L.I. Medved's Research Center of Preventive Toxigology, Food and Chemical Safety Ministry of Health of Ukraine, Kyiv, Ukraine
Abstract. Imazamox and imazapyr are a widely use herbicides for the control of wide range of weeds in agriculture. Imazamox and imazapyr containing formulations are recommended and used for sunflower protection. For the purposes of state registration in Ukraine during 2013–2016 year in L.I. Medved's Research center of preventive toxicology, food and chemical safety, Ministry of health, Ukraine the toxicology-hygienic assessment of imazamox and imazapyr different sources and 6 imazamox and imazapyr formulations had been studied. Also substantiation of hygienic regulation for use of imazamox and imazapyr containing formulations in agriculture for sunflower protection had been done.
Scope. Toxicology-hygienic assessment of use of imazamox and imazapyr containing herbicides on sunflower, risk assessment of imazamox and imazapyr containing herbicides of impacts on agricultural workers and the population.
Methods. The toxicological assessment of formulations and their active ingredients was conducted in accordance with OECD test guidelines. Field trials were conducted in two main agro-climatic zones of Ukraine (Steppe and Forest Steppe). Treatment of the crops was performed in the highest recommended norms and ratio of applications: imazamox — 39,6 g a.i./ha and imazapyr 18,0 g a.i./ha at sunflower growth stages from 12 to 18 BBCH. Residues of of imazamox and imazapyr were analyzed by HPLC method an LOQ of 0,5 mg/kg.
Results. Based on acute toxicity parameters via different ways of exposure imazamox is III hazard class (moderately dangerous) pesticides, imazapyr — II hazard class (hazardous) pesticides; imazamox and imazapyr containing herbicides are III hazard class (moderately dangerous) pesticides. Studied substances are not sensitizers. Long\term effects (cancerogenic, mutagenic and teratogenic activities) are not limiting criteria in assessment of imazamox and imazapyr hazard.
The obtained data of field trials showed that imazamox and imazapyr residues were not detectable in sunflower seeds at the harvest time. The degree of the occupational risk of the possible impact of imazamox and imazapyr on workers’ body via inhalation route and through skin did not exceed the allowable level.
Conclusion. Imazamox and imazapyr containing formulations are III hazard class (moderately dangerous) pesticides. Use of imazamox and imazapyr containing herbicides for sunflower protection will not result in a consumer exposure exceeding the toxicological reference value and is harmless for workers when keeping to the required agricultural and hygienic standards and rules.
Key words: imazamox, imazapyr, assessment, sunflower, residues.
Herbicides based on imidazolinone derivatives are recommended for use on hybrid sunflower breeds resistant to imidazolines, in 2- to 8-true-leaf stage of the agricultural culture at the early stages of the development of mono- and dicotyledonous weeds.
According to the “Supplement to the List of Pesticides and Agrochemicals Permitted for Use in Ukraine” [1], 10 herbicides are used in agriculture for sunflowers, the active substances of which are imazamox in combination with imazapyr.
The chemical name, structural formulas and physical and chemical properties of imazamox and imazapyr are given in Tables 1 and 2.
Table 1
Chemical names and structural formulas for imazamox and imazapyr
Table 2
Physical and chemical properties of imazamox and imazapyr
The State Enterprise ‘Academician L. I. Medved Scientific Centre for Preventive Toxicology, Food and Chemical Safety of the Ministry of Health of Ukraine’ carried out studies on toxicological and hygienic evaluation of imazamox and imazapyr of various manufacturers, six herbicides based on these active substances, as well as on the substantiation of hygienic regulations for the use of products for sunflowers in agriculture.
Materials and methods of the study. Toxicological and hygienic evaluation of imazamox, imazapyr and herbicides on their basis was carried out according to the results of the studies of manufacturers, own studies and literature data [2-8] in accordance with the guidelines [9] and current hygienic classification in Ukraine [10]. The study of residues of imazamox and imazapyr in sunflower seeds, the justification of the maximum permissible levels (MPL) of these substances was carried out in accordance with [9] and the basic principles outlined in [11]. Selection and delivery of field tests for the study were carried out according to the unified rules [12].
The study of residual imazamox and imazapyr in sunflower seeds meets the requirements and guidelines [13, 14]. The limit of quantification (LOQ) of imazamox and imazapyr in sunflower seeds were determined by high-performance liquid chromatography (HPLC) — 0.5 mg/kg.
To predict the risk of the impact of imazamox and imazapyr on agricultural workers who work with them, the coefficients of selectivity (COS) were calculated, which are the ratio of the effective rate of expenditures and the values of median lethal doses and concentrations when applying the substance to the skin (COSs) and when inhaling (COSi).
Results were evaluated on the scale: COS <1 — very low selective action, COS from 1 to 99 — low selective action, COS≥100 — sufficient selective action [15].
The study and evaluation of the risk of products on the basis of imazamox in combination with imazapyr on the workers who use it, as well as potential impact on the population at the border of the sanitary protection zone during treatment and on agricultural workers after spraying were performed in accordance with [9] and recommendations [16]. Determination of the content of imazamox and imazapyr in the objects of the industrial and natural environment was carried out in accordance with the requirements of the guidelines [17-21].
Results and discussion. In accordance with the Hygienic classification according to the degree of danger (DSANPiN 8.8.1.002-98) [10], imazamox belongs to grade 4 of danger in terms of acute oral and dermal toxicity, to grade 3 in terms of inhalation toxicity, to grade 3 in terms of irritating effects on the skin, to grade 2 in terms of the mucous membranes of the eye, to grade 4 of danger in terms of allergenic action.
In subchronic experiments, NOAELs for rats are defined at 20,000 ppm (1,550 mg/kg for males and 1,772 mg/kg for females), NOAELs for dogs — 40,000 ppm (1,333 mg/kg for males and 1,403 mg/kg for females).
In chronic effect, NOAELs of imazamox for rats are 20,000 ppm (1 068 mg/kg for males and 1,284 mg/kg for females), NOAELs for mice — 7,000 ppm (1,053 mg/kg for males and 1,348 mg/kg for females), NOAELs for dogs —– 40,000 ppm (1,174 mg/kg for males and 1,156 mg/kg for females).
Long-term exposure of imazamox causes a general toxic effect.
Imazamox is rapidly absorbed and excreted from the body with urine and faeces without accumulation in animal tissues. It is excreted from the body unchanged and in the form of metabolites — 5-hydroxymethyl-nicotinic acid and 5-carboxy-nicotinic acid.
Imazamox does not possess mutagenic, carcinogenic and teratogenic activity.
NOAEL for pregnant rats — 500 mg/kg and foetuses — 1,000 mg/kg.
NOAEL for pregnant rabbits — 300 mg/kg and foetuses — 900 mg/kg.
Selective effects on the reproductive function were not observed. NOAEL according to the systemic toxicity — 20,000 ppm (1,639 mg/kg).
The approved allowable daily dose (ADD) for imazamox for humans is 3.0 mg/kg.
In accordance with the Hygienic classification according to the degree of danger (DSANPiN 8.8.1.002-98) [10], imazapyr belongs to grade 4 of danger in terms of acute oral and dermal toxicity, to grade 2 in terms of inhalation toxicity, to grade 3 in terms of irritating effects on the skin, to grade 2 in terms of the mucous membranes of the eye, to grade 4 of danger in terms of allergenic action.
In subchronic experiments, NOAEL for rats is 20,000 ppm (1,700 mg/kg).
In chronic exposure, NOAEL for rats is 503 mg/kg, for mice— 1б855 mg/kg, for dogs — 263 mg/kg.
Long-term exposure of imazapyr causes a general toxic effect. High doses may cause toxic effects on the nervous and cardiovascular system, thyroid gland.
Imazapyr is rapidly absorbed and excreted from the body with urine and faeces (87.2 % – 93.3 %), mostly unchanged, without accumulation in tissues and organs, may be excreted in milk. The main metabolites in urine and faeces are CL60,032 (carbamoyl-nicotinic acid) and CL252,974. Skin absorption of imazapyr is insignificant.
Imazapyr does not possess mutagenic and teratogenic activity. Carcinogenic activity in mice was not observed. In rats at high doses, an increase in the number of cases of astrocytoma was observed. Imazapyr belongs to class E in terms of carcinogenic activity according to US EPA.
NOAEL for pregnant rats — 300 mg/kg and foetuses — 1,000 mg/kg.
NOAEL for pregnant rabbits — 250 mg/kg and foetuses — 500 mg/kg.
NOAEL according to the systemic toxicity — 10,000 ppm (738 mg/kg).
The approved allowable daily dose (ADD) for imazapyr for humans is 1.0 mg/kg.
The half-life (T50) of imazamox in the soil under experimental conditions on soils in North Dakota and Indiana (USA) ranges from 12 to 113 days, in the field conditions — 30 days. According to other data T50 of imazamox in the soil in the field conditions is from 5 to 41 days. The main factors that determine the stability of imazamox in the soil are its physical and chemical properties, the content of organic matter in the soil, the mineralogical, mechanical and microbiological composition of soils, acidity and temperature.
Imazamox decomposes in the soil with the formation of two metabolites. The half-life of metabolites is less than 30 days.
According to the soil stability, imazamox can be referred to grade 2 of danger, and its metabolites belong to grade 3 of danger according to the Hygienic Classification of Pesticides (DSANPiN 8.8.1.002-98).
Imazamox refers to slowly biodegradable substances.
In vitro degradation of imazamox in the microecosystem ‘water/sediment’, depending on its nature, T50 of the active substance is 14–61 days in the surface water and T90 — from 103 to 203 days. T50 of imazamox for the system as a whole is 129–154 days and T90 — 428 513 days. Two main metabolites were found, mainly in the aqueous phase, the number of which was at 6 % and 10 % respectively, depending on the nature of the system.
Based on the results of water stability studies, imazamox can be referred to pesticides of grade 1 of danger according to DSANPiN 8.8.1.002-98.
Studies on the determination of residual quantities and metabolism of imazamox in agricultural crops (soybeans, peas, and sunflower) during treatment before and after sprouting showed that the substance was rapidly metabolised in plants and did not accumulate in soybeans, peas and seeds of the sunflower. In the crop of the studied crops, residual amounts of imazamox were less than 0.01 mg/kg (with the limit of quantification (LOQ) by HPLC — 0.01 mg/kg). Concentrations of residual amounts of imazamox and its metabolites in soy and sunflower oil were not observed.
According to Resolution of the Chief State Sanitary Doctor of Ukraine No. 7 of February 9, 2006, and No. 27 of December 18, 2013, hygienic standards for imazamox:
MPL, mg/kg: sunflower (seeds) — 1.0 (LOQ by HPLC — 0.5), sunflower (oil) — does not require.
SRLI (Safe Reference Levels of Impact) in the air of the working zone, mg/m3: 1.0 (LOQ by HPLC — 0.5).
SRLI in atmospheric air, mg/m3: 0.04 (LOQ by HPLC — 0.003).
MPC (Maximum Permissible Concentration) in water of reservoirs, mg/dm3: 0.06, general rules for hygiene (LOQ by HPLC — 0.003).
APC (approximate permissible concentration) in the soil, mg/kg: 0.4 (LOQ by HPLC — 0.0.1).
In the soil in laboratory studies (aerobic conditions), T50 of imazapyr is from 117 to 313 days. The main end product of imazapyr degradation is carbon monoxide.
In the field conditions, imazapyr decomposes faster under the action of heat and moisture due to physical and biological processes, which include photolysis and microbiological destruction. On average, T50 of imazapyr in the field conditions is 24 to 143 days.
Thus, imazapyr can be classified as a pesticide of grade 1 of danger based on its stability in the soil, according to DSANPiN 8.8.1.002-98.
Imazapyr is well bound to soil particles, which limits its mobility based on the soil profile.
The half-life of imazapyr in water is 7 days. The degradation is mainly due to photolysis. Imazapyr can be classified as a pesticide of grade 2 of danger based on its stability in water, according to DSANPiN 8.8.1.002-98.
Imazapyr does not accumulate in plants. After usage of imazapyr-containing herbicides, imazapyr was not detected by HPLC — 0.5 mg/kg on sunflower seeds and rape crops, in the seeds of these crops during the harvesting period.
According to DSANPiN 8.8.1.2.3.4-0002001 [22] and Resolution of the Chief State Sanitary Doctor of Ukraine No. 3 of March 17, 2005, No. 38 of December 6, 2006, No. 10 of April 17, 2013, No. 27 of December 18, 2013, the following hygiene norms have been established for imazapyr:
MPL, mg/kg: sunflower (seeds) — 1.0 (LOQ by HPLC — 0.5), sunflower (oil) — does not require.
SRLI (Safe Reference Levels of Impact) in the air of the working zone, mg/m3: 1.0, dangerous upon contact with skin (LOQ by GLC — 0.017).
SRLI in atmospheric air, mg/m3: 0.05 (LOQ by GLC — 0.02).
MPC (Maximum Permissible Concentration) in water of reservoirs, mg/dm3: 0.1, general rules for hygiene (LOQ by GLC — 0.05).
MPC in the soil, mg/kg: 0.03, water migration (LOQ by HPLC — 0.03).
In accordance with the Hygienic classification according to the degree of danger (DSANPiN 8.8.1.002-98), the studied herbicides based on imazamox and imazapyr belongs to grade 4 of danger in terms of acute oral toxicity, to grades 3–4 in terms of dermal toxicity, to grade 3 in terms of inhalation toxicity, to grade 4 in terms of irritating effects on the skin, to grade 3 in terms of the mucous membranes of the eye, to grade 4 of danger in terms of allergenic action. According to the Limiting Harmful Index, the studied preparations belong to grade 3 of danger.
Taking into account the parameters of the potential and real danger of herbicides containing imazamox and imazapyr as active substances, as well as the recommended scope of their use, in order to assess the safety of agricultural products, we have studied the content of residual amounts of imazamox and imazapyr in sunflower seeds.
Herbicides on sunflower crops were used with the rates of consumption of 39.6 g/ha for imazamox and 18 g/ha for imazapyr. Studies on the content of imazamox and imazapyr in sunflower seeds were conducted in two agroclimatic zones of Ukraine at various stages of the agricultural culture development, including the maturity stage as well. For each herbicide, two terms (periods) of sampling after treatment were foreseen. Along with this only samples of sunflower crops processed with the herbicide were selected from other experimental sites.
As a result of the conducted studies, it was established that in all periods after treatment no residual amounts of imazapyr and imazamox were detected in sunflower seeds at the level of detection limit by HPLC — 0.2 mg/kg.
It is recommended to use the previously established MPL values in sunflower seeds to control the use of products on the basis of the toxicological and hygienic assessment of the properties of herbicides and active substances, results of the studies on the content of imazapyr and imazamox in sunflower seeds, as well as guided by methodological approaches generally accepted in hygienic rating: imazamox — 1.0 mg/kg (LOQ by HPLC — 0.5 mg/kg) and imazapyr — 1.0 mg/kg (LOQ by HPLC — 0.5 mg/kg). Taking into account the results of the studies on the content of active substances in sunflower seeds, their low Kow values, early periods of herbicide usage (2–8 leaves phase), and long growing season of sunflowers, it is not appropriate to normalize the residual amounts of imazamox and imazapyr in sunflower oil.
It is recommended to control the content of herbicides in sunflower seeds based on imazamox and imazapyr. Given the technology of the use of the products and the results of the studies, it is not required to establish the waiting time for the sunflower harvesting.
The results of studies of hazardous effects of imidazolinone herbicides on the agricultural workers and population during and after their use (hose spraying, the rate of consumption of 1.2 l/ha, working fluid of 300 l/ha) indicate that no active substances were detected in the air of the breathing zone of the refueller and the tractor operator, in the air of the zone of aerosol wind drift, of the studied drugs, at a distance of 300 m from the boundary of the site during spraying and at the same place, 1 hour after spraying, in the air of the working area above the site in 1 hour and 3 days after spraying. Imazamox and imazapyr were not detected at the LOQ level in the soil of the zone of possible wind drift at a distance of 300 m from the boundary of the site 1 hour after spraying and in the soil of the treated area 3 days after spraying.
In accordance with МР 8.8.1.4-162-2009 [16] and the study results, possible exposure inhalation (Di) and dermal (Dd) doses (mg of the studied product/kg body weight), which influenced the refueller and the tractor operator during the working shifts (6 hours) were established; approximate permissible inhalation (PDi) and dermal (PDd) doses, mg of the studied product/kg body weight a day, for workers were justified, (imazamox: PDi = 0.15 and PDd= 20.0; imazapyr: PDi = 0.15 and PDd= 16.0.
The results of the comparison of possible exposure and approximate permissible doses indicate that the coefficients and indices of the risk of the complex and combined effects of imazamox and imazapyr on workers were significantly below the permissible level.
CONCLUSIONS
1. According to the Limiting Harmful Index, imazamox refers to pesticides of grade 3 of danger, imazapyr to pesticides of grade 2 of danger.
2. The studied herbicides containing imazamox in combination with imazapyr as active substances are pesticides of grade 3 of danger in terms of acute toxicity and are highly-persistent in the soil and water.
3. The maximum permissible levels (MPL) of the residual amounts of imazamox in sunflower seeds are 1.0 mg/kg (LOQ by HPLC — 0.5 mg/kg) and are not normalized in sunflower oil; of imazapyr in sunflower seeds — 1.0 mg/kg (LOQ by HPLC — 0.5 mg/kg) and are not normalized in sunflower oil.
It is not necessary to set the waiting time for the sunflower harvesting. It is recommended to reduce the multiplicity of sampling when investigating the content of residual quantities of imazamox and imazapyr in sunflower seeds to one (harvest of agricultural crops).
4. In compliance with the current rules of pesticide management, the levels of imazamox and imazapyr content in the production environment, as well as the level of their external inhalation and dermal exposure are to some extent safe for workers involved in the use of herbicides on their basis. Compliance with the sanitary protection zone with the use of hose sprayers guarantees the safety of the population and environmental objects during the period of use of these products. The production environment is safe for workers working on treated areas using mechanized means, 3 days after spraying.
5. When using herbicides based on imazamox in combination with imazapyr, it is recommended to control the contents of the products in industrial and environmental facilities, sunflower seeds for both active substances.
6. Usage of imidazolinone herbicides on sunflowers with compliance with hygienic regulations is not dangerous from the standpoint of the possibility of contamination of sunflower seeds by active substances.
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