce/home.aspx http://www.emedco.info/ Provides a link to Emedco (Innovative NMAM signs & safety solutions) Uses Many NIOSH The Clayton Group methods (for http://labonline.claytongrp.com/ pesticides) http://staging.aiha.org/Content/Ac links to NIOSH AIHA cessInfo/links/governmentlinks.ht m IRSST (Institut de has a link to NMAM Recherche Robert-Sauvé http://irsst.qc.ca/en/_print_RSST6 (Under measurement en santé et en securité du 923-22-4.html & Instrumentation)
travail) Association of Societies for Occupational Safety and Health (ASOSH) Web Site AgHealth at UC Davis, CA European Health and Safety organization
also recommends NMAM method 5600 provides link to NIOSH http://www.asosh.org/ http://agcenter.ucdavis.edu/lserver/ Cites NIOSH lserver.php (general) Cites NIOSH http://www.eurosh.com/ehs.htm (general)
Project Number: 9277421 Title: Take-home Pesticide Exposure Division: DSHEFS Project Officer: Brian Curwin PO Degree: MS PO Area of Expertise: Industrial Hygiene Start Date: 10/1/2000 End Date: 12/31/2007 Total Budget over the Project Period: $766,268 Goal: Chronic Effects of Agricultural Exposure Sub Goal: Exposure Assessment Research Challenge/Issues: Exposure to pesticides can be a serious health concern, particularly for vulnerable populations such as children, or workers and farmers who have the potential for significant chronic exposure. The scientific literature suggests a variety of adverse health outcomes among persons with chronic pesticide exposures. According to the U.S. Department of Agriculture, approximately 2.5 million workers are employed in agriculture, and they are potentially exposed to numerous pesticides--herbicides, insecticides, fungicides, fumigants, and growth regulators. The EPA estimates that tens of thousands of acute illnesses occur annually to agricultural workers as a result of occupational exposure to pesticides. Pesticides have been reported to cause dermatitis, respiratory irritation, neurological dysfunction through cholinesterase inhibition, and death due to acute poisoning. Families are potentially exposed to contaminants that are inadvertently brought into the home by working members of the household. Farm homes may become contaminated with pesticides through spray drift and take-home exposures. Children and other family members living on or near these farms may be exposed. Children, who spend much time on the floor and may come into intimate contact with pesticide residue on carpets, hard floors and yard dirt, are particularly vulnerable due to differences in physiology, behavior patterns and hygiene. Although the public health importance of preventing injury to farm children has been wellrecognized, the hazards of exposure to pesticides and other chemicals to children in the farm environment have received relatively little attention. Federal pesticide regulators in Canada and the U.S. consider dietary but not residential and environmental exposure to children when evaluating the safety of agricultural pesticides. Concern for pesticide exposure among the children of farmers and farm workers was raised by the National Institute for Occupational Safety and Health (NIOSH) with the Report to Congress on Workers’ Home Contamination Study Conducted Under the Workers’ Family Protection Act (29 U.S.C. 671a). The Natural Resources Defense Council (NRDC) considers pesticides to be one of the top 5 environmental threats to children’s health and considers farm children to be the most highly pesticide-exposed subgroup in the U.S. The U.S. Environmental Protection Agency (EPA) has been criticized for not doing enough to protect children from the potential adverse effects of pesticide exposure, particularly children of
agricultural families. The EPA has attempted to address the issue of children’s and other family member’s pesticide exposure in farm homes in their Draft Standard Operating Procedures for Residential Exposure Assessment. The EPA acknowledges however, that the research to date, although providing useful insight, does not provide answers regarding the potential bioavailabilty of pesticides from this source of exposure. The primary purpose of this project was to investigate take-home pesticide exposure among farm families who grow corn and soybean in Iowa. There were three objectives of this research study: 1) to evaluate the extent of farm home pesticide contamination and take-home pesticide exposures among farm families to seven primary pesticides; 2) to identify potential behavioral and environmental risk factors; 3) to develop recommendations for the prevention of pesticide exposure to families resident on farms. Activities: Twenty-five farms and 25 non-farms were originally enrolled in this research study to evaluate the extent of take-home pesticide exposures among farm families, and to identify potential behavioral and environmental risk factors. Environmental (house dust, surface wipe, air, water) and urine samples were collected during field surveys conducted in the spring and summer of 2001. An additional 32 additional farm families were recruited in 2005. House dust and urine samples were collected form these families during the spring and fall of 2005. The samples were collected to investigate changes in farm family take home pesticide exposure between farming and non-farming season. Commercial pesticide applicators will be recruited and house dust and urine samples will be collected during the application and non-application seasons in the fall of 2006 and spring of 2007. Samples are being collected to investigate take-home pesticide exposure among this group. The additional field work for the study is expected to be completed by late spring 2007. Data analysis and manuscript preparation is expected to continue until December 2007. Over $1,500,000 has been put toward this effort. The bulk of the costs for the project stemmed from salaries and the analysis of the collected samples for pesticides. Over 2500 individual samples using various sampling media were collected and analyzed at a cost of roughly $100$150 per sample. Field work logistics, including sampling equipment and supplies, shipping, travel, and recruiting, accounted for the a large portion of the remainder of the costs. Several key personnel were involved in the study from NIOSH and other government agencies (National Cancer Institute, National Center for Environmental Health), agricultural centers (University of Iowa’s Great Plains Center for Agricultural Health) and research organizations (Battelle Memorial Institute). The personnel consisted of three industrial hygienists, three chemists, a statistician, an industrial hygiene technician and two epidemiologists. The National Cancer Institute and the Great Plains Center for Agricultural Health were instrumental in recruiting participants for this study and Great Plains Center for Agricultural Health provided laboratory space and field logistic support for the field teams. The National Center for Environmental Health, Battelle Memorial Institute and NIOSH’s Division of Applied
Research and technology were instrumental in conducting the sample analysis for pesticides. This study would not have been completed without the efforts of these organizations. Take-home pesticide exposure is a relatively new field of pesticide exposure assessment; in the last decade only 16 papers have been published on the subject, three of which are from this project. The results from this study have therefore furthered the knowledge in this area. Outputs: The following results have been produced from the study are contained in the outputs below: o Farm homes are more likely to be contaminated with pesticides then non-farm homes and farms that apply a particular pesticide to crops have higher levels of that pesticide inside the home than farms that do not apply the pesticide. o Farmers who reported applying a pesticide had significantly higher urinary metabolite levels than non-farmers, farmers who did not apply that pesticide, and farmers who had the pesticide commercially sprayed (p-value < 0.05). Generally, there were no differences in urinary pesticide metabolite levels between non-farmers, farmers who did not apply the pesticide and farmers who had the pesticide commercially applied. o Farm children are more exposed to pesticides than non-farm children, but the exposure is generally below EPA reference doses. This knowledge will aid in the design of future research investigating take-home pesticide exposure and will inform farmers and their families of the possibility of inadvertent exposure to pesticides via home contamination. Article published, professional (juried publication): B. Curwin, M. Hein, W. Sanderson, M. Nishioka, S. Reynolds, E. Ward, M. Alavanja. (2005) Pesticide contamination inside farm and non-farm homes. Journal of Occupational and Environmental Hygiene 2(7):357-367 [cited 1 time] B. Curwin, M. Hein, W. Sanderson, D. Barr, D. Heederik, S. Reynolds, E. Ward, M. Alavanja. (2005) Urinary and hand wipe pesticide levels among farmers and non- farmers in Iowa. Journal of Exposure Analysis and Environmental Epidemiology 15(6):500-508 doi:10.1038/sj.jea.7500428 B. Curwin, W. Sanderson, S. Reynolds, M. Hein, M. Alavanja (2002). Pesticide Use and Practices in an Iowa Farm Family Pesticide Exposure Study. Journal of Agricultural Safety and Health 8(4):423-433 Abstract: B. Curwin, M. Hein, W. Sanderson, C. Striley, D. Heederik, S. Reynolds, E. Ward, M. Alavanja. Urinary pesticide levels in Iowa farm spouses and children. Abstract presented at the 15th Annual Conference of the International Society for Exposure Analysis, Tuscon, Arizona October 30 – November 3, 2005
B. Curwin, M. Hein, W. Sanderson, D. Barr, S. Reynolds, E. Ward, M. Alavanja. Urinary Pesticide Levels Among Farmers and Non-Farmers in Iowa. Abstract presented at X2004: Exposure Assessment in a Changing Environment, Utrecht, Netherlands June 1618, 2004 B. Curwin, M. Hein, W. Sanderson, S. Reynolds, M. Nishioka, E. Ward, M. Alavanja. Farm Family Take-Home Pesticide Exposure Study. Abstract presented at 2003 American Industrial Hygiene Conference and Expo, Dallas, Texas May 12-15, 2003 B. Curwin, W. Sanderson, S. Reynolds, M. Nishioka, E. Ward, M. Alavanja. Pesticide Contamination Inside Farm and Non-Farm Homes and Vehicles. Abstract presented at the 12th Annual conference of the International Society for Exposure Analysis, Vancouver, British Columbia, Canada August 11-15, 2002. B. Curwin, W. Sanderson, S. Reynolds, M. Hein, M. Alavanja. Pesticide Use and Practice Among 25 Farms Enrolled in the Iowa Farm Family Pesticide Exposure Study. Abstract presented at the 2002 American Industrial Hygiene Conference and Expo, San Diego, California June 3-6, 2002. B. Curwin, D Booher, D Watkins. Modifying the HVS3 Dust Sampler. Abstract presented at the 11th Annual Conference of the International Society for Exposure Analysis, Charleston South Carolina November 4-8, 2001 Manuscripts: B. Curwin, M. Hein, W. Sanderson, C. Striley, D. Heederick, S. Reynolds, E. Ward, M. Alavanja, H Kromhout. (submitted) Pesticide dose estimates for children of Iowa farmers. Environmental Health Perspectives B. Curwin, M. Hein, W. Sanderson, C. Striley, D. Heederick, S. Reynolds, E. Ward, M. Alavanja, H. Kromhout. (in press) Urinary pesticide concentrations among children, mothers, and fathers living in farm and non-farm households in Iowa. Annals of Occupational Hygiene Fact Sheet: Pesticide Exposure in the Homes of Farm Families. Developed by the University of Iowa, summer 2006. Thesis: Bringing work home: take-home pesticide exposure among farm families, PhD Thesis, Utrecht University, July 2006. Intermediate Outcomes: Results from this study have been used by researchers at the Utrecht University, Netherlands and the University of Iowa to further their research in this field. At Utrecht University, researchers
have conducted preliminary work on take-home pesticides. Discussions have been on-going with them to conduct additional pesticide take-home work among farmers in the Netherlands based on their preliminary results and results from the NIOSH take-home pesticide study. Researchers at the University of Iowa have initiated further research on the take-home pesticide issue. The study protocol was largely developed based on results from the take home study. NIOSH has been asked to be a collaborator on this initiative. In addition to the published articles in peer reviewed journals, this project has also generated press, whereby information was further disseminated to lay populations with an interest in the subject. The project officer, Brian Curwin was interviewed on take-home toxins, including pesticides, in December 2002 for an article for OHS Canada Magazine. The article was published in April 2003. OHS Canada is a Canadian Occupational Health and Safety trade magazine. The University of Iowa created a press release on the pesticide take-home study. The University of Iowa has also created a fact sheet for dissemination among Iowa participants of the National Cancer Institute’s Agricultural Health Study, Iowa agricultural extension agents and Iowa pesticide educators. The fact sheet highlights the results presented in the pesticide contamination paper and includes recommendations to reduce potential take-home exposure to pesticides. End Outcomes: No measurable end outcomes were generated. External Factors: The National Cancer Institute and the Great Plains Center for Agricultural Health were instrumental in recruiting participants for this study and the Great Plains Center for Agricultural Health provided laboratory space and field logistic support for the field teams. The National Center for Environmental Health, Battelle Memorial Institute and NIOSH’s Division of Applied Research and Technology were instrumental in developing and validating the analytical methods used and conducting the sample analysis for pesticides. This study would not have been completed without the efforts of these organizations. Future Directions: In 2005 further research was conducted to investigate the difference between take-home pesticide exposures in the spring (planting season) and fall (off season). In 2006, this activity was expanded to include commercial pesticide applicators.