PESTICIDE RESIDUES IN FOOD - 1979 Sponsored jointly by FAO and WHO EVALUATIONS 1979 Joint meeting of the FAO Panel of Experts on Pesticide Residues in Food and the Environment and the WHO Expert Group on Pesticide Residues Geneva, 3-12 December 1979 DIPHENYLAMINE Explanation Diphenylamine was first evaluated in 1969 when an ADI was allocated and a MRL for apples. In 1976 additional toxicological and residue data from Australia and the Netherlands were received and the meeting confirmed the ADI and recommended that, unless countries had a need to maintain the MRL for apples at 10 mg/kg, it should be reduced to 5 mg/kg. Residue data have been generated in Australia and additional information has been obtained from USA and the open scientific literature to permit the meeting to further evaluate the MRL. RESIDUES IN FOOD AND THEIR EVALUATION Since the evaluation in 1976 indicated that residues on apples are generally less than 2 mg/kg, the data considered in 1969 have been re-evaluated with a view to seeking an explanation for the higher MRL proposed on that occasion. The difference can be explained by the following: 1. The concentration of diphenylamine dip solutions used over recent years is substantially less than those used in experiments in the late 1950's. 2. The quality and stability of the formulation has an important bearing on the amount of diphenylamine deposited on fruit from dips and sprays. The quality of diphenylamine emulsion and wettable powder formulations has been improved considerably with a result that they give more uniform and lower deposits. 3. All of the residue data reported by Harvey and Clark (1959) and apparently much of that reported by Bruce (1958) used as a basis for the evaluation in 1969, refer to residues in the peel rather than the whole fruit. These and later studies have usually shown that the concentration is much higher in the peel than in the whole fruit. Importance of formulation and stability of dips Denmead et al (1961) used a diphenylamine emulsion which was homogenised by passing five times through a colloid mill until a uniform globule size was achieved; most globules being between 1 and 4 microns diameter, with very few exceeding 5 microns. It was noted that without homogenisation less uniform emulsions with much larger globules were formed and that these coarse emulsions gradually broke down during their passage through the spray equipment. Diphenylamine uptake was found to be negatively correlated with globule size and until fine uniform emulsions were formed, it was not possible to obtain reproducible uptake of diphenylamine. During drenching operations the diphenylamine concentration in the dip gradually fell as a result of uptake of diphenylamine by apples and dilution of the emulsions by water introduced on the wet apples. The concentration of the bath before and after treatment differed by as much as 30 percent. Gorman and Row (1977) investigated the properties of two different commercial diphenylamine formulations and showed that emulsion breakdown was accompanied by phytotoxicity due to the uneven and excessive deposition of diphenylamine on the skin of fruit. The practice of combining calcium chloride with diphenylamine dips to control bitter pit as well as superficial scald can result in rapid breaking of the emulsion. The spraying operation, which greatly increased aeration, also resulted in the rapid breaking of the diphenylamine emulsion. The quality of the water used for diluting the emulsion also had a distinct bearing on its stability. Gorman and Rowe (1977) also showed that stable formulations give a lower deposit on apples and consequently are not as effective in controlling superficial scald. This can be overcome by increasing the concentration in the dip bath. In dipping tests, one preparation yielded initial deposits three to six times higher than the more stable preparation applied at the same concentration for the same time. The unstable emulsion tended to give a much higher deposit when the dip time was increased from 60 to 180 seconds. The residual deposit from the stable preparation was not significantly affected by the dipping times. Little et al (1977) drew attention to the effect of additives (calcium chloride, benomyl and on fruit susceptibility to phytotoxic damage. Calcium chloride benomyl caused the active ingredient to be stripped out rapidly onto the fruit. Denmead et al (1961) used a standard diphenylamine solution in oil, emulsified with water to prepare a range of concentrations from 0.05% to 0.3%. These were used to dip two varieties of apples. The uptake of diphenylamine was measured by analyzing the fruit. Hanekom et al (1976) demonstrated the effect of immersion time and diphenylamine concentration on the uptake of diphenylamine by Granny Smith apples. This could be readily correlated to the percentage reduction of superficial scald. Their results are summarised in Table 1 (see also comment under "Residues resulting from Supervised trials, Cornell University.) Table 1. Effect of immersion time and DPA concentration on the uptake of DPA (ppm) by Granny Smith apples (Percentage superficial scald given in brackets) Immersion time (sec.) DPA concentration (ppm) 600 1200 1800 30 0.7 (91) 1.7 (83) 1.6 (78) 75 1.4 (80) 1.7 (95) 2.4 (77) 120 1.8 (74) 2.5 (71) 3.5 (4) LSD (P = 0.05) Immersion time × DPA concentration = 0.6 Constant factors: Picking stage = 150 days Fruit Temperature = 20°C Temp. of immersion solution = 20°C Hanekom at al (1976) Application temperature Hanekom et al (1976) investigated the effect of fruit temperature and temperature of immersion solution on the uptake of diphenylamine by Granny Smith apples and showed that this was readily correlated with percentage superficial scald. Optimum results were obtained when the immersion solution was at 40°C and the fruit temperature between 10°C and 20°C. Their results are given in Table 2. The higher temperatures lead to higher deposits on the fruit. Table 2. Effect of immersion solution and fruit temperatures on the uptake of DPA by Granny Smith apples (Percentage superficial scald given in brackets) Temp. of immersion Fruit temperature (°C) solution (°C) -0,5 10 20 20 1.0 (91) 1.0 (100) 2.4 (89) 30 1.8 (85) 1.4 (84) 2.6 (50) 40 3.2 (30) 3.8 (0) 3.6 (2) LSD (P = 0.05) Immersion solution × fruit temperature = 0.7 Constant factors: DPA concentration of immersion solution = 1 200 ppm Picking stage = 150 days Immersion time = 75 sec. Hanekom et al (1976) Effect of variety The diphenylamine uptake was measured for a number of varieties of apples in studies by Denmead et al (1961). A 0.2 percent emulsion of diphenylamine was applied as a drench for one minute and the uptake was determined by analyzing the fruit. The results are given in Table 3. Table 3. Variation of DPA uptake with variety DPA uptake Variety gamma/cm2 Worcester Pearmain 14.5 Gravenstein 14.5 Cox's Orange Pippin 6.8 Ballarat (1) 4.0 Ballarat (2) 1.6 Dougherty 2.9 Granny Smith (1) 1.0 Granny Smith (2) 0.76 Denmead et al (1961) Effect of size of fruit on uptake of diphenylamine Since superficial scald and diphenylamine uptake are both surface phenomena, some investigators have expressed the diphenylamine concentration as mg/cm2 rather than as mg/kg, though the former figure is not suitable for expressing residue concentration. The surface area of apples was obtained by assuming them to be spheres and applying the surface to volume relationship of a sphere (Denmead et al 1961). When the concentration of diphenylamine expressed as mg/cm2 and mg/kg on 8 apples of different weights were plotted against surface area and weight respectively, it was apparent that the diphenylamine concentration expressed as mg/kg was negatively correlated with the weight of individual apples whereas when expressed as mg/cm2 it was independent of surface area. For an apple weighing 180 g with a volume of 220 ml for example, the values of diphenylamine uptake expressed as either mg/kg or mg/cm2 were numerically equal. For larger apples the mg/kg figure became progressively smaller than the mg/cm2 and conversely for smaller apples. Rate of loss on storage Hall et al (1961) showed that the concentration of diphenylamine on apples fell greatly during storage. The concentration in the skin at the end of seven months was only about 1/30th of that in the skin at the time of treatment. The concentration in the whole apple fell by a like amount. Table 4 (Denmead et al, 1961) sets out the initial and final diphenylamine concentrations on three varieties of apples held in cold storage. By measuring diphenylamine concentration at intervals during storage, the rate of loss was obtained for a sample of Doughtery apples. When the concentrations were plotted against storage times for four samples of different initial concentrations, the rate of loss was found to be almost constant and independent of the amount applied to the apple. Table 4. Loss of DPA from apples during storage DPA concentrations Storage Before storage After storage Variety period Co-efficient days p.p.m. of variation % p.p.m. Granny Smith 199 ) 15.6 18 1.0 ) 11.0 22 0.9 ) 4.5 11 0.4 ) 1.8 14 0.3 Ballarat 207 ) 6.7 11 0.5 ) 4.6 16 0.3 ) 1.4 22 0.2 Dougherty 172 ) 12.4 9 1.1 ) 4.8 8 0.5 ) 1.4 11 0.3 Denmead et al (1961) Distribution on fruit With the exception of Ginsburg (1962) all authors appear to agree that the bulk of the residue is located in the natural wax on the fruit with over 90% occurring in the peelings. Harvey and Clark (1959) report that irrespective of variety, method of treatment or concentration of diphenylamine applied, over 95% of the diphenylamine is distributed in the peeling even after the fruit has been in cool storage for lengthy periods. Hanekom et al (1976) studied the percentile distribution of diphenylamine in different fractions of the fruit after different storage periods. Whilst there was a tendency for apples, in which superficial scald was completely controlled, to have significantly more in the cuticle wax layer, all fruit had from 52-77% in the wax layer with as little as 1.3 to 5.6% in the hypodermis. This is important as the diphenylamine is mainly restricted to parts of the fruit where superficial scald initiates and develops, and therefore the treatment is specifically effective at the site where it is most needed. Hall et al (1961) reported diphenylamine was practically confined to the peel irrespective of the level and method of treatment or the time in storage. These observations were borne out in recent studies in Australia (Luke 1978, Gorman and Rowe, 1977). However, Ginsburg (1962) using the methods of Harvey (1958) found that the amount of diphenylamine remaining on the surface was negligible and the amount found in the pulp was always much higher than in the skin except in one instance. The one difference in technique was that most reports in the literature are for studies carried out on apples immediately after cold storage, whilst the work reported by Ginsburg was done after the apples had been held at room temperature (15-20°C) for one week. Luke (1978), reporting the results of analysis of approximately 50 different samples, treated both with dips and paper wraps, from many parts of Australia, showed that diphenylamine does not penetrate beyond 2-4 mm from the peel surface and that the residue levels in peel are similar to those reported by Harvey and Clark (1959). RESIDUES RESULTING FROM SUPERVISED TRIALS The work of Harvey and Clark (1959) reviewed by the meeting in 1969 refers entirely to levels of residues found in peelings and pulp and nowhere in the paper is any attempt made to report or calculate these on the whole fruit basis. (But this fact is not clear in the 1969 monographs.) Luke (1978) reviewed the data in the light of Australian experience, and calculated the approximate level in using his own experience of the ratio of skin to whole fruit. He found the diphenylamine residue level on whole fruit for the data reported by Harvey and Clark to range from less than 0.1 mg/kg to 0.4 mg/kg. Bruce et al (1958) found 3.23 to 3.64 mg/kg diphenylamine residue immediately after use of a 1000 mg/l bath and 1.59 to 1.77 mg/kg after 5 months storage. Hall et al (1961) have published the results of extensive trials which encompass most of the variables likely to be encountered in practice. With the exception of residues determined in fruit one day after dipping, all values recorded for whole fruit were 1 mg/kg or less. The high values recorded immediately after treatment decreased to about 2 percent of the original level during the time the fruit was in cold storage. The USDA (1961) reported studies carried out in Wenatchee, Washington, in which the effect of four variations of treatment and storage times were examined. Residues on the surface and in the pulp were determined separately. Results are given in Table 5. The total diphenylamine residue ranged from 5 mg/kg immediately after dipping to 0.5 mg/kg after storage for nine months. The pulp contained a higher fraction of the total residue in the samples which had been stored for two months (58%) or nine months (52 to 83%) than was the case one day after dipping (18%). The colorimetric procedure (Bruce et al 1958) used in these investigations gave a high apparent value in untreated control samples. Cornell University (1962), reporting trials carried out in 1961 at Ithaca, N.Y., showed that the nature and stability of the formulation was critical in determining the level and uniformity of diphenylamine deposits on apples. The report points to unsatisfactory results obtained with alcoholic solutions due to the deposition of crystals of diphenylamine in the dipping bath. When satisfactory wettable powder formulations were used the deposit, determined immediately after treatment, remained generally below 3 mg/kg irrespective of the concentration of diphenylamine in the dip bath (Table 6 and 7) or whether the treatment was carried out immediately after harvest or after a period in cold storage (Table 8). All of the data reported by Ginsburg (1962) are for fruit which has been held in cold storage for an extended period and then for one week at room temperature (15°C to 20°C) prior to analysis. The diphenylamine residue level on whole fruit at the end of this storage in all cases was well below 1 mg/kg, usually below 0.2 mg/kg. Gorman and Rowe (1977) report that laboratory dipping trials with different formulations produced residues of the order of 2 mg/kg to 4 mg/kg on the day of treatment, but that these had fallen, to less than 1 mg/kg after 14 to 28 days in cool storage. Unstable formulations used at high dip concentrations gave rise to residues which after 21 days in storage at minus 0.5°C ranged up to 2.5 mg/kg. Hanekom et al (1976) report the level of residues in whole apples, four days after immersion for various periods in diphenylamine emulsions at several concentrations. The highest concentrations and longest time gave rise to residues of the order of 3.5 mg/kg, though this concentration fell to approximately half during ten week storage. Sproul and Sivyer (1976) investigated the use of diphenylamine dips, prior to fumigation with methyl bromide, to prevent phytotoxic damage from the fumigation. They showed that fruit dipped in diphenylamine baths containing 250 mg/L to 1,000 mg/L were completely free of any injury following fumigation. The residues in such fruit ranged from 0.6 mg/kg to 1.9 mg/kg after three weeks in cold storage. Rippon (1977) reported the results of one trial in which apples were treated in baths containing 1,000 mg/L and 1,250 mg/L of diphenylamine. The residues resulting from such treatment ranged from 0.36 mg/kg to 0.86 mg/kg on the whole fruit. Table 5. Diphenylamine Residues on Apples following Different Treatments and Storage Times (USDA Data) Treatment Storage Variety Diphenylamine Residues Time Value Surface Pulp Total Number 2 2 0 None None Delicious Range 0.02-0.03 0.23-0.29 - Mean 0.03 0.26 0.29+ Number 5 2 0 None None Winesap Range 0.01-0.07 0.28 - Mean 0.03 0.28 0.31+ Number 4 4 2 1000 ppm 1 day Winesap Range 4.2-5.1 0.9-1.0 - (42% WWP) Mean 4.3 0.9 5.2 Number 4 4 1 1000 ppm 2 mo. Winesap Range 1.5-1.7 1.8-2.4 - (42% W) Mean 1.6 2.2 3.8 Number 4 3 1 1000 ppm 9 mo. Delicious Range 0.16-0.20 0.40-0.42 - (42% WWP) Mean 0.18 0.40 0.48 Number 4 4 1 1000 ppm 9 mo. Delicious Range 0.23-0.27 0.24-0.29 - (50% Emul) Mean 0.25 0.26 0.51 * Total residue in these instances was calculated by addition of amount found on surface and pulp. Table 6. Effect of Formulation on Diphenylamine residues on single, whole McIntosh apples resulting from Dipping. (Residues immediately after Treatment but treated after storage) Actual DPA applied Formulation DPA residues ppm ppm 1000 alcohol 1.7 1000 alcohol 2.2 2000 alcohol 17.6 1000 42% DW* 2.1 1000 42% DW 0.8 2000 42% DW 1.1 2000 42% DW 0.4 3000 42% DW 3.3 2000 84% DW 2.3 2000 84% DW 1.8 3000 84% DW 1.6 * DW = dry wettable. (See Cornell, 1962). Analytical method of Bruce et al, (1958). Table 7. Effect of Formulation on Diphenylamine Residues on 20 Apple Samples of whole McIntosh Apples resulting from Dipping. (Residues immediately after treatment) Actual DPA residues DPA applied Formulation Avg. of two samples 1000 alcohol 3.0 1000 alcohol 2000 alcohol 5.6 2000 alcohol 3000 alcohol 6.0 3000 alcohol 1000 84% DW 0.6 1000 84% DW 2000 84% DW 1.8 2000 84% DW 3000 84% DW 2.1 3000 84% DW See Cornell, 1962. Bruce et al (1958). Table 8. Diphenylamine Residues on Whole Apples with Dry Wettable formulation (Residues Immediately after treatment* at Harvest time). Analytical Actual Active Variety DPA residues (avg. of 2 Method DPA Ingredient corrected for control applied, ppm % ppm By dipping Bruce et al (1958) 2000 42 Cortland 3.0 " " 2000 42 " Harvey et al (1959) 2000 42 " 2.7 " " 2000 83 R.I. Greening 1.9 " " 2000 83 " " " 2000 83 " 1.4 " " 2000 83 " " " 1000 83 McIntosh 1.6 " " 1000 83 " " " 1000 83 Cortland 2.2 " " 1000 83 " " " 2000 83 " 3.9 " " 2000 83 " By Crate Sprays Bruce et al (1958) 2000 42 Cortland 8.5 " " 2000 42 Harvey et al (1959) 1000 83 McIntosh 2.3 " " 1000 83 " " " 1000 83 Cortland 2.3 " " 1000 83 " " " 2000 83 " 4.7 " " 2000 83 " Box Immersion Harvey et al (1959) 1000 83 McIntosh 2.0 " " 1000 83 " " " 1000 83 Cortland 3.0 " " 1000 83 " Apples frozen in sealed poly bags until time of analysed. First box dipped in 1 gallon of 2000 ppm DPA. 16th box dipped in 1 gallon of 2000 ppm DPA. Recoveries 70 -95% Allen et al (1979) reporting on-going studies in the United Kingdom indicated that the deposit on Bramley apples increased with increasing dip concentration (Table 9). The initial concentration deposited from the unusually high dip concentration of 1,000 mg/L was 6 mg/cm2 (approximately 6 mg/kg). Table 9. Effect of dip concentration of residue deposit Dip concentration Mean initial deposit (S D) (ppm) (µg cm2) 500 1.32 (0.25) 1000 2.27 (0.42) 2000 3.62 (0.89) 4000 6.01 (1.26) The levels after 5 months' storage were less than 0.25 µg cm2 and after nine months storage, less than 0.01 µg cm2, from all concentrations of dip solution. For Bramley apples, an amount per unit area (µg cm2) is approximately equal to the whole fruit concentration (ppm or mg/kg). Further work is in progress to determine if deposits or efficacy vary between two commercial formulations of DPA when applied in the laboratory. Similar work, with one of these formulations, was carried out under commercial conditions on farms in 1977, and is being repeated in 1978. Preliminary work suggests that problems may arise if DPA dip solution is mixed with certain other chemicals. Extensive investigations carried out in Australia over three years (Snelson, 1979) in which apples from 88 packing houses were analyzed for diphenylamine residues, reveal that only 1% of the samples contained residues above 3 mg/kg when examined after approximately 8 weeks in cold storage. The distribution of residues is indicated in Table 10. It will be noted that 86% of the residues in whole fruit are at levels below 1 mg/kg. 99% of the samples contained less than 3 mg/kg, notwithstanding the fact that in some samples the peel contained more than 20 mg/kg of diphenylamine. Table 10. Distribution of Diphenylamine Residues in Australian Apples PEEL WHOLE FRUIT Range of Range of Residue No. of % residue No. of % Levels samples Levels samples 1.0 10 11 0.1 8 9 1.1 - 2.0 14 16 0.1-0.5 46 52 2.1 - 5.0 27 31 0.51-1.0 22 25 5.1 -10.0 28 31 1.1-2.0 7 6 10.1-20.0 5 6 2.1-3.0 5 6 20 4 5 3.0 1 1 Total 88 100 88 100 Snelson (1979) METHODS OF RESIDUE ANALYSIS No new information has become available on improved analytical techniques. The Ad Hoc Working Group on Methods of Analysis of the Codex Committee on Pesticide Residues has recommended that the method published in Pesticides Analytical Manual, Volume 2, US Food and Drug Administration, Washington DC, USA (1977) is suitable for regulatory purposes and should be used for the determination of phenylamine residues on apples. It should be recognized that since the bulk of the residue is in the peel, it is not necessary to process the whole fruit. The peel may be removed and processed for analysis so long as the ratio of peel to whole fruit is determined on each sample. The considerably higher concentration in the peel greatly facilitates the cleanup and quantitation steps. NATIONAL RESIDUE LIMITS REPORTED TO THE MEETING The meeting was made aware that national governments had proclaimed the following maximum residue limits: Federal Republic of Germany 3 Netherlands 3 Sweden 3 United Kingdom 3 APPRAISAL Following the recommendations of the 1976 Meeting and a request from CCPR, the available data on residues on apples has been reviewed and the results of additional surveys and trials have been made available. Although some results from supervised trials made in 1961 suggest that residues could reach levels of the order of 10 mg/kg, later data suggest that, in some cases, the higher and variable residue levels obtained at that time were due to the use of formulations which have since been replaced by preparations which do not separate in dip baths. The meeting was aware that following normal treatment in packing houses, the residue level in some treated apples could exceed 5 mg/kg for a few days, but this is of little practical consequence since treated fruit is usually not presented for sale immediately. Treatment is normally only applied to fruit going into cold storage and even minimum storage results in a significant decline of diphenylamine residues from the skin surface. At room temperature, the surface deposit disappears in a few days. The meeting agreed that there is little justification for retaining the maximum residue limit at the value of 10 mg/kg established in 1969. Available information indicates that a MRL of 5 mg/kg is adequate to deal with residues in apples in commerce, resulting from typical levels and methods of treatment especially if the period between application and release into trade is 21 days or more. Use patterns and application practices appear to have changed since the early 60's when the data considered at the 1969 meeting were generated. The meeting requested further information on current practices and residues resulting therefrom from countries where higher MRLs have been established. RECOMMENDATIONS The meeting recommends that the existing maximum residue limit of 10 mg/kg for diphenylamine on apples should be lowered to 5 mg/kg. FURTHER WORK OR INFORMATION Desirable Information on current practices, formulations, use patterns and selective surveys of residues in crops known to have been treated under practical circumstances. REFERENCES Allen, J.G., Hall, K. L., Martin, S., Sharples, R.O. and Johnson, D.S. Diphenylamine for scald control. Rep. E. Mathing Res. Sta. for 1978. p. 114. Bruce, R.B., Howard, J.W. and Zink, J.B. - Determination of diphenylamine residues on apples. J. Agr. Food Chem. 6: 597-600. Denmead, C.F., Vere-Jones, N.W. and Atkinson, J.D. - A commercial method of controlling apple scald with diphenylamine emulsions. J. Hort. Sci. 36: 73-84. Cornell University - Diphenylamine residues on apples. Information supplied to US Food and Drug Administration February 26, 1962. Ginsberg, L. - Superficial scald and its control on South African apples. The Deciduous Fruitgrower Feb. 1962 pp. 34-41. Gorman, R.C. and Rowe, N.B. - Investigation into the preparation, stability and effectiveness of apple dipping emulsions of diphenylamine. Report to Pesticides Co-ordinator August 1977 from Western Australian Government Chemical Laboratory. Hall, E.G., Scott, K.J. and Cook, G.C. - Control of superficial scald on Granny Smith apples with diphenylamine. Aust. J. Agric. Res 12 (5): 834-853. Hanekom, A.N., Scheepers, J.L. and DeVilliers, J.F. - Factors influencing the uptake of diphenylamine by apple fruit. The Deciduous Fruitgrower, October 1976 pp. 402-411. Hardisty, S.E. - Bitter pit control could save export Granny Smith apples. J. Agric. W.A. p. 28-30. Harvey, Helen and Clark, P.J. - Diphenylamine residues on apples. NZ J. Sci. 2: 266-72. Little, C.R. - Post-harvest treatment for pome fruit - some practical implications. Proceedings of Fruit and Vegetable Post-Harvest Research Workshop, Glenelg, South Australia, Sept. 1977 pp. 140-145, CSIRO Canberra, Australia. Luke, B. - Diphenylamine residues on apples. Report to Australian Government Analyst, 28 July 1978. Rippon, L.E. - Pesticide residues in fruit resulting from post harvest treatments: Proceedings - Fruit and Vegetable post-harvest Research Workshop, Glenelg, South Australia, September 1977. CSIRO, Canberra, Australia. Snelson, J.T. - Diphenylamine residues in apples. Report from Dept. of Primary Industry, Canberra, 12 October 1976. Sproul, A.N. and Sivyer, M. - Residues resulting from the use of diphenylamine to reduce injury from methyl bromide. Report to Fresh Fruit Disinfestation Committee from Western Australian Department of Agriculture. Sproul, A.N., O'Loughlin, J.B., Terands, A., and Hardisty, S. - The use of diphenylamine to protect apples from methyl bromide injury. Aust. J. Agric. Res., 27, 541-5. USDA - Determination of diphenylamine residue in apples. Report by the Handling, Storage and Transport Investigations Unit, Agricultural Marketing Service, U.S. Department of Agriculture, Wenatatchec, Washington (September 1961) to US Food and Drug Administration.
See Also: Toxicological Abbreviations Diphenylamine (ICSC) Diphenylamine (FAO/PL:1969/M/17/1) Diphenylamine (Pesticide residues in food: 1976 evaluations) Diphenylamine (Pesticide residues in food: 1982 evaluations) Diphenylamine (Pesticide residues in food: 1984 evaluations) Diphenylamine (Pesticide residues in food: 1984 evaluations)