Project Number: 9278413 Project Title: Analytical Method Development for Emerging problems Division: DART Project Officer (PO): Robert P. Streicher Other personnel: AA Grote, YT Gagnon, C Lorberau, DL Sammons PO Degree: Ph.D. PO Area of Expertise (scientific discipline): Organic Chemistry Project Start Date: 1996 Project End Date: Continuing project (period referenced = 1996 to 2005) Total Budget over the Project Period: $499,902.00 Goal/Sub-Goal: Exposure Assessment Research Challenge/Issue: This project develops new or improved analytical methods in response to needs for sampling and analytical methodologies to determine worker exposures to workplace contaminants. It supports initial research on emerging industrial hygiene sampling and analytical problems. Method development research has been completed for air and dermal sampling methods for acephate, dimethoate, chlorpyriphos, diazinon, and piperalin. Coordination of laboratory and field activities is also a function supported by this project. A collaborative study, between NIOSH and EPA, has been conducted for pesticides used in restricted entry situations for small business greenhouses. Sampling materials have been investigated to determine their suitability for measurement of skin exposure to pesticides. GC/high resolution MS is also used for the identification and quantitative determination of certain workplace contaminants, such as nitrosamines in MWFs and chlorophenoxy acid herbicides in urine. This work supports research efforts within DART, DSHEFS, DRDS, SRL, NIOSH regional offices and MSHA. The methods that result from this project allow industrial hygienists, epidemiologists, and engineers to measure worker exposure and evaluate the effectiveness of changes intended to reduce exposure. Activities: A method is now available for assessing worker exposure to some common pesticides. A lengthy, complex research project has produced a fully evaluated method, capable of determining the presence and amount of any of 14 common "organonitrogen" pesticides. These pesticides are in wide use, and the method has already been used to measure pesticides accurately at low levels. The method will be published in the next supplement to the NIOSH Manual of Analytical Methods (NMAM 5601). A paper based on research to develop this method was prepared and submitted to the American Industrial Hygiene Association Journal for publication. GC/high resolution Mass Spectrometry is used for the identification and quantitative determination of chlorophenoxy acid herbicides in urine. Pesticide method development has been conducted in coordination with DataChem Laboratories. Air and dermal sampling methods for atrazine, alachlor, acetochlor, metolachlor, chlorpyriphos, 2,4-D and glyphosate have been developed.
Outputs: Method 2520: Methyl Bromide (issued 15/05/1996, NMAM). NIOSH Analytical Methods (to be issued pending external review) Method 9203: Wipe method acephate, diazinon, dimethoate, chlorpyrifos, and piperalin (greenhouse rosegrowers); Method 9208: Captan in Air Samples by GC/MS (CASC) Method 5604: Acephate, chlorpyrifos, diazinon, dimethoate, & piperalin Publications: Health Hazard Evaluation of Methyl Bromide Soil Fumigations, Appl. Occup. Environ. Hyg. S. W. Lenhart, Y. T. Gagnon, 14:7:407-412. July 1, 1999. A Laboratory Comparison of Two Media for Use in the Assessment of Dermal Exposure to Pesticides - C. D. Lorberau and J. L. Pride [2000] Appl. Occup. Environ. Hyg. 15:946-950. Documents generated while working with Standard-setting organizations: Analytical Performance Criteria Standards Activities of the ASTM International Committee on Atmospheric Sampling and Analysis, K. Ashley, [2004] Journal of Occupational and Environmental Hygiene, 1: D7–D9. ASTM Standards for Monitoring Chemical Hazards in the Workplace - K. Ashley and M. Harper [2004] Sampling Environmental Media ASTM STP 1282 - K. Ashley, P. C. Schlecht, R. Song, H. A. Feng, G. Dewalt and M.E. McKnight [1996], 125-136. Ashley K, Harper M, Analytical Performance Criteria: ASTM International Standards for Monitoring Chemical Hazards in Workplaces, J OCCUP ENVIRON HYG 2 (6): D44-D47 JUN 2005 HETA Reports: Lenhart SW, Gagnon YT [Nov. 1998]. NIOSH Health Hazard Evaluation Report for U.S. Dept. of Agriculture Animal and Plant Health Inspection Service, Department of Health and Human Services, Public Health Service, Centers for Disease Control and Prevention, National Institute for Occupational Safety and Health, NIOSH report No. HETA 93-0012-2711. "Development of analytical methods for agricultural chemicals," E.R. Kennedy, M.T. Abell, J. Reynolds and D. Wickman, Scand. J. Work, Environ. Health 18, 63-5 (1992). "A sampling and analytical method for the simultaneous determination of multiple organophosphorus pesticides in air," E.R. Kennedy, M.T. Abell, J. Reynolds, and D. Wickman, Am. Ind. Hyg. Assoc. J., 55, 1172-1177 (1994).
Intermediate Outcomes: These methods provide surveillance and control technology research with the tools (analytical methods) that confirm the effectiveness of changes in the work environment by substitution, behavior changes or protective equipment. Any Intermediate outcomes tend to be several steps removed from this method development process. End Outcomes: External Factors: NA NA
Future Directions: This project will continue to provide method development research support as requested or appropriate as new technology, media or improved instrumentation become available 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.
Project Number: 9277132 Project Title: Ag Health Study, Pesticide Exposure Among Farmer Applicators Division: DSHEFS Project Officer (PO): Cynthia Hines PO Degree: Masters PO Area of Expertise (scientific discipline): Industrial Hygiene Project Start Date: 10/1/1998 Project End Date: 9/30/2005 Total Budget over the Project Period: $1,495,830 Goal: Chronic Effects of Agricultural Exposure Sub-Goal: Exposure Assessment Research Challenge/Issue: This study is assessing the exposure of farmers in North Carolina and Iowa who personally apply the fungicides captan, thiophanate-methyl, and benomyl to apple and peach orchards. The study is being done in collaboration with the Agricultural Health Study (AHS), a large prospective health study of licensed private (farmer) and commercial applicators, and the spouses of private applicators. The AHS is sponsored by the National Cancer Institute, the National Institute of Environmental Health Sciences and the Environmental Protection Agency. Retinal degeneration among applicators in the AHS has been associated with fungicide use (Kamel F. et al., 2000*; Kirrane E. et al., 2005**). Fungicides are heavily used in orchards in the South and Midwest. Minimal monitoring data are available on fungicide exposures among U.S. orchard applicators. Agent-specific exposure classification in the AHS is based primarily on questionnaire data. The AHS has developed an algorithm to estimate exposure intensity using questionnaire data. This algorithm includes factors believed to either increase or decrease exposure with a “weight” assigned to each factor to reflect the relative impact of the factor on exposure intensity. These weights have been taken largely from exposure monitoring data for non-AHS study populations in the literature. Actual exposure data are needed to validate the algorithm, to evaluate the appropriateness of the assigned weights, and to identify or confirm important exposure determinants. Fungicides are applied at regular intervals during spring and summer in orchards. Captan is a frequently applied fungicide that is serving as the primary marker for fungicide exposure in orchards in this study. Captan is metabolized to tetrahydrophthalimide, which is excreted in the urine. Because of the likelihood of substantial within-worker variability, a repeated-measures design was used. Agricultural extension agents from North Carolina and Iowa provided input on fungicide application practices on apples and peaches in the study states, arranged for site visits to orchards to talk to farmers, and provided input on possible factors influencing exposure.
*Kamel F., W.K. Boyes, B.C. Gladen, A.S. Rowland, M.C.R. Alavanja, A. Blair, and D.P. Sandler. 2000. Retinal degeneration in licensed pesticide applicators. Am. J. Ind. Med. 37:618-628. **Kirrane E.F., J.A. Hoppin, F. Kamel, D.M. Umbach, W.K. Boyes, A.J. DeRoos, M. Alavanja, and D.P. Sandler. 2005. Retinal degeneration and other eye disorders in wives of farmer pesticide applicators enrolled in the Agricultural Health Study. Am. J. Epidemiology 161:1020-1029.
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Activities: A study protocol was developed and approved by all relevant IRBs in 2001. Analytical methods for measurement of the target fungicides in air, hand rinse, and dermal patch samples were developed in 2001. Initial development of an HPLC method for captan was followed by development of a confirmatory GC/MS method after phosmet interferences were detected in field samples. These methods have been adapted for inclusion in the NIOSH Manual of Analytical Methods. Participants from the AHS were selected based on planned use of captan. Field data collection was conducted in 2002 and 2003 in Iowa and North Carolina. Seventy –four applicators participated in the study for a participation rate of 73%. These applicators were monitored on 144 days (~ 2 days/applicator). Air, dermal patch, hand rinse, and urine samples were collected from all participating farmers on each day. Laboratory analyses were completed in 2003. Observational and measurement data were coded and entered into databases in 2004 and 2005. Data analysis to evaluate the algorithm and to identify exposure determinants is ongoing. The first manuscript on work practices and personal protective equipment use of the orchard farmers is in internal review (2006). The second manuscript on exposure levels and the algorithm evaluation is in preparation. Personnel resources on this project included the NIOSH project officer [Cynthia Hines], two NIOSH chemists to develop the sampling and analytical methods [Larry Jaycox, Ronnee Andrews], two contract laboratories (DataChem Laboratories and Morse Laboratories) to analyze the samples, two NIOSH chemists to oversee the quality control for the environmental and for the biological exposure monitoring [Jensen Groff and Cynthia Striley], two industrial hygiene field technicians to prepare, deliver, and re-stock all supplies [Kevin L. Dunn, Belinda Johnson], a contractor (Battelle) to provide six industrial hygiene field staff to recruit and sample participants during the spraying season, and to provide data management support for coding, entering, and proofing data, and a statistician [James Deddens] for data analysis. Outputs: Manuscripts Hines CJ, Deddens JA, Coble J, Alavanja MCR: Fungicide Application Practices and Personal Protective Equipment Use Among Orchard Farmers in the Agricultural Health Study (draft in review). * This manuscript provides extensive information on the mixing and application practices of orchard farmers, their personal protective equipment use, and their hygiene practices. The information will be useful for identifying areas needing additional pesticide safety training, and for designing intervention or other studies to examine factors that may be associated with the behaviors and practices observed in this study. As many of the farmers in this study had small orchards, information in this paper may be especially useful in targeting safety messages to small farmers. NIOSH Manual of Analytical Methods Method 9202: Captan and Thiophanate-methyl in hand rinse (HPLC) 2
Method 9205: Captan and Thiophanate-methyl in dermal patch (HPLC) Method 9208: Captan in Air Samples by GC/MS * These methods are detailed sampling and analytical procedures for measuring captan and thiophanate-methyl in air, hand rinse, and dermal patch samples. The methods expand the capability of researches and practitioners to measure the exposure of farmers, farm workers, families, and others to captan and thiophanate-methyl in several exposure matrices. In particular, two of the methods address dermal exposure, an often important route of exposure to pesticides. Accurate measurement and characterization of exposure leads to improved risk assessment. Intermediate Outcomes: This study is not completed and intermediate outcomes are not yet available. End Outcomes: This study is not completed and end outcomes cannot be assessed yet. External Factors: This project is a collaborative effort with the Agricultural Health Study, a study jointly funded by the National Cancer Institute, the National Institute of Environmental Health Sciences, and the Environmental Protection Agency. The Agricultural Health Study provided access to its participants for recruitment purposes. The Captan Task Force, an industry-based group of scientists, is interested in this project and has been following its progress regularly. The Task Force has provided assistance on captan product information and in reviewing pre-publication manuscript drafts under tri-partite review. Persons or organizations likely to benefit from this project include pesticide safety educators, co-operative extension agents and pesticide manufacturers. Future Directions: Although data analysis is ongoing, it appears that exposure risk is higher among farmers who use air blast application methods as compared to those who use hand spray methods. Future studies to reduce exposure should focus primarily on air blast application. Many farmers were not following the EPA label with respect to wearing personal protective equipment. Of particular importance is the low use of eye protection during mixing (35%) and applying (41%) since captan is considered a serious eye irritant. Also, use of chemical-resistant gloves during mixing (68%) and applying (59%), while better than eye protection, could to be improved. Studies are needed to determine barriers to the use of personal protective equipment. The contribution to exposure from residues on spraying equipment and tractors is also not well described. Additional activities include notifying participants of the study results and presenting the study findings to scientific and agricultural audiences. It is hoped that the dissemination of the study findings will stimulate follow-up studies and influence the content of pesticide safety training curricula.
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