Dynamics of residual concentrations of organochlorine pesticides in

– Питання біоіндикації та екології. – 2014. – Вип. 19, № 1. – 156
УДК: 631.4:632.95.028
DYNAMICS OF RESIDUAL CONCENTRATIONS OF
ORGANOCHLORINE PESTICIDES IN THE SOILS OF
ZAPORIZHZHYA REGION
*Dudareva G.F., Cezonenko O.O., Mozolyuk I.I., Karabut L.P.,
Kuritsyna L.O.
*Zaporizhzhya National University
Zaporizhya branch SI " Derzhhruntohorona "
[email protected]
Лабораторными
исследованиями,
проведенными
лабораторией
экологической
безопасности
земель,
окружающей среды и качества сельскохозяйственной
продукции
Запорожского
филиала
Государственного
учреждения «Держгрунтохорона» определено, что площади
загрязнения стойкими хлорсодержащими пестицидами ДДТ и
альфа- и гамма-изомерами ГХЦГ, длительно сохраняются и
трансформируются в почве уменьшаются вследствие их
миграции в более глубокие слои почвы и распада препарата
под воздействием природных факторов. Остатки стойких
хлорорганических соединений в 2006-2010 гг было
обнаружено в 1,07 % проб почв, в т.ч. 0,33 % с превышением
ПДК, что наблюдается преимущественно на земельных
участках , которые прилегают к бывшим складам пестицидов,
растворных узлов и реже на полях, которые были под
старыми виноградниками, садами. Сейчас остатки стойких
хлорорганических соединений встречаются в 0,42 %
почвенных проб в.т. числе с содержанием выше ПДК 0,23 %.
Выявлено что содержание ДДТ в высоко загрязненных
почвах достигает 12,3 %, что свидетельствует о замедленном
ходе деградации пестицида. Остатков 2,4 ам. соли,
фосфорорганических и симтриазиновых препаратов в
отобранных образцах почвы на уровне чувствительности
метода не обнаружено.
Мониторинг почв, почвенных образцов, MPC (Extreme
допустимая концентрация), CLP (остаточное количество
пестицидов), хлорорганических пестицидов.
INTRODUCTION
It is known that the stability of agriculture and the level of
productivity is largely dependent on the phytosanitary status of
crops. Thus, according to the FAO, the global agriculture loses at
157– Питання біоіндикації та екології. – 2014. – Вип. 19, № 1. –
least a third of the crop because of pests, and during their mass
breeding crop dies almost completely.
Given this importance of increasing the quantity and
improving the quality of products, the introduction of effective
methods and means of protection of plants from pests, diseases and
weeds, including the chemical method, is highly valuable. Therefore,
the use of pesticides (HZZR) in agricultural production is given a
high degree of importance.
In addition to direct purpose, pesticides exert multilateral
indirect impact on the biosphere, the scale of which is compared with
the global environmental factors [4–8].
The main polluters were mostly organochlorine pesticides –
hexachlorocyclohexane (HCH), dychlordyfeniltrychloretan (DDT),
which were widely used in the 40-50s of the twentieth century. DDT
has a wide spectrum of activity and great resistance to decomposition
and can pile up in different links of the food chain in large quantities,
leading to quite well-known negative effects. In 2001, 129 countries,
including Ukraine, in reference to the provisions of international
environmental conventions, especially the Rotterdam and Basel and
the relevant provisions of the Declaration on Environment and
Development, have signed the Stockholm Convention on Persistent
Organic Pollutants (POPs). Convention has banned production and
use of pesticides that have the above characteristics. High resistance
of organochlorine and triazine pesticides to decomposition is an
important prerequisite for their migration profile of the soil and in
the adjacent medium, which poses a risk to natural ecosystems and,
consequently, of human existence. Despite the fact that the HOP are
prohibited for use in Ukraine, they still migrate into environmental
objects and enter the food chain. Therefore, it is important to
environmentally assess the present soil contamination by pesticide
residues.
Long-term and large-scale use of HOP resulted in the
contamination of ecosystems in locations of disposition of pesticides
by high concentrations of these compounds. The main reason for the
accumulation of obsolete and banned pesticides (WIP) was the
– Питання біоіндикації та екології. – 2014. – Вип. 19, № 1. – 158
prohibition of their use as plant protectors due to their high toxicity
and the possibility to accumulate in the environment. At the present
time, in most cases, waste is stored in buildings that are being
destroyed, and in some cases – in the open, in bags, containers or
simply in mounds. Most of the warehouses that store pesticides are in
poor condition and are used for other purposes. Systematic
monitoring of soil fertility in agricultural lands requires
comprehensive information about their agrochemical status and level
of pesticide contamination. Such work is being done in Zaporizhzhya
Branch Public Institution “Derzhhruntohorona” in compliance with
regulations, including the "Methodology of agrochemical
certification of the agricultural lands" [1].
The aim of the research is the continuous monitoring of the
accumulation of pesticide residues in soils of Zaporizhzhya region
and suitability for growing agricultural products for food that’s
aimed at infants and people in need of dietary products on the basis
of chemical analysis.
MATERIALS AND METHODS RESEARCH
Research was conducted in soil samples from 19 districts and
performed in accordance with existing regulations and guidelines [1–
3]. Determination of CLP has been prepared by thin-layer and gasliquid chromatography. Soil samples were taken in areas of rural
areas in the arable soil layer (0,25 cm) in August-September, after
the last pesticide application period for the determination of pesticide
residues.
Identified content of residual amounts in soil samples in the
laboratory of ecological safety of land, environment and quality of
agricultural products of Zaporizhzhya branch of the State Institution
"Derzhhruntohorona."
RESULTS AND DISCUSSION
The program of agrochemical certification of agricultural
lands in the last round of overall agrochemical examination of
agricultural land – for the period 2006–2010, we studied the
159– Питання біоіндикації та екології. – 2014. – Вип. 19, № 1. –
dynamics of accumulation of pesticide residues in 70–80 years of
production. These are global pollutants of HOP – organochlorine
compounds (DDT and its metabolites, HCH and its isomers and
metabolites PHP). Despite the fact that since 1970, DDT was
removed from the list approved for use in agriculture, it continued to
show up till this day.
Nonperforming warehouses and surroundings are major
sources of pollution of the environment by toxicants, including
organochlorine pesticides, trace amounts of which remain in the soil
for decades; their physical, chemical and biological properties
change.
On the content of pesticide residues 13698 soil samples out of
1649,7 hectares have been analyzed. Thus, residues of persistent
organochlorine compounds were detected in 1,07 % of soil samples
including 0,33 % in excess of the MCL, which occurs mainly on land
that lied near former storehouses, soluble nodes and less on the fields
that were under the old vineyards, orchards. Residues of 2,4 am. salt,
phosphorus and simtriazine drugs in selected soil samples at the level
of sensitivity of the method were not found.
The most heavily contaminated are the agricultural areas in
Belozersky District. 23,5 hectares of farmland have been examined.
Determination of pesticide residues (CLP) was conducted out of 318
soil samples. Residues of DDT are found in 39 samples, thus
representing 12,3 %. HSC in quantities exceeding the MCL for DDT
are found in only 4 of total amount of soil samples – 1,3% out of all
that has been analyzed. The maximum content of DDT was 0,23
mg/kg of soil (with MAC 0,1 mg / kg) in the Red Village Council.
Pollution is present in agricultural lands of Berdyansk district.
Determination of pesticide residues (CLP) conducted out of 807 soil
samples. Residues of DDT were detected in 46 samples, representing
5,7 %, of which 6 samples contained higher MPC – 0,7 % of the
analyzed. Excess found on the territory of such farms as: AC № 52
LLC CMI. Lenin; PSP "Horizon (Obriy)", Mykolayivs’ka &
Dmitrivs’ka village councils. The maximum content of DDT was
0,64 mg per kg soil at MCL of 0,1 mg per kg.
– Питання біоіндикації та екології. – 2014. – Вип. 19, № 1. – 160
On the territory of Orikhiv area, 124 thousand hectares were
selected and 885 soil samples were analyzed. Residues of DDT were
found in 13 samples of soil. HSC in quantities exceeding the MCL
for DDT were found in 8 samples analyzed by 1 %. The maximum
content of DDT was 0,24 mg/kg soil on the territory of
Omelyanivs’ka village council.
On the territory of Polohy area 959 soil samples were analyzed
HSC in quantities that were exceeding the MCL, out of which 7
samples of soil (0,7 % of the analyzed) were found for DDT. DDT in
the maximum amount of 0,2 mg / kg of soil was found in the fields
Semenivs’ka, Kins’ko-Rozdorivs’ka, Chapayev’ska village councils
of Polohy area.
On farmland of Melitopol district 180 soil samples were
selected and analyzed. Residues of DDT are found in 4 samples,
which is 2,2 %. HSC in quantities in excess of the MCL over DDT
are detected in 3 samples of soil — 1,6 % out of total amount. The
maximum content of DDT was 0,73 mg / kg soil (with MAC 0,1 mg
/ kg) in the fields Novobohdanivs’ka village council.
In Gulyaipils’ka area 96,4 hectares of farmland were
examined. Determination of pesticide residues (CLP) was conducted
out of 976 soil samples. Residues of DDT were detected in 4 samples
out of about 0,4 %, of which 3 samples contained even higher MPC
— 0,3 % out of the total amount. Excess found on farmlands "Agro
Continent № 2", JSC "Agrarian House". The maximum content of
DDT was 0,55 mg/kg soil at the level of MCL of 0,1 mg/kg.
In the Priazovs’ka area 138,6 thousand hectares of
agricultural areas were examined. Determination of pesticide
residues (CLP) was conducted in 523 soil samples. Residues of DDT
were detected in 3 samples that contained higher MPC, which was
0,6 %. Excess was found in fields of Stepanivka village, LLC
"Tabula", Georgiyivs’ka Village Council. The maximum content of
DDT was 0,44 mg/kg of soil while the level of MCL was 0,1 mg/kg.
The remaining amount of HCH and its isomers in quantities
exceeding the MCL is found only in isolated samples of soil and
161– Питання біоіндикації та екології. – 2014. – Вип. 19, № 1. –
contains higher MAC only in 1 sample in Yakymivsky area in an
amount of 0,22 mg/kg soil (with MPC — 0,1 mg/kg ).
During 2012, the number of analyzed samples (2144 samples)
of residual pesticide (CLP) was observed and 9 samples were taken,
5 of which contained higher MPC. The total area of contamination is
450 hectares (тable 1).
Table 1 – Pesticide residues in soils of agricultural lands of
Zaporizhzhya region in 2012
Quantity of the contaminated samples, %
Pesticide
s
HOP
(Total
amount
of DDT
and
metabol
ytes)
HOP
(Total
amount
of HCH
and
isomers)
Total
amount,
N=2144
Priazovsky,
Prymorsky,
Veselivsky,
N=200
N=1480
N=300
Conta- Exceed Conta- Exceed Conta- Exceeds
mis
the mis
the mithe
nated
MPC
nated
MPC
nated
MPC
level
level
level
2,5
1,5
0,14
Unk0,33
0,33
nown
Unknown
Unknown
0,07
0,07
Unknown
Unknown
Yakymivsky,
N=164
ContaEsceeds
mi-nated the MPC
level
Unknown
Unknown
Unknown
Unknown
Contaminated — 0,42%; including 0.23% in excess of the MCL
Ecotoxicological soil examination showed the presence of
persistent organic pollutants (POPs), organochlorine compounds
(HOP) in the Azov farms, coastal and Vesyolovskoye areas. Small
local area, which are contaminated with pesticides and exceed doses
of DDT that have been observed in fields, which are intensively
processed with chlorine-organic drugs (vineyards, berries, orchards).
These are farmsteads — Priazovsky region: Voskresens’ka Village
Council (1 sample with the highest content of DDT and its
metabolites - 0,112 mg / kg, the area of contamination is 10,3 ha);
– Питання біоіндикації та екології. – 2014. – Вип. 19, № 1. – 162
Dmytrivs’ka Village Council (1 sample with the highest content of
DDT – 0,11 mg / kg, the area of contamination is 129,4 ha); FG
"Time" (1 sample with the highest content of DDT – 0,216 mg / kg,
the area of contamination is 7 hectares); Primorsky region:
Yuryivs’ka village council (containing HCH isomers and 0,156
mg/kg, contaminated area — 58,4 ha). Vesyolovskoye area –
Tavriys’ka Village Council (1 sample with the highest content of
DDT – 0,51 mg / kg, the contaminated area is 201 hectares).
DDT and especially its metabolic products are the most stable
in biological systems. It will be manifested in our soils and
constantly serve as a potential source of pollution of agricultural
products and environment, meaning it remains a powerful
environmental factor for more than a year.
Content of HCH isomers and their frequency of detection in
soil is significantly lower than that of DDT.
Over time, the content of pesticide residues and metabolites
gradually decreases due to their migration to deeper soil layers and
the dissolution of the drug by natural factors.
Gradual transition to the use of safe agricultural producers of
pesticides significantly reduced the risk of pollution of the soil and
crop production. Today, remnants of persistent organochlorine
compounds are found only in 0,42% of soil samples including those
containing 0,23% above the MCL that are selected in areas near
chemical composition, sites of ancient vineyards, orchards. Small
local areas, which are contaminated with pesticides must be
registered to create an appropriate information base and the
introduction of measures to restore them.
In recent years, chemical methods have seen significant
changes. The range of pesticides that were used until 1990 was
almost completely changed. Modern drugs are less persistent and
toxic to humans and warm-blooded animals. Their consumption
standards reduced almost in half. Modern technologies of agriculture
involve the use of pesticides based on economic threshold of
harmfulness (EPSH), which significantly reduces the pesticide load
on the environment.
163– Питання біоіндикації та екології. – 2014. – Вип. 19, № 1. –
Amount of application of pesticides in farms rises each year.
According to the Head of Agricultural Development of Zaporizhzhya
Regional State Administration in 2012 in the field of agricultural
enterprises of different forms of management and ownership has
used 1,328 tons of various plant protection products in order to
perform chemical cultivation of crops. The area that was treated with
pesticides constituted 1758,7 thousand hectares, which implied that
load per hectare of arable land for agricultural purposes was 0,75 kg
of pesticides, which was 0,7-0,11 kg more than in 2007. Dynamics of
application of plant protection in the region over the years is shown
in тable 2.
Given the significant cost of pesticides, there was no recorded
evidence of excess dosage of these agrochemicals or their
uncontrolled and excessive application in that region. According to
results of research we can assume, that in general ecotoxicological
situation, that’s caused by the use of pesticides in the Zaporizhzhya
region from 2007 to 2012, is barely dangerous. To avoid the adverse
effects of pesticides in private households, it is reasonable
improvement range for the inclusion of current medications 4-7
degree of danger by a 7-point scale integrated classification.
Table 2 – The use of plant protection products in the
Zaporizhzhya region
Costs of plant
protection
products,
in
thousands
of
tonns
The area where
pesticides were
applied,
in
thousands
of
hectares
Quantity
of
pesticides applied
per 1 hectare, in
kilograms
2007
0,860
2008
1,224
2009
0,9785
2010
1,225
2011
1,328
2012
-
1307,3
1594,7
1633,1
1695,8
1758,7
778,2
0,65
0,76
0,6
0,72
0,75
-
– Питання біоіндикації та екології. – 2014. – Вип. 19, № 1. – 164
CONCLUSIONS
1. According to the examination of 2006-2010 research,
residues of persistent organochlorine compounds have been detected
in 1,07 % of soil samples, including less than 0,33 % in excess of the
MCL, which occurs mainly on lands, which are adjacent to former
storehouses of pesticides, soluble nodes, and less often on the fields
that are under the old vineyards, orchards.
2. Contents of DDT in highly contaminated soils reaches
12,3 %, which indicates a slow progress of the degradation of the
pesticide. Residues of 2,4 am. salt, organophosphorus and
simtriazine drugs in taken soil samples at the level of sensitivity of
the method were not found.
3. It has been found that the area of persistent chlorinated
pesticides DDT and alpha- and gamma-HCH isomers, that are long
preserved and transformed in the soil, are reduced as a result of their
migration to deeper soil layers and the dissolution of the drug by
natural factors. Today, remnants of persistent organochlorine
compounds are found only in 0,42 % of soil samples including those
containing 0,23 % above the MCL.
4. In general, ecotoxicological situation that is caused by the
use of pesticides in the Zaporizhzhya region from 2007 to 2012, is
barely dangerous: 1 ha of land includes 0,75 kg of pesticides. To
avoid the adverse effects of pesticides in private households, it is
advisable to improve the range of the inclusion of current fertilizers
of 4–7 th degree of danger on a 7 point scale of integral
classification.
REFERENCES:
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lands / S.M. Ryzhuk, NV Forest, D.M Bentsarovsky. – K., 2003. –
64 p.
2. Sozinov A.A. Methodology of continuous agrochemical monitoring
of soil and agricultural lands of Ukraine / Sozinov A.A., Priester B.S.
– K.: 1994. – 162 p.
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3. Methodological designations for the determination of
microquantities of pesticides in food, fodder and the environment. –
M., S. 1–31, K., № 26. – S. 51–332, № 29. – S. 6–32; № 32. – S. 19–
24; № 47. – S. 135–151.
4. Sekun M.P., Guide to Pesticides / Sekun M.P., Zherebko V.M.,
Lana A.О. / Ed. Professor M. Sekun. – K.: Kolobig, 2007. – 360 p.
5. Fedorenko V. Integrated protection of agriculture in Ukraine /
Fedorenko V. // International scientific and practical conference. K.,
2004. – 328 p.
6. Yeremenko M.V. The list of pesticides and agrochemicals
permitted for use in Ukraine: Product / M.V. Yeremenko,
M.I. Tkachuk, N.V. Lyubach. – Dnepropetrovsk: ART Press, 2006. –
312 р.
7. Permissible doses, concentration, quantity and levels of pesticides
in agricultural raw materials, food, air in working area, atmospheric
air, water reservoirs, soil: DSanPiN 8.8.1.2.3.4-000-2001 approved.
Ministry of Health of Ukraine 20.09.2001, № 137. – K., 2001. –
244 р.
8. Hygienic classification of pesticides according to the degree of
danger: DSanPiN 8.8.1.002.-98 approved. MOH divide in Ukraine
09.28.98, № 2. – K., 1998. – 20 р.
УДК: 631.4:632.95.028
Дударєва Г.Ф. Динамика залишкових концентрацій хлорорганічних
пестицдів в грунтах Запорізької
області / Дударєва Г.Ф.,
Cезоненко О.О., Мозолюк І.І., Карабута Л.П., Куріцина Л.О. // Питання
біоіндикації та екології . – Запоріжжя: ЗНУ, 2014. – Вип. 19, № 1. –
С. 156–166.
Лабораторними
дослідженнями,
проведеними
лабораторією
екологічної безпеки земель, довкілля та якості сільськогосподарської
продукції Запорізької філії Державної установи «Держгрунтохорона»
визначено, що площі забруднення стійкими хлорвмісними
пестицидами ДДТ та альфа - і гамма-ізомерами ГХЦГ, які тривалий
час зберігаються і трансформуються в ґрунті зменшуються внаслідок
їх міграції в більш глибокі шари ґрунту та розпаду препарату під
впливом природних чинників. Залишки стійких хлорорганічних сполук
в 2006–2010 рр. було виявлено у 1,07 % проб ґрунтів, у т.ч. 0,33 % з
перевищенням ГДК, що спостерігається переважно на земельних
– Питання біоіндикації та екології. – 2014. – Вип. 19, № 1. – 166
ділянках, які прилигають до колишніх складів пестицидів, розчинних
вузлів, та рідше на полях, що були під давніми виноградниками,
садами. Нині залишки стійких хлорорганічних сполук зустрічаються
лише у 0,42 % ґрунтових проб в. т. числі із вмістом вище ГДК 0,23 %.
Виявлено, що вміст ДДТ у високо забруднених ґрунтах сягає 12,3 %,
що свідчить про уповільнений перебіг деградації пестициду. Залишків
2,4 ам. солі, фосфорорганічних та симтриазинових препаратів у
відібраних зразках ґрунту на рівні чутливості методу не виявлено.
Бібл. 10. Табл. 2.

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