ABSTRACT - The application of foliar fungicides in vineyards and orchards can increase soil concentration of heavymetals such as copper (Cu) and zinc (Zn), up to the toxicity threshold for fruit trees and cover crops. However, some agronomic practices, such as liming, addition of organic fertilizers, cultivation of soil cover crops and inoculation of young plants with arbuscular mycorrhizal fungi can decrease the availability and the potential of heavy metal toxicity to fruit trees. This review aims to compile and present information about the effects of increasing concentrations of heavymetals, especially Cu and Zn, on soils cultivated with fruit trees and provides some agronomic practices of remediation. Information about the sources of heavymetals found in soils cultivated with fruit trees are presented; mechanisms of absorption, transport, accumulation and potential toxicity to plants are described.
Chromolaena odorata twigs of 10-12 cm length, each with four pairs of unfolded leaves were collected from plants wildly growing in Calicut University (C.U.) campus. Cuttings were treated with Indole butyric acid (IBA 50μM) to induce root initiation and rooted cuttings were transferred to 120 ml half strength modified Hoagland solution (Epstein, 1972) taken in glass bottles (8.5 x 5.5 cm). The hydroponic systems were kept in polyhouse at 27±3ºC and RH 78±3. The propagules thus developed were used for treatment with different concentrations of heavymetals under hydroponic conditions and untreated samples served as control. Heavymetals selected for the study includes aluminium, cadmium, iron, mercury, chromium, copper, lead, nickel and zinc. The tolerable limits of each metal salt were determined based on a series of standardization steps. The heavy metal salt concentration which was the tolerance limit as indicated by the growth of C. odorata is given in Table 1.
The artificial recharge of aquifers with reclaimed water is a practice that can be useful for water management practices. Soil Aquifer Treatment (SAT) has been shown to be a technical and economical feasible alternative for the refining of secondary treatment effluents prior to their inclusion in aquifers. However, if the soil does not present favourable conditions for the infiltration of reclaimed water, the pollutant residual loads of these waters, such as heavymetals, can be a disadvantage to groundwater quality. The clays present in the soil have reactive properties that allow them to remove metallic cations essentially by sorption mechanisms (e.g., adsorption, cation exchange and complexation-precipitation), as demonstrated by several studies [1–6]. Thus, the objective of this work was to evaluate the removal of five heavymetals, namely chromium (Cr), copper (Cu), nickel (Ni), lead (Pb) and zinc (Zn), using a granitic residual soil and laboratory experiments in downflow column, namely for verifying the main sorption mechanisms responsible for their removal.
The lack of a standard method to regulate heavy metal determination in Brazilian fertilizers and the subsequent use of several digestion methods have produced variations in the results, hampering interpretation. Thus, the aim of this study was to compare the effectiveness of three digestion methods for determination of metals such as Cd, Ni, Pb, and Cr in fertilizers. Samples of 45 fertilizers marketed in northeastern Brazil were used. A fertilizer sample with heavy metal contents certified by the US National Institute of Standards and Technology (NIST) was used as control. The following fertilizers were tested: rock phosphate; organo-mineral fertilizer with rock phosphate; single superphosphate; triple superphosphate; mixed N-P-K fertilizer; and fertilizer with micronutrients. The substances were digested according to the method recommended by the Ministry for Agriculture, Livestock and Supply of Brazil (MAPA) and by the two methods 3051A and 3052 of the United States Environmental Protection Agency (USEPA). By the USEPA method 3052, higher portions of the less soluble metals such as Ni and Pb were recovered, indicating that the conventional digestion methods for fertilizers underestimate the total amount of these elements. The results of the USEPA method 3051A were very similar to those of the method currently used in Brazil (Brasil, 2006). The latter is preferable, in view of the lower cost requirement for acids, a shorter digestion period and greater reproducibility.
The marine ecosystems of Todos os Santos Bay (TSB, The State of Bahia, Brazil) have been impacted by the presence on its coast of a large metropolitan area as well as of chemical and petrochemical activities. Despite its ecological importance, there is a lack of scientific information concerning metal contamination in TSB marine biota. Thus, we analyzed concentrations of metalsin four species of marine benthic organisms (two seaweeds, Padina gymnospora and Sargassum sp. one seagrass, Halodule wrightii and one oyster, Crassostrea rhizophorae) in three sites from the TSB region that have been most affected by industrial activities. The concentrations of Al, Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn were determined by Atomic Absorption Spectrophometry. The obtained data indicates that cadmium and copperin seaweeds, oysters and seagrass, as well as Ni concentrations in oysters, were in range of contaminated coastal areas. Cadmium and copper are available to organisms through suspended particles, dissolved fraction of water column and bottom sediment interstitial water. As oysters and other mollusks are used as food sources by the local population, the metal levels found in oysters in TSB may constitute a health risk for this population. Our results suggest implanting a heavymetals biomonitoring program in the TSB marine ecosystems.
The amount of work about developing analytical techniques for the quantification of cork heavymetals is extremely low , being known some results [3,4], which had led to the validation of a method and to laboratorial certification . The present work shows that it is possible to use electroanalytical techniques, namely Differential Pulse Stripping Voltammetry with a Hanging Mercury Drop Electrode.
with significant incidence of private occupation of farmland. Soil contaminated with metals is a primary route of toxic element exposure to humans. Toxic metals can enter the human body by consumption of contaminated food crops, water or inhalation of dust.and cause damage to the organism, its toxic efects. (Mahmoode et al. 2013)Vegetables are the important life-supporting materials for human beings and animals because vegetables contain essential components as proteins, vitamin, iron, calcium and other nutrients Yang et al. 2011). At the same time, however, the possibility of accumulation of risk elements vegetables grown on contaminated soil (Luo et al. 2010).Heavymetals released from industrial production penetrate the soils where vegetables and crops are grown by contaminating irrigation water and through direct deposition by air. Plants can take up these metals from soil by their roots, transport them upwards to their shoots, and ﬁnally accumulate them inside their tissues, s, although there are large variations among different plant species in terms of metal accumulation ability (Luo et al. 2010). Most dangerous elements in terms of their content in the soil to a possible accumulation of plants in this area appear Hg, Cd, Pb, and Cu. Toxic effect of Hg and its compounds is largely the reaction of Hg ion with SH- groups of biomolecules with subsequent changes in the permeability of cell membranes and damage cellular enzymes. Mercury has the ability to accumulate
Arcobacter butzleri is an emerging pathogen that has been associated with abortion and enteritis in animals and with diarrhea and bacteremia in adults and children. This Arcobacter species seems to be the most frequent in human beings. A. butzleri recognizes a wide reservoir range, being isolated from domestic and free living mammals and birds, from shellfish and environmental water bodies as well. It has been suggested that water may play an important role in the transmission of these organisms (6,12).
reduce the loss of nitrate from the soil by leaching (Ding et al., 2010) and also suppress N2O emissions (Yanai et al., 2007). Mechanistic explanations include increased ammonium adsorption through increased cation exchange capacity (CEC) (Liang et al., 2006); altered nitrification rates in forest soils expressing no net nitrification (DeLuca et al., 2006). Nitrate concentration was lower in the silt loam soil amended with sawdust. In the case of sandy soil, the concentration was higher. Burned solid waste and vegetable waste were also successful in retarding nitrate leaching but with vegetable waste the concentration was lower as compared to other amendments. In burned solid waste, a higher nitrate concentration was observed in the upper layer of sandy soil and the lower layer of silt loam soil. Wood ash contains very little carbon and nitrogen. Therefore, its application to the soil may reduce the total contents of C and N by increasing the solubility of organic carbon and the nitrification rate (Weber et al., 1985). As such, wood ash can be regarded as an N-free fertilizer, and is particularly suited for forest soils where nutrient unbalances, especially increased N/P ratios, can be expected due to acid depositions. Wood ash is essentially a direct source of other major elements, notably P, Ca, Mg and especially K in soils (Unger and Fernandez, 1990).
to excessive levels of Pb exhibit neuropathology. There is association between Pb in human body and the increase of blood pressure in adults (Maihara and Fávaro, 2006). Although Pb effects are more relevant for children, cal- culations for risk assessment were made for adults and children. The daily intake of Pb was estimated to 0.102 mg, which is 41.7 % of R f D value of 0.245 mg per day for a 70 kg adult. Although Pb concentrations were high in some vegetables, low consumption of vegetables re- sults in low intake of this element. This value was below those reported in literature (0.025 and 0.521 mg per day) (Santos et al., 2004; Tripathi et al., 1997). Rice contrib- uted with approximately 16.84 % for the Pb intake, fol- lowed by the ‘pêra’ orange (6.68 %), bean 2 (5.73 %), ‘prata’ banana (5.52 %) and onion (4.59 %).
HEAVYMETALSIN FRESH WATERS FOR EVALUATION OF HYDROGRAPHIC BASINS. The input of heavymetals concentrations determinated by ICP-AES, in samples of the Cambé river basin, was evaluated by using the Principal Component Analysis. The results distinguishes clearly one site, which is strongly influenced by almost all elements studied. Special attention was given to Pb, because of the presence of one battery industry in this area. Some downstream samples were associated with the same characteristics of this site, showing residual action of contaminants along the basin. Other sites presented influence of soil elements, plus Cr near a tannery industry. This study allowed to distinguish different sites in the upper basin of the Cambé (Londrina-PR- BR), in accordance to elements input.
also observed by Atanossova & Okazaki (1997). The importance of organic matter as the main reservoir of potentially available Cu for plants was reported (McLaren & Crawford, 1973a; Shuman, 1985; Sims, 1986). It seems that the OM fraction, in equilibrium with the AFeOx and CFeOx fractions, is responsible for supplying Cu to the soil solution under intensive cultivation, when the existing Cu is insufficient for maintaining adequate plant growth. The organic matter seems to be a source of specific sites for Cu complexation in the soil (McLaren & Crawford, 1973a, b), due to the affinity of the Cu ion to form inner sphere complexes with humic substances (McBride, 1994). The increase in pH due to liming resulted in a reduction of Cu in the Exchangeable (Ex) fraction and, mainly, in the Organic Matter (OM) fraction, with Cu being transferred to Mn and Fe Oxide fractions, which retained 27% of the Total Cu (Table 2). Similar results were observed by Jarvis (1981) and Sims (1986) and were, probably, due to a specific adsorption process which would cause a decrease in Cu availability. These results for Cu content in the fractions suggest an equilibrium for Cu distribution in the Exchangeable, Organic Matter, and Oxide fractions, which would be modified with Cu being transferred to the more available fractions Ex and OM, as pH is reduced. The Mn Oxide fraction presented, proportionally, the higher increment in the Cu adsorption. Manganese oxides have particularly high selectivity for Cu which indicates that covalent bonds have important contribution for Cu adsorption (McBride, 1994). McLaren & Crawford (1973b) concluded that Mn oxides were the dominant mineral constituents in the specific adsorption of Cu by soils. For more weathered soils, however, the Fe oxides are found in higher concentrations and become, quantitatively, more important for Cu adsorption (Table 2). An important factor to be considered concerning the Cu retention by soil fractions is the reaction time between the element and the soil. A more extended time of equilibrium with the soil would result in more stable forms of Cu in the presence of crystalline oxides since the reaction could continue slowly due to the diffusion of adsorbed ions into the interior of the particles (Barrow, 1993). In the present work this was observed for the soils which did not receive liming nor Cu addition (Table 2). These results demonstrate the importance of the time in the transformations of the added Cu to the soils and indicate that in soils fertilized with Cu the residual effect of the fertilizer decreases with its residing time in the soil, as observed by Levesque & Mathur (1986). This effect is incremented by liming.
pollutants in water and therefore be seen as a barrier against the dispersion of pollu- tants in the environment. Heavymetals are important environmental pollutants. The presence of metal ions in several anthropogenic activities has been proven to be haz- ardous and entail threats to the environment. Metal ions like copper, lead, mercury, cadmium and chromium are known to be toxic in nature, non-biodegradable and tend to accumulate in living organisms, causing an assortment of diseases and disorders . Several treatment methods have been suggested for heavymetals mitigation in the environment, like chemical precipitation, membrane filtration, ion exchange, carbon adsorption, and co-precipitation/adsorption. Nevertheless, the search for cost effective, alternative technologies or sorbents for metals treatment from contaminated waste- water streams is needed. Natural materials that are available in large quantities, or even certain waste products from industrial or agricultural operations may have poten- tial as inexpensive sorbents . In fact, Ho et al.  reported natural products to be good sorbents for heavymetals. The authors quote materials like peat, wood, pine bark, banana pith, rice bran, soybean and cottonseed hulls, peanut shells, hazelnut shell, rice husk, sawdust, wool, orange peel, compost and leaves to have an important sorbent behavior.
Necessity of excessive soil acidity correction is related to soil reaction influence to a whole range of che- mical, biological and physical soil properties. Therefore, liming represents common amelioration measure for conditioning of excessive acid soil reaction. Most heavymetals availability is impacted by soil pH. Liming is also widely recommended strategy to reduce mobility and plant availability of soil contaminants such as cadmi- um (Smolders et al., 1999). For elements such as Pb and Cd it has been shown that large quantities in soils and consequently in food chain produce toxic effects because they tend to accumulate in body, vital organs and tissues (Lončarić et al., 2012). Consequently, heavymetals toxicity is one of the main forms of abiotic stre- ss that may cause harmful effects to plant and animal health (Lisjak et al., 2008). So, the aim of this paper was to determine the influence of acid soils liming and initial soil acidity as well as organic matter content on availa- bility of four heavymetals (Zn, Pb, Cr and Cd).
Currently, the diversity of human activities and demographic growth contribute to increase residue production. Improper disposal of those residues results in environmental degradation of landfills (KORF et al., 2008). Sewage sludge or biosolids is the residue obtained from domestic wastewater treatments, in a way that allows treated effluents to return to environment, causing no pollution (SINGH; AGRAWAL, 2008). If final disposal of those biosolids is not appropriate, it can become a new environmental problem.
he paper addresses a current topic in the ield of ecotoxicology. Considering the fact that urban living today is in direct correlation with the rapid growth of many industries, biomonitoring is becoming an integral part of preventive medical surveillance in occupations with actual or potential ecotoxicological hazard. he concept of professional risk involves the probability that because of the exposure of workers to certain harmful agents in the work environment, negative efects on their health and life will manifest. he concept of this research was to determine the need for biological monitoring as a set of activities to identify and quantitatively determine the concen- trations of heavymetals (lead, zinc and cadmium), their primary or secondary metabolites in biological forms such as blood, in a speciied category of pro-
Considering the importance of plant growth hor- mones (e.g., abscisic acid, auxins, brassinosteroids and eth- ylene) for alleviating heavy metal stress, further research is expected to contribute to a deeper knowledge on the endog- enous regulation of plant hormone metabolism in such harmful conditions. There are several studies already in support of the importance of plant hormones under heavy metal exposure as well as other abiotic stresses. It is also in- teresting to note that the critical plant tolerance achieved by phytohormones can be promoted directly or indirectly. For example, ethylene signaling is mediated by EIN2, and some studies also show that the EIN2 gene mediates Pb re- sistance through AtPDR12, an efflux pump at the plasma membrane. But phytohormone tolerance can also be in- duced indirectly, as the one promoted by brassinosteroids, which improves antioxidant systems efficiency in remov- ing ROS and, as a consequence, attenuates detrimental ef- fects from heavy metal stress. In the same way, hormonal treatments were not able to overcome the adverse effects of heavymetals on plant nutrient acquisition, but they were able to efficiently inhibit heavy metal incorporation, such as in stomatal closure guided by ABA that ultimately de- crease toxic metals uptake and translocation from roots to shoots.
Figure 1.1. World distribution of lagoon coastlines (Reproduced from Barnes (1980), Coastal Lagoons) .................................................................................................................................................................... 14 Figure 1.2. Model for available trace elements in sediments (Found in Moreira da Silva, 2008) .............. 20 Figure 1.3 A root section showing the symplasmic (A) and the apoplasmic (B) pathways of ions transport across the root (adapted from Marschner, 1995; found in Moreira da Silva, 2008). .................................. 24 Figure 1.4. Location of the river Jacaraipe basin within the Hydrographic Unit of the North-Central coast of Espirito Santo – UHLCN (Lellis and Barroso, 2007.) ............................................................................ 28 Figure 1.5. Sub-basins of the Jacunem lagoon, Serra (ES), (Lellis, 2010) ................................................. 29 Figure 1.6. Mosaic of land use in the Jacunem basin, Serra (ES). (Adopted and modified from Lellis, 2010.) .......................................................................................................................................................... 30 Figure 1.7. Land use of the Jacaraipe river basin (Adapted from Lellis, 2010). ......................................... 31 Figure 1.8*. Populated area connected to the sewage network within the River Jacaraipe basin, Serra (ES) (PMS (2008) and IEMA (2009), adopted and modified from Lellis, 2010) ............................................... 32 Figure 1.9**. Populated area covered by the septic tank sewage collection, within the Jacaraipe river basin, Serra (ES). (PMS (2008) and IEMA (2009), adopted and modified from Lellis, 2010) .................. 34 Figure 1.10. Water hyacinth (Eichhornia crassipes) (IFAS, Center for aquatic plants, University of Florida, Gianesville, 1996
SPECIATION OF COPPER AND ZINC IN URINE – IMPORTANCE OF METALSIN NEURODEGENERATIVE DISEASES. Metals such as copper and zinc are essential for the development and maintenance of numerous enzymatic activities, mitochondrial functions, neurotransmission, and also for memorization and learning. However, disruption in their homeostasis can cause neurodegenerative disorders such as the Alzheimer and Parkinson diseases. In this work, the speciation of copper and zinc in urine samples was carried out. To this end, free and total metal concentrations were determined by square wave anodic stripping voltammetry using a glassy carbon electrode coated with bismuth film. The digestion of the samples was performed in a microwave with the addition of oxidant reagents.