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Evaluation of the risk of oral administration of residual amounts of insecticides after disinsection of food grain reserve

  • Authors: S.G. Sergeev, O.P. Kravchuk, N.V. Kolontaeva, A.P. Grynko, O.A. Makarova
  • UDC: 613:632.95-035.63/.64:502
  • DOI: 10.33273/2663-4570-2018-81-1-5-16
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L.I. Medved's Research Center of Preventive Toxicology, Food and Chemical Safety, Ministry of Health of Ukraine, Kyiv, Ukraine

Abstract. Introduction. Treatment of grain reserves (GR) with insecticides at the beginning of storage is a common technology for combating insect pests. In Ukraine, deltamethrin (synthetic pyrethroid), pirimiphos-methyl and chlorpyrifos-methyl (organophosphorus compounds) are used for GR disinsection. The use of GR with residual insecticides can be a significant risk to human health. Objective of the study. To evaluate the risk of toxic effects after oral administration of residual amounts (RA) of insecticides after disinsection of food grain reserves.
Materials and methods. To identify the risk and evaluate the exposure, physical and chemical properties, LD50 per os, consumption rate of active substances (AS) of insecticides, ratio of consumption rate and LD50 per os, results of AS RA measurement in GR (gas-liquid chromatography), half-life of insecticides in grain (T50), ratio of possible daily intake (DI) of AS RA to allowable daily intake (ADI), processing factors (PF), daily consumption of grain products were analysed. An integral exposure vector (combining DDI, DI, T50) was calculated, which was evaluated according to the proposed scale.
Results. The coefficients of selectivity of insecticide action are obtained, physical and chemical properties contributing to AS stability in the processed grain, the relationship between the consumption rate and RA are determined. AS with the largest values of the integral exposure vector is established. Based on the relationship between theoretical DI and DDI both without and taking into account PF and daily consumption of grain products, AS with the highest and lowest exposure levels are determined.
Conclusions. AS have a sufficient selectivity of action: their effective consumption rates when protecting GR 180–640 times below LD50 per os. Low solubility in water, hydrolytic stability and high lipophilicity contribute to AS stability and their concentration in bran and germ seeds after processing GR. Due to high AS resistance per RA in grain at the end of the study (up to 90 days), the initial consumption rates, which increase in the range of deltamethrin — chlorpyrifos-methyl-pirimiphos-methyl, play an important role. With conservative evaluation, 80–90 days after the treatment, theoretical DI of deltamethrin did not exceed DDI, whereas DI of pirimiphos-methyl exceeded DDI by 5 times and chlorpyrifos-methyl — by 11 times. When exposed at the level of residues, the greatest risk is represented by insecticides with the highest values of the integral exposure vector — pirimiphos-methyl and chlorpyrifos-methyl. Upon a more realistic assessment, the largest exposure to pirimiphos-methyl is associated with the consumption of whole wheat bread (at DDI level), to chlorpyrifos-methyl — with the consumption of whole wheat bread with bran (2,4 and 2,3 times higher than DI, respectively); the smallest exposure level of pirimiphos-methyl and chlorpyrifos-methyl is possible when consuming white flour and white bread.
Upon exceeding the allowable value of DI theoretical level of insecticides with treated grain reserves in the period of its use as food raw materials, it is expedient to carry out studies on the content of insecticide RA in grain products in order to assess the exposure when consuming these products at the level of scientifically substantiated and accepted norms.
Key words: insecticides, grain stocks, risk assessment, exposure, oral intake.

Grain crop production in Ukraine takes one of the leading places in the world. According to official statistics [1, 2], the production of grain and grain legume crops in Ukraine in 2010 amounted to 39.3 million tons, in 2015 it increased to 60 million tons, and in 2016 — to 65.95 million tons. Export rates of grain and grain legume crops to foreign markets are also increasing: In 2014–2015, 34.8 million tons of grain were exported, in 2015–2016 — 39.4 million tons, in 2016–2017 — 43.8 million tons. For comparison, in 2013–2014, grain exports amounted to 32.4 million tons, and in 2012–2013, — only 22.85 million tons.

Seasonal production variability and consumption of grain throughout the year require the long-term storage of large quantities of stocks both in the system of cultivation (farms, joint stock companies) and in the harvesting system (elevators, cereal receiving stations). Significant losses may occur during storage due to inadequate technologies and levels of availability of equipment of the granaries. In addition, grain storage pests — insects and mites — cause losses and lower the grain quality during storage.

There are more than 400 types of agricultural product pests in the world, more than 100 of which are found in Ukraine, including mite — 34, insects — 60 (hard-wing — 51, lepidopteral — 9) [3].

Pests populating grain stocks use it as food and habitat. As a result, the weight, sowing and eating qualities of the grain decrease, pests pollute with their waste products. Stocks become unsuitable for economic use. As a result, global grain losses due to insects during storage amount to about 50 million tons or 10 % of gross volume annually.

A radical destructive measure to control grain storage pests is chemical desinsection of the grain before the start of storage, which is carried out by spraying aqueous solutions of insecticides or their preparations without pre-dilution. For the last 15 years, European countries have been using the technology of direct grain processing (DGP), according to which the insecticide is evenly distributed through the special equipment in the mass of grain. To date, the European experience in DGP with ultralow spraying (ULS) agents based on deltamethrin, pirimiphos-methyl and chlorpyrifos-methyl allows using of this technology for the long-term control of immature development stages of insects (larvae) developed after treatment with agents with the knock-down effect mainly in adult insects (fumigation with phosphine). In Europe, up to 41 % of grain stored in storage facilities is decontaminated with fumigation, and about 59 % — with the use of DGP [4].

Grain stocks (GS) treated with insecticides can be a significant source of their residual amounts (RA) that can affect humans orally [5].

The most studied insecticides used in grain storage are organophosphorus — malathion, pirimiphos-methyl and chlorpyrifos-methyl. Their decomposition in 5–8 months of storage varies from 50 to 86 %, depending on n-octanol/water partition coefficient (Kow) of the active substance, chemical class of the pesticide, storage temperature and humidity [5]. The predicted mechanism of the decomposition is that the insecticides adsorbed on the grain are desorbed with water and become available for degradation by fungi accumulated during storage, by enzymes, metal ions, and other active compounds. The decomposition of natural and synthetic pyrethroids after their application was also studied. It was established that grain decomposition during storage was higher for the residues of natural pyrethrins (complete disappearance was observed after 8 months of storage at ambient temperature, and lower for chloroorganic substances and synthetic pyrethroids, which are very stable (non-volatile substances with high Kow values, hydrolytically stable) in the described main mechanisms of decomposition in typical storage conditions [5].

The duration of the pesticide content in the processed grain is largely due to the concentration of pesticides in triglycerides contained in the grain bran and germs. Thus, based on data on lipophilicity of pesticides, it is possible to predict the proportion of residues in processed products at the stage of grain grinding. As a result, Kow can adequately explain the differences in the reduction of the content of various pesticides found in wheat as a result of grinding: reduction in malathion and fenitrothion in flour was about 95–100 %, reduction of deltamethrin — about 57.6 % [5].

Insecticides belonging to the classes of pyrethroids and organophosphorus compounds are used in Ukraine for GS disinsection [6].

The answer to the question about the degree of adverse effects upon oral ingestion of the residues of these insecticides after GS disinsection is possible at the testing stage, which includes hazard identification and exposure assessment as necessary elements of the risk assessment procedure. In this case, the risk of toxic effects of insecticides on a person is the function of the hazard of their active substances (AS), amount of residues and probable exposure duration. In turn, the hazard is determined by toxicity parameters setting the allowable daily dose (ADD) — a hazard assessment criterion. The amount of residues in the product forms the possible daily intake (DI) to the body or exposure level and depends on the rate of GS consumption and physical and chemical properties. The possible duration of exposure is characterised by the period of insecticide preservation in food.

With growing volumes of production and, consequently, grain storage, finding the optimal balance between the production efficiency and risk of using insecticides is an urgent problem, whose solution, on the one hand, will contribute to food security, on the other hand, to the preservation of human health.

The objective of the study. To evaluate the risk of toxic effects after oral administration of residual amounts of insecticides after desinsection of food grain reserves.

Materials and methods of the study. To assess the risk of toxic effects of insecticide RA, we used information on GS pest control insecticide AS subjected to the state trials in Ukraine. These include deltamethrin (synthetic pyrethroid), pirimiphos-methyl and chlorpyrifos-methyl (organophosphorus compounds). Physical and chemical properties of AS are presented in Table 1, their assessment was made in accordance with [7].

Table 1. Physical and chemical properties of insecticides for controlling grain storage pests [7, 8]

Insecticides were used for direct grain processing on the belt conveyor. Deltamethrin, pirimiphos-methyl and chlorpyrifos-methyl were added to the wheat grain in the form of an aerosol of the working solution of products. AS name, processing objects and rates of insecticide consumption are given in Table 2.

Table 2. Processing objects and insecticide consumption rate

Acute oral toxicity parameters of deltamethrin, pirimiphos-methyl and chlorpyrifos-methyl, presented according to the literature [9, 10, 11, 22], were evaluated in accordance with the hygienic classification in force in Ukraine [12]. The above parameters, as well as insecticide ADD are shown in Table 3.

Table 3. Parameters of insecticide acute oral toxicity and ADD [7, 9, 10, 11, 22]

To characterise the risk of acute oral effects of insecticides on humans, we use the principle of determining the selectivity effect coefficient (SEC), which is the ratio of the effective consumption rate to the median lethal dose when entered into the stomach. The results were evaluated using the following scale: SEC <1° — extremely low selectivity of action, SEC from 1 to 99° — low selectivity of action, SEC ≥ 100° — sufficient selectivity of action [13].

The study of the dynamics of the insecticide content after their use to control grain storage pests was carried out in accordance with the requirements of the guidelines [14] and the basic principles set forth in the FAO Guidelines [15]. Selection and delivery of the study samples were conducted in accordance with the unified rules [16]. The study of the content of deltamethrin, pirimiphos-methyl and chlorpyrifos-methyl in cereal grains after the application of the products on the basis of these active substances was performed in accordance with the requirements of the guidelines [17, 18, 19].

The following parameters were used to assess the exposure of humans to insecticide RA: ADD smallest values, mg/kg bw. (Table 3) – as a characteristic of hazard; theoretically possible daily intake (DI, mg/kg bw) of AS residues with grain (380 g in terms of flour) to a human body weighing 60 kg calculated according to the guidelines [14] – as a possible exposure value; half-lives of insecticides in grain (T50, days) calculated on the basis of the study results of the dynamics of AS content in the grain using the one-component first-order kinetics model [20] – as the possible duration of exposure. For the comparative exposure evaluation within the analysed values, the selected parameters were evaluated in points and the principle of establishing an integral vector [21, 22] was used.

The exposure value was also evaluated based on the ratio of the theoretically possible value of DI (mg/person weighing 60 kg) residues of insecticide AS with a standardised amount of grain consumption (380 g in terms of flour) by a human to the corresponding allowable daily intake (ADI), mg/person weighing 60 kg (ADI is a product of multiplying ADD, mg/kg by 60 kg body weight in accordance with [14]). DI values at the level of RA in grain during the period of conduction and completion of observations were used.

In calculating the expected residuals of insecticide AS in the products of wheat grain processing, the factors of mechanical and thermal processing (PF), presented in [23, 24], were used. For the more realistic evaluation of the exposure value (the ratio of theoretically possible DI of insecticide residues in the period of completion of observations to the corresponding DDI values), the recommended reference values [25, 26, 27] of daily consumption of the following products of grain processing were used: bran, coarse flour, white flour — 30 g each, white bread and wholewheat bread — 170 g.

Results of the study and their discussion. As it follows from the data given in table 1, insecticides have, firstly, low solubility in water, indicating their weak ability to pass from the surface of the treated grain into a solution; secondly, the hydrolytic stability of deltamethrin and pirimiphos-methyl indicates the possibility of long-term preservation of the residues in the transition to a solution, chlorpyrifos-methyl is relatively less stable. Thirdly, due to high lipophilicity, AS can concentrate mainly in bran and germs. Fourthly, pirimiphos-methyl and chlorpyrifos-methyl are able to evaporate from the processed surfaces, and deltamethrin has a relatively less potential for evaporation.

Parameters of acute oral toxicity of insecticides presented in Table 3 indicate that deltamethrin and pirimiphos-methyl belong to moderately hazardous (hazard class 3) pesticides and chlorpyrifos-methyl — to practically nontoxic pesticides (hazard class 4) in accordance with the Hygienic Classification of Pesticides [12].

Using the data of Tables 2 and 3 SEC was calculated (see Table 4), which characterises the danger of acute effects upon oral administration of insecticides to the human body at the level of residues in the GS equal to effective consumption rate.

Table 4. Selectivity effect coefficient (SEC) of insecticides at the level of residues in the GS, equal to effective consumption rate

The results presented in Table 4, indicate that deltamethrin, pirimiphos-methyl and chlorpyrifos-methyl have sufficient selectivity of action, that is effective consumption rates of these insecticides 180–639 times lower than their median lethal doses when injected into the stomach.

The following parameters were used for the comparative assessment the exposure of humans to insecticide RA:

– smallest ADD presented in Table 3;
– insecticide DI in the human body at the end of the observation, mg/kg bw: deltamethrin — 0.0018, pirimiphos-methyl — 0.021, chlorpyrifos-methyl — 0.0114;
– T50 of insecticides in processed grain, days: deltamethrin — 61.3 (determination coefficient R2 = 0.98), pirimiphos-methyl — 55 (R2 = 0.89), chlorpyrifos-methyl — 133.3 (R2 = 0,95).

ADD, DI and T50 values were divided into four levels of hazard. Each level of hazard is assigned with the following values in points: low — 30, medium — 50, high — 80, very high — 100.

The assessment scale of hazard parameters of insecticides, their possible impact and duration of the content in the processed grain is presented in Table 5.

Table 5. Assessment scale of hazard parameters of insecticides, their possible impact and duration of the content in the processed grain

The integral exposure vector R was calculated by the formula:

,       (1)

where x is ADD, y is DI, z is T50, expressed in points.

The assessment scale of the value of the integral exposure vector of insecticide RA in grain per person is given in Table 6.

Table 6. Assessment scale of the value of the integral exposure vector of insecticide RA in grain per person

Using the above initial parameters and the assessment scale (Table 5) the parameter values were expressed in points, then the integral exposure vectors of insecticide RA in grain per person were calculated. The values of integral vectors were evaluated according to the proposed scale (Table 6). The results are presented in Table 7.

Table 7. Values of initial parameters, integral vectors and assessment of exposure levels of insecticide RA in grain per person

The results show that the highest levels of exposure are associated with the insecticides that have the highest values of the integral vector, combining high levels of hazard, as well as high residual values(which form DI). They are preserved in the processed grain for a long time (50 points and above) according to the appropriate assessment scale (Table 5).

Among the products under consideration, pirimiphos-methyl is characterised by high level of exposure, and chlorpyrifos-methyl — by a very high level of exposure. At the same time, pirimiphos-methyl has the highest score of DI due to high RA, and chlorpyrifos-methyl has the highest scores for all three components — hazard, DI and duration of content in grain (Table 6).

Fig. 1–3 show the dynamics of residues of insecticide AS and the ratio of theoretically possible DI of their residues with grain without its mechanical and thermal processing to the corresponding allowable daily intake (ADI) to the human body.

Fig. 1. Dynamics of the content of deltamethrin in wheat grains and hazard associated with its intake by humans.

 

Fig. 2. Dynamics of the content of pirimiphos-methyl in wheat grains and hazard associated with its intake by humans.

 

Fig. 3. Dynamics of the content of chlorpyrifos-methyl in wheat grains and hazard associated with its intake by humans.

 

The values of the integral vector R and the dynamics of hazard (Fig. 1–3) are obtained by a rather conservative approach, which provides for oral administration of residues of insecticide AS in the human body with grain (380 g), which is not processed by generally accepted methods.

Nevertheless, the ratio of DI/ ADI for this insecticide was 0.9 and 0.6, respectively, in 60 and 90 days after grain processing with deltamethrin (following the observation period at the maximum recommended pH value of 0.504 mg AS/kg of grain), i.e. its content in agricultural raw materials was already safe after the end of the considered period (Fig. 1). The ratio of DI/ADI for pirimiphos-methyl 80 days after processing is 2 at ADI = 0.01 mg/kg bw/day (Ukraine) and 5 — at ADI = 0.004 mg/kg bw/day (EU), for chlorpyrifos-methyl 90 days after treatment — 11 (Fig. 2 and 3). In the latter case, ADI excess indicates the hazard of grain stocks containing the residues of these AS.

As noted above, the period of preservation of insecticides in processed grain reserves forms the exposure duration. According to the stability criterion in agricultural raw materials insecticide AS belong to hazard class 1 in accordance with the Hygienic Classification [12]. Due to the high AS stability, the consumption rate affects the number of residues in the grain in the period of observation (80–90 days)/ The data shown in Table 2 and Fig. 1–3, confirm this dependence: consumption rate and residues increase proportionally in the range of deltamethrin - chlorpyrifos-methyl - pirimiphos-methyl. Long-term preservation of these residues in the grain stocks and the risk of excessive ADI require a more detailed assessment of the content of pirimiphos-methyl and chlorpyrifos-methyl after mechanical and thermal grain processing.

The content of pirimiphos-methyl in wheat grain 80 days after processing was 3.3 mg/kg (see Fig. 2). Table 8 shows the estimated residuals and evaluation of exposure levels of this insecticide (DI to ADI ratio based on ADD established in Ukraine and the EU), taking into account the PF and the recommended daily consumption of wheat grain processing products.

Table 8. Predictable residues of pirimiphos-methyl and assessment of exposure levels with recommended daily consumption of wheat grain processing products

Note: ADI1 = 0.6 mg/person/day at ADD = 0.01 mg/kg bw/day (Ukraine); ADI2 = 0.24  mg/person/day at ADD = 0.004 mg/kg bw/day (EU).

These results (Table 5) indicate that at the recommended dietary allowances of grain processing products and ADI of pirimiphos-methyl equal to 0.6 mg/person/day (Ukraine), the exposure does not exceed the permissible value and decreases in a row: whole-wheat bread – bran – coarse flour – white bread – breakfast cereal with bran – white flour. With ADI equal to 0.24 mg/person/day (EU), the consumption of wholewheat bread may use up ADI, with subsequent products, the exposure decreases and does not exceed the permissible value, however, the hazard of exposure levels when consuming each processing product is proportionally high by 2,5 times than in the previous case.

The content of chlorpyrifos-methyl in wheat grain 90 days after processing was 1.8 mg/kg (see Fig. 3). The estimated residuals of chlorpyrifos-methyl and their hazard (DI to ADI ratio based on ADD established in Ukraine), taking into account the PF for wheat products and the recommended daily consumption of these products are given in Table 9.

Table 9. Predictable residues of chlorpyrifos-methyl and assessment of exposure levels with recommended daily consumption of wheat grain processing products

The data shown in Table 9 indicate that at the recommended dietary allowances of grain processing products and ADI of chlorpyrifos-methyl equal to 0.6 mg/person/day, the consumption of wholewheat bread with insecticide residues can result in exceeding the allowable value by 2.4 times when consuming bran — 2.3 times. When consuming other processed products, the exposure of chlorpyrifos-methyl does not exceed the allowable value and decreases in a row: coarse flour — white bread —white flour.

Table 8 and 9 illustrate the dependence of exposure levels of pirimiphos-methyl and chlorpyrifos-methyl with the consumption of grain processing products on PF, a corresponding amount of residues, the consumption rate of these products, and the value of the evaluation criterion. The obtained results indicate that exposure levels are proportional to PF value, the amount of residues and consumption of grain processing products, and the hazard of exposure levels is inversely proportional to the value of the evaluation criterion.

Conclusions

1. According to median average lethal dose when injected into the stomach, pirimiphos-methyl and deltamethrin belong to moderately hazardous (hazard class 3) pesticides and chlorpyrifos-methyl — to practically non-toxic pesticides (hazard class 4) in accordance with the Hygienic Classification of Pesticides [12]. The AS have a sufficient selectivity of action, their effective consumption rate is 180–639 times lower than the median lethal dose with a single injection into the stomach.

2. Low water solubility, hydrolytic stability and high lipophilicity contribute to the stability of deltamethrin, pirimiphos-methyl and chlorpyrifos-methyl, as well as their concentration in bran and germs after processing of wheat stocks. According to the stability criterion in agricultural raw materials, the active substances of insecticides belong to hazard 1 class in accordance with the Hygienic Classification of Pesticides. Due to the high stability, the consumption rate affects the absolute amount of residues in the grain in the period of observation (80–90 days). The consumption rate and residues increase proportionally in the range of deltamethrin – chlorpyrifos-methyl – pirimiphos-methyl.

3. When assessing the possibility of multiple exposure at the level of residual quantities by ADD, DI and T50, the greatest risk of toxic effects is associated with insecticide RA which have the greatest values of the integral exposure vector due to the combination of high levels of hazard, residues and duration of the content in the processed grain (50 points and above at the appropriate scale). In this group, pirimiphos-methyl and chlorpyrifos-methyl belong to these insecticides.

4. With a rather conservative approach to the assessment (oral intake of residues of insecticide AS in the human body with grain without mechanical and thermal processing), it was shown that 80–90 days after treatment at the recommended maximum consumption rate of deltamethrin, its theoretical DI did not exceed ADI, whereas DI of pirimiphos-methyl exceeded the permissible value by 5 times, and chlorpyrifos-methyl — by 11 times.

5. Upon a more realistic assessment (using the estimated daily intake of wheat grain products and PF-adjusted insecticide content), the largest exposure to pirimiphos-methyl may be associated with the consumption of wholewheat bread (at DDI level), to chlorpyrifos-methyl — with the consumption of wholewheat bread with bran (2.4 and 2.3 times higher than ADI, respectively); the smallest exposure level of pirimiphos-methyl (0.08–0.28 of ADI) and chlorpyrifos-methyl (0.22–0.26 of ADI) is possible when consuming white flour and white bread.

6. Upon exceeding the allowable value of DI theoretical level of insecticides with treated grain reserves in the period of its use as food raw materials, it is expedient to carry out studies on the content of insecticide RA in grain products in order to assess the exposure when consuming these products at the level of scientifically substantiated and accepted norms.

7. It is recommended to evaluate the exposure levels when using food raw materials and products of their processing that contain insecticide RA with the use of the least well-grounded criterion. In this regard, it is advisable to consider the possibility of amending the ADD approved in Ukraine for pirimiphos-methyl from 0.01 to 0.004 mg/kg bw/day adopted in the EU.

 

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Надійшла до редакції 08.02.2018 р.

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