Bioremediation and Bioeconomy

book.

Section 1

Bioproducts from Contaminated Substrates (Soil and Water)

Chapter 1

Production of Biodiesel Feedstock from the Trace Element Contaminated Lands in Ukraine

O. Sytar¹; M.N.V. Prasad²    ¹ Kyiv National University of Taras Shevchenko, Kyiv, Ukraine

² University of Hyderabad, Hyderabad, Telangana, India

Abstract

The modern situation regarding possible production of biodiesel feedstock from the trace element-contaminated lands in Ukraine has been studied. This chapter presents the monitoring of heavy metal pollution in Ukraine based on the available literature of national and international scientific reports. The monitoring analysis shows Pb, Cr, and Cu are dominant contaminants/pollutants. In Ukraine the regions of Kharkiv, Zaporizhia, Donetsk, and Chernivtsi show a high level of Cr due to their high concentration of industries. In many areas of Ukrainian territory, the content of Ni, Zn, and Co in the soil is at less than maximal permissible level. In Ukraine the sunflower, rapeseed, and soybean are the most widespread oilseed crops that are possible to use for phytoremediation process and production of biodiesel and biogas. Last year Ukraine managed to improve oilseed yields (especially rapeseed) after their initial decline following the collapse of the Soviet Union. The biodiesel produced from oilseed crops is discussed. The source of biodiesel usually depends on the crops amenable to the regional climate. The comparative characteristics of different quality parameters of biodiesel from the United States, Brazil, EU countries, and Ukraine have been presented.

Keywords

Heavy metals

Polluted agrocenose

Phytomanagement

Soybean

Sunflower

Rapeseed

Biodiesel

Acknowledgments

Thanks are due to the European Environment Agency and the UNEP Regional Office for Europe for authorization to use contaminated soil map. The authors would like to thank Paul Prasad Chandramohan, for his helpful comments and assistance.

1 Introduction

The total area of Ukraine is about 60.37 million ha of which agricultural land is 41.76 million ha. Ukraine has several rivers and lakes. The prominent crops cultivated for grain production are winter rye, oats, corn, barley, and buckwheat (in recent years about 15% of the world’s production has come from Ukraine). Flax, hops, sugar beets, and potatoes are other important crops in Ukraine. Soybean, rapeseed, and sunflower production has increased in recent years, boosting agro-based economy (Figure 1).

Figure 1 Primary feed-stock for production of biodiesel in Ukraine.

After the Chernobyl accident in 1986, the trace element pollution and contamination in Ukraine received considerable attention. In total, air pollution-related mortality represents about 6% of total mortality in Ukraine (Mnatsakanian, 1992; Strukova et al., 2006). In the Donets Basin (48.3°N, 38.0°E) of eastern Ukraine, there are about 1200 mine-waste dumpsites, mostly from coal mining. These have accumulated over more than 200 years of mining (Panov et al., 1999). Ore processing and the use of metal-enriched coal in coal-fired electric generation and home heating have led to widespread contamination of the environment (Panov et al., 1999; Kolker et al., 2009). Of the 26 elements considered to be pollutants in the Donets Basin, arsenic (As) and mercury (Hg) are of primary concern; most of the As-polluted soils in this region are near burning-coal waste heaps (Panov et al., 1999; Conko et al., 2013). For more than 50 years, the largest Hg production facility of the former Soviet Union operated in Horlivka (Gorlovka, Russian spelling), a city of approximately 300,000 residents in the Donets Basin. During this period, about 30,000 metric tons of Hg were produced from ore extracted from the adjacent Mykytivka (Nikitovka) mines.

The contaminated land that is unsuitable for food production and of little or no economic return could be used for the production of bioenergy. The problem of competition for fertile land can be alleviated by using contaminated land for the production of bioenergy plants.

Using biomass for fuel production is an attractive option for three main reasons. First, it is a renewable resource and thus its development could be sustained in the future. Second, because there is no net release of carbon dioxide and sulfur contents are low, it is environmentally attractive. Thirdly, given the rise in fossil fuel prices, it is also economically advantageous (Demirbas, 2009).

This review chapter presents the nowadays situation of heavy metals pollution on Ukraine territory and the possibility of using oilseed crops (rapeseed, soybean, and sunflower) for 50% cleanup of the areas polluted by heavy metals.

2 Monitoring of Heavy Metals Pollution in Ukraine

The report of EEA-UNEP (2000) regarding the status of soil contamination in Europe (Figure 2) has shown that in Eastern Europe problems of diffuse soil contamination is greatest compared to other European countries. The high contamination of heavy metals is shown in Ukraine, especially in the Chernobyl area. Unfortunately, the international literature is still missing detailed analysis of heavy metals contamination in Ukraine.

Figure 2 Probable problem areas of diffuse contamination in Europe (EEA-UNEP, 2000) * - agricultural areas which can use chemical during plant cultivation.

The Ministry of Nature Protection of Ukraine reported that lead concentrations in the capital city of Kyiv were 4.6 times higher than the permissible limit. It was reported that the main source of lead in the air and soil is from automobile activities. Major sources of lead include gasoline combustion, also nonferrous smelting, and mining (Chiras, 2009).

About 90% of toxic metals accumulate from atmosphere to soil, where they migrate in groundwater, become absorbed by plants, and get into the trophic chains (Lozanovskaya et al., 1998; Anonymous, 1998; Trahtenberg, 1998; Alekseeva, 1987). According to coefficient of load factor, it has been established that in some regions of Ukraine the level of metal pollution of soil, including mobile forms, exceeds the permissible level by 2-14 times (Gaevsky and Pelypets, 1999; Nikolaychuk and Hrabovsky, 2000). In particular, the content of lead in soils of northern agricultural regions (Zhytomyr, Sumy, Rivne, Chernihiv, and Kyiv) exceeds the permissible level by 3 to 9 times (Shestapalov et al., 1996). A similar tendency is observed for soil in the region of Kyiv Polesye, where concentration of metal exceeds the natural level by 3 times (Brooks, 1982; Shestapalov et al., 1996) (Figure 3).

Figure 3 The map of lead pollution on territory of Ukraine.

Second place among heavy metals highly contaminating Ukraine soil is nickel. It’s known that the main anthropogenic source of nickel emission is combustion of fossil fuels and traffic (Krstić et al., 2007). Nickel is widely used in silver refineries, alloy, pigments electroplating, zinc-based casting, and storage batteries too, which also can have the effect of increasing nickel pollution.

The greatest Ni content found in soils of the regions of Zhytomyr, Kyiv, Zaporizhia Donetsk, and Lugansk (in the soil 25-50 mg/kg when maximal permissible level 50 mg/kg) Figure 2. At these regions it is possible to get relatively safe crops with tolerance to Ni but in limited quantities. The agricultural land Volyn, Poltava, Vinnytsia, and partly other regions have pollution levels 5-10 and 10-15 mg/kg of soil areas for ecological agriculture nowadays. In these areas it is possible to grow vegetable raw materials suitable for the production of baby food. Soils with the average pollution level of Ni (15-25 mg/kg) (Figure 2) are mainly distributed in Chernihiv, Sumy, Zaporizhya, Ivano-Frankivsk, Rivne, and Transcarpathian region (Anonymous, 2004). High level of copper found in Kiev, Chernihiv, Zgytomyr, Volyn, Zakarpatiya regions. Chernivtsi, Kharkiv, Donetsk and Zaporizhya resgins has been characterized high level of chromium (Figure 3). In the Ivano-Frankivsk region, Pb concentrations exceed toxic levels in the areas close to industrial sectors (10% of the region territory). Local background levels of heavy metals are greatly exceeded in snow close to industrial regions. Cd and Mo accumulate in forest soils in the Ukrainian Carpathians region (Shparyk and Parpan, 2004) (Figure 3). A similar situation has been observed with pollution of soil with Zn and Co. The maximal permissible level of Zn and Co in air is 300 and 50 Clarke, respectively (Clarke is unit of each element and in soil it is 50 and 8 mg/kg, respectively). In general, for these three heavy metals (Ni, Zn, and Co) in many areas of Ukrainian territory their content in the soil is at less than maximal permissible level (Figures 4 and 5).

Figure 4 The map of nickel pollution on territory of Ukraine.

Figure 5 The map of copper and chromium pollution on territory of Ukraine.

It’s known that the maximum permissible level of Pb in soil is 30 mg/kg of dry soil (Samokhvalova et al., 2001). The limits of maximum permissible level depend on the complex of soil and ecological conditions, among which the most important are soil pH and content of hummus (Glazovskaya, 1994; Kabata-Pendias and Pendias, 1989; Obuhov et al., 1980). It has been proved that the main quantity of heavy metals is concentrated in the upper layer of arable soil (0-10 cm) (Glazovskaya, 1994; Trahtenberg, 1998). The period of heavy metal removal from soil is near 740 to 5900 years (for example, cadmium and lead) (Dobrovolsky, 1997). Most inorganic compounds of Pb and Cd are insoluble or poorly soluble in water. However, their dissolubility depends on soil pH. Dissolubility reaches a 4.0, but in the range of 6.5-8.0, dissolubility declines distinctly, but after further increasing of pH, slightly increases (Glazovskaya, 1994). The redox system, level of gross content, and the granulometric composition of soil have an influence on solubility of heavy metal compounds in the soil (Lysenko et al., 2001). Soils serve as a comprehensive geochemical barrier that keeps solid compounds and water-soluble compounds of heavy metals in the form of organo-mineral, mineral complexes, and compounds (Glazovskaya, 1994). It is known that soil has a buffer capacity as to toxic effect of pollutants, which provides for transformation of pollutants at not-soluble forms for plants. Granulometric structure of soil rich in organic matter and carbonate usually has the highest buffer capacity (Grakovsky et al., 1994).

3 Economical Background of Biodiesel Production in Ukraine and in the World

It is known that humus-rich black soil of Ukraine is world famous. Since the dissolution of the Soviet Union with ongoing land reform and decreasing activity in the agriculture sector, Ukraine has not been making full use of its agricultural potential (Schaffartzik et al., 2014).

Ukraine is often singled out for its potential as a supplier of agricultural goods to the EU region. 42 of 60 Mha of Ukraine can be used for crop production (Elbersen et al., 2009). At 0.7 hectare per person (ha/cap), Ukraine has more land available than any other European country, except for Russia (0.9 ha/cap), significantly surpassing France (0.3 ha/cap) and Germany (0.1 ha/cap) (FAOSTAT, 2012), for example. The country’s geographical location as neighbor to the countries of the European Union and its access to the Black Sea is additionally advantageous to its role as a global supplier of biomass resources. Ukraine is a major exporter of agricultural primary products: In 2010 and in physical units, it ranked second among the international top exporters of barley, third among the exporters of rapeseed, seventh for exports of sunflower seed, and ninth among the exporters of wheat. Rapeseed production and exports drastically increased from 2004 onwards and grew by a factor of almost 20 until 2008 (FAOSTAT, 2012).

In Ukraine the sunflower, rapeseed, and soybean are the most widespread oilseed crops that can be used for phytoremediation process and production of biodiesel and biogas. In Eastern Europe, problems of diffuse soil contamination are greatest in Azerbaijan, Belarus, Moldova, Russia, and Ukraine (Denisov et al., 1997). In the total cultivation area of these crops in Ukraine, the area of heavy metals-contaminated soils is approximately 15-20%.

At the same time biofuels are currently not produced or consumed in relevant amounts within Ukraine. Yet in Ukraine potential is mainly as an alternative to liquid fossil fuel use and not to the use of natural gas and coal in industrial applications and electricity generation. The production of biofuel requires energy inputs. But the biggest advantage that biodiesel has over gasoline and petroleum diesel is its environmental friendliness. Biodiesel burns similar to petroleum diesel as it concerns regulated pollutants. On the other hand, biodiesel probably has better efficiency than gasoline. One such fuel for compression ignition engines that exhibits great potential is biodiesel. Diesel fuel can also be replaced by biodiesel made from vegetable oils. Biodiesel is now mainly being produced from soybean, rapeseed, and palm oils.

The higher heating values (HHVs) of biodiesels are relatively high. The HHVs of biodiesels (39-41 MJ/kg) are slightly lower than that of gasoline (46 MJ/kg), petrol diesel (43 MJ/kg), or petroleum (42 MJ/kg), but higher than coal (32-37 MJ/kg). Biodiesel has over double the price of petrol diesel (Demirbas, 2007). The major economic factor to consider for input costs of biodiesel production is the feedstock, which is about 80% of the total operating cost. The high price of biodiesel is in large part due to the high price of the feedstock. Economic benefits of a biodiesel industry would include value added to the feedstock, an increased number of rural manufacturing jobs, increased income taxes, and investments in plant and equipment.

The production and utilization of biodiesel is facilitated first through the agricultural policy of subsidizing the cultivation of nonfood crops (rapeseed, for example). Second, biodiesel is exempt from the oil tax. The European Union in 2005 got nearly 89% of all biodiesel production worldwide. Germany produced 1.9 billion liters or more than half the world total. In Germany biodiesel is also sold at a lower price than fossil diesel fuel. Biodiesel is treated like any other vehicle fuel in the UK. Other countries with significant biodiesel markets included France, the United States, Italy, and Brazil. All other countries combined accounted for only 11% of world biodiesel consumption. By 2004, the United States is expected to become the world's largest single biodiesel market, accounting for roughly 18% of world biodiesel consumption, followed by Germany (EBB, 2004). For Ukraine with its very low share of renewables in TPES, the promise of reduced environmental burdens is especially appealing (Schaffartzik et al., 2014).

Rapeseed, as an important feedstock for biofuel, contributed only about 2% to the agricultural Ukrainian harvest in 2008 but wheat, maize, sugar beets, and sunflower seeds (all also potential feedstock for biofuel production) figured much more prominently. Yet, while overall agricultural production decreased, rapeseed production grew by factor 65 between 1993 and 2008. Almost all of this production is designated for export. In 2008, 83% of Ukraine's direct material input of rapeseed was exported. In 2009, this share reached 99% (calculations by the authors based on data extracted from FAOSTAT (2012)).

The production of oilseeds in Ukraine has increased considerably during the last decade and with respect to sunflower seed in 2013 with total cultivation area 5051 thousand hectares and yield 21.7 centner per hectare (State Statistics Service of Ukraine, 2013). Ukraine is one of the biggest sunflower producers in the world besides Russia and the EU. From the mid-2000s onward, production of rapeseed also increased significantly (from about 0.14 million tons in 2000 to about 1.5 million tons in 2010) (van Leeuwen et al., 2012). The total oilseeds area harvested in Ukraine is projected to grow only slightly over the projection period. While the area for sunflower seeds is projected to actually decrease after 2015, more land will be allocated to rapeseed and soybeans (Figure 5).

Ukraine is considered an important (potential) source of rapeseed for the European market (Nekhay, 2012). Yields for this crop in Ukraine, however, are lower than in almost any other European country with the exception of Russia. While, in 2010, Germany was able to harvest 3.9 t/ha of rapeseed, harvest in Ukraine only amounted to 1.7 and in Russia to 1.1 t/ha. Özdemir et al. (2009) calculate biofuel yield in tons of oil equivalent per hectare and year as the gross energy yield in the period from 2000 to 2007 and found that Ukraine’s rapeseed yield is consistently lower than that of the EU. In the dry southern part of Ukraine, the attainable biofuel energy yields are among the lowest in Europe at around 40 gigajoules per hectare (GJ/ha) (Fischer et al., 2010b). Although Ukraine managed to improve rapeseed yields after their initial decline following the collapse of the Soviet Union, the focus of expanding rapeseed production was on extensification rather than on the intensification required for improving yields (World Bank, 2008). The climatic risk of winter kill in many areas of the country adds to the decreasing attractiveness of this crop for farmers.

Figures 6–8 show the yield patterns of the oilseeds. Also based on former trends, oilseed yields are projected to grow faster than cereals yields.

Figure 6 Rape-seed oil production in Ukraine (Myrna van Leeuwen et al., 2012).

Figure 7 Soybean oil production in Ukraine (Myrna van Leeuwen et al., 2012).

Figure 8 Sunflower oil production in Ukraine (Myrna van Leeuwen et al., 2012).

Although there are currently rumors of Chinese investments into the distillation of bioethanol in Ukraine, and a cooperation agreement was signed in Spring 2013 between the Finnish and the Ukrainian governments to foster biofuel production (Schaffartzik et al., 2014), foreign engagement and investment continue to be stronger for production feedstock than for fuels. For instance, in Ukraine there is no direct support for the production of fuels through the European Bank for Reconstruction and Development (EBRD); the bank is, however, an important credit grantor in the agricultural sector (EBRD, 2013). Moreover, Germany in particular has supported crop production in Ukraine in the past, for example through a GIZ project on sustainable biofuel production (IER, 2010) as well as through seminars and conferences on (sustainable) biofuel production embedded in the activities of the German-Ukrainian Agricultural Policy Dialogue (APD, 2013). This is due to the fact that according to the Renewable Energy Directive (European Parliament and Council, 2009) liquid biofuels have to follow certain sustainability criteria (e.g., sustainable crops must not be grown on areas with high biodiversity or with high existing carbon stock). The economic and social benefits that Ukraine can gain from its agricultural sector depend very strongly not just on the development of that sector itself but also on the benefits gained from the further use of this output. As a producer of rapeseed (and other crops) for the global market and thus as a producer of biofuel feedstock for other economies, Ukraine can follow the trajectory of other economies dependent on primary commodity exports (Schaffartzik et al., 2014).

4 Biodiesel Produced from Oilseed Crops

Plant triacylglycerols are energy-rich compounds of reduced carbon available from nature. Most plant oils are derived from triacylglycerols stored in seeds (Srivastava and Prasad, 2000; Demirbas, 2006). During seed development, photosynthate from the mother plant is imported in the form of sugars, and the seed converts these into precursors of fatty acid biosynthesis. Given their chemical similarities, plant oils represent a logical substitute for conventional diesel, a nonrenewable energy source. However, as plant oils are too viscous for use in modern diesel engines, they are converted to fatty acid esters. Most plant labels have a viscosity range that is much higher than that of conventional diesel: 17.3-32.9 mm²/s compared to 1.9-4.1 mm²/s, respectively (Knothe and Steidley, 2005). The fatty acid methyl esters (FAMEs) found in biodiesel have a high energy density as reflected by their high heat of combustion, which is similar, if not greater, than that of conventional diesel (Knothe, 2005). Similarly, the cetane number (a measure of diesel ignition quality) of the FAMEs found in biodiesel exceeds that of conventional diesel (Knothe, 2005).

The higher oxygenated state compared to conventional diesel leads to lower carbon monoxide (CO) production and reduced emission of particulate matter (Graboski and McCormick, 1998). This latter air pollutant is especially problematic in European cities, motivating temporary curfews for diesel-powered vehicles. Biodiesel also contains little or no sulfur or aromatic compounds; in conventional diesel, the former contributes to the formation of sulfur oxide and sulfuric acid, while the aromatic compounds also increase particulate emissions and are considered carcinogens. In addition to the reduced CO and particulate emissions, the use of biodiesel confers additional advantages, including a higher flashpoint, faster biodegradation, and greater lubricity (EBB, 2004; Demirbas, 2007). Therefore, plant oil production needs to be greatly increased for biodiesel to replace a major proportion of the current and future fuel needs of the world.

The source of biodiesel usually depends on the crops amenable to the regional climate. Biodiesel is the monoalkyl esters of long-chain fatty acids derived from renewable feedstocks, such as vegetable oil or animal fats, for use in engine. Biodiesel is composed of FAMEs that can be prepared from triglycerides in vegetable oils by transesterification with methanol. The biodiesel is quite similar to conventional diesel fuel in its main characteristics (Meher et al., 2006). In the United States, soybean oil is the most commonly grown biodiesel feedstock, whereas the rapeseed (canola) oil and palm oil are the most common source for biodiesel in Europe and in tropical countries, respectively (Knothe, 2002). However, any vegetable oil—corn, cottonseed, peanut, sunflower, safflower, coconut, or palm—could be used to produce biodiesel (Demirbas, 2006). From a chemical point of view, oils from different sources have different fatty acid compositions. The fatty acids vary in their carbon chain length and in the number of unsaturated bonds they contain (Table 1). Fats and oils are primarily water-insoluble, hydrophobic substances in the plant and animal kingdom that are made up of one mole of glycerol and three moles of fatty acids and are commonly referred as triglycerides.

Table 1

Fatty Acid Composition of Rapeseed, Sunflower, and Soybean Oil from Different Sources (%)

a,b,c data regarding fatty acids content were not available

Twenty-one fatty acids are screened in all the samples. The fatty acids commonly found in vegetable oil and fat are stearic, palmitic, oleic, linoleic. Other fatty acids that are also present in many of the oils and fats are myristic (tetradecanoic), palmitoleic, acachidic, linolenic, and octadecatetraenoic. Many other fatty acids are also found in oils with the above-mentioned common fatty acids. Erucle fatty acid is found only in three oils: crambe, camellia oil, and Brassica carinata. In the oil of sunflower and soybean, the content of the fatty acid is different in the same plant species, which may be due to either the varietal or instrumental difference or in the different parts of plants.

Chemically the oil/fats consist of 90-98% triglycerides and small amount of mono- and diglycerides. Triglycerides are esters of three fatty acids and one glycerol. These contain a substantial amount of oxygen in their structures. When three fatty acids are identical, the product is simple triglycerides; when they are dissimilar, the product is mixed triglycerides, fatty acids which are fully saturated with hydrogen have no double bonds. Fatty acids with one missing hydrogen molecule have one double bond between carbon atoms and are called monosaturated. The fatty acids that have more than one missing hydrogen molecule or have more than one double bond are called polyunsaturated. Fully saturated triglycerides lead to excessive carbon deposits in engines. The fatty acids are different in relation to the chain length, degree of unsaturation, or presence of other chemical functions. Chemically, biodiesel is referred to as the mono alkyl esters of long-chain fatty acids derived from renewable lipid sources. Biodiesel is the name for a variety of ester-based oxygenated fuel from renewable biological sources. It can be used in compression ignition engines with little or no modification (Demirbas, 2002).

Biodiesel is made in a chemical process called transesterification, in which organically derived oils (vegetable oils, animal fats, and recycled restaurant greases) are combined with alcohol (usually methanol) and chemically altered to form fatty esters such as methyl ester. Biodiesel consists of alkyl (usually methyl) esters instead of the alkanes and aromatic hydrocarbons of petroleum-derived diesel. Diesel has no oxygen compound. It is a good quality of fuel (Singh and Singh, 2010).

Oil, ester, and diesel have different numbers of carbon and hydrogen compounds. On the other hand, in the case of vegetable oils oxidation resistance is markedly affected by the fatty acid composition. The large size of vegetable oil molecules (typically three or more times larger than hydrocarbon fuel molecules) and the presence of oxygen in the molecules suggest that some fuel properties of vegetable oil would differ markedly from those of hydrocarbon fuels (Goering et al., 1982).

Since biodiesel is produced in quite differently scaled plants from vegetable oils of varying origin and quality, it was necessary to create standards for fuel quality to guarantee engine performance without any difficulties. Austria was the first country in the world to define and approve the standards for rapeseed oil methyl esters as diesel fuel. As standardization is a prerequisite for successful market introduction and penetration of biodiesel, standards or guidelines for the quality of biodiesel has also been defined in other countries such as Germany, Italy, France, the Czech Republic, and the United States (Meher et al., 2006).

The parameters that define the quality of biodiesel can be divided into two groups. One group contains general parameters, which are also used for mineral oil-based fuel, and the other group describes the chemical composition and purity of fatty acid alkyl esters (Mittelbach, 1996). The second group contains the general and third group: the vegetable oil-specific parameters and the corresponding value of FAMEs according to standards of the countries mentioned (Tables 2 and 3).

Table 2

General Parameters of the Quality of Biodiesel

Table 3

Vegetable Oil-Specific Parameters for the Quality of Biodiesel

Among the general parameters for biodiesel, the viscosity controls the characteristics of the injection from the diesel injector. The viscosity of FAMEs can reach very high levels, and hence it is important to control it within an acceptable level to avoid negative impacts on fuel injector system performance. Therefore, the viscosity specifications proposed are nearly the same as that of the diesel fuel. The flashpoint of a fuel is the temperature at which it will ignite when exposed to a flame or spark. The flashpoint of biodiesel is higher than that of petrodiesel, which is safe for transport purpose.

The possibilities of using different types of alternative fuels have been analyzed and investigated in the past 10 years at Khar’kov Polytechnical Institute National Technical University, Ukraine. Important attention has been focused on liquid and gaseous fuels from renewable resources: plant leaves, stems, or seeds. Most of these fuels differ significantly from traditional liquid hydrocarbon fuels in the physicochemical properties that affect both organization of operation and the technical and economic and environmental indexes of ICE.

The analysis showed that in the conditions of Ukraine, an alternative fuel produced by blending liquid hydrocarbon fuels with rape oil (RO) derivatives—methyl esters (ROME)—is promising for ICE (Table 4).

Table 4

Properties of diesel and rapeseed oils produced in Ukraine

Biodiesel fuel (BDF) on the basis of ROs has passed tests and encouraging results have been received. The data of the specialized firms of Germany, Poland, the United States, and also the Ukrainian Agrarian Academy of Sciences, Research Transport Institute (Kiev), etc., are simultaneously generalized. Extensive researches on BDF with RO have also been carried out in Austria, France, Italy, Spain, and Great Britain (Topilin, 2002). The generalized data on the properties of RO and traditional diesel fuel are presented in Table 5.

Table 5

Properties of rape Oil and Traditional Diesel Fuel

As Table 5 shows, BDF on the basis of RO can be suitable for use in engines of all sorts without their constructive change. German BDF of the firm Tessol Stuttgart is made by dispersion from 20% of spirit, 25% gas, and 55% of coldly pressed filtered RO. Such fuel mix was widely used in diesel engines by the technical universities of Stuttgart, the Kaiser-Slautern and Hohenheim. Studies have established that emissions of the fulfilled gases under condition of transition to a rape methyl ester are reduced by 50% in case of the maximal loading of a diesel engine. Emissions of firm particles decrease by 20%. Ukraine had about 80 bio-ethanol factories with an average capacity of 670 millions liters per year per factory. The known domestic requirement is only 200 million liters per year from one factory. Therefore, it is rational to direct surplus of spirit to manufacture of fuel mixes for cars and other types of transport. Consumers have already been using liquid fuel from Odessa and Drogobych oil manufactures.

In Ukraine there are all opportunities for an organization of BDF manufacture on the basis of ROs. The appreciable effect can be received without radical reequipment of diesel engines of a batch production, having mastered technology of BDF production, consisting of a hydrodynamically activated mix of a petroleum origin with RO (Topilin, 2002). It is especially important for Ukraine, which has huge opportunities of rape growing (for example, on the polluted grounds of the Chernobyl zone) and which is characterized by considerable deficiency of mineral oil. Use of BDF will allow reducing needs for petroleum by 1-2 million tons (depending on the volume of BDF manufacture).

5 Cleanup of Heavy Metals from Soil by Using Oilseed Crops

The remediation of metal-contaminated sites often involves expensive and environmentally invasive and civil engineering-based practices (Marques et al. 2008). A range of technologies such as fixation, leaching, soil excavation, and landfill of the top contaminated soil ex situ have been used for the removal of metals. Many of these methods have high maintenance costs and may cause secondary pollution (Haque et al., 2008) or have an adverse effect on biological activities, soil structure, and fertility (Pulford and Watson, 2003). Phytoremediation is an emerging technology that should be considered for remediation of contaminated sites because of its cost effectiveness, aesthetic advantages, and long-term applicability.

This technology is based on element accumulating via plants that grow on contaminated soil and later can be harvested in order to remove the specific elements from the soil (Salt et al., 1995; Alkorta et al., 2004; Witters et al., 2012). An alternative soil remediation technology has been proposed that uses rare, heavy metal tolerant-plant species that work as hyperaccumulators of heavy metals via the plants’ roots and shoots.

The crops can be divided into four groups, which differ considerably in their ability to accumulate heavy metals: (1) low accumulators (maize and peas); (2) moderate accumulators (barley, lentils, gram, sunflower, sesame, fennel, coriander, dill, peppermint, basil, cotton, potatoes, datura) (Gholamabbas et al., 2009), (3) high accumulators (wheat, soybean, beans, rape, peanuts, anise, black mustard, flax, hemp, sugar beet, fodder beet), and (4) hyperaccumulators (Salvia sclarea L., Talinum triangulare, tobacco, etc.) (Kumar et al., 2012).

To date, a number of plants have been well characterized as hyperaccumulators (those that accumulate high levels of toxic contaminants versus nonaccumulator species) but have the distinct disadvantage of having slow growth rate and being low biomass producers. For example, these are Thlaspi caerulescens, Arabidopsis halleri, Armeria maritima (Baker and Brooks, 1989; Brown et al., 1994). Also, these plants are endemic to certain areas and do not perform well in other areas. The ideal characteristics of an effective plant-phytoremediator are fast growths, deep and extensive roots (phreatophytes), high biomass, easy to harvest.

The application of plants for phytoremediation has two advantages; the remediation of contaminated soil and the production of biofuel. The plant species is the most important factor that needs to be satisfied. The following information is required for effective remediation and the abundant production of biofuel: (1) heavy metal tolerance of species, (2) heavy metal accumulation capacity of the plants, and (3) biofuel production capacity per unit area. Not only sunflowers but also rape and soybean have been used as principal biofuel sources. Moreover, these plants have been studied for their potential in phytoremediation in order to clean up contaminated soils (Chen et al., 2004; Ru et al., 2004; Murakami et al., 2007). Sunflowers have good tolerance for various heavy metals such as Ni, Cu, As, Pb, and Cd (Lin et al., 2009; Turgut et al., 2004).

Use of sunflower (Helianthus annuus L.) for Cu phytoextraction and oilseed production on Cu-contaminated topsoils was investigated in a field trial at a former wood preservation site, and it has been confirmed that among six experimental cultivars, sunflower cultivar energic seed yield (3.9 Mg air-DW/ha) would be sufficient to produce oil. Phenotype traits and shoot Cu removal depended on sunflower types and Cu exposure (Kolbas et al., 2011).

The accumulation and distribution of Cd and Pb in plant parts and evaluation of the potential problem caused by heavy metals when biofuel is produced by plant seeds cultivated from Cd- and Pb-contaminated soil have been investigated. Based on the germination test results, sunflowers were selected as the target plant because of their high germination rate and IC50 compared to other plants. The trends of accumulated amounts and concentrations of Cd and Pb in sunflowers were not identical. The accumulation of Cd in the plant parts was in the order of: seeds > stem > leaves > petals > roots, with the accumulation of Pb: stem > roots > leaves > petals > seeds. Pb did not accumulate in the seeds. These findings show that there should not be any significant problem producing biofuel from sunflower seeds cultivated in Pb-contaminated soil (Lee et al., 2013). At the same time sunflower species can be used for revegetation of areas contaminated with As up to the safe limit of 150 mg As/dm³ soil (Melo et al., 2012).

To identify oil crops that can be cultivated in Zn-contaminated soil for biodiesel production, the ability of Zn tolerance and accumulation of eight oil crops were evaluated under 200-800 mg Zn/kg sand substrates (DW) conditions. Results showed that all crops, except sunflower, could grow quite well under 400-800 mg/kg Zn stress. Among them, hemp, flax, and rapeseed showed small inhibitions in plant growth and photosynthetic activities, indicating these crops had a strong tolerance to high Zn concentrations and could be cultivated in Zn-contaminated soils. Peanut and soybean exhibited higher Zn concentrations in shoots, higher bioconcentration factor, and higher total Zn uptake, as well as higher biomass. These crops, therefore, are good candidates for the implementation of the new strategy of cultivating biodiesel crops for phytoremediation of Zn-contaminated soils (Gangrong Shi and Cai, 2010).

The soybean roots can accumulate the highest value of Pb—294.8 mg/kg, Zn—644.4 mg/kg, Cu—34.4 mg/kg, Cd—10.9 mg/kg (Angelova et al., 2003). In the roots of soybean were fixed and accumulated a great part of the heavy metals that had entered the soil, as soybean plants form a powerful root system with strong absorbing ability on depth as well as on width, including a great volume of soil. Soybean roots can accumulate nickel in high quantity (Malan and Farrant, 1998). Nickel uptake by plants is positively correlated with the metal's concentrations in soil solution.

The roots of sunflower are able to accumulate more quantity of Zn (2514.2 mg/kg), Cu (255.7 mg/kg), and Cd (53.2 mg/kg) (Sayyad et al. 2009) in comparison with soybean plants. We suggest that soybean plants can be a hyperaccumulator of lead and nickel. Therefore, these crops accumulate trace element beyond permissible level in their vegetative mass. Phytoextraction of metals, metalloids, and radionuclides is one of the promising options for contaminant cleanup. However, some schools have expressed reservations for application in field situations for environmental cleanup (Venselaar, 2004; Rascioa and Navari-Izzo, 2011).

At the same time, compost and vermicompost application led to effective immobilization of Pb, Zn, and Cd mobile forms in soil. The efficacy of the sunflower plant for phytoremediation of contaminated soils in the absence and presence of organic soil amendments (compost and vermicompost) has been studied (Angelova et al., 2012). A correlation was found between the quantity of the mobile forms and uptake of Pb, Zn, and Cd by the sunflower seeds. Tested organic amendments significantly influenced the uptake of Pb, Cu, Zn, and Cd by sunflower plants. Oil content and fatty acids composition were affected by compost and vermicompost amendment treatments. The compost and vermicompost treatments significantly reduced heavy metals concentration in sunflower seeds, meals, and oils, but the effect differed among them.

Trace element uptake by sunflower and its implications for biofuel and biochar production is actual topic of research activities (Prasad, 2008; Evangelou et al., 2010). The increasing demand for energy and the decreasing reserves of fossil fuels have turned the focus of governments to energy production from biomass (biofuels, biogas). As biomass is currently the only renewable source of organic carbon, it appears to be an ideal source for the production of transport fuels. However, because production of biofuel crops demands fertile agricultural land, it comes into conflict with an ever-increasing demand for food. This conflict is intensifying, as much arable land is lost through erosion and contamination. On the other hand, contaminated land that is unsuitable for food production and of little or no economic return could be used for the production of bioenergy. Phytoremediation, the use of vegetation for in situ restoration of contaminated soils, is generally considered a cost-effective and environmentally friendly approach (Arthur et al., 2005). However, it is increasingly recognized that the success of phytoremediation depends on its capacity to produce valuable biomass (Conesa et al., 2012).

Sunflower would be a suitable crop for the production of bioenergy on contaminated land. It can be used for the production of biodiesel (seed oil), as well as for biogas (straw). Since it has been used as a crop for centuries, cultivation techniques and infrastructure for harvesting and processing are already available.

However, cultivating metal-contaminated soils is complicated because, in most instances, several growth-limiting factors for the plants, such as a high phytotoxicity of the pollutants and poor fertility conditions, are acting simultaneously (Tordoff et al., 2000). Soil amendments are usually necessary to render the substrate suitable for the plant establishment (Brown et al., 2003; Houben et al., 2012). But the risks of contaminant transfer from the contaminated site into the environment, in particular water and food chains, need to be taken into account and limited to tolerable levels. Among others, trace elements uptake by the harvested plant parts must be kept at a minimum. This could be achieved by breeding for trace elements exclusion from uptake. Attention also has to be given to the residues of fuel burning, like ashes, and to by-products generated when the harvested biomass is converted into fuel or gas (Evangelou et al., 2012).

There are known beneficial effects of biochar application to contaminated soils on the bioavailability of Cd, Pb and Zn, and the biomass production of rapeseed (Brassica napus L.) (Ru et al., 2004; Houben et al., 2013). The Brassicaceae family includes numerous plant species cultivated in Ukraine and all around the world. Rapeseed (Brassica napus), brown mustard (Brassica juncea), dutch flax (Camelina sativa), and naven (Brassica rapa) are planted as oil crops (Hablaka and Chechenevab, 2009; State Checklist of Plant Cultivars Suitable for Distribution in Ukraine, 2011). B. napus L. accessions are suitable for phytoextraction of moderately heavy metal-contaminated soils (Grispen et al., 2006).

Treatment with 10% biochar proved equally efficient in reducing metal concentrations in shoots, but the biomass production tripled as a result of the soil fertility improvement. Thus, in addition to C sequestration, the incorporation of biochar into metal-contaminated soils could make it possible to cultivate bioenergy crops without encroaching on agricultural lands. Although additional investigations are needed, we suggest that the harvested biomass might in turn be used as feedstock for pyrolysis to produce both bioenergy and new biochar, which could contribute further to the reduction of CO2 emission (Houben et al., 2013).

The study about phytoremediation of a copper mine soil with Brassica juncea L., compost, and biochar has shown that mustards extracted Ni efficiently from soils, suggesting that B. juncea L. is a good phytoextractor of Ni in mine soils. Amendments and planting mustards decreased the pseudototal concentration of this metal, reduced the extreme soil acidity, and increased the soil concentrations of C and TN. Both treatments also decreased the CaCl2-extractable Co, Cu, and Ni concentrations (Rodríguez-Vila et al., 2014).

It is now known that phytoextraction is not feasible in moderate to highly contaminated soils with naturally occurring metal hyperaccumulators for some of the disadvantages mentioned. Obviously agricultural crops that produce high biomass would be the right choice. Trace element contamination/pollution in agrocoenose, application of environmental crops (e.g., sunflower, rapeseed, and soybean for phytomanage are ments of trace element-contaminated soils, possible scope for development of phytoproducts, and establishment of sustainable agrocoenose (Figures 9 and 10).

Figure 9 (a) Sunflower and (b) rape seed are popular as environmental crops. These crops reported to be efficient in phytoremediation of inorganic and organic contaminants including radionuclides.

Figure 10 Production of biodiesel, bioproducts, glycerine, and electricity from the seeds of sunflower applied in phytoremediation.

6 Conclusions

The high concentration of heavy metal is harmful to human health through contaminated agro-production. The most heavy metals accumulate in soil after long-time addition. This chapter raised the issue of heavy metal pollution in the world and more specifically in Ukraine. The most dangerous aspect of this pollution is high levels of lead and nickel in soils of Ukraine territory. The proposed method for cleanup of polluted soils has been using heavy metal-tolerant plant species that are able to hyperaccumulate metals in plant roots and shoots. The widespread agricultures on Ukraine territory such as soybean, rapeseed, and sunflower can be accumulators of heavy metals. But the main part of harvest of these crops cannot be used for ecologically pure agricultural production according to international standards. For cleanup of contaminated soils, it will be better to use the part of this harvest on biodiesel production during one year. From the economic side this can be profitable also. At the same time it will be possible to clean up the most contaminated soils on the territory of Ukraine. But after a biogeochemical cycle, heavy metal will again appear in the environment. For full cleanup of soil by plants it is better to use the electrolysis method (placing the harvest in an oxide solution and using electrical power to gather metal under solid form).

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