Keywords: Heavy metal, bioindicator, biomonitor, ecosystem health, human impact. 1. ...... Journal of Dr. NTR University of Health Sciences,. 4(2), 75.
! " #
$ % & ' %
( ! " ) ( ! *& $+, - . ! $/ 0 % $
!"#$ % "
! & ' & ( )*! &
./ 01 2 . 3,)* % "
! & ' & ( " "3,)*
Heavy Element Pollution, Their Meaning in Literature and Using Organisms to Monitor This Pollution =H\QHS$\GR÷DQhPLWøQFHNDUD Narman Vocational School of Higher Education, Atatürk University, Narman, Erzurum, Turkey Faculty of Science, Department of Biology, Atatürk University, Erzurum, Turkey
Contents &RQWHQWV«««««.««««««««««««««««««««««««««««««2 $EVWUDFW««««««««.«««««««««««««««««««««««««««3 ,QWURGXFWLRQ«««««««««««««...««««««««««««««««««3 Heavy Metal Pollution Sources...««««««««««««««««««««««««««3 /LVWRIKHDY\PHWDOSROOXWDQWVRXUFHV«...«««««««««««««««««««««4 'HILQLWLRQRI+HDY\0HWDOV«««««......«««««««««««««««««««««...5 +HDY\0HWDOVDQG7KHLU+D]DUGRXV(IIHFWV««««««««««««««««««..«10 2.1. Environmental Pollution: How the environment impacts our lives?...........................................10 2.1.1. Air Pollution«««««««««««««««................................12 2.1.2. Soil Pollution««««««««««««««««..............13 2.1.3. Water Pollution««««««««««««««««..............15 3. Biomonitoring Heavy Metals: Use of Biota, Sediment and Water in the Environmental 0RQLWRULQJ««««««««««««««««.................18 5HIHUHQFHV««««««««««««««««..............29 Figures Figure 1. Heavy metal pollution sources«««««««««««««««««««««««3 Figure 2. Anthropogenic pollution sources and their effects««««««««««««««« Figure 3. Biomonitor and bioindicator organisms and their response to element contamination.«19
Abstract Today the ecosystem is rapidly changing, unfortunately in parallel with the increase in human activities. An ecosystem, consisting of live and inanimate items, each piece is related to each other at different grades, and each item is in harmony with itself and with other things. Natural life which based on various balances continues as long as the balance between living organism and environment can be maintained. For this reason, all living beings, including humans, need appropriate environments where they can maintain their lives on a regular basis. Heavy metal pollution and its effects are covered by lots of disciplines and the extent of this chapter is limited. In this contribution, we review the heavy metal their sources, definitions in the literature and effects of the organisms, and bioassessment of these pollution with organisms are expressed here. In this FKDSWHUWKHWHUP³PHWDO´UHIHUVWRDQ\HOHPHQWWKDWmay pose a toxic to biota and abiota. Keywords: Heavy metal, bioindicator, biomonitor, ecosystem health, human impact. 1. Introduction Heavy Metal Pollution Sources
Figure 1. Heavy metal pollution sources (Oves et al. 2012). In general, pollution sources can be categorized as domestic, agricultural, industrial and mining. There are also several factors and their cumulative effects like deforestation, unplanned urbanization, over population, profit oriented society and technological advancement are responsible for the widespread pollution on the earth. There are three reasons that affect mobilization and distribution of the elements. First one is the magma which forms in the centre of ϯ
earth at high temperature and pressure. These phenomena lead to concentration of elements in certain type of rock, known as ores. The second is physic-chemical and biologic conditions effect the mobilization of the elements. The last one is human activities. Excessive extraction of elements which are concentrated in ores cause potential environmental hazards. Plentiful usage of heavy metal in industrial, domestically, agricultural and technological areas have led to their widespread distribution in the environment. The contents of domestic sewages are lavatories and water used for washing and cooking. Agricultural wastes are produced by various farming activities such as horticulture, dairy farming and livestock breeding. Industrial and mining activities are the most important source of pollution. All of these pollution sources mostly contain metabolic wastes, solvents, various detergent, dyes and pigments, batteries, electronic appliances, organo-chemicals, pharmaceutics, pesticides, fertilizers, automotive products and heavy metals. Some of these wastes can biodegradable but most of these chemicals like heavy metals are non-biodegradable thus even in small doses these chemicals can persist in the environment also aquatic ecosystems and decrease the quality of the environment and aquatic habitats (Ololade et al. 2008). Because of their persistent nature they tend to accumulate in abiota such as soil and sediment and biomagnifiated in biota as is in the food chain (Shrader 1983; Victor et al. 2012). If heavy metals increase in the environment, they enter biogeochemical cycle and cause toxicity. This means that the environmental stock in the food chain is growing rapidly and permanently this process is known as bioaccumulation and biomagnification, thereby create a serious risk for the environment and causes various health problems and survival of the aquatic animals, including human (Bini and Bech 2014; Rajeswari and Sailaja 2014). List of heavy metal pollutant sources: -Fertilizers: Cu, Mn, As, Cd, Cr, Pb, Hg, Mo, U, V, Zn, (In the phosphatic fertilizer there are Cd and U) -Pesticides: Cu, Se, As, Hg, Pb, Mn, Zn (some fungicides include Cu, Zn and Mn) -Wood preservative: As, Cu -Poultry productions: As, Cu -Paper and pulp: Hg -Composts: Cd, Cu, Ni, Pb, Zn, As -Sewage sludge: There are many elements but especially Cd, Ni, Pb, Zn, As, Cu, Sn -Corrosion of metal objects: Zn, Cd ϰ
-Chloro-alkali: Cr, Cu, Zn, Se, Hg, Cd -Petroleum refining: Zn, Cd, Cu, Cr, Pb -Electroplating (Galvanoplasty): Ni, Zn, Cr, Cu -Metallurgical Industries: V, Mn, Pb, W, Mo, Cr, Co, Ni, Cu, Zn, Cd, Li, As, Ag, Hg, Se -Batteries: Pb, Sb, Zn, Cd, Hg -Paints: Cr, Cu, Pb, Hg, Se, Sb, As, Cd, Mo, Si, Co, Zn -Catalysts: Ni, Mo, I, Co, Rh -Polymer stabilizers:Pb, Sn, Zn, Cd -Printing and graphics: Se, Pb, Zn, Cd -Medical use-dental alloys and drugs: Ag, Sn, Hg, Cu, Zn, As, Sb, Bi, Ba, Se, Li, Ta -Additive in fuels and lubricants: Pb, Se, Te, Mo, Li -Textile and Leather: Cr In contrast to these benefits, heavy metals are dangerous because they tend to accumulate. Among contaminants, heavy metals including both essential and non-essential have attracted a great attention; because of their long persistence, toxicity, non-biodegradable nature, long-biological half-lives, tendency to accumulate in organisms; once they enter the food chain, there is no getting rid of them (Nehring 1976; Zhou 2008). Their higher concentration than the standart levels has detrimental effects even death on living organisms and human. Therefore, it affects fauna, flora and other biotic and abiotic components of the ecosystem. Definition of Heavy Metals When we look at the history of discovery of elements and their list in periodic table, Lavoisier, who gave the first modern list of chemical elements, defined an element as a substance that cannot be decomposed by any chemical reaction into simpler substances and he listed 33 substances as elements in 1789. By 1818, 49 accepted elements were determined. But first description of Periodic Table was maden by Russian chemist Dmitri Mendeleev in 1867. After then, by 1919, there were 72 known elements and in 1955 there were 101 discovered elements. As of 2010, 118 elements are observed. Of these 11 HOHPHQWV HOHPHQWV RFFXU QDWXUDOO\ RQ (DUWK¶V FUXVW and the remaining elements (atomic numbers from 95 to 118) not found on Earth, have been derived artificially or nuclear reactors (Emsley 2011; Ebbing and Gammon 2017; Anonymous 1). Periodic table shows ϱ
WKH HOHPHQWV¶ QDPHV V\PEROV DWRPLF QXPEHUV DQG DWRPLF PDVV It has seven horizontal rows called as periods and sixteen vertical columns known as groups. It is useful for understanding the structure and predicting chemical behavior of an element. All elements from atomic numbers 1 (Hydrogen) to 118 (organesson) are arranged in periodic table by their atomic number, electron configurations and chemical properties. The elements in this table divided into metals, nonmetals, semi-metals and noble gases. The layout of the periodic table has been refined and extended over time and scientists continue to develop new materials and to discover new properties of the old ones. Elements are everywhere and interwoven into our life, not only in nature but also in our everyday life. Elements are distributed in different proportions in lithosphere, hydrosphere, atmosphere and biosphere. All elements, which are present on the earth, are found in the nature in the form of ores and minerals. Elements are defined chemically as a simplest substance and contain only one kind of atom, hence cannot be broken down into a simpler substance by any non nuclear chemical reaction. Each of these elements may be effective in a variety of ways of living life. Some elements, aside from their toxicological effects, play a major role in biochemistry of biological organisms but certain ones are extremely toxic to human and also environment. Increasing usage and extraction of these elements in anthropogenic activity leads to increase in their concentration and distribution on the earth. In periodic table out of 118 identified elements, about 80 of them are called metals. Even anthropogenic activities contribute increasing of heavy metals, they are natural components of earth crust and they DUH IRXQG WKURXJKRXW WKH HDUWK¶V FUXVW in the form of ores and minerals. A metal defined by chemist as an element that is a good conductor of electricity, high density, high thermal conductivity and has chemical reactions (Jones and Atkin 2004; Müller 2007). As elements, metals have unique physical, chemical, biological and toxicological properties, can also exist in the environment and transform from one chemical form or valance (electron configuration) to another form/valance. Environmental conditions like biotic component of environment, pH, temperature, redox potential, ionic strength, soil types help changes to this form. Heavy metals which concentrated in the environment have three main anthropogenic sources that are mining, metal industry and industrial enterprises, actually found in the nature and main constituent of the rocks and minerals constitute majority of elements. Heavy metals in environments have been intensively studied because of concern about their toxicity in drinking water, significance in natural biogeochemical cycles and long term effects on living organisms, chemical hazards and their safe use of in human health. Not only anthropogenic activity but also natural activities can increase the concentration of heavy metal levels in any environment. But in these days anthropogenic activities are major reason for input of metals to the environment than natural input. ϲ
7KH WHUP ³KHDY\ PHWDOV´ KDYH EHHQ XVHG LQ YDULRXV SXEOLFDWLRQV UHODWHG WR FKHPLVWU\ SK\VLFV medicine, ecology, environmental toxicology and even in legal regulations. And in these areas this term generally used as connotation of pollution or toxicity. Nowadays, heavy metals (either essential or toxic) are extremely important problem both human and environment health but when is looked at the literature there is no consensus on the definition of heavy metal. Interestingly, even non-metals like Selenium (Se), Brom (Br), metalloids like Arsenic (As) and Antimony (Sb) are considered under heavy metal category, and this make it appear that the term is a misnomer. Although several authors have stressed the importance of heavy metal toxicity there are many definitions of heavy metal as chemically and biologically which are discussed DV D ³PHDQLQJOHVV WHUP´ in an International Union of Pure and Applied Chemistry (IUPAC) technical report (Duffus 2002). Out of 118 identified elements, about 80 of them are called metals. Terminology of heavy metal is variable and often confusing. 7KH WHUP ³+HDY\ 0HWDO´ FRQVWLWXWHV D KHWHURJHQHRXV JURXS RI elements that include metals, semi-metals, non-metals, lanthanides and actinides, and as it seen more definitions have been proposed but none of them have obtained widespread acceptance. As a VFLHQWLILFDOO\WKLVWHUPZDVILUVWGHILQHGLQ%MHUUXP¶V,QRUJDQLF&KHPLVWU\WUDQVODWHGE\%HOOLQWKH third Danish edition (1932) and published in London in 1936 (Foster 1936). The book categorized metals as; non-metals, light metals and heavy metals. The term defined with regard to specific gravity of the metals which had a specific gravity of 7 or more in their pure elemental form (Woodriff 2013). Heavy metals have extensive literature concerning their accumulation in biotic and abiotic factors and there is no standardize definition, thus can be defined in several ways. The most used definitions are; heavy metals are normally considered as a density of 3.5 ± 5 g/cm3 and higher (Falbe et al. 1990; Lenntech 2004; Tchounwou et al. 2012). According to this definition, threshold levels of density can be change depending on the author and all elements heavier than titanium (Ti) are heavy metals, but its physical property is quite meaningless. Another definition; heavy metal refers to any element that is toxic at low quantity, have ions in solution, have high atomic weight or specific gravity and a density 5 times greater than that of water (Hutton and Symon 1986; Fergusson 1990; Govind and Madhuri 2014; Rajeswari and Sailaja 2014). Hawkes (1997) defined all transition and post-transition metals (metals and semi-metals) as a heavy metal (in periodic table group 3 to 16 that are in periods 4 and greater) and have above 5 g/cm3 densities, generally excluding alkali metals. Another possible definition is the following; heavy metals are serious pollutants of aquatic ecosystems because of their environmental persistence, toxicity and ability to be magnified into food chains (Rishi and Jain 1998; Kishe 2003). Biologist including ecotoxicologist and environmental scientists XVHWKHWHUP³KHDY\PHWDO´DVDFRQQRWDWLRQRIWR[LFLW\ ϳ
and define it, as the elements below or above a certain threshold level or excessive concentration, they have potentially toxic and cause both environmental and health problems (Appenroth 2010; Singh et al. 2011). 7KLV GHILQLWLRQ LV LUUHVSHFWLYH RI KHDY\ PHWDOV¶ DWRPLF ZHLJKW DQG GHQVLW\ DQG any metal may be toxic and called heavy metal. 7KH WHUP ³KHDY\ PHWDO´ XVHG IRU HYHU\ HOHPHQW ZKLFK FDXVHV KHDOWK SUREOHPV RU HQYLURQPHQWDO damages. Most of these elements taken by the human body via food, water and air and are absolutely necessary for all living organisms in a certain dose. Also geologic background of an element is also important because if we know the concentration of an element in a ground this may provide information about its potential bioavailability. However, some of the metals like Fe, Cu and Zn are toxic only in high concentrations and they exist in uncontaminated soil too. When we look at the definition of all of these definition above it can be concluded that all so-called ³KHDY\ PHWDOs´ are any elements that irrespective of its density and atomic weight it has environmental concern, and this term originated with reference to harmful and toxic effect on living organisms including human and environment. There are many definitions according to their density, atomic number, atomic weight or position in the periodic table but its physical as well as chemical property (allotrope or oxidation state) is ignored. Density criteria generally start from 3.5 g/cm3 to upper degree. According to its gravity or density some elements grater from 5 gr/cm3 such as zinc (7.13 g/cm3), manganese (7.43 g/cm3), iron (7.87 g/cm3), cobalt (8.9 g/cm3), copper (8.96 gr/cm3) but these are also essential elements and certain amount of these elements required for organisms. Even though gold has high density (19.32 g/cm3 ), there is no known toxic effect to organisms. Atomic weight definition criteria start from sodium (22.98) to greater than it. When we look at the definitions which are maden by some authors that a heavy metal is any element their density greater than 3.5 g/cm3, atomic weight greater than 22.98 (Na) and atomic numbers generally greater than 20 to 92 (Lyman 1995), periodic table position range from in group 3 to 16, in periods 4 and greater (Blake 1984; Hawkes 1997; Dufus2002; Khlifi and Ming-Ho 2005). It is understood from these definitions, heavy metals are general collective term which are the group of metals and semimetals with an atomic density greater than 3 g/cm³. Therefore, there is no correlation between density of the metal and its toxicological effect to organism, toxicity varies depending on the oxidation state of the element. The oxide form of some heavy elements is not toxic and using in treatment of some disease (Singh et al. 2011). It is well known that form of the metal influenced by environmental properties, such as pH, temperature, particle size, moisture, redox potential, organic matter, cation exchange capacity, and DFLGYRODWLOHVXOILGHVDOVRWKLVLQIOXHQFHVWKHPHWDO¶VELRDFFHVVLELOLW\ELRDYDLODELOLW\IDWH solubility, ϴ
mobility and effects (Evanko and Dzombak 1997). Thus, the speciation or the form of metals in abiotic and biotic environment influences their bioaccessibility, bioavailability, bioaccumulation and toxicity to influenced organisms. The toxicity of elements mostly depends on its oxidationreduction degree and generally ionic form of an element is the most toxic form. Zero valance forms of most element are not soluble, thus bioavailability and toxicity of these elements depends on its soluble salts and its combination with other elements. For example, hexavalent chromium Cr (VI) is deadly whereas trivalent chromium Cr (III) is an important bio-element for organisms. Generally, inorganic arsenic compounds more toxic than organic arsenic compounds (Govind et al. 2014). The mobility, bioavailability and the impact of toxicity of heavy metals in the environment depend not only on the total metal concentration but strongly on their specific chemical types (Radojevic and Bashkin, 1999). Thus toxicity and accumulation in an abiota or biota of metal change and depend on its form. Heavy metal toxicity depends on several factors including the climatological conditions, soil geochemistry, water and sediment chemistry, dose, exposure route, form of the metal or metal compound and chemical species, as well as the VSHFLHV¶ age, gender, genetics, pregnancy status, feeding ecology and ability to regulate or store the element and nutritional status of exposed individuals (Phillips 1990). These elements are considered systemic toxicants that are known to induce multiple organ damage, even at lower levels of exposure. They are also classified as known or probable human carcinogens according to the US Environmental Protection Agency, and the International Agency for Research on Cancer. Apart from their toxicity some of the heavy metals are also considered as essential elements because of necessary for health of organisms in small amount, but excess exposure to the elements are toxic or at low concentrations it is necessary and can cause cellular damage and disease (Kabata-Pendias and Pendias 2001). Specifically, excess metal ions can interact with nucleic acids, structural proteins, co-factor in various metabolic enzymes, cellular components, and interfere with their functioning, altering the cell cycle, leading to carcinogenesis or causing cell death. Similarly, inadequate or low concentration of these metals results in a deficiency disease (WHO 1996). Some of these heavy metals have bio-importance play irreplaceable role in biological systems, vital to life in small quantities and are described as micronutrients or essential elements; needed for metabolism, to facilitate growth and proper functioning of the living organism and their dietary or medical allowances have been recommended. For example, copper (Cu) deficiency causes bone disorders, demyelination of nerves, weight loss, graying of hair etc (Pandey 1983). But in literature there are similar essential elements terminologies like microelements, micronutrients, minor elements, essential nutrients, trace elements etc. (Frieden 1974; Prashanth et al. 2015). Depending ϵ
on their roles, essential elements refer to any element that is required in minute quantities for various biochemical and physiological functions and total absence in the organism causes variety of deficiency diseases and severe damages LQRUJDQLVP¶VLQWHUQDOHTXLOLEULXP (WHO 1996). Thus they are necessary for biosynthesis, cell functions, nucleicacids, normal growth, development and well being of organisms at chemical, biological and molecular levels (Prashanth et al. 2015). A typical diet should include less than 50 ppm (parts per million) essential elements and this essential doses of any biologic importance metals related to typically biological activity, life-stage and gender (Pais and Jones 1997). But even they have biological roles in an organism, when the concentrations exceed in the body or permissive level in the environment, they become hazardous to organisms including human health. Like toxicity, essentiality also related to dose for the species. Organisms within a given ecosystem are variously contaminated in different level along their cycles of food chain. Due to this toxicity it is needed to control their concentration in the environment. Beside to essential elements, some elements are clearly toxic like Pb, Hg, Cd. Elements can disrupt RUJDQLVP¶V PHWDEROLVP LQ WZR ZD\V they can accumulate in vital organs and disrupt their functioning and they can display the necessary elements from their original place (Singh et al. 2001). At least 60 detectable elements present in the human body, but only about 25 of these elements are thought to participate of the human body (Chellan and Sadler 2015). Until excreted or detoxified, elements do not break down and stay in the body (Nordberg et al. 2014). Some elements store in organs and tissues for years or decades like liver, bones and kidneys. 2. Heavy Metals and Their Hazardous Effects 2.1. Environmental Pollution: How the environment impacts our lives? Pollution problem has not appeared suddenly, has become enriched over time. Unfortunately, today ecosystems are changing rapidly parallel to the increase of human activities. The development of industry, which is a consequence of development, has led to excessive population growth, energy and nutrient insufficiency, more pesticide usage, intense migration from rural areas to the cities, with irregular urbanization, insufficient infrastructure and destruction of natural areas. In addition to all these, technological developments on one hand make our life easier; on the other hand, it threats to our life because absence of treatment system in a large part of industrial plants and agricultural, domestic wastes contaminate the source of life and threatens our lives. Contamination (pollution) which emerged as an inevitable result of industrialization and nowadays increasingly presence of feel has entered the agenda of national and international countries and nobody will remain indifferent to this problem.
Figure 2. Anthropogenic pollution sources and their effects (Oves et al. 2012). As a result of all kinds of anthropogenic activities, which occur in the air, water and soil, increase the destroying; make it difficult for the living things to live with by polluting the living resources; anything that disrupts the ecosystem balance come across as a direct or indirect environmental pollution. The level of occurrence of elements in the environment must be below the tolerance limits or, in other words, at 'desired or acceptable' intervals. Environmental pollution begins when unconsciously increasing production in order to provide better living conditions for an increasing SRSXODWLRQ DQG WKHUHIRUH LQFUHDVLQJ XVDJH RI KHDY\ PHWDOV DQG H[FHHGV WKH QDWXUH¶V VHOI-renewal capacity. Because anthropogenic entry of elements exceeds natural entry. Environmental problems are at the head of the most important threats to natural balance and human health, and these problems come across in increasing size. Although the problem of environmental pollution seems to be a problem of developed and developing countries, undeveloped countries are also suffering from this pollution due to the fact that their pollution reaches international dimensions (Duce et al. 1975; Akimoto 2003). Heavy element concentrations in ecosystems are generally monitored physically, chemically and biologically by using water, sediment and biologic organisms. Physical and chemical monitoring gives information about one moment in time. In order ϭϭ
to get information over a long time we should take into consideration biological organisms that live in a certain environment. Physical and chemical monitoring provides momentarily data about environment whereas biological samples reflect long term impairment. But all the three give a complete assessment of ecology. In water, the concentration of heavy elements is measured in low value whereas concentration of sediment and biota attain considerable degree (Wagh et al. 2015). Environmental problems first apparently affect natural systems and then affect human. Environmental pollution is a multifaceted phenomenon. Although some researchers have investigated the environmental pollution in various groups, air, water and soil environments are closely linked to each other where the pollution phenomenon develops. Environmental pollution, which occurs in nature in a triple circle and ultimately affects all ecosystems, including man, can be investigated as air, soil and water pollution. 2.1.1. Air Pollution Atmospheric pollution that begins with the presence of fire, continuously increased the reasons like due to industrial development in the 20th century, increased number of vehicles and increased use of fossil fuels which originated in anthropogenic activities or as well as the reasons like volcanic explosions, forest fires, carbon oxides, methane, etc. that are released during biological changes which originated in the natural. ,QWRGD\¶VZRUOGLQGXVWULDOWHFKQRORJLFDODQGDJULFXOWXUDOJURZWKDQGLQFUHDVLQJQHHGDQGHPLVVLRQ of these elements have increased. Anthropogenic pollutants which are the most dangerous pollutants especially heavy elements are transported by atmospheric movements, along with rainfall, and they mix with soil and water. It was considered that element concentration of soil is related to geological background and enriched on local scale, but recent studies show that the surface layer of soils are affected by airborne supply of elements from anthropogenic as well as natural sources thus enriched regional scale (Steinnes et al. 1997). In this sense Hg and Pb are the most emissive form of heavy elements due to present in coal and fossil fuels. The best known air pollution crisis in European history is the great smoke of 1952 in England. Sulfuric acid particles which released by coal burning for residential and power plant use, vehicle exhaust is contribute to the fog and created a public health disaster. With this air pollution disaster, it is estimated that 8.000 to 12.000 people died (Klein 2012). Consequently, the transference of these toxic elements from the environment to biota, and their accumulation are the concern of most environmental protection agencies.
2.1.2. Soil Pollution Although soil pollution is considered as an agricultural issue, it is an environment that must be watched because of it can record the changes that occur in the environment. With the increase of modern agriculture and industrialization, soil pollution has emerged as an environmental problem. Also the establishment of industrial facilities and cities on fertile agricultural lands constitute soil problems. Industrial activities, mining, waste from residential areas, exhaust gases from motor vehicles, wastewater irrigation, polluted atmosphere, agrochemical and chemical fertilizers are the reason of soil pollution in other words are the reason of heavy metals reaching the soil. The physical, chemical and biological properties of soils are degraded which are contaminated with heavy metals therefore, the yield decrease. When considering the place in human nutrition and ecological balance, the soil must be used in a sustainable way. Soils not only reserve the elements but also transfer the elements to water, plants, animal and the atmosphere (Kelly et al. 1996; Deng et al. 2017). It is therefore, quality of soil is important, excessive level of heavy elements can cause pollution of waters foods, plants, animals and ultimately human that feed up them (Uchida et al. 2007). Soil can accumulate the elements released into the environment from variety of anthropogenic sources like industrial, agricultural, rural and urban activities (Niragu 1991). It is clear that heavy element concentration increase with these activities but their concentrations also depend on local geological background (Zhong-Sheng 2009; Hu et al. 2011). Increasing element pollution in soil might have influence the agricultural production quality and its possible risk for food web as well (Chen et al. 2008; Deng et al. 2017). The properties of soil types like pH the type of organisms present in the area, seasons, temperature, water chemistry, various phases of elements and other environmental variables affect the bioavailability of heavy element and its mobilization in the environment (Mudroch et al. 1998; Ntakirutimana et al. 2013). Therefore, biological and geological cycle affect the concentration of heavy elements (Rusu et al. 2000). Generally, if the temperature increased chemical reaction rates increased and pH from neutral to alkaline condition heavy elements showed low mobility. That is, if WKHVRLO¶VS+ORZPRELOLW\DQGVRUSWLRQRIKHDY\HOHPHQWLQFUHDVLQJ7KXVLQWKHORZHUFRQGLWLRQRI pH, more elements can be found in solution and mobilized form (Sherene 2010, Bing et al. 2016). Low pH values considerably increase the bioavailability of some certain elements like copper (Cu) and lead (Pb). Alkaline conditions show that water is contaminated with ions like hydroxide, bicarbonate and carbonate (Traichaiyaporn 2000). Organic matter of soil is important factor for mobilizing and absorbing for elements. Humus rich organic layers have ability to sorbs elements and prevent their movement down the soil profile. For example, Cd sinks in organic soils and so its mobility reduces (Rusu et al. 2000). ϭϯ
Sediment quality is also important as well as soil quality; due to it is habitat and nutrient source for aquatic organisms. Each of two environments influences the ground water, surface water and also plants, animals and humans that feed upon them (Nriagu 1991; Uchida et al. 2007; Olubunmi and Olorunsola 2010). Because, data from sediment is a good natural archives of recent environmental changes (Davies and Abowei 2009). Many researchers think that, the sediment provides useful information on the history of the water body quality and extremely important to transfer contaminant various tropic level of food web (Burton Jr 2002).Physicochemical characteristics of sediment affect its element accumulation ability, so sediment¶V HOHPHQW concentration differs sediment to sediment. For example high organic content sediment, like mud, bind more element than low organic content sediment, like sand (Rainbow 2006). Collecting sediment samples for analyses of heavy element contaminants in an environmental study is not simple as collect with bucket and shovel. It is complicated than soil sampling because except during erosion by water or wind soil is stable. Unlike soil, sediment is not stable due to water depth, flow speed and fine grained sediment. Also the reactions between elements and water or chemical changes within the sediments change the concentration of heavy metal levels in sediments (Mudroch and Azcue 1995). Sediment sampling and monitoring is a good way to understand the effects of anthropogenic effluents on an aquatic ecosystem and give detail survey in geochemical prospecting. Many researchers think that sediments can provide good data for heavy element contaminants in aquatic waterbodies and also health of their ecosystems because of bioaccumulative and persistent nature of heavy elements (Swarnalatha and Nair 2017). Sediment considered as archive of pollutants because when an element enters in an aquatic environments enrich in the sediment, change the quality of sediment and also water, affect aquatic biota adversely and biomagnifiated in the food chain and ultimately affect the human beings. There are some definitions of sediments like following; sediment is a heterogeneous complex of liquid, solid, gaseous, organic, inorganic, and living organisms and controlled by these physical, chemical and biological variables (Mudroch et al. 1998). Another definition is like that, sediment settle at the bottom of the water body and contains some type of soil particle like loose sand, clay silt (Davies and Abowei 2009). Sediment sampling in most environmental studies involves the collection of fine grained sediments to determine the presence of contaminants. And many studies have been carried out to evaluate the effect of these polluted sediments on water and biota quality in different kind of freshwaters (Mudroch and Azcue 1995).In this respect, sediment quality is needed for the effective protection of ecosystems.
There are some methods to estimate how much the sediment impacted both naturally and anthropogenically with heavy elements are enrichment factor, geological accumulation index, pollution load index, contamination index, secondary phase enrichment factor, Nemerow synthetical pollution index, potential ecological risk index and integrated pollution index (Yu et al. 2003; Ding et al. 2005: Huu et al. 2010; Ntakirutimana et al. 2013). These methods have been developed for clarify the information of heavy elements and their potential ecological risk. 2.1.3. Water Pollution It is clear that water is one of the major things responsible for life on earth. Life cannot exist without water. Wherever water flows on an area you can be sure to find life. 7KDW¶VZK\1$6$¶V PRWWRWRH[SORUHH[WUDWHUUHVWULDO OLIH LV³IROORZWKHZDWHU´:HDOONQRZKRZLPSRUWDQWZDWHULVWR us. As a life giver, human welfare and health are strictly tied to water sources. When we look at the earth more than %70 of earth is covered in water and it is easy to think that water is plentiful. But in reality the total volume of freshwater on earth is about 2.5 %. Rivers and lakes constitute only 0.3 % of the freshwater resources and the total usable freshwater for ecosystems and humans less than 1 % of all freshwater resources (Anonymous 2012). There are many sentences which express the crucial
Prophet Muhammad¶V Hadith with each bottle of water ³Do not waste water even if you were at a running stream´ $QG (QJOLVK SRHW $XGHQ WH is expressed his feelings about water with these VHQWHQFHV³7KRXVDQGVKDYHOLYHGZLWKRXWORYHQRWRQHZLWKRXWZDWHU´,WLVQRWDQH[DJJHUDWLRQEXW 7KH8QLWHG1DWLRQVDLG LQ :RUOG(QYLURQPHQW'D\ LQ OLNHWKDW³:DWHUELOOLRQSHRSOHDUH dying for it´ All life strongly depends on water. Every living creature need water because the ELRFKHPLFDOSURFHVVRIOLIHWDNHSODFHLQIOXLGZLWKRXWLWWKHUHZRXOGQ¶WEHYHJHWDWLRQRQVRLOVDQG oxygen on air. From the moment we wake up to asleep, humans use water in his larger scale of daily life like in industry, transport goods or products, also it allows humans to grow crops, raise livestock, etc. It is critical because all socio-economic and environmental activities depend on water. Water is a nutrient which is required to sustain life and provides the digestion of food, transportation of food to tissues, removing waste product, and the regulation of body temperature. Water can carry things into and out of the cell. Without water, cells within the human body would die. Further in the body physical functions, such as breathing, digestion, brain activity or muscle movement could not take place. Despite to this dependency to the water, all types of water bodies especially inland water bodies are vulnerable to human impacts. Chemical and physical properties of water are essential to human survival. Air and soil are a whole with water via hydrological cycle. Both soils and air pollution often result in water pollution. ϭϱ
Because all kinds of waste which thrown to the soil do not stay in the region, reach via rain, flood and other ways to the underground and surface waters, affect the physical, chemical and biological properties of these waters and cause to their pollution. Most of our domestic and industrial wastes, acidic rain breaking down soils and releasing heavy metals into streams, lakes, rivers, and ground waters. Streams and rivers are watersheds and as waters containing these effluents are used increasingly for agricultural, industrial, and recreational uses as well as sources for food, drinking water. $TXDWLF HQYLURQPHQWV¶ SROOXWLRQ LV D PDMRU FDXVH LQ WKH GHFOLQH RI SK\VLFRFKHPLFDO DQG ELRORJLF features of water. Heavy metals are concentrated in aquatic environments physical-chemical and biological processes. Aquatic environments which constitute an important part of the ecosystems have been seen for most of wastes like domestic and industrial effluent as a cheap, ideal discharges area and unlimited capacity waste sites. Anthropogenic activities have the greatest impact on the quality of different variety of water bodies even in remote areas like rivers, streams, wetlands in all part of the world. Water is an excellent solvent. Many different types of materials can dissolve in water. The chemistry of water also influences mobility of elements for example, the corrosive nature of water also helps to transfer heavy elements from sediment or rock to aquatic environments. Polluted water directly effects soil in different areas like industrial, agricultural areas, rivers and streams (Kisku et al. 2000). Heavy element concentration in soils and sediments contribute to the pollution of aquatic environments due to their persistence, non-biodegradation, toxicity and easy accumulation (Hu et al. 2011). Due to carrier and solvent properties of water, it facilitates to transport the chemicals to the environment and also passage to the food chain. As a result of this it became a most polluted environment compared to water and soil. All living things dependent on healthy water resources so, protection and conservation of different type of water bodies are necessity. Human health and welfare are strictly tied to water resources and their quality and that human activities can affect the environment in a number of ways. Rivers and streams, called surface waters are ecosystems that have a great ecological value with a rich biodiversity and consist of complex communities. In contrast to these ecological value rivers and streams are among the most affected ecosystems in the world. Today few rivers and streams are pristine and both domestic and industrial wastes affect rivers badly. Intensive usage of fertilizers and pesticides in agriculture has contributed to eutrophication and pollution of aquatic ecosystems (Tilman and Clark 2015). Building dams also alter the ecological characteristics of running water basins deliberately (Mackay et al. 2014). According to Dudgeon et al. (2006), there are five main threats of freshwater biodiversity: over exploitation, water pollution, eutrophication and acidification, flow modification, destruction or degradation of habitat, and invasion by exotic ϭϲ
species. These activities which mentioned above leave element residues and elements in soil and sediment make contribution to the contamination of aquatic ecosystem due to their persistence, easy accumulation, difficult degradation and toxicity (Yuan et al. 2004; Hu et al. 2011). Wetlands as a kind of aquatic ecosystems are important because they are natural guardian of disaster and have the most productive RIWKHZRUOG¶VHFRV\VWHPV (EPA 2012). They provide food, store carbon and regulate the water flows. Like a natural sponge or buffer, they absorb and store excess rainfall and as a result the holding capacity of wetlands helps to reduce flooding. Besides during the dry season, they release the absorbed water. Thus wetlands help to moderate global climate conditions and regulate the water regimes, so any degradation or loss of wetlands affects climate change worse and people become more vulnerable to floods, droughts and famine. Managing water and, de facto, the managing of wetlands is the responsibility of all of us. Government agencies, civil society organizations, private sector concerns and individuals are responsible to protect water and wetland management. Therefore, it needs multi-sectoral and multidisciplinary approach. Mississippi River is a good example of to understand the importance of wetland that Mississippi River once stored at least 60 days of floodwater but now they store only 12 days because most of them have been filled or drained. Due to wetlands have rich food webs it can be thought as "biological supermarkets and kidney of the earth" (Mitsch et al. 2015). An immense variety of species use wetlands part of or all of their life-cycle for food, water and shelter, especially during migration and breeding (EPA 2016).To protect the wetlands have also international importance because some species of migratory birds are completely depending on certain wetlands and if those wetlands were destroyed, they would become extinct (USEPA 1995). There is an interrelationship between wetland and human health. For this reason, biomonitoring of wetlands is important because if the wetlands are healthy the community which lives in a specific wetland can deal with a disaster (Anonymous 2012). Monitoring and management of the ecological character of wetlands is vital because when we monitor these vulnerable areas we can get comprehensive and statistically valid current information at various intervals. These data also give us to understand and evaluate the changes over time and we have opportunity to overview of past and present ecological state of the wetlands. Wetlands keep our environment healthy. Thus it can be said that without wetlands there will be no water. Our actions influence the future of wetlands and of course the water. Although wetlands are often wet and some of them are only seasonally wet, wetlands are transition zones of the soil and the water. In a simply way, they defined as land areas that are water covers the soil, is present seasonally or permanently. 5DPVDU&RQYHQWLRQGHILQHVZHWODQGDV³DUHDVRIPDUVK ϭϳ
fen, peatland or water, whether natural or artificial, permanent or temporary, with water that is static or flowing, fresh, brackish or salt, including areas of marine water the depth of which at low tide GRHVQRWH[FHHGVL[ PHWHUV´Anonymous 2017).Beside to this geographically definition, it should also include the characterization of flora and fauna or its biological contents. Regional or local differences in land, climate, topography, and vegetation, physical and chemical properties of water cause various types of wetlands. Except Antarctica, wetlands are found on every continent. Wetlands can be categorized in three titles; coastal (marine) or tidal wetlands, inland or non-tidal wetlands and human-made wetlands. From these wetlands, there are 952 coastal (marine) or tidal wetlands, 1843 inland or non-tidal wetlands and 766 human-made wetlands in the world (EPA 2016; Anonymous 2017). In this respect contaminating the wetland with elements can affect on human health adversely thus, protecting the wetlands in turn can protect our health and welfare. 3. Biomonitoring Heavy Metals: Use of Biota, Sediment and Water in the Environmental Monitoring An ecosystem composed of biotic and abiotic factors and these factors interact each other. The combination of natural background and anthropogenic entry constitute element concentration of an environment. In natural ecosystems, elements occur in low concentrations ranging at the nanogram to microgram per liter level. Various kinds of human activities increased the element concentration and this lead to alter geochemical cycle of these elements. It is quite obvious that biota is daily contaminated by the elements via drinking water, air, soil, food and manual handling. The major routes of elements uptake by organisms are food, drinking water and air. Any element species may EH FRQVLGHUHG D ³FRQWDPLQDQW´ LI LW RFFXUV XQZDQWHG LQ D IRUP RU FRQFHQWUDWLRQ WKDW FDXVHV D detrimental human effect or eco-degradation. Heavy metals are dangerous and persistent nature they have been the subject of particular attention because they tend to bio-accumulate. Bioaccumulation means concentration of any elements increasing in a biological organism over time in comparison to the element in the surrounding environment (Gupta 2013). Bioaccumulation is the general term describing a process that amount of an element increase in a SDUWRIRUJDQLVPERG\GXHWRWKHUDWHRILQWDNHH[FHHGVWKHRUJDQLVP¶VDELOLW\WRUHPRYHWKHelement from the body. Non-biodegradable feature of elements cause accumulation in soils, sediments freshwater and thus undergo biomagnifications in living organisms (Schrader et al. 1983; Clark 1992). Like bioaccumulation, biomagnification is a process the increasing of the concentration of a substance in living tissue as it moves up the food web. When organisms accumulate elements in greater concentration than their environment in which they live, bioconcentration occurs (Shrader et al. 1983; Victor et al. 2012). ϭϴ
Figure 3. Biomonitor and bioindicator organisms and their response to element contamination. 7RGD\¶VRQHRIWKHKRWWRSLFV LQHQYLURQPHQWDOVWXGLHVDUHLQUHJDUGWRPRQLWRULQJDQGSUHYHQWLQJ heavy element pollution in an environment. Increasing element contamination in the environment, food products and their mutagenic, neurotoxic, teratogenic, carcinogenic and cytotoxic effect in organisms has attracted the attention of the scientists all over the world (Nehring 1976; Holt and Miller 2011; Ntakirutimana et al. 2013; Rahmanpour2016). Mercury, leads, cadmium etc. are not necessary to organisms but they have dramatically increased in recent years and biomagnified in the upper tropic levels. Nowadays, many studies are available in literature in terms of heavy element pollution and its effect on human and environment health (Nehring 1976; Cesa et al. 2015; Rahmanpour et al. 2016). Also there are many study of various international institutes and organizations like WHO (World Health Organization), EPA (Environmental Protection Analysis), IUCN (International Union for Conservation of Nature) related to environmental pollution due to heavy element pollution on the literature. The use of biota in the monitoring and evaluating of environment quality is important to detect anthropogenic impact (Gray 1989). Presence of elements in an organism organs or tissues such as ϭϵ
gill, gut, muscle, exoskeleton or root suggests that organisms are contaminated by water and food (Hare et al. 1991). It is difficult to understand synergistic and antagonistic effects of heavy element in an environment by measure chemically but monitoring environmental changes by biologically give integrated approach to evaluate environmental quality. Some elements are antagonistic or synergistic effect when they are present together. To assess accurately, it requires knowledge of the form of the element and existence of biota and abiota. Thus, in an investigation of the environment water, sediment and biota samples should be taken into consideration in the study program (Traichaiyaporn 2000; Ololade et al. 2008; Zhou et al. 2008; Rahmanpour et al. 2016). All organisms tolerate a limited range of physical, chemical and biological conditions and response these conditions in different way. Biological quality control is not new phenomena. Early biomonitoring studies are based on bacteriological aspects (Hynes 1960), and then bioindicators mostly used for estimating air pollution but recently it is used for estimating and measuring water, soil, sediment pollution and environment quality (Mulgrewet al. 2004). There is an example with this phenomenon, in the early time of the industrial revolution canaries had been using as an early ZDUQLQJWRRORIFRDOPLQHV,IPLQHV¶FRQGLWLRQVZHUHSRRUFDQDULHVVKRZHGDGYHUVHUHDFWLRQVWKHQ miners left the mine (Cairns and Pratt 1993). Also presences of some algae, bacteria, aquatic earthworm, midge larva, leech, blackfly larva indicate poor water quality with organic waste. Besides Stonefly nymph, Mayfly nymph, Caddisfly nymph, Dobsonfly nymph indicates the good water quality (Cairns and Pratt 1993; López-López and Sedeño-Díaz 2015; Oeding and Taffs 2015). This two terms can be considered as have same meaning and are interchangeable, but both of them are completely different in meaning (Phillips and Rainbow 1994; Markert et al. 2003). Biological indicators or bioindicators are organisms that their presence or absence indicates presence or plentifulness of the critical factors in the environment. The presence, absence or changing numbers of bioindicators species gives an idea of the assessment of environmental quality. These species display environmental conditions effectively because of their tolerances to environmental variability. Bioindicators is a species, communities or biomaterials that used for evaluation of HQYLURQPHQW¶V FKDQJLQJ TXDOLW\ RYHU WLPH +ROW DQG 0Lller 2011). Bio-indicator is a feedback PHFKDQLVP WKDW XVLQJ WKH UHVSRQVHV RI RUJDQLVPV WR HYDOXDWH HQYLURQPHQW¶V TXDOLW\ ZKHWKHU LV favorable to organisms or not. According to this idea certain species can be used to indicate their environmental conditions which the habitat is suitable to their live. Scientists are employed bioindicators at a range of scales from the cellular level in an organism to the ecosystem level (Adamo et al. 2007; Mehrotra 2016; Yu et al. 2017). A cellular level bioindicators also called biosensor. There are various types of biosensor like cell based, tissue ϮϬ
based, enzyme based, DNA biosensors, immune sensors etc. For example, metallothioenin proteins serve as a biosensor which has been found in plants, microorganisms and animals are good and fast detection methods of heavy metal contaminated organism (Gutiérrez et al 2009). Many studies which were dedicated to the bioindicator/biosensor methods provide significant results in regard to quality of environment. For example, Lichen and bryophytes are air quality indicators and used for assessing air quality (Adamo et al. 2007; Cesa et al. 2015). Presence of lichens in somewhere indicates good air quality but lichens diversity reductions indicate poor air quality. In this sense bioindicator indicates the changes at physical, chemical and biodiversity. Another example by *OVHUDQG(UGR÷DQ in their study comparison of heavy element content at varying distances (5m, 25m, 45m) from the near intense traffic road to understand whether intense traffic alter the surrounding environment or not and, they found significant positive correlation among the samples. In this example soil microbial enzyme activities were used as a bioindicator/biosensor. The ELRLQGLFDWRUV¶UHVSRQVHFDQEHVHHQDQGLQIRUPDERXWRXUDFWLRQVDQGLWJLYHVDQLGHDLIWKHDLUVRLO water or environment has good quality or not. Thus environmentally disturbances directly affect bioindicator species growth, population distribution, abundance and living behavior. In a nutshell, bioindicators have sensitivity or intolerant and function as early warning signals to environmental disturbances. Bioindicator organisms evaluate environmental changes qualitatively and provide a picture of conditions at the time of sampling, whereas biomonitor organisms determine the stress quantitatively and provide cumulative impacts of environmental alterations over certain period of time like take a videotape, even contaminant level change rapidly with time (Rosenberg et al.1986; Markert et al. 2003; Chakrabortty and Paratkar 2006). A biomonitor always acts as a bioindicator but a bioindicator does not always a biomonitor (Markert et al 2003). Biomonitoring can carry out at different level of biological materials, from at the community hierarchy down to molecular level in the organisms. Biomonitoring is the use of organisms to survey the environment (Gerhartd 2000). Biomonitoring studies provide an integrated view of an ecosystems and the quality of its surroundings. Thus biomonitoring provides an appealing tool for assessment of aquatic pollution (Zhou 2008; Sharanamd Sinha 2011). Biomonitoring is a better way to understand the effect of global environmental change on abiota and biotic communities in the future. Because it provides the best information about present and past state of the certain environment (Rosenberg et al. 1986). In practice, a suitable biomonitor have some specific features have to be met like: it has wide disturbance throughout the world; it has enough abundance in all over the monitoring area and represented in large numbers for repetition the study; it has ability to accumulate and tolerance to organic and inorganic elements without Ϯϭ
deaths; it can be found in different types of water and habitat; it can be reflect the conditions overtime; it should be tolerant to disturbances at measurable levels; it has long life span for compare in various age; it has to present during all season for sampling; it should have reasonable size for analysis; it can be easy to sample and identified well taxonomically (Butler et al. 1971; Wittig 1993; Chakrabortty and Paratkar 2006;Zhou et al. 2008). Heavy metals in aquatic environments intensively studied as a result of concern about their toxicity in drinking water, significance in biogeochemical cycles and also accumulative effects on human health. Thus, knowledge of their toxicity to aquatic organisms is important. Biomonitoring programs with well-designed and hypothesis-based will help to protect environment from global heavy metal pollutions. In this context the most used organisms are mentioned below; Plants Ferns, grass, different part of higher plants have been used in heavy metal biomonitoring studies for many years (Reboredo 1992; Gratton et al. 2000). Different parts of plants such as tree barks (Zhou et al. 2015), tree rings (Beramendi-Orosco et al. 2013), leaves(Clemens et al. 2002), cones (Reboredo et al. 2012), pine needles (Gratton et al. 2000), branches (Serbula et al. 2012) fruits (Bonanno 2014), flowers and root or stem ()LOLSRYLü-7UDMNRYLüHWDO) have been used for this purpose. According to Krstic et al. (2007) heavy metal accumulation in plants reaches highest level at the end of the their vegetation period. The elements may enter plants from the soil via roots, from air via leaves which transported from roots to leaves or precipitation (Rucandio et al. 2011). Bonanno (2014) in his study show that fruit of Ricinus communis (castor oil plant) is accepted better element accumulator of atmospheric pollution than the leaves. In his study, the fruits accumulate higher level of Pb and Zn than the leaves whereas the leaves Al, Cr, Hg and Ni levels greater than the fruit. Besides, due to leaf vacuoles have ability to store high concentration of elements, leaves of several species of plants have been thought suitable biomonitors of atmospheric pollution (Clemens et al. 2002). Kovacs et al. (1981) monitored three tree species leaves of rural and urban environments showed that the urban tree leaves accumulate elements 1.2 to 9 times higher than the rural tree environment. Easy sapling, large surface, long life and high lipid content make tree bark suitable for heavy metal studies (Zhou et al. 2015). To assess the traffic pollution or emission, conifers and its compartments like bark, cone and needles have been widely used (Gratton et al. 2000; Baslar et al. 2009; Reboredo et al. 2012). Mosses and lichens generally used in biomonitoring of air quality studies because they do not have direct contact with soil and obtain their nutrient from atmosphere (Lippo ϮϮ
et al 1995). But in urban and industrial areas these organisms do not exist therefore, vascular plants have gained importance in biomonitoring studies (Bonanno 2014). Plant species, plant organ, soil type which the plant live, interaction of element in the environment, species interactions and type of element affects distribution of metals in plants. It can be concluded that pROOXWHGHQYLURQPHQW¶VSODQWVDFFXPXODWHHOHPHQWVDWKLJKFRQFHQWUDWLRQDQGZKHQWKHVHHGLEOH plants or their parts consumed this will cause serious risk to human health. Also plant-insect interaction with pollinator insects leads to mobilization of elements through the food web (through plants) because of the accumulation features of plants (Boyd 1998). Zooplankton Zooplankton is a heterotrophic organism that they are weak swimmers found near the surface of the water and usually drift along with the current. Zooplankton includes protozoa (flagellates, ciliates, foraminiferas, radiolarias), crustacean (cladocera, copepod), amphipods, krills etc. comprises the important part of aquatic food web and their special features may offer an advantages for biomonitoring studies. Their environmental conditions have been forced them to develop certain structural adaptations to the environmental factors like turbulence, pollution, Ph, element availability, temperature, level of light and salinity. Due to they are important part of aquatic food web, they have species diversity, wide geographic distribution, huge biomass and abundance etc. they can indicate the environmental changes and be used to evaluate the health of an ecosystem (Battuello et al. 2016).In spite of all this, there are few biomonitoring studies with zooplankton. If these organisms live in a metal polluted environments, they are able to accumulate heavy metals at higher levels (Leborans et al. 1998) thus affect the food web. These benthic organisms consume elements generally via food, from bottom sediment and water from their habitat (Luoma et al. 1992). Protozoa or protists are eukaryotic and produce energy by photosynthesis and so are primary producers of marine food web. They have been used in biomonitoring studies due to well-known biology, ecological characteristics and advantage of practical handling in the laboratory (FernandezLeborans and Novillo 1994). Copepod is a small aquatic Crustaceans that constitute the most abundant (at least 70% of the zooplankton fauna) and dominant species of zooplankton communities with its ten orders. They are suspension-feeding grazers on phytoplankton and microzooplankton. They are link between primary production i.e. phytoplankton and secondary consumers in aquatic food web (Kadam and Tiwari 2015; Battuello et al. 2017). Therefore, they have important value in biomonitoring studies. Hsiao et al. (2011) reported that copepods are the Ϯϯ
most heavy metal accumulator zooplankton species and the accumulation level varies significantly between inter and intra-species. .QRZOHGJH DERXW ]RRSODQNWRQ FRPPXQLWLHV¶ KHDY\ PHWDO ELRavailabilities, provide great information about heavy metal accumulation and its transfer through the food web. Bivalve Bivalve also known as Lamellibranchiais one of the six classes of molluscs and so many of its members are eaten by people in large amounts (Gosling 2008). Beside to its commercial importance bivalves have been widely and successfully used as essential biomonitoring organisms in many countries for heavy element pollution monitoring, DQG WKLV DSSURDFK FDOOHG ³0XVVHO :DWFK 3URJUDP´ proposed to use by Edward Goldberg in 1975 (Goldberg 1975). Because of their lifestyle like wide geographical distribution, sedentary or semi-mobile life, have a reasonable size and a long life span, abundant population in coastal and estuarine areas, tolerant to various environmental alterations and have high bioaccumulation and bioconcentration ability to environmental contaminants, bivalves provide a suitable long-term monitoring tool (Bocchetti and Regoli 2006; Rainbow 2006; Zhou et al. 2008; Bezuidenhout et al. 2015). Adults form of these animals are bottom dweller and have been adapted to the benthic habitat and are living as a semi-mobile in benthos or attached to shells or rocks (Gosling 2008). Most of them burrow deeply (>30 cm) and live in it permanently but some of them live as attached on the surface (Rainbow 2006; Gosling 2008). By virtue of their sedimentary filter and suspension feeding habit they can sample the suspended particles in the water column and in sediment as well (Rainbow 2006; Sarkar et al. 2008). These organisms are able to accumulate several classes of pollutants and may serve as a risk assessment tool for environmental pollution and human health. Mosses Mosses are cryptogams and especially Ectohydric mosses have been used as biomonitors of atmospheric pollution (Onianwa 2001). They have been used for atmospheric pollution due to lack of real roots so they cannot take their nutrient from soil; have wide distribution; they are perennial and have slow growth rate; it has undeveloped vascular bundles; presence the areas ranging from less polluted regions to highly polluted regions and easy to sampling (Wolterbeek et al. 1996). Due to their cell walls have high cation exchange capacity, they can accumulate high concentration of elements (Markert et al. 2003). They accumulate elements rain and atmosphere by ion exchange capacity and chelation because they are lack of developed root system (Rucandio et al. 2011).
Mosses have been used at many countries from the time 1960s in national and international atmospheric metal transferring studies (Rühling 1994). Mosses and lichens metal accumulation behavior so they cannot be used to replace each another. High level of the pollutant accumulates in mosses through wet deposition whereas lichens better accumulate in arid conditions (Chakrabortty and Paratkar 2006). Besides, mosses more easily accumulate dust than lichens (Steinnes 1995; Chakrabortty et al. 2006). Algae Algae have high bioaccumulation abilities and transform heavy element pollutants through the aquatic food web and this may pose biomagnifications in animals and human health. Algae have high capacity to bind elements because of hydroxyl, carboxyl sulfate and amino groups of polysaccharide cellular wall act as ion exchangers and bind metal cations (Pinto et al. 2003). These features, therefore, some scientist make think to be used monitoring environmental deterioration. Element uptake capacity of algae depends on species phylogeny, growth, generation, thallus morphology as well as environmental factors like geology, pH, element interactions, season, temperature, salinity (McCormick and Cairns 1994; Trifan et al. 2015). Fishes Fish meat is healthy, nutritious and has an important value in balanced diet and support human health, well being due to have essential source of many proteins, amino acids, lipids, liposoluble vitamins, minerals and long chain polysaturated fatty acid (omega-3 and omega-6 fatty acids) (Belitz and Grosch1999; FAO 2010). It is healthy because, according to epidemiological studies coronary heart disease, hypertension and cancer risk are lower at regularly fish consumers (Simopolpoulos 1997), and thus it is highly recommended by doctors and dietitians. Beside to these usefulness, can be toxic if it live in a contaminated environment. Because, frequent consumption of the contaminated fish may cause hazardous health risks. Fishes are situated at the top position in the aquatic food chain and found almost every aquatic habitat, have a long lifespan, well defined taxonomy, have variety in their feeding habits and prone to accumulate more metals make them good monitoring tool of aquatic environment. Bioaccumulation degree in fish species influenced by a number of factors such as element type, exposure period, fish species, size, age, sex, feeding habit, tropic level, seasonal factors, sediment characteristics, oxygen concentration, water chemistry, pH value, temperature, salinity, hardness and sampling area (Asuquo et al. 2004; Carvalho et al. 2005; Adhikari et al. 2009).
Heavy metals enter to fish body via foods, gills, skin, suspended particles and oral consumption of water (Milanov et al. 2016). During their life, they feed mainly on insects, algae, small fish, crustaceans, rotifers and plants. Heavy metal accumulation studies with fish have been extensively studied and well documented (AlibabiüHWDOUysal et al. 2009; Sonne et al. 2014). Use of fish as a biomonitor is important because to ability of accumulate elements cause chronic or acute contamination in human who consumed fish regularly. For this purpose, muscle, liver, gill, skeleton, operculum heavy element levels are measured for indicate contaminant level in fish body (Culioli et al. 2009; Uysal et al. 2009; Sonne et al. 2014). Beside metallothionein levels (Linde$ULDV HW DO LQKLELWLRQ RI FKROLQHVWHUDVHV *DUFÕD HW DO OLSLG SHUR[LGDWLRQ OHYHO DQG activity of antioxidant enzymes (López-López et al. 2011), free radical degree sign of element accumulation in fish species and can be used as a biosensor/biomarkers studies. Sonne et al. (2014) studied common sculpin (Myoxocephalus scorpius) organ histology as bioindicator for element exposure, living in an inactive mining area show that 23 years after the mine was closed, some elements like Pb, As, Hg concentration in sculpin liver are still measurable level and decrease with the distance from the contaminant source. Culioli et al. (2009) studied a freshwater fish, living in a nearly 70 years after the mining activity suspended, indicate that As levels in water and fish still high and thought that Salmo trutta is a suitable species for biomonitoring studies. Apart from usefulness and suitability of fish species in biomonitoring environmental quality studies, it is also important to measure element content in fish species due to important value for human diet and nutrition. Thus, due to elemenWV¶ FXPXODWLYH EHKDYLRU DQG WR[LFLW\ NQRZOHGJH RI periodically monitored element concentrations in fish, other aquatic organisms and their abiotic environment, which are taken in the same place, is important for human health. Insects The earliest insect fossils about 400 million years ago in Devonian Period and Paleozoic Era (Grimaldi and Engel 2005; Price et al. 2011). Thus they live in various kind of climatic condition they have high adaptive ability then other animal. They can live almost everywhere from thermal pools (25-40 °C in Yellowstone National Park) to brine waters. They are in small size and this contributes to them live with huge biomass in narrow place and they make do with less food. They have different kind of life stage and every stage feed differently during their life span. The dominance of insects on earth also is due to its ability to fly. To have wing provides some advantages such as become abundance, escape from their enemy, easy to find food and spreading. As an invertebrate, the number of insects enormous than all combined vertebrate groups (Price et al. 2011). Insects have different feeding habits so in food web they occupy different position. Beside to this features insects are significant protein source for many inverbrates and vertebrates like Ϯϲ
amphibians, fish, reptiles, birds and mammals; they decomposed the plant biomass and animal corpses and accelerate their recycling in nature thus plays important roles in ecosystem functioning. Therefore, insects become a most diverse group and maintain their biodiversity on earth. They can be considered as key stone species because if they extinct ecosystem functioning could be collapse. Aquatic insects are inseparable part of freshwater ecosystems. To evaluate the quality, assessing and classifying the health status of aquatic ecosystem aquatic insects or water beetles provide better information about the environmental condition. A lot of work has been done all over the world related to the heavy metal biomonitoring of aquatic insects (Rosenberg et al. 1986; Borowska et al. 2004; Bonada et al. 2006; Burghelea HWDO$\GR÷DQHWDO$\GR÷DQHWDO 7KHVH insects have been used as bioindicator or biomonitor due to their intolerant behavior or capacity to accumulate contaminants in predictable amounts, even long after the pollution ceases (Nehring 1976; Nummelin et al. 2007). Insect transform the heavy elements to higher position throughout the food web (ZheQJ HW DO $W OHDVW RQH SDUW RI DTXDWLF EHHWOHV¶ OLIH Vpends in various aquatic habitats therefore any change in quality of these habitats can affect their numbers, diversity, species richness and also feeding habits. Thus aquatic insects are considered as biomonitoring organisms because of their species richness, cosmopolitan lifestyle and sensitivity of any quality change in their habitat. Among the aquatic beetle, predatory beetles such as Dytiscidae are prone to accumulate and transfer the heavy elements from lower levels of the food web (Burghelea et al. 2011). Besides Hydrophilidae are fed on mainly decaying plants considered as good biomonitor for KHDY\ HOHPHQWV $\GR÷DQ HW DO ,Q FRQWUDVW WR WROHUDQW VSHFLHV VRPH LQVHFWV OLNH (37 (Ephemeroptera, Plecoptera, Trichoptera) are sensitive to pollutants and so good indicator of high water quality whereas some of them like Chironomidae (Diptera) considerate as tolerant to environmental disturbances and capable to surviving in low quality of water (Wahizatul et al. 2011). Their composition, distribution, scarcity or abundance reflects the environmental change and they encompass most of the criteria generally accepted in the selection of biomonitor taxa. Heavy element accumulation behavior in organisms can vary between species. Heavy element uptake and excretion mechanism, their body size, requirements, prey choice, element type, high level of elements in their environment or life history lead to variation in element concentrations between species. For example, Zhong-Sheng (et al. 2009) showed in their heavy element accumulation study in the samples from same habitat, mercury (Hg) was the most bio-magnified element in carnivorous insects whereas lead (Pb) and cadmium (Cd) were not accumulated when it is considered food web extended to the secondary consumers. In their study elements moved soil to plants, plants to herbivorous insects and herbivorous insects to carnivorous insects. Boyd (2009) in his study shows that Ni hyper-accumulator insects which feed on Ni hyper-accumulator plants, Ϯϳ
accumulate more Ni than WKH RWKHU LQVHFW VSHFLHV $\GR÷DQ HW DO VWXGLHG +\GURSKLOLGDH (Coleoptera) species as a biomonitor of heavy element pollution show that Paracymus chalceolus and Berosus spinosus species have high capabilities to accumulate certain heavy elements than their environments. Heavy metals would firstly be absorbed by plants in soil then assimilate and transfer along to the food chain by animals and pass on from one tropic levels to another (Nehring 1976; ZheQJHWDO$\GR÷DQHWDO 6RFRQFHntration factor is affected by elements and biota in the food chain. The following conclusions can be drawn; World natural heritages (rivers, seas, oceans, wetlands etc.) have been contaminated, exploited, mistreated and eradicated. Without water, there is no life. If we don't care for it, respectful to it, preserve it and abuse it we will end up destroying ourselves. We must learn to value, conserve, and take care of the waters we have. Scientists are still putting together pieces of the heavy element pollution puzzle. We can simply help prevent water pollution by not littering. Because once water is contaminated, it is difficult, expensive, and sometimes impossible to remove pollutants. Element pollution not only affect quality of food but also influence quality of air, soil, water bodies and threaten living organisms and human beings by the way of food web (Zhang 1999). Unless protect our wildlife human health cannot be protected (Newman 2010). When food chain is considered, heavy elements may reach to one organism to another at the end, human beings. By using biotic indices, we can summarize the ecological quality in a simple way. Biological monitoring and evaluation is used in some countries like Australia, United States of America, and European Community members and is a government obligation (López-López and Sedeño-Díaz 2015). Moreover cosmopolitan heavy element biomonitoring studies provide cross reference across large geographical areas (Rainbow 2006). Every country must create government policies and constitute new units about environment and its quality. These units should continuously monitor aquatic habitat like streams, lakes, rivers and groundwater as well as soil and air quality to ensure quality of environment and minimize environmental degradation. Long-term monitoring strategy keep environment healthy and away from elemental disease. Beside if we continue the biomonitoring studies we will understand whether species adapted the polluted environment by genetically or not. Metal concentration varies among the different species even in taxonomically close species. Comparative approach among the different species can provide critical information to understand bio-kinetic of metal and its accumulation between different species (Wang and Rainbow 2008).
The analytical quality of heavy element (sample preservation, preparation and analysis) in both biotic and abiotic samples is important and made in calibrated laboratories. Otherwise the information which given in any study will be wrong. Besides to analytical information statistical information is also important. For examples analyzed biological tissues, age, sex, size, species and time between sampling make the comparison complex and it is not enough to evaluate only geometric means, arithmetic means and median values. Also, in contrast to organic pollutants such as PCBs (polychlorinated biphenyls), PAHs (polycyclic aromatic hydrocarbons), HCBs (hexachloro cyclohexane) heavy elements are generally nondegredable. To prevent an environment a monitoring program should be established not only for trace metals but also for hydrocarbons and organo chlorine pesticides. References Adamo P, Crisafulli P, Giordano S, Minganti V, Modenesi P, Monaci F. 2007. Lichen and moss bags as monitoring devices in urban areas. Part II: trace element content in living and dead biomonitors and comparison with synthetic materials. Environ Pollut, 146, 392e399. Adhikari S, Ghosh L, Rai S, Ayyappan S. 2009. Metal concentrations in water, sediment, and fish from sewage-fed aquaculture ponds of Kolkata, India. Environ Monit Assess, 159, 217±230 Akimoto H. 2003. Global Air Quality and Pollution. Science, 302 (5651), 1716-1719. Doi: 10.1126/science.1092666. Alibabiü V, Vahþiü N, Bajramoviü M. 2007. Bioaccumulation of metals in fish of Salmonidae family and the impact on fish meat quality. Environ Monit Assess, 131, 349±364. Anonymous
files/documents/library/leaflet_1.pdf (Accessed: 02.10.2017). Anonymous 2017. http://www.ramsar.org/ (Accessed 02.09.2017). Anonymus 1. Chemistry. Pedia Press. http://pediapress.com/books/show/chemistry-by-wikipedians/ Appenroth KJ. 'HILQLWLRQRI³+HDY\0HWDOV´DQGWKHLUUROHLQELRORJLFDOV\VWHPV,Q6RLO Heavy Metals. Soil Biology, 19, 19-29, Springer, Berlin, Heidelberg. Asuquo FE, Ewa-Oboho I, Asuquo EF, Udo PJ. 2004. Fish species used as biomarker for heavy metal and hydrocarbon contamination for Cross river, Nigeria. The Environmentalist, 2, 29±37.
$\GR÷DQ=*URO $øQFHNDUDh7KHLQYHVWLJDWLRQRIKHDY\HOHPHQWDFFXPXODWLRQLQVRPH Hydrophilidae (Coleoptera) species. Environmental monitoring and assessment, 188(4), 204. $\GR÷DQ = ùLúPDQ 7 øQFHNDUD h *URO $ +HDY\ PHWDO DFFXPXODWLRQ LQ VRPH DTXDWLF insects (Coleoptera: Hydrophilidae) and tissues of Chondrostoma regium (Heckel, 1843) relevant to their concentration in water and sediments from Karasu River, Erzurum, Turkey. Environ Sci Pollut Res, 24 (10), 9566-9574. Doi: 10.1007/s11356-017-8629-x. Baslar S, Dogan Y, Durkan N andBag H. 2009. Biomonitoring of zinc and manganese in bark of Turkish redpine of western Anatolia. J Environ Biol, 30, 831±834. Battuello M, Brizio P, Sartor RM, Nurra N, Pessani D, Abete MC, Squadrone S. 2016. Zooplankton from a North Western Mediterranean area as a model of metal transfer in a marine environment. Ecological Indicators, 66, 440-451. http://dx.doi.org/10.1016/j.ecolind.2016.11.041 1 Battuello M, Sartor RM, Brizio P, Nurra N, Pessani D, Abete MC, Squadrone S. 2017. The influence of feeding strategies on trace element bioaccumulation in copepods (Calanoida). Ecological Indicators, 74, 311-320. Belitz HD, Grosch W. 1999. Food chemistry. Springer, Berlin Heidelberg New York, 992±998. Beramendi-Orosco LE, Rodriguez-Estrada ML, Morton-Bermea O, Romero FM, GonzalezHernandez G, Hernandez-Alvarez E. 2013. Correlations between metals in tree-rings of Prosopis julifora as indicators of sources of heavy metal contamination. Applied geochemistry, 39, 78-84. Bezuidenhout J, Dames N, Botha A, Frontasyeva MV, Goryainova ZI, Pavlov D. 2015. Trace elements in Mediterranean mussels Mytilus galloprovincialis from the South African West Coast. Ecological Chemistry and Engineering S, 22(4), 489-498. Bing H, Zhou J, Wu Y, Wang X, Sun H, Li R. 2016. Current state, sources, and potential risk of heavy metals in sediments of Three Gorges Reservoir, China. Environmental Pollution, 214, 485496. Bini C, Bech J. 2014. PHEs, environment and human health, 401±463, Dordrecht, Springer. Blake J. 1884. On the Connection between Physiological Action and Chemical Constitution. The Journal of Physiology, 5, 36-44. http://dx.doi.org/10.1113/jphsiol.1884.sp000148.
Bocchetti R and Regoli F. 2006. Seasonal variability of oxidative biomarkers, lysosomal parameters, metallothioneins and peroxisomal enzymes in the Mediterranean mussel Mytilus galloprovincialis from Adriatic Sea. Chemosphere 65, 913±921. Bonada N, Prat N, Resh VH, Statzner B. 2006. Developments in Aquatic Insect Biomonitoring: A Comparative Analysis of Recent Approaches. Annual Review of Entomology, 52: 495-523. Bonanno G. 2014. Ricinus communis as an Element Biomonitor of Atmospheric. Water Air Soil Pollut, 225: 1852. Doi: 10.1007/s11270-013-1852-2. Borowska J, Sulima B, Nikiliñska M, Pyza E. 2004. Heavy metal accumulation and its effects on development, survival and immuno-competent cells of the housefly Musca domestica from closed laboratory populations as model organism. Fresenisus Environ. Bull. 13: 1402-1409. Boyd RS. 1998. The significance of metal hyperaccumulation for biotic interactions. Chemoecology, 8, 1-7. Boyd RS. 2009. High-nickel insects and nickel hyperaccumulator plants: A review. Insect Science, 16, 19-31, Doi 10.1111/j.1744-7917.2009.00250.x. Burghelea CI, Zaharescu DG, Hooda PS, Palanca-Soler A. 2011. Predatory aquatic beetles, suitable trace elements bioindicators. J Environ Monit, 13, 1308. Doi: 10.1039/c1em10016e. Burton Jr, GA. 2002. Sediment quality criteria in use around the world. Limnology, 3(2), 65-76. https://doi.org/10.1007/s102010200008. Butler PA, Andren L, Bonde GJ, Jernelov A, Reisch DJ. 1971. Monitoring organisms. FAO fisheries reports, 99(1), 101-112. Cairns J, Pratt JR. 1993. A History of Biological Monitoring Using Benthic Macroinvertebrates. Freshwater Biomonitoring and Benthic Macroinvertebrates, Rosenberg DM and Resh VH eds., Chapman & Hall, NY. Carvalho ML, Santiago S, Nunes ML. 2005. Assessment of the essential element and heavy metal content of edible fish muscle. Analytical and Bioanalytical Chemistry, 382(2), 426-432. Cesa M, Bertossi A, Cherubini G, Gava E, Mazzilis D, Piccoli E, Verardo P, Nimis PL. 2015. Development of a standard protocol for monitoring trace elements in continental waters with moss
bags: inter- and intra specific differences. Environ Sci Pollut Res, 22 (7), 5030-5040. http://dx.doi.org/10.1007/s11356-015-4129-z. Chakrabortty S, Paratkar GT. 2006. Biomonitoring of trace element air pollution using mosses. Aerosol and Air Quality Research, 6(3), 247-258. Chellan P, Sadler PJ. 2015. The elements of life and medicines. Phil Trans R Soc A, 373(2037), 20140182. 373.2037: 20140182. Doi: 10.1098/rsta.2014.0182. Chen T, Liu X, Zhu M, Zhao K, Wu J, Xu J, Huang P. 2008. Identification of trace element sources and associated risk assessment in vegetable soils of the urban±rural transitional area of Hangzhou, China Environ Pollut, 151, 67±78. Clark RB. 1992. Marine Pollution. Cleavendo Press, 128-212, Oxford. UK. Clemens S, Plamgren MG, Kramer U. 2002. A long way ahead: understanding and engineering plant metal accumulation. Trends in Plant Science, 7(7), 309±315. Culioli JL, Calendini S, Mori C, Orsini A. 2009. Arsenic accumulation in a freshwater fish living in a contaminated river of Corsica, France. Ecotoxicology and environmental safety, 72(5), 14401445. Davies OA and Abowei JFN. 2009. Sediment quality of lower reaches of Okpoka Creek, Niger Delta, Nigeria. European Journal of Scientific Research26 (3): 437 ± 442. Deng W, Li X, An Z, Yang L, Hou, K, Zhang, Y. 2017. Identification of sources of metal in the agricultural soils of the Guanzhong Plain, northwest China. Environmental toxicology and chemistry, 36(6), 1510-1516. Ding XG, Ye SY, Gao ZJ. 2005. Methods of heavy metal pollution evaluation for offshore sediments. Marine Geol Lett. 21, (8), 31. Duce RA, Hoffman GL, Zoller WH. 1975. Atmospheric Trace Metals at Remote Northern and Southern Hemisphere Sites: Pollution or Natural? Science, 187(4171), 59-61. Doi: 10.1126/ science.187.4171.59. Dudgeon D, Arthington AH, Gessner MO, Kawabata ZI, Knowler DJ, Lévêque C, Naiman RJ, Richard AHP, Soto D, Stiassny MLJ, Sullivan CA. 2006. Freshwater biodiversity: importance, threats, status and conservation challenges. Biological reviews, 81 (2), 163-182. ϯϮ
Duffus JH. 2002. Heavy Metal; A Meaningless Term? Pure and Applied Chemistry, 74, 793-807. http://dx.doi.org/10.1351/pac200274050793 Ebbing DD, Gammon SD. 2017. General Chemistry. 11. Edt., 1152 p, Cengage Learning, Boston, USA. Emsley J. 2011. Nature's Building Blocks: An A-Z Guide to the Elements (New ed.). New York, NY: Oxford University Press. ISBN 978-0-19-960563-7. EPA (Environmental Protection Agency). 2012. Wetlands. Available from: http://water.epa.gov/ type/wetlands/index.cfm EPA (Environmental Protection Agency). 2016. https://www.epa.gov/sites/production/files /201602/documents/wetlandfunctionsvalues.pdf (Accessed 02.10.2017) Evanko CR, Dzombak DA. 1997. Remediation of metals-contaminated soils and groundwater. Ground-water remediation technologies analysis center, Pittsburg, USA. FAO. 2010. Nutritional elements of fish. http://www.fao.org/fishery/topic/12319/en. (Accessed 20 March 2016). Fergusson JE. 1990. The Heavy Elements: Chemistry, Environmental Impact and Health Effects. Pergamon Press, Oxford. FernandezǦLeborans G, Novillo A. 1994. Experimental Approach to Cadmium Effects on a Marine Protozoan Community Untersuchungen zum Einfluß
von Cadmium auf eine
ProtozoenǦGemeinschaft. CLEAN±Soil, Air, Water, 22(1), 19-27. )LOLSRYLü-7UDMNRYLü 5 ,OLü =6 âXQLü / $QGMHONRYLü 6 7KH potential of different plant species for heavy metals accumulation and distribution. J Food Agric Environ, 10(1), 959-964. Foster W. 1936. Inorganic Chemistry (Niels Bjerrum). Frieden E. 1974. The evolution of metals as essential elements (with special reference to iron and copper). Adv Exp Med Biol;48:1-29. Gerhardt A. 2000. Biomonitoring of polluted water. Trans Tech Publications Ltd, Switzerland, 120. Govind P, Madhuri S. 2014. Heavy metals causing toxicity in animals and fishes. Research Journal of Animal, Veterinary and Fishery Sciences, 2(2), 17-23.
Goldberg E. 1975. The mussel watch - a first step in global marine monitoring. Marine Pollut Bull. 6, 7, 111-123. Doi: 10.1016/0025-326X(75)90271-4. Gosling E. 2008. Bivalve Molluscs: Biology, Ecology and Culture. John Willey and Sons, 456. Govind P, Madhuri S and Shrivastav AB. 2014. Fish Cancer by Environmental Pollutants, 1st Ed, Narendra Publishing House, Delhi, India. Gratton WS, Nkongolo KK and Spiers GA. 2000. Heavy metal accumulation in soil and jack pine (Pinus banksiana) needles in Sudbury, Ontario, Canada. Bull Environ Contam Toxicol, 64, 550± 557. Gutiérrez JC, Amaro F, Martín-González A. 2009. From heavy metal-binders to biosensors: Ciliate metallothioneins discussed. Bio Essays, 31(7), 805-816. Doi: 10.1002/bies.200900011. Gupta V. 2013. Mammalian Feces as Bio-Indicator of Heavy Metal Contamination in Bikaner Zoological Garden, Rajasthan, India. Res. J. Animal, Veterinary and Fishery Sci., 1(5), 10-15. *OVHU)(UGR÷DQ(7KHHIIHFWVRIKHDY\PHWDOSROOXWLRQRQHQ]\PHDFWLYLWLHVDQGEDVDOVRLO respiration of roadside soils. Environmental monitoring and assessment, 145(1), 127-133. Gray JS. 1989. Effects of environmental stress on species rich assemblages. Biological Journal of the Linnean Society 37:19±32. Hare L, Saouter E, Campbell PGC, Tessier A, Ribeyre F, Boudou A. 1991. Dynamics of cadmium, lead, and zinc exchange between nymphs of the bumwing mayfly Mexcogenia rigida (Ephemeroptera) and the environment. Can J Fish Aquat Sci, 48 (1), 39-47. https://doi.org/ 10.1139/f91-006. Hsiao S-H, Hwang J-S, Fang T-H. 2011. Copepod species and their trace metal contents in coastal northern Taiwan. J Mar Syst, 88: 232±238. doi:10.1016/j.jmarsys.2011.04.009. Hawkes SJ.
1997. What Is a Heavy Metal? Journal of Chemical Education, 74, 1374.
http://dx.doi.org/10.1021/ed074p1374 Holt EA, Miller SW. 2011. Bioindicators: Using Organisms to Measure Environmental Impacts. Nature Education Knowledge 2(2), 8.
Hu G, Yu R, Zhao J, Chen L. 2011. Distribution and enrichment of acid-leachable heavy elements in the intertidal sediments from Quanzhou Bay, southeast coast of China. Environmental Monitoring and Assessment, 173 (1-4), 107-116. Huu HH, Rudy S, Van Damme A. 2010. Distribution and contamination status of heavy metals in estuarine sediments near Cau Ong harbor, Ha Long Bay, Vietnam. Geology Belgica,13 (1-2), 37 ± 47. Hynes HBN. 1960. The Biology of Polluted Waters. Liverpool, UK: Liverpool Univ. Press. 202p. +DZNHV6-:KDWLV³+HDY\0HWDO"´-&KHP Educ 74(11), 1374. Doi: 10.1021/ ed074p1374. Hutton M and Symon C. 1986. The quantities of cadmium, lead, mercury and arsenic entering the UK environment from human activities. Science of the total environment, 57, 129-150. Jones L, Atkins PW. 2004. Chemistry: molecules, matter and change. TPB. Kabata-Pendias A and Pendias H. 2001. Trace element in soil and plants. Boca Raton. 413 p. Kadam SS, Tiwari LR. 2015. Distribution, abundance and species diversity of copepods from dandi creek west coast of India. Kelly J, Thornton I, Simpson P. 1996. Urban geochemistry: A study of the influence of anthropogenic activity on the heavy metal content of soils in traditionally industrial and nonindustrialareas of Britain. Appl Geo chem., 11, 363±370. Kishe MA, Machiwa JF. 2003. Distribution of heavy metals in sediments of Mwanza Gulf of Lake Victoria, Tanzania. Environment International, 28, 619± 625. Kisku GC, Barman SC, Bhrgava SK. 2000. Contamination of soil and plants with potentially toxic elements irrigated with mixed industrial effluent and its impact on the environment. Water Air and Soil Pollution, 120(1-2), 121-137. Klein C. 2012. The Great Smog of 1952. http://www.history.com/news/the-killer-fog-thatblanketed-london-60-years-ago (Accessed 09.10.2017). Kovacs M, Podani J, Klincsek P. 1981. Element composition of the leaves of some deciduous trees and the biological indication of heavy metals in an urban-industrial environment. In Acta Bot Acad Sci Hung, 27, 43-52.
Krstic B, Stankovic D, Igic R andNikolic N. 2007. The potential of different plant species for nickel accumulation. J Biotechnol Equip, 21, 431-436. Leborans GF, Herrero YO, Novillo A. 1998. Toxicity and bioaccumulation of lead in marine protozoa communities. Ecotoxicology and environmental safety, 39 (3), 172-178. Lenntech K. 2004. Water treatment and air purification. Published by Rotter Dam Seweg, Netherlands. Lippo H, Poikolainen J, Kubin E. 1995. The use of moss, lichen and pine bark in the nation wide monitoring of atmospheric heavy metal deposition in Finland. Water, Air, and Soil Pollution, 85(4), 2241-2246. López-López E, Sedeño - Díaz JE, Soto C, Favari L. 2011. Responses of antioxidant enzymes, lipid peroxidation, and Na+/K+-ATPase in liver of the fish Goodea atripinnis exposed to Lake Yuriria water. Fish Physiol Biochem 37, 511±522. López-López E, Sedeño-Díaz JE. 2015. Biological Indicators of Water Quality: The Role of Fish and Macroinvertebrates as Indicators of Water Quality. In: Armon R., Hänninen O. (eds) Environmental Indicators. Springer, Dordrecht. doi: 10.1007/978-94-017-9499-2_37. Luoma SN, Johns C, Fisher NS, Steinberg NA, Oremland RS, Reinfelder JR. 1992. Determination of selenium bioavailability to a benthic bivalve from particulate and solute pathways. Environ Sci Technol, 26, 485±491. Lyman WJ. 1995. Transport and transformation processes. In Fundamentals of Aquatic Toxicology, GM Rand (Ed.), Taylor & Francis, Washington DC. Mackay SJ, Arthington AH, James CS. 2014. Classification and comparison of natural and altered flow regimes to support an Australian trial of the Ecological Limits of Hydrologic Alteration framework. Ecohydrology, 7 (6), 1485-1507. Doi: 10.1002/eco.1473. Markert BA, Breure AM, Zechmeister HG. 2003. Definitions, strategies and principles for bioindication/biomonitoring of the environment. Trace Metals and other Contaminants in the Environment, 6, 3-39. McCormick PV, Cairns J. 1994. Algae as indicators of environmental change. Journal of Applied Phycology, 6(5-6), 509-526.
Mehrotra P. 2016. Biosensors and their applications. A review. Journal of Oral Biology and Craniofacial Research, 6 (2), 153-159. https://doi.org/10.1016/j.jobcr.2015.12.002. 0LODQRY5.UVWLü00DUNRYLü5-RYDQRYLü'%DOWLü%,YDQRYLü--RYHWLü 0%DOWLüä0 Analysis of heavy metals concentration in tissues of three different fish species included in human diet from Danube River, in the Belgrade Region, Serbia. Acta Vet (Beograd), 66(1), 89±102 Ming-Ho Y. 2005. Environmental Toxicology: Biological and Health Effects of Pollutants, Chap. 12, CRC Press LLC, ISBN 1-56670-670-2, 2nd Edition, Boca Raton, USA. Mitsch WJ, Bernal B, Hernandez ME. 2015. Ecosystem services of wetlands. International Journal of Biodiversity Science, Ecosystem Services & Management, 11(1), 1-4. http://dx.doi.org/ 10.1080/21513732.2015.1006250. Mudroch A, Azcue JM, Mudroch P. 1998. Manual of Bioassessment of Aquatic Sediment Quality. CRC Press, 256p. Mudroch A, Azcue JM. 1995. Manual of Aquatic Sediment Sampling. CRC Press, 240p. Mulgrew A and Williams P 2004. Biomonitoring of air quality using plants. Air Hygiene Report No. 10. PP:1-100. Müller U. 2007. Inorganic Structural Chemistry. John Wiley, Chichefster. Nehring RB. 1976. Aquatic insects as biological monitors of heavy metal pollution. Bull Environ ContamToxicol 15 (2), 147±154. Newman MC. 2010. Fundamental of Ecotoxicology. 3rd edition, CRC Press, 551. Nordberg GF, Fowler BA, Nordberg M. (Eds.). 2014. Handbook on the Toxicology of Metals. Academic Press. Nriagu JO. 1991. Human influence on the global cycling of the metals. In J.G. Farmer (ed.) heavy metals in the environment. CEP consultants Ltd., Edinburgh, UK. 1: 1-5. Ntakirutimana T, Du G, Guo JS, Gao X, Huang L. 2013. Pollution and Potential Ecological Risk Assessment of Heavy Metals in a Lake. Pol J Environ Stud, 22 (4), 1129-1134. Nummelin M, Lodenius M, Tulisalo E, Hirvonen H, Alanko T. 2007. Predatory insects as bioindicators of heavy metal pollution. Environ Pollut, 145, 339±347.
Oeding S, Taffs KH. 2015. Are diatoms a reliable and valuable bio-indicator to assess sub-tropical river ecosystem health? Hydrobiologia, 758 (1), 151-169. https://doi.org/10.1007/s10750-015-22870. Ololade IA, Lajide L, Amoo IA, Oladoja NA. 2008. Investigation of heavy metals contamination of edible marine seafood. African Journal of Pure and Applied Chemistry, 2 (12), 121-131 Olubunmi FE and Olorunsola OE. 2010. Evaluation of the Status of Heavy Metal Pollution of Sediment of Agbabu Bitumen Deposit Area, Nigeria. European Journal of Scientific Research, 41 (3), 373-382. Onianwa PC. 2001. Monitoring Atmospheric Metal Pollution: A Review of the Use of Mosses as Indicators. Environ Monit Assess, 71, 13-50. Oves M, Khan MS, Zaidi A, Ahmad E. 2012. Soil contamination, nutritive value, and human health risk assessment of heavy metals: an overview. In Toxicity of heavy metals to legumes and bioremediation. Springer Vienna, pp. 1-27. Pais I, Jones Jr JB. 1997. The handbook of trace elements. CRC Press. Pandey BL. 1983. A study of the effect of Tamrabhasma on experimental gastric ulcers and secretions. Indian J Exp Biol, 21, 25±64. Pinto E, SigaudǦkutner T, Leitao MA, Okamoto OK, Morse D, Colepicolo P. 2003. Heavy metal± induced oxidative stress in algae. Journal of Phycology, 39(6), 1008-1018. Phillips DJH. 1990. In: Furness RW, Rainbow PS (eds) Heavy Metals in the Marine Environment, Boca Raton: CRC Press. Phillips DJH, Rainbow PS. 1994. Biomonitoring of trace aquatic contaminants. Chapman & Hall, 293, London. Prashanth L, Kattapagari KK, Chitturi RT, Baddam VRR, Prasad LK. 2015. A review on role of essential trace elements in health and disease. Journal of Dr. NTR University of Health Sciences, 4(2), 75. Rahmanpour S, Ashtiyani SML, Ghorghani NF. 2016. Biomonitoring of heavy metals using bottom fish and crab as bioindicator species, the Arvand River. Toxicology and Industrial Health, 32(7) 1208±1214. Doi: 10.1177/0748233714554410. ϯϴ
Rainbow PS. 2006. Biomonitoring of Trace Metals in Estuarine and Marine Environments. Australasian journal of Ecotoxicology, 12 (3), 107-122. Radojevic M, Bashkin VN. 1999. Practical Environmental Analysis, Royal Society of Chemistry, UK. Rajeswari TR, and Sailaja N. 2014. Impact of heavy metals on environmental pollution. J of Chemical and Pharmaceutical Sciences, 3, 175-181. Reboredo, F. 1992. Cadmium accumulation by Halimione portulacoides (L.) Aellen: A seasonal study. Mar Environ Res 33, 17±29. Reboredo F, Barbosa R, Mendes B. 2012. Can Cone Scales and Bark of Aleppo Pine Be Used in the Biomonitoring of Some Heavy Metals? Soil and Sediment Contamination: An International Journal, 21(7), 789-801. Rishi KK, Jain M. 1998. Effect of toxicity of cadmium on scale morphology in Cyprinus carpio (Cyprinidae). Bulletin of environmental contamination and toxicology, 60(2), 323-328. Rosenberg DM, DanksHV, Lehmkuhl D0 øPSRUWDQFH RI LQVHFWV LQ HYLURQPHQWDO LPSDFW assessment. Environmental Management, 10 (6), 773-783. Rucandio MI, Petit-Domínguez MD, Fidalgo-Hijano C, García-Giménez R. 2011. Biomonitoring of chemical elements in an urban environment using arboreal and bush plant species. Environmental Science and Pollution Research, 18(1), 51-63. Rusu AM, Dubbin W, Har N, Bartok K, Purvis W, Williamson B. 2000. Heavy metal soil content as an indicator of pollution. Studia universitatis %DEHú-%RO\DÕ*HRORJLD;/9-113. Sarkar SK, Cabral H, Chatterjee M, Cardoso I, Bhattacharya AK, Satpathy KK, Alam MA. 2008. Biomonitoring of heavy metals using the bivalve molluscs in Sunderban mangrove wetland, northeast coast of Bay of Bengal (India): possible risks to human health. CLEAN±Soil, Air, Water, 36(2), 187-194. Serbula SM, Miljkovic DD, Kovacevic RM, Ilic AA. 2012. Assessment of airborne heavy metal pollution using plant parts and topsoil. Ecotoxicology and Environmental Safety, 76, 209-214. Sherene T. 2010. Mobility and transport of heavy metals in polluted soil environment. Biological Forum, An International Journal, 2(2): 112-121. ϯϵ
Shrader DE, Lucinda MV, Covick LA. 1983. The Determination of toxic metals in waters and wastes by furnace Atomic Absorption. Varian Instruments at Work, Varian Atomic Absorption. No. AA-31, June. Simopolpoulos AP. 1997. Seafood from producer to consumer: natural aspects of the fish. In: Lutten JB, Borresen T, Oehlenschla¨ ger J (eds) Elsevier, Amsterdam, vol 38, pp 587±607 Singh R, Gautam N, Mishra A, Gupta R. 2011. Heavy metals and living systems: An overview. Indian J Pharmacol, 43 (3), 246±253. doi: 10.4103/0253-7613.81505 Sonne C, Bach L, Søndergaard J, Rigét FF, Dietz R, Mosbech A, Leifsson PS, Gustavson K. 2014. Evaluation of the use of common sculpin (Myoxocephalus scorpius) organ histology as bioindicator for element exposure in the fjord of the mining area Maarmorilik, West Greenland. Environmental research, 133, 304-311. Steinnes E, Allen RO, Petersen HM, Ramback JP,Varskog P. 1997. Evidence of large-scale heavy metal contamination of natural surface soils in Norway from long-range atmospheric transport. Science of the Total Environment, 205, 255. Swarnalatha K, Nair AG. 2017. Assessment of sediment quality of a tropical lake using sediment quality
Doi: 10.1111/lre.12162. Tchounwou PB, Yedjou CG, Patlolla AK, Sutton DJ. 2012. Heavy metals toxicity and the environment. EXS, 101, 133±164. doi: 10.1007/978-3-7643-8340-4_6 Tilman D and Clark M. 2015. Food, Agriculture & the Environment: Can We Feed the World & Save the Earth? Daedalus, 144 (4), 8-23. Traichaiyaporn S. 2000. Water Quality Analysis. Biology Department, Faculty of Science, Chiang Mai University. 7ULIDQ$%UHDEăQ,*6DYD'%XFXU/7RPa CC, Miron A. 2015. Heavy Metal Content in macro algae from Roumanian Black Sea. Rev Roum Chim, 60(9), 915-920. Uchida S, Tagami K, Hirai I.2007. Soil-to-Plant Transfer Factors of Stable Elements and Naturally Occurring Radionuclides: (2) Rice Collected in Japan J Nucl Sci Technol, 44, 779±790.
USEPA (US Environmental Protection Agency). 1995. America's Wetlands: Our Vital Link Between Land and Water. EPA843-K-95-001. Washington, DC: U.S. Environmental Protection Agency, Office of Water, Office of Wetlands, Oceans and Watersheds. Uysal K, Köse E, Bülbül M, Dönmez M, Erdo÷an Y, Koyun M, Ömero÷lu Ç, Özmal F. 2009. The comparison of heavy metal accumulation ratios of some fish species in Enne Dame Lake (Kütahya/Turkey). Environ Monit Assess, 157, 355±362. Wahizatul AA, Long SH, Ahmad A. 2011. Composition and distribution of aquatic insect communities in relation to water quality in two freshwater streams of Hulu Terengganu, Terengganu. Journal of Sustainability Science and Management 6 (1), 148-155. Wang WX and Rainbow PS. 2008. Comparative approaches to understand metal bioaccumulation in aquatic animals. Comparative Biochemistry and Physiology Part C: Toxicology & Pharmacology, 148(4), 315-323. WHO (World Health Organization). 1996. Trace elements in human nutrition and health. World Health Organization. Wolterbeek HT, Bode P, Verburg TG. 1996. Assessing the Quality of Biomonitoring Via Signal-toNoise Ratio Analysis. Sci Total Environ, 180, 107-116. Woodriff AM. 2013. Heavy metals. What does this term mean? http://22.214.171.124 /~heavymet/wpcontent/uploads/2013/07/HeavyMetals.AnnWoodriff1.pdf (accessed 05.04.2016) Victor JN, Nor Hasyimah AK, Pearline NHC, Lee CY, The YY. 2012. A comparative study of Cd and Pb concentration in selected commercial marine fishes from wet markets and supermarkets in Klang Valley, Malaysia. Health Environ J 3, 25±37