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ASSESSMENT OF ECOTOXICOLOGICAL HAZARD AND RISK OF GROUNDWATER CONTAMINATION WITH DIFFERENT GROUPS OF PESTICIDES
Institute of Hygiene and ecology (HEI) of O. O. Bogomolets National medical university Hygiene and ecology department Peremogy av., 34, Kyiv, 03057, Ukraine
1нститут гтени та екологИ' Нацiонального медичного Утверситету iM. О. О. Богомольця
кафедра гтени та екологи
пр. Перемоги, 34, Kuïe, 03057, Укра'та
e-mail: elena-vavrinevich@ukr. net
Key words: pesticides, ecotoxicological risk, groundwater, herbicides, insecticides, fungicides
Ключовi слова: пестициди, екотоксикологiчний ризик, тдземт води. гербщиди, iнсектициди, фунгщиди
УДК 632.954:631.432:631.813
P. V. Stavnichenko, L.O. Novohatska, A.M. Antonenko, O.P. Vavrinevych
Abstract. Assessment of ecotoxicological hazard and risk of contamination of groundwater with different groups of pesticides. Stavnichenko P.V., Novohatska L.O., Antonenko A.M., Vavrinevych O.P. The aim of our work was to determine ecotoxicological risk of herbicides, insecticides, fungicides of different chemical classes with different mechanisms of action by the method of Melnikov MM. and leaching potential index by the method of Sergeev S. G. and co-workers. It was established that in soil and climatic conditions of Ukraine ecotoxicological hazard of studied herbicides by (1-6) orders of magnitude, fungicides - by (3-5) orders, insecticides - by (2-3) orders lower than DDT. The least ecotoxic are herbicides of the last generations, then fungicides and the most ecotoxic are insecticides and herbicides of the old first generations. It was proved the high danger of groundwater contamination with studied herbicides, insecticides and fungicides, except for mesotrione, the application of which has moderate danger in the soil and climatic conditions of Ukraine. It was shown that in soil and climatic conditions of Ukraine, ability of migration from the soil into groundwater of metribuzin, thiamethoxam, paclobutrazole is high, topramezone and mesotrione -moderate, for other substances - low; in terms of hygienic standards in the ground itallows to avoid them getting into the soil flow and minimize the danger of groundwater contamination to public health
Реферат. Оцшка екотоксиколопчноТ небезпечносп та ризику забруднення пщземних вод рiзними групами пестицидiв. Ставшченко П.В., Новохацька Л.О., Антоненко А.М., Вавршевич О.П. Метою роботи була оцтка eкoтoксикoлoгiчнoi небезпеч-Hocmi гербiцидiв, iнсектицидiв, фунгiцидiв pi-зних xiMi4Hux клаав з pi3HUM мехатзмом dii за методом Мельникова М.М. та тдексу вимивання в tpyrnnoei води за методом Сергеева С.Г. та спiвaвтoрiв. Встановлено, що в Трунтово-^матичних умовах Украти eкoтoксикoлoгiчний ризик до^джуваних гeрбiцидiв на (1-6) порядюв, фунгiцидiв - на (3-5) порядюв, iнсeктицидiв - на (2-3) порядюв нижче, тж ДДТ. Найменш екотоксичними е гербщиди oстaннix поколть, за ними йдуть фунгщиди, а найбшьш екотоксичн - тсектициди та гербщиди старих генерацт. Доведено високу небезпечтсть забруднення пiдзeмниx вод у Трунтово-^матичних умовах Украти до^джуваними гербщидами, тсектицидами та фунгщидами, за винятком мезотрюну, при застосувант якого юнуе середня небезпечтсть. Показано, що в Трунтово-^матичних умовах Украти здаттсть мiгрaцii з Трунту в тдземш води метрибузину, тiaмeтoксaму, паклобутразолу - висока, топрамезону та мезотрюну - середня, для решти речовин - низька, що за умови дотримання гiгiенiчнoгo нормативу в Трунтi дозволяе уникнути 1'х потрапляння в Трунтовий потж та мiнiмiзувaти небезпечтсть забруднення пiдзeмниx вод для здоров 'я населення.
Introduction. Population growth, industrial development and intensification of agriculture in Ukraine led to increased pollution of the environment with ecotoxicants. Many toxic substances entering the atmosphere, soil and water sources cause a negative impact on autochthonous flora of surface water and soil, plants, animals and human [17].
Among these ecotoxic substances pesticides occupy a special place. First of all, because they are designed to killing and limitation of living organisms - weeds, pathogens of plants, insects and rodents. However, pesticides are potentially harmful both for many species of flora and fauna and for humans.
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Therefore, assessment of environmental safety of pesticides and risk of their application is mandatory for their development and registration [10, 15].
Therefore, the aim of our study was to assess the ecotoxicological risk of herbicides, insecticides, fungicides of different chemical classes with different mechanisms of action.
MATERIALS AND METHODS
For the calculation of ecotoxicological risk, so-called ecotox, the method proposed by M.M. Melnikov was used for assessment of potential risk of fungicides, insecticides, herbicides application for ecosystems and biocenosis [11].
Mathematical modeling method that provides calculatied reproduction of process of pesticides destruction by actual data to predict their persistence was used for calculaion of half-life periods (DT50) of substances in the soil [13, 14].
For the prediction of groundwater pollution with studied pesticides, calculation of integrated vectors of hazard according to Sergeev S.G. et al. methodology was used [6]. The calculated indicator values expressed in points were used for calculation of integral vectors of groundwater contamination.
RESULTS AND DISCUSSION
As a result of field studies, we found that the concentration of the compounds in the soil and crops during the vegetation season was gradually decreasing and was not found at harvest. Based on the evidence on the dynamics of residual amounts of these substances in soil, the DT50 values were calculated. According to obtained data and to "Hygienic classification of pesticides and agroche-micals" State Standards 8.8.1.002-98 [16] herbicides isoxaflutole and mesotrione pertain to hazard class 4 (unstable); fungicides topramezone, fluxapyroxad, cyflufenamid, famoxadone, oxathiapiprolin and herbicide metribuzin - to class 3 (moderately stable); herbicide flufenacet and insecticides thiametho-xam, imidacloprid - to class 2 (stable) Other studied compounds - class 1 (stable).
We have calculated the ecotox values of studied substances in the agro-climatic conditions of Ukraine (table. 1). Their values range between 1,20x10"6 and 2,75 x10-1 for herbicides; between 1,18* 10-5 and 2,40* 10-3 for fungicides and between 2,79*10-3 and 1,26*10-2 for insecticides. Thus, ecotoxicological hazard of studied herbicides by (1 -6) orders of magnitude, fungicides - by (3-5) orders, insecticides -by (2-3) orders lower than DDT.
It can also be concluded that the least ecotoxic are herbicides of the last generations, then - fungicides, and the most ecotoxic are insecticides and herbicides of the old first generations (table 1).
Evaluation of hazard to the environment of test substances except for ecotoxicological hazard prediction, involves determining the potential risk of groundwater contamination in rural areas, which are widely used as a source of decentralized drinking water supply.
The integrated vectors were calculated for the prediction of groundwater pollution with test groups of pesticides. Initial data and results of GUS and Z biol.ef. calculations are shown in table 2.
The values of the indicators were expressed in points, and then integral vectors of hazard of groundwater contamination were calculated and evaluated according to a scale provided in [6]. The results are shown in table 3.
The data in table 3 indicate a high danger of groundwater contamination in the soil and climatic conditions of Ukraine with studied herbicides, insecticides and fungicides. except for mesotrione, the application of which is of danger for secondary contamination of groundwater. There is a moderate hazard of groundwater contamination with me-sotrione, which is an exception among all studied pesticides.
The high danger of groundwater contamination with topramezone, isoxaflutole, famoxadone is determined mainly by their toxicity and cumulati-veness in warm-blooded animals. Fluxapyroxad, oxathiapiprolin, imidacloprid, flufenacet, diquat have high hydrolytic stability, cyflufenamide, difenoconazole - have both characteristics.
At the same time, all of these substances, except for metribuzin, thiamethoxam, paclobutrazole, have average or low ability to migrate from the soil into groundwater. In terms of observance of hygienic standards in the soil, this allows to avoid them from getting into the soil flow.
In soil and climatic conditions of Ukraine according to GUS indeces hazard of the test substances migration from the soil into groundwater is: for metribuzin, thiamethoxam, paclobutrazole -high, topramezone and mesotrione - moderate, for the rest of substances - low. The above mentioned suggests necessity of considering migration process of metribuzin, thiamethoxam, paclobutrazole in the "soil-groundwater" system in justifying their hygiene standards in soil using calculation method.
Tab le 1
Comparative assessment of ecotoxicological hazard of different groups, classes and generations of pesticides
Mode of action class Chemical class Substance Ecotox Reference
Herbicides
Photosynthesis inhibitors triazines simazine atrazine propazine 7,45x10-2 3,09x10-2 1,17x10-2 [12]
benzothiadiazinone bentazone 1,02x10-2
triazinones metribuzin 3,00x10-3 AR2
ALS1 inhibitors imidazolinones imazethapyr imazapyr imazamox 2,07x10-4 3,00x10-5 1,60x10-5 [5]
sulfonylureas prosulfuron foramsulfuron tritosulfuron tribenuron-methyl 3,04x10-5 1,90x10-5 1,60x10-5 3,76x10-6 [7]
triasulfuron 1,24x10-6 [1]
iodosulfuron 1,20x10-6
-methyl-sodium
Inhibition of cell division oxyacetamide flufenacet 3,89x10-2 [2]
PS-I-electron diversion bipyridylium diquat 2,75x10-1
Inhibition of pigment synthesis benzoylpyrazoles triketone topramezone mesotrione 8,25x10-5 3,90x10-5
oxazole isoxaflutole 2,48x10-5
Insecticides
Nicotinic acetylcholine neonicotinoid thiamethoxam 1,20x10-6 AR
receptor agonists imidacloprid 1,20x10-6
Fungicides
SDHI3 inhibitors pyrazole -4- carboxamides fluxapyroxad 1,39x10-4 AR
amide cyflufenamide 4,18x10-5
pyridine carboxamides boscalid 2,7x10-4 [3]
Inhibitors of complex III oximino-cytochrome bc1 (ubiquinol acetates oxidase) at Qo site kresoxim-methyl trifloxystrobin 1,60x10-4 1,20x10-4 0,6±0,1x10-4 [9] [3]
methoxy-carbamates pyraclostrobin 0,7±0,2x10-4
methoxy-acrylates azoxystrobin 1,7x10-4
oxazolidine- famoxadone 2,2x10-3 AR
diones
Inhibitors C14-demethylase triazoles tebuconazole 2,4±1,2x10-4 [3]
in sterol biosynthesis penconazole difenoconazole paclobutrazole 2,2±1,0x10-4 7,0±1,8x10-4 1,9x10-3 2,4x10-3 AR
Oxidation enzymes dithiocarbamates metiram 9,5x10-4 [4]
inhibitors mancozeb 7,00x10-4 [4]
Osmotic signal transductor cyanopyrrole fludioxonil 2,0x10-4 [3]
- piperidinyl thiazole isoxazoline oxathiapiprolin 2,2x10-4 AR
Notes: 1. ALS - acetolactate synthetase; 2. AR - author's research; 3. SDHI - succinate dehydrogenase inhibitor.
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Ta b le 2
Migration, stability and toxicity parameters of studied pesticides
Substance DT501 in soil, day Koc2, ml/g [8] GUS3 DT50 1 in water, day [8] LD504, mg/kg [8] Limch5 [8] Z biol.ef.6
Herbicides
Metribuzin 22,8 37.92 3.2 34 322 1,3 247,7
Flufenacet 38,8 401 2.1 stable 598 1,14 524,6
Diquat 98,1 2185000 -4.2 stable 214 0,5 428,0
Topramezone 15,7 93 2,40 30 2000 0,4 5000,0
Isoxaflutole 7,9 112 1,80 11 5000 2,0 2500,0
Mesotrione 8,8 80 1,97 >30 5000 154,0 32,5
Insecticides
Thiamethoxam 48,6 56.2 3.78 11,5 >1563 2,6 601,2
Imidacloprid 47,1 225 2.6 1 pi к 131 6,0 21,8
Fungicides
Fluxapyroxad 30,8 728 1,70 >100 2000 2,1 952,4
Cyflufenamide 19,6 1595 1,04 642 5000 1,04 4807,5
Famoxadone 16,9 3847 0.48 2 >5000 1,2 4166,7
Difenoconazole 70,9 400-7730 1.96 стаб. 1453 1,0 1453
Paclobutrazole 155,9 400 3.49 30 1336 2,2 607,3
Oxathiapiprolin 18,7 9673.8 0.01 стаб. >5000 104 48,1
Notas : 1. DT50 - half-life period; 2. Koc - organic carbon sorption constant; 3. GUS - groundwater ubiquity score; 4. LD50 - per oral half lethal concentration; 5. Limch - limit of chronic effect; 6. Z biol.ef. - zone of biological effect.
Ta b le 3
Integral assessment of groundwater contamination hazard with studied pesticides
Indices values, score
Substance GUS Water hydrolysis Z biol.ef. Integral hazard vector (R) Level of hazard
Herbicides
Metribuzin 80 50 50 106,8 high
Flufenacet 50 100 50 122,5 high
Diquat 30 100 50 115,8 high
Topramezone 50 50 80 106,8 high
Isoxaflutole 50 30 80 98,9 high
Mesotrione 50 50 30 76,8 moderate
Insecticides
Thiamethoxam 80 30 50 98,9 high
Imidacloprid 50 100 30 115,8 high
Fungicides
Fluxapyroxad 30 80 50 99,0 high
Cyflufenamide 30 80 80 117,0 high
Famoxadone 30 30 80 90,6 high
Difenoconazole 50 100 80 137,5 high
Paclobutrazole 80 30 50 98,9 high
Oxathiapiprolin 30 100 30 108,6 high
CONCLUSIONS
1. It was established that in soil and climatic tude lower than DDT. The least ecotoxic are
conditions of Ukraine ecotoxicological hazard of herbicides of the last generations, then - fungicides,
studied herbicides by (1-6) orders, fungicides - by and the most ecotoxic are insecticides and herbicides
(3-5) orders, insecticides - by (2-3) orders of magni- of old first generations.
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2. It was proved a high danger of groundwater contamination with studied herbicides, insecticides and fungicides, except for mesotrione, the application of which has moderate danger in the soil and climatic conditions of Ukraine.
3. It was shown that in soil and climatic conditions of Ukraine ability of migration of metribuzin,
thiamethoxam, paclobutrazole from the soil into groundwater is high, topramezone and mesotrione -moderate, of other substances - low, in terms of following of hygienic standards in the ground this allows to avoid them from getting into the soil and to minimize the danger to public health of ground-water contamination.
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