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«Dissertation zur Erlangung des Grades “Doktor der Naturwissenschaften” Im Promotionsfach Geowissenschaften Am Fachbereich Chemie, Pharmazie und ...»

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1983). The calculated mean for the Cu background level of 25 soil samples in the vicinity of the industrial complex of Port Kembla, NSW, Australia with a copper smelter, steelworks and associated industries was 49 mg/kg at a depth of 0–5 cm with maximum reached 599 mg/kg and 38 mg/kg at the depth of 5-20 cm with maximum reached 1597 mg/kg. Copper concentrations were high closer to the contamination sources and decreased rapidly within the first 5 km, the Cu decrease trend followed an exponential function and the Cu contamination complex was considered to be within 4 km from the complex (Martley et al. 2004). Soils exposed to emissions from the Ventanas copper smelter in central Chile were collected and analyzed. Total copper concentrations in the topsoils were found in a range of 310-640 mg/kg in contrast with 30–60 mg/kg range at depth 30–60 cm (Neaman et al. 2009). Copper in agricultural soils next to over 40 years mining activities at the Jinchang, Gansu province, China showed total Cu content ranged from 131 mg/kg to 828mg/kg with mean total copper concentration 277 mg/kg (Shengli et al. 2009).

Introduction

Several studies reported copper-enriched roadside soils and dust well over background levels. Mean copper concentrations in Moncton, New Brunswick, roadside soils were 45 mg/kg and ranged from 6 to 162 mg/kg (Cool et al. 1980). Roadside soils and dusts from the UK and New Zealand had higher mean concentrations ranging from 42.5 to 115 mg/kg (Harrison et al.

1981; Thornton et al. 1985; Ward 1990; Ward et al. 1977). Christoforidis et al. (2009) analyzed 96 street dusts and 96 roadside soils samples from three different localities (urban, industrial, peripheral) of the city of Kavala (Greece) and found the mean copper value in street dust was

123.9 mg/kg and roadside soil at 42.7 mg/kg. In general, street and highway dusts contained higher copper concentrations than the corresponding roadside soils.

Total copper was studied in 170 surface layers of soils from seven vineyard regions located in the NWIberian Peninsula (Rías Baixas, Ribeira Sacra, Ribeiro, Monterrei, Valdeorras, O Bierzo and Vinhos Verdes) in Spain. Total Cu content in Ribeiro (248±130 mg/kg) and Ribeira Sacra (259±118 mg/kg) soils were significantly higher than those observed for the rest of the vineyard regions (169±90, 139±122, 115±42, 103±42 and 100±48 mg/kg in Valdeorras, Rías Baixas, O Bierzo, Vinhos Verdes and Monterrei, respectively) (Fernández-Calviño et al. 2009).

The increased Copper concentrations were due to long term application of Cu based fungicides.

Copper contaminated non-active vineyard soils (168 mg/kg) exceeding EU limit from small wine producers in Marefy area at the Czech Republic was reported. The highest Cu concentrations were found in the superficial soil layers (0–20 cm) and decreased with depth. Copper possessed with non-biodegradable nature, long-term biological half-lives and was immobilized by soil sorption complex. (Komárek et al. 2008). Extremely high concentrations exceeding 3000 mg/kg of Cu have been documented by Mirlean et al. (2007) in Brazilian vineyard soils. Hog manure and sewage sludges are added to soils as a source of essential plant nutrients and organic matter however can also contain high levels of copper. Agricultural amendments can enrich the soils with copper in a range of 50-8000 mg/kg (Ross 1994). High Cu concentrations in soils can potentially contaminate the groundwater and cause serious threat to human community.

–  –  –

(1.2.4) Copper in plant, micro-organisms, animal and the relevant toxicity The process of metal uptake and accumulation by different plants depend on the concentration and solubility of available metals in soil, and plant species growing on these soils (Barman et al., 2000). Normal concentrations of copper in mature leaf tissue range from 5 to 30 mg/kg (Kabata-Pendias and Pendias 1992) with 20 mg/kg copper concentration at shoots is considered to be at health level. Shengli et al. (2009) demonstrated the sequences of Cu average concentrations in different parts were roots leaves shells grains stocks for the wheat plants grown in contaminated soils from the oasis, northwest China. Brun et al. (2003) found that increased Cu concentrations affected the phenology, growth and reproduction of some ruderal plant species. In general the copper in plants depend on the soil copper concentration, soil properties (e.g. pH, redox potential), microbial activity of the soil, environmental conditions and the species of the plant (NAS 1977).

The transfer coefficient of copper from soil to plants is relatively low compared to other metals with the order range from 0.1-1 (Kloke et al. 1984). Jeyakumar et al. (2010) showed polplar treated with high copper soil concentrations would result 0.8 bio-concentration factor in maximum. Shengli et al. (2009) showed the average bio-concentration factor of Cu in wheat plants were root leaves shell grain stock with average range between 0.02-0.25. Plants demand copper in numerous metabolic processes such as oxidation, photosynthesis and protein metabolism. Copper often contributes different roles in CO 2 assimilation and ATP synthesis.

Insufficient uptake of copper can lead to wilting, white twisted tips and disturbance of lignifications. This leads to plant growth retardation and leaf chlorosis (Lewis et al. 2001). For various cereals, legumes, and citrus plants, the deficiency limits range from 0.8 to 3.0 mg/kg.





Excess of Cu in soil plays a cytotoxic role, induces stress and causes injury to plants (KabataPendias and Pendias 1992).

Introduction

Copper toxicity affected the growth of Alyssum montanum (Ouzounidou 1994). Copper and Cd in combination have affected adversely the germination, seedling length and number of lateral roots in Solanum melongena (Neelima and Reddy 2002). Snap beans (Phaseous vulgaris) were exposed to CuSO4 in concentration range 0 to 2000 mg/kg in Yolo loam soil (Wallace et al.

1977). Leaf yield at 200 mg/kg Cu concentration was decreased by 26% and at 500 mg/kg the growth of P.vulgaris was stopped completely. Patterson and Olson (1982) tested the effect of copper as CuSO4 on radical elongation in seven tree species grown on a coarse loamy mixed soil.

Paper birch (Betula papyrifera) was most sensitive with an 18% decrease in radical elongation when compared to controls at 50 mg/kg. Guo et al. (2010) showed reduced Cu toxicity assessed by barely root elongation with addition of EDTA, NTA. The CuNTA- and CuEDTA2- complexes were not toxic to barely root elongation. Red pine grown in typical Borohemist soils was much less affected by the addition of high copper concentration due to the higher organic matter content in the typical Borohemist soil when compared to the typical Dystrochrept.

Copper is an essential nutrient for all animals. Copper deficiencies are not unknown and the most common symptons are hypocupremia and inadequate absorption by animals. In western Canada (Brockman 1977; Gooneratne and Christensen 1989) for cattle a liver copper concentration of 6 mg/kg ww (25 mg/kg dry weight) is regarded as a probable indication of copper deficiency (Gooneratne and Christensen 1989). In a survey of 256 Saskatchewan slaughter animals, Gooneratne and Christensen (1989) determined that approximately 48% had liver copper concentrations below 25 mg/kg dry weight.

Introduction

Interest has been developed in the use of earthworms as an indicator of environmental contamination. Various copper compounds on the reproduction and growth of earthworms had been studied and found out the toxic effects on growth in decreasing order are: nitrate chloride acetate = carbonate sulphate oxide. Mortality (LC50 values), reproduction (cocoon production) and change in body mass are the three most common parameters monitored to evaluate the effects of copper on earthworms (Malecki et al., 1982). Physical properties such as solubility can be a contributing factor to different copper toxicity. Ma (1982) studied the effect of copper chloride on mortality to the earthworm species L. rubellus in a sandy loam soil and found out the LC50 in 1000 mg/kg with no observed effect concentrations at 150 mg/kg. Arnold et al.

(2009) showed that with an increase of using EDTA as chelating agent could reduce earthworm mortalities in which consistent with the decrease of free Cu 2+ concentrations. Huang et al. (2009) studied earthworms being exposed to quartz sand percolated with different concentrations of Cu and ciprofloxacin (CIP). The results suggested that with increased application of CIP would decrease free Cu2+ ions in solution and mortalities of earthworm. Copper contents in earthworms could increase with CIP resided in heat-stable proteins fraction.

Increased Cu concentrations especially with free Cu2+ ions can be to a great extent adversely affecting soil microorganism numbers, diversity and activity (Dumestre et al., 1999).

Jeyakumar et al. (2010) showed copper was toxic to soil microorganisms between 12-226 mg/kg Cu addition. Parmelee et al. (1993) conducted a soil microcosm toxicity study for several chemicals on two soil fauna communities (nematodes and microarthropods). Soil from the Ahorizon of a mature oak-beech forest was used (CEC = 6.2 meq/100 g, pH = 3.8) as the test medium on which CuSO4 was applied at 0, 100, 200, 400 and 600 mg/kg. The most sensitive organisms were omnivore-predator nematodes and mesostigmata microarthropods, which demonstrated a statistically significant population decline relative to controls at 100 mg/kg. The total nematode and microarthropod population declined when the CuSO 4 concentration was greater than 200 mg/kg.

Introduction

One route of copper exposure in animals is through dietary consumption of soil. Ingested copper can be accumulated in the liver and kidney. High intake level of copper can be demetabloised with researchers proposed sulphur normally bound within proteins can be released by the microbial flora and be free to combine with dietary copper to from insoluble CuS and then eliminated in the feces. Animal such as sheep are particularly intolerant of excess dietary copper in a result of their inability to maintain copper homeostasis. Chronic exposure to excess dietary copper culminates in acute toxicological symptoms such as haemolysis, jaundice, and/or death.

Cattle in contrast are intolerant to low dietary copper levels but tolerate relatively high dietary copper concentrations before exhibiting toxicological symptoms. Swine are relatively tolerant to high dietary copper levels.

Copper is an essential nutrient in humans and animals and is required in many enzymatic reactions. Intake of copper that seems to be adequate and safe is 2.0 mg/d in Canada (HWC 1990) and 1.5-3.0 mg/d in the United States (NAS 1989). The total amount of copper in an adult body is estimated to be 70-80 mg (Leichtmann and Sitrin 1991). Copper can be absorbed in the stomach and small intestine (Leichtmann and Sitrin 1991), in humans, with a dietary intake of 1mg/d, the overall absorption ranges from 25 to 40% of the administered oral dose (Turnlund et al. 1989). Copper can be absorbed from the gastrointestinal tract as ionic copper or bound to amino acids. Absorbed copper can loosely bind to plasma albumin and amino acids in the portal blood circulation and is taken to the liver (Alt et al. 1990; Marceau et al. 1970; Winge and Mehra 1990). In the liver, copper is incorporated into ceruloplasmin and released into the plasma (Alt et al. 1990; Leichtmann and Sitrin 1991). The metabolism of copper consists mainly of its transfer to and from various ligands, most notably sulfhydryl and imidazole groups on amino acids and proteins. In the liver and other tissues, copper is stored bound to metallothionein and amino acids and in association with copper-dependent enzymes (Abdel-Mageed and Oehme 1990a; Winge and Mehra 1990). Copper in liver cells are predominantly in lysosomes and cytosol (Kumaratilake and Howell 1989a). Bile is the major pathway for the excretion of copper (Leichtmann and Sitrin 1991; Winge and Mehra 1990). Under normal circumstances 0.5%-3.0% of daily copper intake is excreted into the urine (Cartwright and Wintrobe 1964). The regulation of the copper balance in the body appears to be controlled by both the absorption and excretion mechanisms.

Introduction

Hepatotoxicity of copper in animals has been investigated with most prominent toxicity effect is centrilobular necrosis followed by regeneration (ATSDR 1990). Acute LD 50 values for rats range from 66 to 416 mg/kg bw depending on the chemical form of copper (Janus et al.

1990). Short term toxicity of copper in animals can lead to decreased body weight gain, anorexia, hepatotoxicity, renal toxicity and death (Boyden et al. 1938; Haywood 1980, 1985; Haywood and Comerford 1980; Haywood and Loughran 1985; Haywood et al. 1985; Rana and Kumar 1980; Kumar and Sharma 1987; Epstein et al. 1982). High intake of copper (1500 ppm) for male rats can induce damage to the liver and kidney (Fuentealba et al. 1989 a, b) with the copper being accumulated within the nucleus can directly injure the cell’s organelle and lead to the death of the whole kidney and liver cells. Copper can penetrate the placental barrier into the fetus (Adelstein and Vallee 1961; Suzuki et al. 1990). Low levels of copper sulphate in diet can stimulate embryonic development whereas high levels can increase fetal mortality, reduce weight and produce malformations (lecyk 1980).

Ingestion of excess copper to human adults can cause centrolobular necrosis and necrosis of renal tubular cells. Several suicide cases have been reported with intaking copper sulphate (Chuttani et al. 1965). Gastrointestinal, hepatic and renal effects could happen following the consumption of copper-contaminated water with copper sulphate in attempted suicide cases.



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