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The legacy of persistent organic pollutants in Azerbaijan: An assessment of past use and current contamination
Abstract
Azerbaijan has a history of production and heavy use of organochlorine pesticides (OCPs) with use focused in the main agricultural lowland region centred on the Kur River. Using a number of data sources, including archived reports from several government ministries, we attempt to construct production and use inventories for dichlorodiphenyltrichloroethane (DDT) and HCHs and compare these to scientific estimates of production and use of these chemicals in the 1960s to the 1980s. Notable discrepancies are evident particularly for DDT, with Azeri government records indicating much higher use (147-fold) than that estimated by the international scientific community. Soil and river sediment data from the 1980s and 2000s are also presented. While it is recognised that analytical uncertainties remain high for these older data (generated by GC-ECD), there is some evidence to show a decline in concentrations for some OCPs over this period. Extremely high concentrations of OCPs are evident for soils sampled in the vicinity of obsolete pesticide storage sites (found in numerous locations around the agricultural lowlands) and these levels may pose a health risk to wildlife and humans. River sediment data indicate high levels of both OCPs and polychlorinated biphenyls (PCBs), particularly downstream of the confluence of the two main rivers, the Kur and Araz. Particle-bound annual fluxes from the Kur River into the Caspian Sea are estimated for PCBs and OCPs and these are likely to influence levels observed in local coastal sediments, with agreement between river sediment data generated in the early 2000s and coastal marine sediment data generated from separate studies. We recommend that monitoring efforts should focus on soils in agricultural areas and around pesticide storage and production facilities as these soils will continue to provide a source of POPs to the regional environment.
... Those values were considerably higher compared to similar reports published by other investigators, related to various European countries [4,6,7,19,[25][26][27]. As mentioned before, the data reported by Aliyeva [28] from Azerbaijan were much lower than our results, but these studies were carried out in other area of Azerbaijan. According to Li et al. [29], the total amount of DDTs used in the Azerbaijan in the years 1946-1990 was assessed as 250,000-520,000 tones. ...
... The isomeric composition of DDT can be influenced substantially by different environmental processes. The abundance of 2,4'-DDE and 4,4'-DDE in samples indicates their environmental degradation in the processes of weathering and aging [28,30], which may be related to microbial activity, sorption by organic matter or the influence of other environmental factors. The abundance of 2,4′-DDE and 4,4'-DDE metabolites in soils were overall responsible for 10% of the total ∑6DDTs content. ...
... The concentrations of Σ3HCHs were much lower than those observed for DDTs and ranged from 0.1 × 10 −4 μg kg −1 to 166.7 μg kg −1 . Alyieva et al. [28] reported lower concentrations of HCH in soils in Azerbaijan, varying in the range 0.9 × 24.5 μg kg −1 . The dominant compound was α-HCH, which contributed about 73 % of the Σ3HCHs, followed by β-HCH and γ-HCH (Table 1). ...
The aim of this study was to identify and examine the levels of organochlorine pesticides (OCPs), polycyclic aromatic hydrocarbons (PAHs), and polychlorinated biphenyls (PCBs) in soil collected from the surroundings of historical pesticide storage facilities on former agricultural aerodromes, warehouses, and pesticide distribution sites located in the most important agricultural regions in Azerbaijan. The conducted research included determination of three groups of POPs (occurring together), in the natural soil environment influenced for many years by abiotic and biotic factors that could have caused their transformations or decomposition. In this study, soil samples were collected in 21 georeferenced points located in the administrative area of Bilasuvar, Saatly, Sabirabad, Salyan and Jalilabad districts of Azerbaijan. Soil chemical analysis involved determination of organochlorine compounds (OCP): hexachlorocyclohexanes (HCHs) (three isomers α-HCH, β-HCH and γ-HCH) and dichlorodiphenyltrichloroethanes (DDTs) (six congeners 2,4′DDT; 4,4′DDT; 2,4′DDE; 4,4′DDE; 2,4′DDE; and 4,4′DDE); polycyclic aromatic hydrocarbons (PAHs): 16 compounds from the United States Environmental Protection Agency US EPA list and, PCBs (seven congeners identified with the following IUPAC numbers: 28, 52, 101, 118, 138, 153, and 180). Our research showed that OCPs reached the highest concentration in the studied areas. The total concentrations of OCPs ranged from 0.01 to 21,888 mg•kg −1 with significantly higher concentrations of Σ6DDTs (0.01 μg kg −1 to 21880 mg kg −1) compared to ΣHCH (0.14 ng kg −1 to 166.72 μg kg −1). The total concentrations of PCBs in the studied soils was varied from 0.02 to 147.30 μg·kg −1 but only PCB138 and PCB180 were detected in all analyzed samples. The concentrations of Σ16 PAHs were also strongly diversified throughout the sampling areas and ranged from 0.15 to 16,026 mg kg −1. The obtained results confirmed that the agricultural soils of Azerbaijan contained much lower (up to by three orders of magnitude) concentrations of PCBs and PAHs than DDT. It is supported by the fact that PCBs and PAHs were not directly used by agriculture sector and their content results from secondary sources, such as combustion and various industrial processes. Moreover, the high concentrations of PAHs in studied soils were associated with their location in direct neighborhood of the airport, as well as with accumulation of contaminants from dispersed Molecules 2020, 25, 1815 2 of 15 sources and long range transport. The high concentrations of pesticides confirm that deposition of parent OCPs have occurred from obsolete pesticide landfills.
... Those values were considerably higher compared to similar reports published by other investigators, related to various European countries [4,6,7,19,[25][26][27]. As mentioned before, the data reported by Aliyeva [28] from Azerbaijan were much lower than our results, but these studies were carried out in other area of Azerbaijan. According to Li et al. [29], the total amount of DDTs used in the Azerbaijan in the years 1946-1990 was assessed as 250,000-520,000 tones. ...
... The isomeric composition of DDT can be influenced substantially by different environmental processes. The abundance of 2,4'-DDE and 4,4'-DDE in samples indicates their environmental degradation in the processes of weathering and aging [28,30], which may be related to microbial activity, sorption by organic matter or the influence of other environmental factors. The abundance of 2,4′-DDE and 4,4'-DDE metabolites in soils were overall responsible for 10% of the total ∑6DDTs content. ...
... The concentrations of Σ3HCHs were much lower than those observed for DDTs and ranged from 0.1 × 10 −4 μg kg −1 to 166.7 μg kg −1 . Alyieva et al. [28] reported lower concentrations of HCH in soils in Azerbaijan, varying in the range 0.9 × 24.5 μg kg −1 . The dominant compound was α-HCH, which contributed about 73 % of the Σ3HCHs, followed by β-HCH and γ-HCH (Table 1). ...
The aim of this study was to identify and examine the levels of organochlorine pesticides (OCPs), polycyclic aromatic hydrocarbons (PAHs), and polychlorinated biphenyls (PCBs) in soil collected from the surroundings of historical pesticide storage facilities on former agricultural aerodromes, warehouses, and pesticide distribution sites located in the most important agricultural regions in Azerbaijan. The conducted research included determination of three groups of POPs (occurring together), in the natural soil environment influenced for many years by abiotic and biotic factors that could have caused their transformations or decomposition. In this study, soil samples were collected in 21 georeferenced points located in the administrative area of Bilasuvar, Saatly, Sabirabad, Salyan and Jalilabad districts of Azerbaijan. Soil chemical analysis involved determination of organochlorine compounds (OCP): hexachlorocyclohexanes (HCHs) (three isomers α-HCH, β-HCH and γ-HCH) and dichlorodiphenyltrichloroethanes (DDTs) (six congeners 2,4′DDT; 4,4′DDT; 2,4′DDE; 4,4′DDE; 2,4′DDE; and 4,4′DDE); polycyclic aromatic hydrocarbons (PAHs): 16 compounds from the United States Environmental Protection Agency US EPA list and, PCBs (seven congeners identified with the following IUPAC numbers: 28, 52, 101, 118, 138, 153, and 180). Our research showed that OCPs reached the highest concentration in the studied areas. The total concentrations of OCPs ranged from 0.01 to 21,888 mg∙kg−1 with significantly higher concentrations of Σ6DDTs (0.01 μg kg−1 to 21880 mg kg−1) compared to ΣHCH (0.14 ng kg−1 to 166.72 µg kg−1). The total concentrations of PCBs in the studied soils was varied from 0.02 to 147.30 μg·kg−1 but only PCB138 and PCB180 were detected in all analyzed samples. The concentrations of Σ16 PAHs were also strongly diversified throughout the sampling areas and ranged from 0.15 to 16,026 mg kg−1. The obtained results confirmed that the agricultural soils of Azerbaijan contained much lower (up to by three orders of magnitude) concentrations of PCBs and PAHs than DDT. It is supported by the fact that PCBs and PAHs were not directly used by agriculture sector and their content results from secondary sources, such as combustion and various industrial processes. Moreover, the high concentrations of PAHs in studied soils were associated with their location in direct neighborhood of the airport, as well as with accumulation of contaminants from dispersed sources and long range transport. The high concentrations of pesticides confirm that deposition of parent OCPs have occurred from obsolete pesticide landfills.
... These transport routes are primarily initiated during heavy precipitation events and lead to transient peak concentrations often exceeding current ecological quality criteria (Bundschuh et al., 2014;Liess and von der Ohe, 2005;Schulz, 2004). In contrast, legacy pesticides may enter surface water continuously via groundwater inflow (Barth et al., 2007;Gilliom, 2007;McKnight et al., 2015), atmospheric deposition (Konstantinou et al., 2006;Weber et al., 2010) or through continuous leaching from agricultural soils and landfills (Aliyeva et al., 2013). Consequently, legacy pesticides may generate a relatively constant exposure regime in surface waters. ...
... Based on water samples mainly analysed for herbicides and four sediment samples mainly analysed for insecticides, McKnight et al. (2015) suggested that legacy pesticides could still be prominent players driving observed impairments of freshwater invertebrates, and the authors urged for more extensive studies that allow for quantifying the predicted toxicological potency of legacy pesticides in comparison to current use pesticides. To our knowledge, such an extensive study of the potential toxicity of legacy pesticides to aquatic biota relative to that of contemporary pesticides is still lacking despite a substantial body of literature addressing the occurrence, concentrations and predicted toxicities of selected legacy pesticides (Aliyeva et al., 2013;Gilliom, 2007;McKnight et al., 2015;Weber et al., 2010). The novelty element is therefore to quantify the possible toxicity of legacy pesticides as an integral part of current risk assessment. ...
... The majority of the legacy pesticides included in this study (e.g. organochlorines and triazines) have the potential to persist for several decades in agricultural soils to which the compounds have been applied in the past (Aliyeva et al., 2013;Manz et al., 2001). In consequence, agricultural soils may still be important sources providing continuous fluxes of legacy pesticides to freshwater ecosystems (Barth et al., 2007;Gilliom, 2007). ...
We revealed a history of legacy pesticides in water and sediment samples from 19 small streams across an agricultural landscape. Dominant legacy compounds included organochlorine pesticides, such as DDT and lindane, the organophosphate chlorpyrifos and triazine herbicides such as terbutylazine and simazine which have long been banned in the EU. The highest concentrations of legacy pesticides were found in streams draining catchments with a large proportion of arable farmland suggesting that they originated from past agricultural applications. The sum of toxic units (SumTUD.magna) based on storm water samples from agriculturally impacted streams was significantly higher when legacy pesticides were included compared to when they were omitted. Legacy pesticides did not significantly change the predicted toxicity of water samples to algae or fish. However, pesticide concentrations in bed sediment and suspended sediment samples exceeded safety thresholds in 50% of the samples and the average contribution of legacy pesticides to the SumTUC.riparius was >90%. Our results suggest that legacy pesticides can be highly significant contributors to the current toxic exposure of stream biota, especially macroinvertebrate communities, and that those communities were primarily exposed to legacy pesticides via the sediment. Additionally, our results suggest that neglecting legacy pesticides in the risk assessment of pesticides in streams may severely underestimate the risk of ecological effects.
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... Azerbaijan was also one of the main producers and users of toxic substances for industrial and agricultural production . Estimations and inventories confirmed during the Soviet period, that~25,000 tons of DDT pesticide were used in Azerbaijan yearly (Aliyeva et al. 2013), which lead to large scale, and unmanageable toxic pollution in the country (Sharov et al. 2016;Swartz et al. 2003). The remaining polluted sites, from the Soviet period, have been found in nearly all parts of Azerbaijan, which include both large and small pollution hotpots (Sharov et al. 2016(Sharov et al. , 2019. ...
... Specifically, during the 1970-1990s, cotton plantations of 100-300 thousand hectares had intensive applications of POPs pesticides (IPEN 2006). These pesticides have migrated through water and air to the remote areas (Aliyeva et al. 2013;Bennett 1981). These identified sites are considered as legacy pesticide Fig. 2 Geographical distribution of pollution sources in Azerbaijan distribution points located in small agricultural villages and provincial towns throughout the country. ...
The need to protect communities from hazardous waste is an important agenda for any nation. Although pollutant management and policy development are attempted in many developing countries, it is not always successful due to limited funds, project resources, and access to trained experts to conduct toxic site identification projects. For this reason, Pure Earth created the Toxic Site Identification Program (TSIP). The goal of the TSIP program is to provide reliable information and data that identifies location of toxic sites and the level of toxic severity. TSIP is significant because it provides developing countries a database of ranked toxic sites identified as hazardous risk to human health. For example, Azerbaijan is one of the most polluted post-Soviet nations, but has limited resources to address and manage its polluted sites. The Azerbaijani TSIP database is the first reliable data source that identifies hazardous pollutants in the country. Our study is significant because it discusses how the TSIP labels and ranks the level of toxic severity to human health. It is also the first data source in Azerbaijan that identifies which Soviet legacy toxic sites are affecting local communities. Although our study is specific to Azerbaijan, the TSIP method can be applied to nations with similar data limitations and the need for a database that identifies country specific environmental and hazardous locations. The data sampling method and results are mapped and accompanied by tables of the collected pollutant types to identify communities at greatest health-risk to legacy toxic sites.
... Azerbaijan was also one of the main producers and users of toxic substances for industrial and agricultural production ( Bickham et al. 2003). Estimations and inventories confirmed during the Soviet period, that ~25,000 tons of DDT pesticide were used in Azerbaijan yearly ( Aliyeva et al. 2013), which lead to large scale, and unmanageable toxic pollution in the country ( Sharov et al. 2016;Swartz et al. 2003). The remaining polluted sites, from the Soviet period, have been found in nearly all parts of Azerbaijan, which include both large and small pollution hotpots ( Sharov et al. 2016Sharov et al. , 2019. ...
... Specifically, during the 1970-1990s, cotton plantations of 100-300 thousand hectares had intensive applications of POPs pesticides (IPEN 2006). These pesticides have migrated through water and air to the remote areas ( Aliyeva et al. 2013;Bennett 1981). These identified sites are considered as legacy pesticide Fig. 2 Geographical distribution of pollution sources in Azerbaijan distribution points located in small agricultural villages and provincial towns throughout the country. ...
Development of an irrigation farming and intensive water use in water catchments areas of Kura basin river of Azerbaijan has
increased consumption to fresh water, which is supplied only by small mountain rivers. Most of water resources of small mountain
rivers of Kura basin are completely consumed by the enterprises of industry and agriculture. Waste of the water resources
of small rivers bring to the “loss of rivers” as an element of landscape in the Small Caucasus region. In lower part of Kura
river basin within the Azerbaijan during the shallow season of year the river flow is completely absent. To prevent such condition
on the mountain rivers needs to reserve a part of the river flow, that is to say, reserve “ecological flow” in the riverbeds.
Ecological flow is such a quantity and condition of the flow, in which is vital for aquatic organisms, quarantines increase
for them, sufficient for transporting all solid materials and sediments. In other words, the ecological flow maintains the
river ecosystem as a part of an environment. To quarantine of these conditions are needed enough quantity, quality and strong
watercourse speed in the riverbeds. The complex assessment of the ecological flow needs systematical and complex hydrological,
biological and ecological investigations and stationary observations on the watersheds. As a result of long-term investigations,
new methodic, which gives a possibility to calculate ecological flow for mountain rivers is proposed. For sufficient situation
of hydroecological safety, ecological flow is needed to estimate for points of concentration of rivers. Points of concentration
in many small rivers are situated very far from the river mouthes and consequently, stationary hydrological observations do
not reflect hydroecological situations in the mountain rivers. By the offered methodic it is possible to estimate ecological
flow for all year period. By this methodic the ecological runoff is estimated not only for water gauge stations, but also
for a mouthes of small rivers. The index of a relativity of a ecological flow is developed. It has been revealed, that the
interrelation between recordable and ecological flows defines an ecological situation in river ecosystem. Such interrelation
may be called relative hydroecological factor of flow (CREF). Relative ecological factor of the water is an indicator of ecological
situation in the river for any period. If the CREF value is higher than the unit is, then the danger of ecological crises
in the river ecosystem does not exist, because, for an exchange of substances and energy in the river there is enough water.
If CREF value is lower than the unit, then insufficient water flow is observed in the river.
... Various carcinogenic persistent organic pollutants from the past are commonly detected in typical lake ecosystems in Europe and Asian. Organochlorine pesticides, polychlorinated biphenyls, and polycyclic aromatic hydrocarbons (Javedankherad et al. 2013), sediments (de Mora et al. 2004;Boehm et al. 2005;Nemirovskaya and Brekhovskikh 2008;Varnosfaderany et al. 2015;Baniemam et al. 2017), organisms (Rajaei et al. 2011;Mashroofeh et al. 2015), the surrounding soils, and atmosphere (Aliyeva et al. 2012(Aliyeva et al. , 2013Shahbazi et al. 2012) of the Caspian Sea located between Europe and Asia, the World's largest lake. ...
Water contamination by emerging contaminants is increasing in the context of rising urbanization, industrialization, and agriculture production. Emerging contaminants refers to contaminants for which there is currently no regulation requiring monitoring or public reporting of their presence in our water supply or wastewaters. There are many emerging contaminants such as pesticides, pharmaceuticals, drugs, cosmetics, personal care products, surfactants, cleaning products, industrial formulations and chemicals, food additives, food packaging, metalloids, rare earth elements, nanomaterials, microplastics, and pathogens. The main sources of emerging contaminants are domestic discharges, hospital effluents, industrial wastewaters, runoff from agriculture, livestock and aquaculture, and landfill leachates. In particular, effluents from municipal wastewater treatment plants are major contributors to the presence of emerging contaminants in waters. Although many chemicals have been recently regulated as priority hazardous substances, conventional plants for wastewater and drinking water treatment were not designed to remove most emerging contaminants. Here, we review key examples of contamination in China, Portugal, Mexico, Colombia, and Brazil. Examples include persistent organic pollutants such as polychlorinated biphenyls, dibenzofurans, and polybrominated diphenyl ethers, in lake and ocean ecosystems in China; emerging contaminants such as alkylphenols, natural and synthetic estrogens, antibiotics, and antidepressants in Portuguese rivers; and pharmaceuticals, hormones, cosmetics, personal care products, and pesticides in Mexican, Brazilian, and Colombian waters. All continents are affected by these contaminants. Wastewater treatment plants should therefore be upgraded, e.g., by addition of tertiary treatment systems, to limit environmental pollution. © 2022, The Author(s), under exclusive licence to Springer Nature Switzerland AG.
... Contamination of agricultural soils is an obstacle for providing food for the world's growing population. In particular, in former Soviet countries in the Southern Caucasus Region the legacy of past pesticide use poses a risk to human health and food safety [1][2][3]. In this region, organochlorine pesticides like DDT (dichloro-diphenyl-trichloroethane) or HCH (hexachlorocyclohexane) were used excessively in the past. ...
This study presents a survey on pesticide use, pesticide storage and pesticide disposal among 100 residents near a former pesticide store in rural Georgia using a standardized paper questionnaire. More than one quarter of the participants responded that the age of the pesticides they use is higher than 20 years. Based on this finding, it cannot be excluded that persistent organic pollutants like Dichloro-diphenyl-trichloroethane and hexachlorocyclohexanes still are released to the environment. Knowledge about active ingredients of pesticides is lacking among farmers: More than two thirds state that they know the active ingredients, while less than 10% mention an active ingredient matching the brand name they report. Purchasing pesticides in containers without labels appears to be common practice. Information about the pesticides is mainly obtained from the pesticide retailer, while the label is less important as a source of information. More than 95% of the participants store the pesticides in a separate store, but appropriate possibilities of hazardous waste disposal seem to be insufficient in rural areas in the region. The finding that pesticides are purchased and stored in repacked secondary containers, poses direct risks and hampers communication of risks to users. Improving (implementation of) regulations for pesticide handling and strengthening local knowledge through better vocational training can improve soil and groundwater protection and sustainable use of resources.
Article highlights
One of the main findings is that residents report using the pesticides for a long time. Not only are the pesticides used way longer than they may remain suitable for use, but also the pesticides could be dating from before international legislation entered into force which was set up to protect from long-lived organic pollutants (the Stockholm Convention). Our results show that often pesticides are repacked and stored in alternative containers such as plastic containers for detergents. This means users cannot find important information on how to use pesticides safely on these alternative containers. The label cannot be used as a source of information for example regarding health risks. This may lead to poisoning of users.
In Georgia, the transition process results in poor implementation of environmental regulations such as laws about waste management. The results show that educational level has a positive influence on choosing safe storage options such as a separate store. The results indicate that especially in rural areas possibilities of proper disposal of old pesticides or other dangerous chemicals are poor. This has implications for the health of residents.
Efforts to better implement environmental regulations should be strengthened especially in rural areas to overcome the legacy of long-lived pesticides which are now banned. Old pesticides might still be in use because they are difficult to dispose of safely.
... In 2001, Kazakhstan's cabinet has approved a rehabilitation and development program for grape and wine production, based on the concept established by the Republic of Kazakhstan (Karibayeva, 2001;Meshkov et al., 2009). Kazakhstan's vineyard acreage will be restored to the 1970s and 1980s levels in the long run, according to this program (Kokishev, 2011;Aliyeva et al., 2013). Furthermore, even in contrast to the 1970s and 1980s, the efficiency of Kazakhstan's vineyards as a whole will improve greatly, and gross grape output might approach 200-220 thousand tons in good years (Syrgabek et al., 2020;Жапар et al., 2021). ...
Variety assortment enhancement is a normal task that involves enhancing the assortment's quality and upgrading varieties. The findings of a research of imported grape varieties in the southeast of Kazakhstan, namely in the Almaty region's bottom-mountain zone, are presented in this article. The onset and conclusion of the main phenological phases of a grape plant throughout the vegetative period were directly influenced by the climatic and meteorological conditions of this district. In comparison to the recognized variety Almaty early-maturing, it has been proven that types Priusadebny, Iyulsky, and Kuibyshevsk early-maturing have a high degree of eyes wintering buds and may provide a high-quality crop in this location.
... Various carcinogenic persistent organic pollutants from the past are commonly detected in typical lake ecosystems in Europe and Asian. Organochlorine pesticides, polychlorinated biphenyls, and polycyclic aromatic hydrocarbons (Javedankherad et al. 2013), sediments (de Mora et al. 2004;Boehm et al. 2005;Nemirovskaya and Brekhovskikh 2008;Varnosfaderany et al. 2015;Baniemam et al. 2017), organisms (Rajaei et al. 2011;Mashroofeh et al. 2015), the surrounding soils, and atmosphere (Aliyeva et al. 2012(Aliyeva et al. , 2013Shahbazi et al. 2012) of the Caspian Sea located between Europe and Asia, the World's largest lake. ...
... In the early 1990s, Former Soviet Union (FSU) countries were still using DDT even though it was already prohibited in 1969/1970 in the Union (Li et al. 2006;Shelton, 2003: 302). Aliyeva et al. (2013) note that as part of the USSR and even after its independence, Azerbaijan had intensively used organochlorine pesticides, in agriculture along the lowlands of the Kura River, which eventually ended up in the Caspian coasts through sediment transfers. ...
This chapter looks at the condition of oil contamination on the Absheron Peninsula. It examines the level of pollution and the extent to which projects to address the pollution are implemented. It starts with a discussion of various accounts about the oil-polluted land, which is important in terms of measuring how much decontamination work has been done until 2020. This enables us to assess whether governmental plans to remedy oil pollution on the Absheron Peninsula have been successful. Additionally, this chapter looks at the amount of finance that has been allotted to alleviate oil pollution. The scale of the decontamination work, the allocation of finance by the government and governmental environmental goals to remedy oil pollution are discussed to evaluate if un-politics holds true in the case of oil pollution.
... Unfortunately, some of these pesticides were accumulated during Soviet Union and are still finding application in most Central Asian countries. Grain crops are often sprayed with insecticides even though some of them are banned in certain countries (for example, malathion, pirimiphos-methyl, chlorpyriphos-methyl, deltamethrin, d-phenothrin, tetramethrin, pirimicarb, or dichlorvos) [7][8][9][10]. To reduce the effect of the fungus, strobilurin, azoxystrobin, trifloxistrobin, kresoximmethyl, as well as nitrogen fungicides chlorothalonil, propiconazole, epoxiconazole, tebuconazole, and boskalid are usually used. ...
Pesticides have been used all over the world since the mid-twentieth century to protect cereals and their derivatives in agriculture from pests, insects and fungi. The release of pesticides into the environment makes up a fraction of one percent of the total amount of chemical pollutants, but given that these compounds are aimed at suppressing certain groups
of organisms, pesticides and their transformation products have a toxic effect on various forms of biota and on human health when ingested with vegetables and fruits, including from their
surface, if they are poorly washed. And also, from cereals, as they can be absorbed into them from the soil. There are no safe pesticides, even when used in small quantities, they can cause
various allergic reactions and poisoning. In the production of agricultural products, approved pesticides are used, but this does not negate the fact that long-term use of the drug can have
negative consequences. Therefore, constant monitoring of the residual amount of pesticides in these products reduces the risk to human health and the environment. Hence, there is a need for
efficient, rapid and cost-effective methods for the determination of pesticide residues. The article reflects the methods of sample preparation in the analysis of pesticides in grain crops, as well as features of the method of solid-phase micro extraction of one of the methods of environmental, green chemistry in the preparation of samples.
... Spain (Aurrekoetxea Agirre et al., 2011;Fern andez et al., 2013), France (Orton et al., 2013), Italy (Battisti et al., 2017;Porta et al., 2013;Thiombane et al., 2018), Germany (Wycisk et al., 2013), Moldova (Tirsina et al., 2017), Slovakia (Sisto et al., 2015), Poland (Łozowicka et al., 2016), Czech Republic (Holt et al., 2017)), in Africa (e.g. Egypt (Abd Al-Rahman, 2012), Ghana (Forkuoh et al., 2018), Nigeria (Mazlan et al., 2017), South Africa (Buah-Kwofie et al., 2018), Senegal (Donald et al., 2016)), Asia (India (Chakraborty et al., 2019(Chakraborty et al., , 2017Kumar et al., 2016;Singare, 2016), Iran (Dahmardeh Behrooz et al., 2012), China (Song et al., 2013;Yi et al., 2013;Zhang et al., 2012Zhang et al., , 2016, Kyrgyzstan (Toichuev et al., 2018), Malaysia (Saadati et al., 2012), Korea (Kim et al., 2013), Japan (Konishi and Kakimoto, 2016;Watanabe et al., 2013), Kazakhstan (Nurzhanova et al., 2013), Azerbaijan (Aliyeva et al., 2013), Russia (Tsygankov et al., 2015), Pakistan (Aamir et al., 2016), Mongolia (Mamontova et al., 2016)), and in the Americas (Mexico (Trejo-Acevedo et al., 2012), Brazil (Macedo et al., 2015;Torres et al., 2013), Guadalupe (Laquitaine et al., 2016), United States (Fry and Power, 2017), Beaufort Sea (Alaska (Pu cko et al., 2013)) and Oceania (Mueller et al., 2008), the Antarctic and Artic (Cincinelli et al., 2011) (Table 1, Fig. 1). ...
Lindane (γ-hexachlorocyclohexane) and its isomers (HCH) are some of the most common and most easily detected organochlorine pesticides in the environment. The widespread distribution of lindane is due to its use as an insecticide, accompanied by its persistence and bioaccumulation, whereas HCH were disposed of as waste in unmanaged landfills. Unfortunately, certain HCH (especially the most reactive ones: γ- and α-HCH) are harmful to the central nervous system and to reproductive and endocrine systems, therefore development of suitable remediation methods is needed to remove them from contaminated soil and water. This paper provides a short history of the use of lindane and a description of the properties of HCH, as well as their determination methods. The main focus of the paper, however, is a review of oxidative and reductive treatment methods. Although these methods of HCH remediation are popular, there are no review papers summarising their principles, history, advantages and disadvantages. Furthermore, recent advances in the chemical treatment of HCH are discussed and risks concerning these processes are given.
... Unfortunately, our knowledge about the impact of environmental and anthropogenic factors on the native biodiversity in the Caspian Sea is largely biased towards few key stressors related to natural water-level fluctuations and human activities, such as fishery and mineral extraction (Malinovskaja et al., 1998;Agah et al., 2007;Zinchenko, 2010, 2011;Khodorevskaya et al., 2014;Yanina, 2014;Latypov, 2015;Mammadov et al., 2016;Poorbagher et al., 2017). Moreover, most previous human impact studies in the Caspian Sea are restricted to coastal areas (Nasrabadi et al., 2011;Aliyeva et al., 2013;Bastami et al., 2014), individual countries (Aliyeva et al., 2013;Dmitrieva et al., 2013;Bastami et al., 2014;Yancheshmeh et al., 2014;Mashroofeh et al., 2015;Varnosfaderany et al., 2015) or selected target species (Bickham et al., 1998;Agah et al., 2007;Dmitrieva et al., 2013;Ermolin and Svolkinas, 2016;Poorbagher et al., 2017). Therefore, a comprehensive understanding of lake-wide spatial differences in combined and individual pressures is lacking and the biological consequences of human impacts are poorly understood. ...
Over the past decades, overall ecological conditions in the Caspian Sea have deteriorated. However, a comprehensive understanding of lake-wide spatial differences in anthropogenic pressures is lacking and the biological consequences of human impacts are poorly understood. This paper therefore aims at assessing the individual and combined effects of critical anthropogenic pressures on the Caspian Sea ecoregions. First, cumulative pressure scores were calculated with a cumulative environmental assessment (CEA) analysis. Then, the individual contribution of anthropogenic pressures was quantified. Finally, ecoregion-specific differences were assessed. The analyses show that both cumulative and individual pressure scores are unevenly distributed across the Caspian Sea. The most important individual pressures are invasive species, chemical pollution and poaching. This uneven distribution of pressure scores across Caspian Sea ecoregions creates new challenges for future conservation strategies, as different ecoregions usually require different conservation measures.
... Unfortunately, our knowledge about the impact of environmental and anthropogenic factors on the native biodiversity in the Caspian Sea is largely biased towards few key stressors related to natural water-level fluctuations and human activities, such as fishery and mineral extraction (Malinovskaja et al., 1998;Agah et al., 2007;Zinchenko, 2010, 2011;Khodorevskaya et al., 2014;Yanina, 2014;Latypov, 2015;Mammadov et al., 2016;Poorbagher et al., 2017). Moreover, most previous human impact studies in the Caspian Sea are restricted to coastal areas (Nasrabadi et al., 2011;Aliyeva et al., 2013;Bastami et al., 2014), individual countries (Aliyeva et al., 2013;Dmitrieva et al., 2013;Bastami et al., 2014;Yancheshmeh et al., 2014;Mashroofeh et al., 2015;Varnosfaderany et al., 2015) or selected target species (Bickham et al., 1998;Agah et al., 2007;Dmitrieva et al., 2013;Ermolin and Svolkinas, 2016;Poorbagher et al., 2017). Therefore, a comprehensive understanding of lake-wide spatial differences in combined and individual pressures is lacking and the biological consequences of human impacts are poorly understood. ...
Over the past decades, overall ecological conditions in the Caspian Sea have deteriorated. However, a comprehensive understanding of lake-wide spatial differences in anthropogenic pressures is lacking and the biological consequences of human impacts are poorly understood. This paper therefore aims at assessing the individual and combined effects of critical anthropogenic pressures on the Caspian Sea ecoregions. First, cumulative pressure scores were calculated with a cumulative environmental assessment (CEA) analysis. Then, the individual contribution of anthropogenic pressures was quantified. Finally, ecoregion-specific differences were assessed. The analyses show that both cumulative and individual pressure scores are unevenly distributed across the Caspian Sea. The most important individual pressures are invasive species, chemical pollution and poaching. This uneven distribution of pressure scores across Caspian Sea ecoregions creates new challenges for future conservation strategies, as different ecoregions usually require different conservation measures.
... Most of the environmental impact of agriculture use comes from applying higher than recommended procedures and dosages, improper usages, illegal use of banned pesticides, as well as improper storage, handling and disposal of pesticides. For several decades, agricultural soils were detected with a major source of persistent pesticides, which makes it a source of continuous pesticide flux to the freshwater system (Aliyeva et al., 2013;Barth et al., 2007). The upper soil layer in catchment areas can be considered as the main reservoirs for such pesticides. ...
Since the industrial revolution, several new chemicals were discovered and introduced in society, and soon after the green revolution, pesticides were also introduced to strengthen food security. However, limited education on their application, handling, and usage resulted in them making their way into the aquatic ecosystem. This chapter defines the different sources of pesticides, based on their point of origin and the way it transports pesticides to the aquatic systems. After this, the pesticide interaction in an aquatic environment with various organic and inorganic substances is described. Each interaction is supported with the recent researches and examples. Following pesticides sources and interactions, its fate in the aquatic system has been defined through various physical and chemical processes. Ultimately, its impact on aquatic organisms is discussed. This chapter is concluded with recommended management practices and future research directions. Some terms are also defined at the end of this chapter.
... However, PBDE use and subsequent occurrence in the wider environment within the former republics of the Soviet Union is poorly understood, and yet for chemicals such as organochlorine pesticides or PCBs the production and use in some republics was substantial (Aliyeva et al. 2012b). Therefore by building on a larger programme to understand the environmental occurrence and legacy of peristent organic pollutants in Azerbaijan (Aliyeva et al. 2012a), the purpose of this study was to examine PBDEs in the wider Azeri environment. Objectives included examining urban-rural gradients for levels in air and soil and seeking evidence of 'hotspots' associated with chemical production, handling and/or disposal. ...
PBDEs were measured in air and soil across Azerbaijan to establish contemporary concentrations at 13 urban and rural sites. Polyurethane foam passive air samplers (PUF-PAS) were deployed for a period of a month with surface soil samples collected at the same sites. Unlike organochlorine pesticides previously surveyed by our group, PBDE concentrations in both contemporary air and soil were low in comparison to recent European and Asian studies. For example, mean ∑9PBDE concentrations in air and soil were 7.13 ± 1.66 pg m−3 and 168 ± 57 pg g−1, respectively. The fully brominated BDE-209 was the most abundant congener observed in soil (174.8 ± 58.5 pg g−1), comprising ~ 96% of ∑10PBDE. However, the PAS-derived air concentrations for highly brominated congeners must be viewed with caution as there is uncertainty over the uptake rates of particle-bound chemicals using these devices. Some of the highest concentrations in air were observed at sites with the highest wind speeds and at several remote locations in the north of the country and this requires further research. Levels of BDE-47 and 99 (the two most abundant congeners in the widely used penta-formulation) were lower than levels reported elsewhere suggesting limited use/import of the penta-BDE formulation in Azerbaijan.
... Some of these compounds are toxic and/or persistent and thus potentially threaten the aquatic environment (Mugni et al., 2013), less than 0.1% of an applied pesticide reaches the target pest, rest of 99.9% as an unintended pollutant in the environment (Pimentel, 1995). The environment contaminates routes by which the pesticides can move from the site of application via drift, runoff (Campo et al., 2013), volatilization (Majewski and Capel, 1995) and leaching (Aliyeva et al., 2013). ...
h i g h l i g h t s Toxicity and recuperation study of insecticides in food fish. Biomarkers of blood and tissues related to oxidative damage. Results indicate high efficiency of depuration process. a b s t r a c t The present research investigated the growth, blood, antioxidant response (liver), AChE (brain and muscle) and Naþ/K þ ATPase in gills of Clarias batrachus exposed to 0 (control), two insecticides, 1.65 mg L À1 chlorpyrifos (CPF) and 2.14 mg L À1 monocrotophos (MCP) for a fixed interval time of 3, 6, 9, 12 and 15 days and follow up depuration process in fresh water for 30 days (at an interval of 7, 15 and 30 days). The toxicants exposed fish indicated significantly (P < 0.05) lower weight gain and HSI. The RBC, Hb, Hct, plasma total protein, glucose, albumin, globulin and respiratory burst activity was reduced. However, WBC, plasma glucose, serum creatinine, and triglycerides were enhanced. The weight gain, HSI and all haematological parameters were reversed following depuration of CPF and MCP exposed fish. Hepatic superoxide dismutase, catalase, lipid peroxidation, reduced glutathione, and glutathione S-transferase activities were significantly activated whereas glutathione peroxidase was inhibited in both tested groups. All the antioxidant enzymes were reversed on day 15 in MCP concentration, whereas CPF on day 30 of depuration process. The inhibition of acetylcholinesterase (brain, muscle) and gill Naþ/ K þ ATPase activities were more in CPF exposure and early recovery in MCP. The results indicated that depuration process might help in detoxification of fish and improve growth, haematological conditions, oxidative stress and AChE, Naþ/K þ ATPase activity. However, further studies are needed in different fish species with different toxicants to support this strategy of depuration process in order to detoxify polluted fish.
... Prometryn has been diachronically detected in Greek surface water bodies from Pinios river and in northeastern Greece (Miliadis and Malatou, 1997;Vryzas et al., 2009), in water samples collected from streams and pumping stations (Albanis, 1992), and in drainage waters of the basins of the rivers Axios and Ardas (Papadopoulou-Mourkidou et al., 2004a, b;Vryzas et al., 2011). The high frequency of prometryn detection could also be attributed to its release from different environmental compartments such as groundwater outflow , atmospheric deposition (Konstantinou et al., 2006;Weber et al., 2010) and probably leaching from agricultural soils (Aliyeva et al., 2013. Trifluralin, a dinitroanile herbicide, which is a photo-chemically unstable compound, is also considered persistent in the environment due to its ability to redistribute from water (where it has a short half-life) to other environmental compartments such as sediment. ...
A pesticide prioritization approach was developed and implemented in the Pinios River Basin of Central Greece. It takes under consideration the Level of Environmental Risk containing information on the frequency of occurrence of pesticides above environmental thresholds, the intensity of this occurrence and the spatial distribution as well as information about the fate and behavior of pesticides in the environment and the potential to have adverse impact on humans' health. Original 3-year monitoring data from 102 Stationary Sampling Sites located on rivers and their tributaries, reservoirs, streams and irrigation/drainage canals giving rise to a collection of 2382 water samples resulting in 7088 data sets, were included in this integrated prioritization study. Among 302 monitored active ingredients, 119 were detected at least once and the concentrations found in the aquatic systems for 41% of compounds were higher than the respective lowest Predicted Non-Effect Concentration (PNEC) values. Sixteen and 5 pesticides were found with risk ratios (MECmax/PNEC) above 10 (high concern) and 100 (very high concern), respectively. However, pesticides with maximum Measured Environmental Concentration (MECmax) values exceeding by 1000 times the respective lowest PNEC values were also found which were considered of extremely high concern; in the latter group were included prometryn, chlorpyrifos, diazinon, λ-cyhalothrin, cypermethrin, α-cypermethrin deltamethrin, ethalfluralin and phosmet. The sensitivity of the analytical methods used in the monitoring study was considered inadequate to meet the toxicological endpoints for 32 pesticides. The widest distribution of occurrence in the Stationary Sampling Sites of the monitoring program was found for the pesticides, prometryn, fluometuron, terbuthylazine, S-metolachlor, chlorpyrifos, diphenylamine, acetochlor, alachlor, 2,4-D, etridiazole, imidacloprid and lindane (γ-ΗCH). Among the 27 priority pesticides included in the Directive 2013/39/EU, in the present study 13 pesticides were considered as candidates for River Basin Specific Pollutants (RBSP) for the River Basin of Pinios. Among the 30 pesticide specific pollutants that were established by the Greek authorities, in the present study only 6 were considered as candidates for RBSP for the river basin of Pinios. As a result of the implementation of the prioritization approach developed in this study a total of 71 pesticides were identified as being RBSP for the river basin of Pinios. The higher Level of Environmental Risk was found to be exerted by the organophosphorus insecticide chlorpyrifos, followed by lindane and prometryn. The present study provides background information for important decisions to be made concerning the selection of pesticides which should be included in the target analyte list of new monitoring and screening programs of surface water quality in the Pinios River Basin. In addition, the prioritization approach proposed here can be useful for the development of River Basin Management Plans.
... Prometryn has been diachronically detected in Greek surface water bodies from Pinios river and in northeastern Greece (Miliadis and Malatou, 1997;Vryzas et al., 2009), in water samples collected from streams and pumping stations (Albanis, 1992), and in drainage waters of the basins of the rivers Axios and Ardas (Papadopoulou-Mourkidou et al., 2004a, b;Vryzas et al., 2011). The high frequency of prometryn detection could also be attributed to its release from different environmental compartments such as groundwater outflow , atmospheric deposition (Konstantinou et al., 2006;Weber et al., 2010) and probably leaching from agricultural soils (Aliyeva et al., 2013. Trifluralin, a dinitroanile herbicide, which is a photo-chemically unstable compound, is also considered persistent in the environment due to its ability to redistribute from water (where it has a short half-life) to other environmental compartments such as sediment. ...
A pesticide prioritization approach was developed and implemented in the Pinios River Basin of Central Greece. It takes under consideration the Level of Environmental Risk containing information on the frequency of occurrence of pesticides above environmental thresholds, the intensity of this occurrence and the spatial distribution as well as information about the fate and behavior of pesticides in the environment and the potential to have adverse impact on humans' health. Original 3-year monitoring data from 102 Stationary Sampling Sites located on rivers and their tributaries, reservoirs, streams and irrigation/drainage canals giving rise to a collection of 2382 water samples resulting in 7088 data sets, were included in this integrated prioritization study.
... There is a growing global priority for the remediation and management of persistent organic pollutants (POPs)-contaminated soil since these POPs are one of the toxic groups of chemical pollutants and listed under the Stockholm Convention for global elimination. They are potentially hazardous to living organism because of their higher degree of halogenations , inclination to bioaccumulate in the lipid component, and their resistance to natural degradation (Weber and Varbelow 2013; Torres et al. 2013a, b; Götz et al. 2013; Younas et al. 2013; Nurzhanova et al. 2013; Sun et al. 2013; Aliyeva et al. 2013; Oliaei et al. 2013; Xu et al. 2013; Vijgen et al. 2013; Miguel et al. 2013; Meire et al. 2013; Domínguez-Cortinas et al. 2013; Wu et al. 2013). Once enter into the pedosphere, these compounds can redistribute and partition into other environmental compartments by various physical, chemical, and biological processes such as adsorption onto soil particles, adsorption onto plant root tissues, volatilization, long-range atmospheric transport, long-range marine transport, microbial degradation and leaching, etc. ...
The rapid expansion of the human population has raised the chemical stress on the environment due to the increased demand of agricultural yields. The use of pesticides is the primary contributor to environmental chemical stress, which is essential for agricultural expansion in order to produce enough food to sustain the burgeoning human population. Pesticide residues in soil have grown to be a subject of rising concern as a result of their high soil retention and potential harm to unintended species. Diverse remediation strategies, such as physical, chemical, and biological, for limiting and getting rid of such contaminants have been put forth to deal with this problem. Bioremediation is one of these techniques, which has been deemed the best for reducing pollution because of its low environmental impact, simplicity of operation and construction. Microorganisms are implemented in this technique to break down and get rid of toxins in the environment or to reduce the toxicity of chemical compounds. This study thoroughly analyses the different composting soil remediation methods, including landfarming, biopiles, and windrows, to reduce and eliminate soil pollution. Although biological treatment is the best option for cleaning up polluted soil, it is still important to evaluate and review the approaches over the long term to determine whether they are effective in the field. It is because the reactivity of the microorganisms is highly dependent on environmental parameters, and the contemporary environment is characterised by unpredictable weather patterns, localised droughts, and temperature fluctuations.
The article presents a one-stage method for the synthesis of mixed diesters based on propylene glycol, synthetic petroleum- and aliphatic fatty acids (C6-C8) using a ZnO catalyst under optimal conditions - temperature -110-120°C, amount of catalyst - 1.3% wt. (by acid), molar ratio of components - acid:alcohol - 2:1.3. The properties of the synthesized mixed diesters were studied and their parameters were determined by analytical and spectral methods. In order to determine the plasticizing properties of the mixed diesters, compositions were prepared under laboratory conditions with the addition 100 m.p. of polyvinyl chloride (PVC) for 30-70 m.p. of synthesized diesters and compared them with an industrial plasticizer - dioctyl phthalate. Also, these diesters have been studied as antioxidants that improve the thermal-oxidative stability of diesel fuel. An analysis of the research results shows that the synthesized mixed diesters can be proposed as effective plasticizers for PVC and new antioxidants for diesel fuels. Keywords: propylene glycol, synthetic petroleum acids, mixed diesters, diesel fuel, antioxidant, polyvinyl chloride, plasticizer
Over the past two decades, the presence of so-called emerging contaminants in various environmental compartments around the world, such as water, sediments, soils and atmosphere, and in a wide variety of consumer products has become a major concern for society, public health authorities, industry (namely food industry and water sector) and the agricultural sector. Some of these substances are endocrine disruptors and others are proven carcinogens and mutagens. In particular, there is a growing concern about the presence of emerging contaminants in water resources.
Persistent organic pollutants (POPs) are highly toxic organic chemicals. Lakes are one of the main sinks of POPs. POPs can be accumulated in multiple matrices in lake ecosystems and biomagnified through the food web, and thus pose a potential threat not only to lake ecosystems, but also to human health. Given their potential persistent risks, they have received much attention over the past decades. This review comprehensively summarizes the data on the levels and distributions of POPs in selected typical lake ecosystems in China and worldwide, involving water, sediments, organisms, and surrounding soils and atmosphere. It was found that current publications on POPs in Chinese lakes are mainly related to lakes in the developed eastern plain area, with only a few studies concerning the less-developed Qinghai-Tibet Plateau area. Similarly, around the world, there are more research on POPs in developed countries and less in relatively less-developed areas. Moreover, there are significant differences in the levels of POPs in different matrices in different lake ecosystems. Legacy POPs, such as polycyclic aromatic hydrocarbons (PAHs), organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), and polybrominated diphenyl ethers (PBDEs), were commonly detected and reported in different lakes, while emerging POPs like perfluorinated compounds (PFCs), polychlorinated naphthalenes (PCNs), Tetrabromobisphenol A (TBBPA), and hexabromocyclododecane (HCBD) were relatively less detected or reported. A comprehensive summarization on the levels and distributions of traditional and emerging POPs in lake ecosystems could be significant for further understanding the behaviors and risks of POPs in lake ecosystems.
Currently, there are large areas of soils contaminated with hexachlorocyclohexane (HCH) isomers which are included in the group of persistent organic pollutants. For the bioremediation of such soils, a new HCH-degrading Rhodococcus wratislaviensis strain Ch628 was isolated from long-term organochlorine contaminated soils. The strain Ch628 was able to degrade 32.3% γ-hexachlorocyclohexane (γ-HCH/lindane), 25.2% hexachlorobenzene, and 100% chlorobenzene in resting cell conditions. The strain Ch628 was bioaugmented in chronically HCH-contaminated soil. The results showed that the bioaugmentation of contaminated soil with the strain Ch628 led to HCH degradation. In the bioaugmented system, the efficiency of HCH removal at the initial concentration of about 238.7 ± 4.9 mg kg⁻¹ soil was 44.8%, while the system with indigenous microflora (without R. wratislaviensis strain Ch628) and the system with abiotic control removed 33.3 and 16.4% of this compound during the same period, respectively. Strain Ch628 could effectively degrade α-, β-, and γ-isomers of HCH (77.1, 100, and 100%, respectively) and heptachlorocyclohexane (69.9%) in the model soil systems. Moreover, the bioaugmentation with the strain Ch628 led to degradation of tri-, tetra-, and penta-chlorobenzenes, which are of HCH degradation metabolites. For the first time, it was found that the bioaugmentation with the bacterial strain Rhodococcus wratislaviensis Сh628 led to a significant reduction of the toxicity of the HCH-contaminated soil for the test organisms, such as Chlorella vulgaris Beijer and Daphnia magna Straus.
Concentrations of selected organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) are reported in air and surface soil in an extensive spatial survey across Azerbaijan, a country bordering the Caspian Sea with a history of OCP production and extensive use. Polyurethane foam disc passive air samplers (PAS) were deployed during October–November 2008 with soil samples collected in July 2009. Levels of Σ7PCB in ambient air were generally low (mean of 0.046 ng m−3, n = 13) and comparable to concentrations reported in countries within Eastern Europe and similar to or lower than concentrations reported in urban air in the UK and other western countries. Surprisingly, PCB concentrations in rural/background soil fell below the method detection limits at most sites, although concentrations were 0.209 and 0.071 ng Σ7PCB g−1 dry weight (dw) for two urban sites, again comparable to PCB levels measured at background sites in Europe. Levels of α-HCH, β-HCH, γ-HCH and p,p′-DDT/E were elevated in ambient air across Azerbaijan in comparison to PAS-derived concentrations reported elsewhere, with concentrations of α-HCH in air ranging from 0.085 to 2.699 ng m−3 and p,p′-DDE, 0.037–2.290 ng m−3. High concentrations of OCPs occurred at several of the urban sites and at sites in proximity to old pesticide storage facilities with concentrations in soil >0.1 μg g−1 dw for p,p′-DDE and p,p′-DDT at several sites. The ratio of p,p′-DDT/p,p′-DDE was close to unity in the soil at these sites, but elsewhere, the ratio was −1 for the HCH isomers (including the β -isomer) and p,p′-DDE. The high levels of OCPs in soils, particularly in the vicinity of obsolete-pesticide storage facilities and at select urban sites are of concern and warrant regular monitoring activities and the development of containment or mitigation strategies.
Mass mortalities among seals and dolphins inhabiting contaminated marine regions have led to speculation about a possible involvement of immunosuppression associated with environmental pollution. To evaluate whether contaminants at ambient environmental levels can affect immune function of seals, we carried out an immunotoxicological study under semifield conditions. Two groups of 11 harbour seals (Phoca vitulina) originating from a relatively uncontaminated area were fed herring from either the highly polluted Baltic Sea or the relatively uncontaminated Atlantic Ocean. Changes in immune function were monitored over a 2 1/2-year period. The seals that were fed contaminated Baltic herring developed significantly higher body burdens of potentially immunotoxic organochlorines and displayed impaired immune responses as demonstrated by suppression of natural killer cell activity and specific T-cell responses. During a 2-week fasting experiment performed at the end of the feeding study, mobilization of organochlorines from the blubber did not lead to a strong increase of contaminant levels in the blood, and no enhancement of the existing immunosuppression was observed. These results demonstrate that chronic exposure to environmental contaminants accumulated through the food chain affects immune function in harbour seals, whereas short-term fasting periods, which are normal for seals, do not seem to pose an additional risk. The seals of this study were not exposed perinatally to high levels of environmental chemicals, and body burdens of organochlorines measured near the end of the study were lower than those generally observed in free-ranging seals inhabiting many contaminated regions. Therefore, it may be expected that environmental contaminants adversely affect immune function of free-ranging seals inhabiting contaminated regions at least as seriously as observed in these studies.
Oil and caviar are the two most economically valuable natural resources for the Republic of Azerbaijan. While the collapse of the Soviet Union has brought about many beneficial changes in the society of this newly independant Republic, it has also revealed a history of ecological abuse under the Soviet system. The oil industry caused some of the most extensively polluted aquatic and terrestrial habitats in the world, at least with respect to petrochemical contamination (Dumont 1995). Because many of the oil fields developed by the soviets are located in shallow water or in the coastal zone of the Caspian Sea, the extensive contamination of the nearshore environment is considered to be potentially devastating to both human health and the productivity of the fishing industry. There are six species of sturgeon that inhabit the Caspian Sea and that use the
Sediment from a wetland adjacent to an industrial wastewater treatment plant in Sumgayit contained concentrations of total PAHs, total PCBs, aldrin, biphenyl, chlordane, DDT, mercury, beta-endosulfan, heptachlor, alpha-hexacyclohexane (alpha-HCH), gamma-HCH, and several individual PAH congeners that were elevated relative to published sediment quality guidelines. Chemical analyses of tissues from European pond turtles (Emys orbicularis) had increased levels of many of the same chemicals including aldrin, chlordane, heptachlor, alpha-HCH, total PCBs, total PAHs, and mercury, compared to reference turtles. In addition, turtle tissues contained elevated levels of DDD, hexachlorobenzene (HCB), and pentachlorobenzene that were not elevated in the sediment sample. Some differences were observed in contaminant levels between European pond turtles and Caspian turtles (Mauremys caspica) taken from the ponds in Sumgayit. Salmonella/microsome mutagenicity assays on pond sediments were negative or weakly positive. Micronuclei in European pond turtles were statistically correlated with tissue levels of mercury, heptachlor, DDD, HCB, and trans-nonachlor. Microcosm experiments using Russian sturgeon (Acipenser gueldenstaedtii) showed a positive dose-response relationship between exposure to suspended contaminated pond sediment and acute toxicity. Chemical and biological assays used in this study show the industrial area of Sumgayit is heavily contaminated with a complex mixture of toxic pollutants. Exposure to contaminated sediments produced acute effects in Russian sturgeon, but genotoxic effects appear to be slight.
This investigation represents the first extensive study of the spatial distribution and sources of aliphatic (n-alkanes and unresolved complex mixture of fossil hydrocarbons) and polycyclic aromatic hydrocarbons (PAHs) in coastal sediments from the Caspian Sea. PAH concentrations, n-alkanes and biomarker profiles all suggested that there was limited petrogenic contamination in the shallow North Caspian Sea sediments, which are coarse with a low total organic carbon content. In contrast, moderate to high petrogenic contamination was found in the South Caspian Sea, in particular in the offshore oil fields near Baku, Azerbaijan. Contaminant patterns indicated that the PAHs were mainly from fossil sources, with higher contributions of pyrolytic only near industrialized and urban areas. A high contribution of perylene, a geochemically derived PAH, to the total PAHs was found in the west and south at sites influenced by the Kura, Safid Rud, Terek, Sulak and Samur Rivers.
Because of the large size of the former Soviet Union (FSU) and the heavy use of organochlorine pesticides (OCPs) in the FSU, usage information regarding OCPs in the FSU is important in compiling global emission inventories and thus in studying the transport of OCPs among different environmental compartments worldwide. The availability of such information is limited. By analyzing the available 1,2,3,4,5,6-hexachlorocyclohexane (HCH) data in the FSU, this article presents estimates of HCH usage in this region from 1950 to 1990, when HCH was officially banned for agricultural use by the FSU government. The creation of HCH usage inventories for the FSU has paved the way to produce HCH emission inventories for this region. Total HCH usages for agricultural purposes in the FSU from 1950 to 1990 were estimated to be 1,960 kt for technical HCH and 40 kt for lindane. The total usage for the isomers was 270 kt for gamma-HCH, 1,270 kt for alpha-HCH, and 170 kt for beta-HCH. Use of HCH reached a peak in 1965: 130 kt for technical HCH, 2.7 kt for lindane, 18 kt for gamma-HCH, 86 kt for alpha-HCH, and 11 kt for beta-HCH. Gridded usage data sets in the FSU of technical HCH and lindane-and the alpha-HCH, beta-HCH and gamma-HCH isomers-on a 1degree x 1degree longitude and latitude grid system for 1980 are freely available to all users at http://www.msc.ec.gc.ca/data/gloperd/.
DDT (Dichlorodiphenyltrichloroethane), an organochlorine pesticide (OCP), is one of 12 persistent organic pollutants (POPs) that is being proposed for elimination or control under the Stockholm Convention on POPs. This paper presents historical DDT usage in the Former Soviet Union (FSU) from different sources. Although the data from different sources do not agree with each other, the data clearly show that the usage of DDT in the FSU were intensive in the 1950s and 1960s, and the use of DDT continued until early 1990s although DDT was officially banned in 1969/1970 by the FSU government. Two estimations (high and low) are made for the historical annual DDT usage in the FSU. The total DDT usage in the FSU from 1946 and 1990 was 520 kt for the high estimation and 250 kt for the low estimation. Gridded DDT usage inventories in the FSU on a 1 degree longitude by 1 degree latitude grid system are created by using the gridded distribution of cropland density for the FSU, and show that DDT usage varied considerably across the FSU. Most DDT was applied in southern regions of the FSU where agricultural activity was greatest, such as in Moldova and Ukraine followed by the Northern Caucasus region of Russia and the Central Asian republics.
The wetlands of Sumgayit in the Azerbaijan Republic contain complex mixtures of contaminants, including polycyclic aromatic hydrocarbons (PAHs), mercury, organochlorine pesticides, and polychlorinated biphenyls. Marsh frogs (Rana ridibunda) were collected from several contaminated wetlands within the city as well as from two reference sites outside the city. Sediment samples revealed heterogeneous patterns of PAH and mercury concentrations throughout Sumgayit, with the highest levels occurring east of the Sumgayit River, within the industrial zone. Flow cytometry and micronucleus assay revealed elevated estimates of genetic damage in frogs from the wetlands east of the Sumgayit River compared to frogs from the reference sites. Flow cytometric data showed a significant correlation with sediment mercury concentrations, whereas population micronucleus frequencies were significantly correlated with high-molecular-weight PAHs.
The Caspian region and specifically the Apsheron peninsula of Azerbaijan are known to be polluted with a variety of environmental contaminants. These complex mixtures of contaminants make risk assessment difficult. We used the flow cytometry method (FCM) and the micronucleus assay (MN) to assess chromosomal damage in aquatic turtles (Emys orbicularis, the European pond turtle; and Mauremys caspica, the Caspian turtle) inhabiting contaminated wetlands in Azerbaijan. Evidence of genetic damage was found for two sites, Neftchala and Sumgayit, relative to a reference site, Ali Bairamly. Sediment samples from each site were analyzed for PAHs and mercury to evaluate potential contaminant associations with genetic damage. A significant positive correlation was documented between three-ring PAH sediment concentrations and FCM estimates of chromosomal damage in E. orbicularis. These data combine to show that the contaminated wetlands in Sumgayit and Neftchala are genotoxic and that three-ring PAHs are likely a significant influence on observed genotoxicity.
We used molecular methods and population genetic analyses to study the effects of chronic contaminant exposure in marsh frogs from Sumgayit, Azerbaijan. Marsh frogs inhabiting wetlands in Sumgayit are exposed to complex mixtures of chemical contaminants, including petroleum products, pesticides, heavy metals, and many other industrial chemicals. Previous results documented elevated estimates of genetic damage in marsh frogs from the two most heavily contaminated sites. Based on mitochondrial DNA (mtDNA) control region sequence data, the Sumgayit region has reduced levels of genetic diversity, likely due to environmental degradation. The Sumgayit region also acts as an ecological sink, with levels of gene flow into the region exceeding gene flow out of the region. Additionally, localized mtDNA heteroplasmy and diversity patterns suggest that one of the most severely contaminated sites in Sumgayit is acting as a source of new mutations resulting from an increased mutation rate. This study provides an integrated method for assessing the cumulative population impacts of chronic contaminant exposure by studying both population genetic and evolutionary effects.
This conclusion completes one more review concerning the natural condition of the Caspian Sea and the principal trends of change in the second half of the 20th century. The change in the mean sea level variations that occurred in the mid-1970s, when the long-term fall was replaced by a rapid and significant rise, represents an important indicator of the changes in the natural regime of the Caspian Sea, including thermohaline structure, and nutrients and oxygen distribution. The most important consideration is chemical pollution (oil and oil products, phenols, detergents in the North Caspian), which grows with the intensification of human activity on the sea coasts and in the sea proper and represents one of the most hazardous kinds of anthropogenic impact on the Caspian ecosystem. The biological section of the monograph discusses the main problems concerning the biological diversity, the introduced species, and the biological resources. One of the most catastrophic aftereffects of anthropogenic intervention into the Caspian ecosystem is related to the population of sturgeons. Special attention is paid to socioeconomic, legal, and political problems in the Caspian Sea region. The unsettled delineation of the Caspian Sea and the uncertainty in its legal status are the main obstacles to successfully coping with many issues, including environmental protection and preservation of the biological resources.
One of the most important groups of physiologically active compounds, having great significance for the vitality of living organisms, is the amines. The pesticidal properties of various amines and their salts with organic and inorganic acids have been studied.
Historical data on physico-chemical and biological characteristics during the last 30 years were used to examine the seasonal nutrient and plankton dynamics in a semi-enclosed area of the Mediterranean Sea, Elefsis Bay, in phase with the development of intermittently hypoxic and anoxic conditions. Sediment records covering most of the Holocene showed that the area was affected by hypoxia and/or anoxia in the past. However, the occurrence of hypoxia in Elefsis Bay need not necessarily be attributed to anthropogenic activities but could be naturally driven by oceanographic – climate forcing. The ecosystem of the Elefsis Bay seems to be very complicated and variable. Its variability over the last 30 years can be attributed to the differences in anoxia intense and the amount of the accumulated organic material. The first observations in the temporal variations of environmental parameters in the bay primarily reflect the impact of decreasing pollution during the last decade rather than climate variability. On the contrary, the observed variation in the intensity of the hypoxia/anoxia developed in the bay appears to be related to local climate variability. However, this variation, together with the decrease in pollution levels in the bay during the last years, seem to have an effect on the N:P ratio which controls planktonic production.
Data on current and historical usage of α-, β- and γ-hexachlorocyclohexane (HCH ) in Europe are presented. The data were collected and estimated as a part of a project studying the regional cycling of persistent organic pollutants (POPs) in the Baltic environment (Popcycling-Baltic). Better data on sources, environmental discharges and atmospheric emissions of HCH and other POPs are needed to study, and hopefully reduce, the impact of these pollutants on the environment. Substantial uncertainties are assigned to the estimated data for individual countries and years, but it seems likely that the general trend of usage in Europe is captured. The quality of the estimates is thought to improve in general throughout the period, thus, reflecting the availability of reliable data. The results suggest that 382 000 t of technical HCH and 81 000 t of lindane were used in Europe from 1970 to 1996. This is equivalent to an estimated cumulative usage of 259 000 t α-HCH, 135 000 t γ-HCH and 20 000 t β-HCH. The usage of technical HCH was the major source of γ-HCH until the late 1970s, and thereafter lindane became the dominating source of this isomer. The use of γ-HCH in 1996 was estimated to still be nearly one-third of the European usage in 1970. The pattern of decreasing concentrations in biota follows the pattern of reductions in usage for the studied period within the Baltic area.
Accurate and complete information on the emissions of persistent organic pollutants (POPs) are essential for interpreting historical, current and future contamination levels in remote areas. However, this information is also crucial for decision makers aiming at further reduction of the environmental loading of these substances on a regional scale. In this study, we identify and discuss specific POP emission inventory features that are deemed essential to understand, predict and control the behaviour of such substances on a European scale. It is shown that the scientific value of official emission data is limited (e.g. for deriving source–receptor relationships on a European scale), as there is insufficient information on spatial, temporal and compound coverage. Likewise, we argue that non-official emission data (i.e. research-driven emission inventories), which are based on aggregated statistics, may be of limited value for the identification of further emission control strategies. It is thus argued that future emission inventories should be developed in a format that is suitable to
serve both policy- and research-oriented applications. Further improvement of official emission data with respect to research-driven features seems to be the most sensible way to proceed. Finally, the empirical basis of current emission inventories remains weak, and further research on emission identification and characterisation seem needed (a) to gain confidence in predicted source–receptor relationship as well as (b) for the development of sound control strategies.
For the first time, a European historical usage and emission inventory for DDT, HCB, PAH (B[a]P) and dioxins and furans have been approached. This paper presents the estimation methodologies and selected results from the emission inventory, carried out as a part of the EU POPCYCLING-Baltic project. The results indicate a decrease in usage and emissions of all the studied compounds under the investigated time-period. The largest reductions are reported for DDT as a result of national measures introduced in various European countries after the 1970s. The estimated reduction in emissions of PCDD/Fs is 67% from 1970 (24.9 kgI-TEQ/yr) to 1995 (8.3 kgI-TEQ/yr). For B[a]P, the corresponding reduction is 53% from 1970 (1253 t/yr) to 1995 (593 t/yr). Finally, the reduction for HCB emissions was estimated to be 88% from 1970 (192 t/yr) to 1995 (23 t/yr). The decrease in emissions of selected compounds duringthis period is mainly caused by implementation of abatement equipment to reduce emissions (PCDD/Fs, B[a]P), as well as national measures to reduce pesticide consumption (DDT, HCB). However, it is clearly recognised that the empirical basis for these estimates are limited, due to a limited database of emission factors and relevant activity data. Therefore, it is also considered difficult to quantify the uncertainties at present. Thus, the results presented here are affected by substantial uncertainties that require proper consideration by potential users of these estimates (e.g. modellers, decision makers). It is suggested that further efforts should be directed towards the identification and quantitative analysis of uncertainties of the data presented here.
Microbial soil sanitation of hexaclorocyclohexane-polluted calcareous sandy loam soil systems has been investigated. The soil systems involved were aerated moist soil, and continuously aerated and intermittently aerated thick soil slurry. Degradation of alpha HCH appeared to proceed according to a first order reaction, while beta HCH concentrations were not affected. During the first four weeks the degradation of alpha was the fastest for the three soil systems: 40, 80 and 37% respectively, although the soil temperatures were the lowest: 10–15, 12–17 and 10–22°C respectively.The degradation rate gradually decreased even if the temperature increased. Addition of microbial biomass did not affect the alpha HCH degradation to any degree. In a continuously aerated thick slurry system the alpha HCH was reduced from approx. 420 to 15 mg·kg−1.It is concluded that in temporate climate regions alpha HCH degradation occurs, provided the soil is aerobic.
Analysis of observational data of the average monthly discharges, air temperatures, and precipitation totals collected at
about 100 hydrological and meteorological stations before 2005 revealed that precipitation fallen on the Eastern Caucasus
river basins in winter and spring plays the principal role in formation of floods that are observed in the period from April
to June. The precipitation and runoff variability over the territory and altitudinal zones was studied and generalized. The
hydrograph decomposition and the rivers classification according to their sources of feeding in the flooding period were performed.
Analysis of correlation between the flood flow and winter and spring precipitation allowed obtaining reliable multiple regression
equations that are suitable for computation and forecasting of the flood flow.
Persistent organic pollutants (POP) are long-lived organic compounds that become concentrated as they move through the food chain. They have toxic effects on animal reproduction, development and immunological function. Understanding how POPs migrate through the global environment has become the focus of growing national and international concern. It is thus timely to evaluate, modify and extend the various concepts of POP distribution, especially in the view of recently announced international intentions to control the use of such substances. 15 refs., 5 figs., 1 tab.
The global usage of technical HCH and lindane in 1980 and 1990 are presented. The total global usage for technical HCH was estimated to be 40 000 t in 1980 and 29 000 t in 1990, and for lindane it was 5900 t in 1980 and 4000 t in 1990. Based on these data, the global usage of both α-HCH and γ-HCH were calculated. The total usage of α-HCH was around 28 000 t in 1980 and 20 400 t in 1990, while the total usage of γ-HCH was around 11 900 t in 1980 and 8400 t in 1990. The ratio of γ-HCH to α-HCH was 0.43 in 1980 and 0.41 in 1990. The usage data on countries are then mapped to a grid system with 1° × 1° longitude/latitude resolution to be useful for modeling. It is suggested that banning usage of technical HCH by a number of countries, such as China in the early 1980s and the former Soviet Union in the beginning of 1990s, may contribute to the decline of the atmospheric concentrations of both α-HCH and γ-HCH in 1992−1993. While many countries banned use of technical HCH in 1980s, lindane was still used by many countries around world in 1990.
Concentrations of organochlorines such as hexachlorocyclohexanes (HCHs), DDTs, chlordanes, and PCBs were determined in the air and surface water from various oceans in 1989-1990, for understanding their recent distribution and the role of ocean in the long-range atmospheric transport and fate on global terms. The atmospheric concentrations were found to be still higher in the Northern Hemisphere than in the Southern Hemisphere, although the distribution pattern suggested the shift or expansion of their major sources from the mid to low latitudes during the last decade. In surface water, HCHs showed a considerable contamination over 40-degrees-N, whereas DDTs were higher near tropical Asia. Chlordanes and PCBs exhibited rather uniform distributions in both the hemispheres. Estimations of fluxes by gas exchange across the air-water interface gave insight into the dispersal of organochlorines through oceanic atmosphere depending on their Henry's law constants and the tendency of more transportable ones to deposit into the cold waters as an ultimate sink.
The contribution of gross riverine organochlorine pesticide (OCP) transport to estuaries of Russian seas and Lake Baikal was determined to help understand OCP transboundary transfer and to provide a basis for estimating Russia's contribution to global pollution by these pesticides. The official OGSNK/GSN data ranks sea/ocean/lake basins in the following order based upon the amounts of total OCPs received from agricultural use: Eastern Arctic>Western Arctic>Pacific>Baltic>Caspian>Azov/Black>Baikal. A similar ranking was obtained using an independent set of data: Eastern Arctic>Pacific>Caspian>Western Arctic>Baltic>Azov/Black. In terms of riverine flow-associated discharge of HCH isomers (i.e., sum of α-, β- and γ-HCH) estuaries of the Kara, Okhotsk and Beloye (White)/Barents seas received more pesticides than other seas. No HCH was discharged to estuaries of the Eastern Siberian and Bering seas. For DDT and its derivative (DDE), estuaries of the Kara, Caspian, Okhotsk and Baltic seas received the greatest amounts. During our study period (1988–1996), HCH transport was more prevalent in the majority of rivers reflecting both the official ban on the use of DDT in the former Soviet Union and the greater popularity of HCH as a pesticide. In general, it appears that Russian rivers play a significant role in OCP contamination of some estuaries of regional seas, especially those of the eastern Arctic basin, such as the Kara Sea.
Concentrations of selected organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) are reported in air and surface soil in an extensive spatial survey across Azerbaijan, a country bordering the Caspian Sea with a history of OCP production and extensive use. Polyurethane foam disc passive air samplers (PAS) were deployed during October–November 2008 with soil samples collected in July 2009. Levels of Σ7PCB in ambient air were generally low (mean of 0.046 ng m−3, n = 13) and comparable to concentrations reported in countries within Eastern Europe and similar to or lower than concentrations reported in urban air in the UK and other western countries. Surprisingly, PCB concentrations in rural/background soil fell below the method detection limits at most sites, although concentrations were 0.209 and 0.071 ng Σ7PCB g−1 dry weight (dw) for two urban sites, again comparable to PCB levels measured at background sites in Europe. Levels of α-HCH, β-HCH, γ-HCH and p,p′-DDT/E were elevated in ambient air across Azerbaijan in comparison to PAS-derived concentrations reported elsewhere, with concentrations of α-HCH in air ranging from 0.085 to 2.699 ng m−3 and p,p′-DDE, 0.037–2.290 ng m−3. High concentrations of OCPs occurred at several of the urban sites and at sites in proximity to old pesticide storage facilities with concentrations in soil >0.1 μg g−1 dw for p,p′-DDE and p,p′-DDT at several sites. The ratio of p,p′-DDT/p,p′-DDE was close to unity in the soil at these sites, but elsewhere, the ratio was −1 for the HCH isomers (including the β -isomer) and p,p′-DDE. The high levels of OCPs in soils, particularly in the vicinity of obsolete-pesticide storage facilities and at select urban sites are of concern and warrant regular monitoring activities and the development of containment or mitigation strategies.
The relationship between the global technical HCH use trends and their impact on the arctic atmospheric environment has been studied. Two significant drops in global technical HCH usage were identified. In 1983, China banned the use of technical HCH. This represented the largest drop ever in global use rates. In 1990 India stopped technical HCH usage in agriculture and the former Soviet Union banned the use of technical HCH. Since 1990, India has been the biggest user of technical HCH in the world. Significant drops in atmospheric alpha-HCH in the arctic were observed between 1982 and 1983, and again between 1990 and 1992. The rapid response in atmospheric concentrations to usage is encouraging; however, since alpha-HCH concentrations in the arctic waters have remained relatively unchanged, the decline in atmospheric alpha-HCH has reversed the net direction of air-sea gas bur. The accumulated mass in oceans and large lakes may represent a new source of HCH to the arctic atmosphere.
Information on historical and future trends in use and emissions of persistent organochlorines on a global scale is essential for interpreting present and predicting future environmental concentrations of these compounds in remote regions. In this study, which is now a recognized project under the Global Emissions Inventory Activity of the International Geosphere Biosphere Program, information on registration status, trends in regional use/emissions, and mode and time of applications of 10 pesticides is being compiled. Results pertaining to four pesticides are presented here. The cumulative global usage accounted for (in metric tonnes) is 450 000 for toxaphene, 1 500 000 for DDT, 550 000 for technical HCH, and 720 000 for lindane. The interpolated usage of toxaphene and DDT was 1 330 000 and 2 600 000 tonnes from 1950 to 1993 and 670 000 and 990 000 tonnes from 1970 to 1993. The compounds are still legally used in several countries, and illegal use in other countries has been suggested. International cooperation, changes in legislations and regulations, and improved record keeping by governments and other bodies are required to restrict usage, as well as to improve the estimates.
Organochlorine compounds (OCs) such as DDTs (DDT and its metabolites), PCBs (polychlorinated biphenyls), CHLs (chlordane compounds), and HCHs (hexachlorocyclohexanes) were determined in the blubber of Baikal seal (Phoca sibirica) and their fish diet collected from Lake Baikal in 1992. Residue levels of DDTs and PCBs were in the ranges of 4.9-160 mu g/g and 3.5-64 mu g/g on a lipid weight basis, respectively. The concentrations of CHLs and HCHs were approximately 1 or 3 orders of magnitude lower than those of DDTs and PCBs. Comparison of OC residue levels with those reported for other pinnipeds suggests that Baikal seal is highly contaminated species vulnerable to OC toxicity. A positive age-dependent accumulation of DDTs, PCBs, and CHLs was found in males, while a steady state observed in females suggested the transfer of these chemicals from mother to pup through gestation and lactation. On the basis of contaminant burdens in adult seals, it was estimated that an adult female Baikal seal transfers about 20% of its total DDTs and 14% of its total PCBs to the pup during a reproductive process. Based on the data from isomer-specific analysis of PCBs, it can be suggested that Baikal seals have a higher or comparable capacity to metabolize toxic contaminants than marine mammals, but it is apparently lower than terrestrial mammals, which seems to be a causative factor for the higher accumulation of OC residues in this species.
This study focused on accumulation of organochlorine compounds (OCs), including dichloro-diphenyl-trichloroethanes (DDTs), hexachlorobenzene (HCB), hexachlorocyclohexanes (HCHs), and polychlorinated biphenyls (PCBs) accumulation in the muscle of four sturgeon (Persian sturgeon, Acipenser persicus; Stellate sturgeon, Acipenser stellatus; Ship sturgeon, Acipenser nudiventris and Beluga sturgeon, Huso huso) from the southern Caspian Sea. The DDT group was prominent in all of the sturgeon muscle tested constituting almost half or more of the total organochlorine content. Contaminant concentration generally followed this order: DDTs>PCBs>HCHs>HCB. The OCs concentrations in Beluga sturgeon (H. huso) were the highest and over four times higher than in the next highest species (A. nudiventris). From an ecotoxicological point of view, the concentrations of OCs in experimental fishes do not reflect a comparatively clean and pollution-free environment; however, results from this study shown that the inflow of organic pollutants into the Caspian Sea has been reduced when compared with prior studies. Levels of measured OCs in sturgeon were relatively low, but the level of some OCs in some of the specimens tested exceeded the guidelines for food; therefore, the maximum allowable daily consumption rate for sturgeon from this watershed may be limited by DDTs and PCBs content for high risk populations.
Control strategies for these contaminants will require a better understanding of how they move around the globe.
This review investigates the fate and behaviour of endosulfan, a current-use organochlorine pesticide, in temperate environments and the Arctic. Usage data and patterns, physical–chemical properties, environmental partitioning and degradation, environmental levels, global distribution and temporal trends are evaluated and discussed in the context of criteria that designate a substance as a persistent organic pollutant. Endosulfan is one of the most abundant OC pesticides in the global atmosphere and is capable of undergoing long range transport to remote locations such as the Arctic. Degradation of the two isomers, α- and β-endosulfan, does occur in temperate/tropical soil and aquatic systems, both by abiotic and biotic processes, although this is highly dependent on the prevailing environmental conditions. Endosulfan sulfate is the major metabolite and this recalcitrant compound has been detected in air and is present in remote mountain lake sediments, although in comparison to α-endosulfan, data for this compound in the wider environment are lacking.
Data on current and historical usage of alpha, beta, and gamma-hexachlorocyclohexane (HCH) in Europe are presented. The data were collected and estimated as a part of a project studying the regional cycling of persistent organic pollutants (POPs) in the Baltic environment (Popcycling-Baltic). Better data on sources, environmental discharges and atmospheric emissions of HCH and other POPs are needed to study, and hopefully reduce, the impact of these pollutants on the environment. Substantial uncertainties are assigned to the estimated data for individual countries and years, but it seems likely that the general trend of usage in Europe is captured. The quality of the estimates is thought to improve in general throughout the period, thus, reflecting the availability of reliable data. The results suggest that 382,000 t of technical HCH and 81,000 t of lindane were used in Europe from 1970 to 1996. This is equivalent to an estimated cumulative usage of 259,000 t alpha-HCH, 235,000 t gamma-HCH and 20,000 t beta-HCH. The usage of technical HCH was the major source of gamma-HCH until the late 1970s, and thereafter lindane became the dominating source of this isomer. The use of gamma-HCH in 1996 was estimated to still be nearly one-third of the European usage in 1970. The pattern of decreasing concentrations in biota follows the pattern of reductions in usage for the studied period within the Baltic area.
Polychlorinated biphenyls (PCBs), organochlorine pesticides and organotin compounds were determined in the blubber and liver of Caspian seals (Phoca caspica) found stranded on the coast of the Caspian Sea during an outbreak of canine distemper virus (CDV) in 2000. Among organochlorines analyzed, DDTs were the most dominant contaminants with concentrations ranging from 6.3 to 470 microg/g on a lipid-weight basis. Caspian seals collected in 2000 during the epizootic had higher concentrations of organochlorines than healthy individuals sampled in 1998. However, the blubber layer was generally thinner in the seals collected in 2000 than those in the previous surveys. Although compositions of organochlorine pesticides in seals suggested that the contamination status in the Caspian Sea is improving, the levels found in Caspian seals in 2000 were comparable to those in other marine mammals that have suffered from epizootics. This implies that the present status of contamination found in Caspian seals poses a risk of immunosuppression. Concentrations of butyltin compounds in livers of seals ranged from 0.49 to 17 ng/g on a wet-weight basis and octyltin compounds were below limit of detection in all the samples analyzed, suggesting less contamination by organotin compounds in the Caspian Sea.
Organochlorine compounds (OCs) were determined in the five species of sturgeons collected from coastal waters of Caspian Sea in Kazakhstan, Azerbaijan, Turkmenistan and Iran during 2001 and 2002 to understand their status of contamination and accumulation features. Among OCs examined, concentrations of DDTs (DDT and its metabolites) were predominant in all the sturgeon samples with concentrations ranging from 73 to 31,000 ng/g on lipid weight basis, followed by PCBs, CHLs, HCHs, HCB, dieldrin, TCPMOH, and heptachlor epoxide in order. The concentrations of OCs in beluga (Huso huso) were the highest among all the five species. When comparing residue levels among same species, OC residues were highest in sturgeons from Azerbaijan and Kazakhstan and lowest in Turkmenistan. However, the concentrations of HCHs, dieldrin, and heptachlor epoxide in sturgeons showed less geographical variability.
Several organochlorinated contaminants, including numerous pesticides, were determined in coastal sediments from the Caspian Sea. The most important contaminants were p,p'-DDT (up to 7400 pg g(-1)) and its breakdown products, p,p'-DDD (up to 3400 pg g(-1)) and p,p'-DDE (up to 1300 pg g(-1)). Although the contamination was most severe in Azerbaijan, the sediment concentrations and percentage distribution of the three DDT-related compounds indicated that such contamination constitutes a contemporary and ubiquitous problem in the Caspian Sea. Lindane represented the second most significant contaminant, particularly in the Russian Federation, with concentrations up to 609 pg g(-1). The concentrations of HCB and other chlorinated pesticides (cis- and trans-chlordane, methoxychlor, heptachlor, heptachlor epoxide, aldrin, endrin, and endosulfans) were lower and not generally of concern, but the pesticides did demonstrate markedly different distributions reflecting differing agricultural usage in the region. The concentrations of Sigma PCBs were also quite low and ranged from 0.03 to 6.4 ng g(-1), with the highest amounts in the Russian Federation and Azerbaijan.
Organochlorine contaminants (pesticides and individual polychlorinated biphenyl congeners, PCBs) were measured in Caspian (Phoca caspica) seal blubber and compared with concentrations in Harbour (Phoca vitulina) seal blubber. Concentrations of total dichlorodiphenyltrichloroethane (DDT) and its metabolites were significantly higher in Caspian seal than Harbour seal samples, whereas PCB congeners were significantly higher in Harbour than Caspian seals. Our finding suggests that Caspian seals are exposed to high levels of DDT pesticides. In contrast, PCBs are circulating in this population at much lower levels than in marine mammals from the North Sea.
Historical global usage and emissions for organochlorine pesticides (OCPs), including hexachlorocyclohexanes (HCHs), dichlorodiphenyltrichloroethane (DDT), toxaphene and endosulfan, are presented. Relationships between the air concentrations of these OCPs and their global emissions are also discussed. Differences between the pathways of alpha- and beta-HCH to the Arctic Ocean are described in the context of environmental concentrating and diluting processes. These concentrating and diluting processes are shown to control the temporal and spatial loading of northern oceans and that the HCH burdens in marine biota from these oceans respond accordingly. The HCHs provide an elegant example of how hemispheric-scale solvent switching processes can alter the ocean into which an HCH congener partitions, how air-water partitioning controls the pathway for HCHs entering the Arctic, and how the various pathways impact spatial and temporal trends of HCH residues in arctic animals feeding out of marine and terrestrial foodwebs.
For legacy and emerging persistent organic pollutants (POPs), surprisingly little is still known in quantitative terms about their global sources and emissions. Atmospheric transport has been identified as the key global dispersal mechanism for most legacy POPs. In contrast, transport by ocean currents may prove to be the main transport route for many polar, emerging POPs. This is linked to the POPs' intrinsic physico-chemical properties, as exemplified by the different fate of hexachlorocyclohexanes in the Arctic. Similarly, our current understanding of POPs' global transport and fate remains sketchy. The importance of organic carbon and global temperature differences have been accepted as key drivers of POPs' global distribution. However, future research will need to understand the various biogeochemical and geophysical cycles under anthropogenic pressures to be able to understand and predict the global fate of POPs accurately.
Persistent organic pollutants including organochlorine pesticides, PCBs, and PCDDs/DFs were determined in the blubber of Caspian seals, which died during an outbreak of canine distemper virus in 2000 and 2001. DDTs were the predominant contaminants that ranged from 3.1 to 560 microg/g lipid. A negative correlation was observed between concentration of contaminants and blubber thickness. During spring, as the blubber layer becomes thin after breeding and moulting, seals may face higher risk due to the increased concentration of organochlorines in their bodies. TEQs in the blubber of Caspian seals (10-340 pg TEQ/g) were lower than those in seals from other locations, suggesting that toxic effects of these contaminants are a deal less in the present population and they are unlikely to be linked to mass mortality. The levels of PCBs and pesticides in Caspian seals, however, comparable to those in other aquatic mammals that have suffered from epizootics, might pose a risk of immunosuppression.
HCH situation in Russian Federation Paper presented at the 3rd HCH and Halogenated Pesticides Forum http://www.ihpa.info/docs/library/forumbooks/3rd/3rdForum_Bilbao_Part1
- Ad Pokarzhevskii
- Florinskii
Report on POPs that are related to the United Nations Stockholm Convention on POPs
- Azerbaijan
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EECCA Obsolete Pesticides Training and Repack-aging Pilot Project -Azerbaijan. Mission Report 9th–16th For the EECCA project team Organochlorinated compounds in Caspian Sea sediments
- Un Cobban
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Cobban R (2011) EECCA Obsolete Pesticides Training and Repack-aging Pilot Project -Azerbaijan. Mission Report 9th–16th March 2011. For the EECCA project team and UN FAO AGMP. de Mora S, Villeneuve J-P, Villeneuve M, Cattini C, Tolosa I (2004) Organochlorinated compounds in Caspian Sea sediments. Mar Pollut Bull 48(1–2):30–43 de
HCH situation in Russian Federation. Paper presented at the 3rd HCH and Halogenated Pesticides Forum
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Pokarzhevskii AD, Florinskii MA (1994) HCH situation in Russian
Federation. Paper presented at the 3rd HCH and Halogenated
Pesticides Forum, 19-20 September, 1994, Bilbao, Spain http://
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Hazard-ous pollutant database for Kura–Araks water quality management Transboundary Water Resources: a Foundation for Regional Sta-bility in Central Asia Chemical contam-inants and their effects in fish and wildlife from the industrial zone of Sumgayit, Republic of Azerbaijan
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Suleymanov B, Ahmedov M, Humbatov F, Ibadov N (2008) Hazard-ous pollutant database for Kura–Araks water quality management. Transboundary Water Resources: a Foundation for Regional Sta-bility in Central Asia. Springer, Dordrecht Swartz CD, Donnelly KC, Islamzadeh A, Rowe GT, Rogers WJ, Palatnikov GM, Mekhtiev AA, Kasimov R, McDonald TJ, Wickliffe JK, Presley BJ, Bickham JW (2003) Chemical contam-inants and their effects in fish and wildlife from the industrial zone of Sumgayit, Republic of Azerbaijan. Ecotoxicology 12 (6):509–521
Pesticides—the toxic blow against the biosphere and man. Publishing House 'Nauka', Moscow, ISBN 5-02-00441-S Fedorov L, Yablokov A (2004) Pesticides: the chemical weapon that kills life (The USSR's tragic experience)
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Fedorov L, Yablokov A (1999) Pesticides—the toxic blow against the biosphere and man. Publishing House 'Nauka', Moscow, ISBN 5-02-00441-S Fedorov L, Yablokov A (2004) Pesticides: the chemical weapon that kills life (The USSR's tragic experience). Pensoft, Sofia-Moscow, 9546422053
Pesticide usage in the former USSR: a report prepared for Environment Canada Sources and pathways of selected organochlorine pesticides to the Arctic and the effect of pathway divergence on HCH trends in biota: a review
- Yi Kundiev
- Ys Kagan
- Toronto
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- Rw Macdonald
Kundiev YI, Kagan YS (1993) Pesticide usage in the former USSR: a
report prepared for Environment Canada. Toronto, Ontario, Canada
Li YF, Macdonald RW (2005) Sources and pathways of selected
organochlorine pesticides to the Arctic and the effect of pathway
divergence on HCH trends in biota: a review. Sci Total Environ
342(1-3):87-106
Aliphatic and aromatic hydrocarbons in coastal Caspian Sea sediments Environmental Performance Reviews Series No. 31, Azerbaijan. Second Review Caucasus Environment Outlook
- I S Mora
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