EDTA- and DTPA-functionalized silica gel and chitosan adsorbents for the removal of heavy metals from aqueous solutions

Adsorbents functionalized with chelating agents are effective in removal of heavy metals from aqueous solutions. Important properties of such adsorbents are high binding affinity as well as regenerability. In this study, aminopolycarboxylic acid, EDTA and DTPA, were immobilized on the surface of silica gel, chitosan, and their hybrid materials to achieve chelating adsorbents for heavy metals such as Co(II), Ni(II), Cd(II), and Pb(II). New knowledge about the adsorption properties of EDTA- and DTPA-functionalizedadsorbents was obtained. Experimental work showed the effectiveness, regenerability, and stability of the studied adsorbents. Both advantages and disadvantages of the adsorbents were evaluated. For example, the EDTA-functionalized chitosan-silica hybrid materials combined the benefits of the silica gel and chitosan while at the same time diminishing their observed drawbacks. Modeling of adsorption kinetics and isotherms is an important step in design process. Therefore, several kinetic and isotherm models were introduced and applied in this work. Important aspects such as effect of error function, data range, initial guess values, and linearization were discussed and investigated. The selection of the most suitable model was conducted by comparing the experimental and simulated data as well as evaluating the correspondence between the theory behind the model and properties of the adsorbent. In addition, modeling of two-component data was conducted using various extended isotherms. Modeling results for both one- and twocomponent systems supported each other. Finally, application testing of EDTA- and DTPA-functionalized adsorbents was conducted. The most important result was the applicability of DTPA-functionalized silica gel and chitosan in the capturing of Co(II) from its aqueous EDTA-chelate. Moreover, these adsorbents were efficient in various solution matrices. In addition, separation of Ni(II) from Co(II) and Ni(II) and Pb(II) from Co(II) and Cd(II) was observed in two- and multimetal systems. Lastly, prior to their analysis, EDTA- and DTPA-functionalized silica gels were successfully used to preconcentrate metal ions from both pure and salty waters

Relationship between weight, age and hatching success and the concentration of heavy metals in nestling blue macaw (Anodorhynchus hyacinthinus Latham, 1790) in the Pantanal,Mato Grosso do Sul

Abstract: The concentration of heavy metals (Cr, Fe, Al, As, Cd, Cu, Pb, Mo, Ni, Se and Zn) was evaluated in the blood of nestling blue macaws (Anodorhynchus hyacinthinus) captured in the Pantanal, Mato Grosso do Sul (n=26) in 2012; this was based on the hypothesis that these birds exhibit levels of these heavy metals in their organism and that these interfere in hatching success, weight and age of the chicks. Blood samples were digested with nitric acid and hydrochloric acid and the quantification of metals was performed by ICP-OES (Optical Emission Spectroscopy and Inductively Coupled Plasma). Blood samples of nestlings showed concentrations of Cr (0.10μg/g) Fe (3.06μg/g) Al (3.46μg/g), Cd (0.25μg/g) Cu (0.74μg/g), Mo (0.33μg/g), Ni (0.61μg/g), Se (0.98μg/g), and Zn (2.08μg/g). The levels of heavy metals found were not associated with weight, age and hatching success of the chicks.

Dynamics And Speciation Of The Heavy Metals In The Lower Reaches Of Chithrapuzha- A Tropical Tidal River

The proposed study is an attempt to quantify and study the seasonal and spatial variations in the distribution of Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd and Pb among the various geochemical phases in the surficial sediments of Chitrapuzha river. The study also estimates the concentration of heavy metals in dissolved, particulate and sediments and their variation in seasonal and spatial distribution. Chitrapuzha River originates as a small stream from the upper reaches of high ranges in the eastern boundary of Kerala, passes through the valley and finally joints in the Cochin backwaters. Numerous industrial units located along the banks of the river discharge treated and untreated effluents into the water. These are long standing local complaints about water pollution causing fish mortality and serious damage to agricultural crops resulting in extensive unemployment in the area. The river is thus of considerable social and economic importance.

Haematological responses of green mussel Perna viridis (Linnaeus) to heavy metals copper and mercury

Department of Marine Biology, Microbiology and Biochemistry, Cochin University of Science and Technology

Sub-Lethal effects of heavy metals on perna indica ( Kuriakose & Nair) and donax incarnatus gmelin

The present scientific investigation of the effects of copper, mercury and cadmium has focussed on their effects on two commercially important marine bivalve species, Perna indica (brown mussel) and Donax incarnatus (wedge clam), conspicuous representatives of the tropical intertidal areas. The investigation centred around delineating the cause and effects of heavy metal stress, individually and in combination on these species under laboratory conditions. A clear understanding of the cause and effect can be had only if laboratory experiments are conducted employing sub-lethal concentrations of the above toxicants. Therefore, during the course of the investigation, sub-lethal concentrations of copper, mercury and cadmium were employed to assess the concentration dependent effects on survival, ventilation rate, O:N ratio and tissues. The results obtained are compared with the already available information and partitioned in sections to make a meaningful presentation.The thesis is presented in five chapters comprising INTRODUCTION, ACUTE TOXICITY, VENTILATION RATE, OXYGEN : NITROGEN RATIO and HISTOPATHOLOGY. Each chapter has been divided into various sections such as INTRODUCTION, REVIEW OF LITERATURE, MATERIAL AND METHODS, RESULTS and DISCUSSION

“Assessment of Heavy Metals in the Environmental Compartments of the Central and Northern Coast of Kerala, India”

The nearshore marine ecosystem is a dynamic environment impacted by many activities, especially the coastal waters and sediments contiguous to major urban areas. Although heavy metals are natural constituents of the marine environment, inputs are considered to be conservative pollutants and are potentially toxic, accumulate in the sediment, are bioconcentrated by organisms and may cause health problems to humans via the food chain. A variety of metals in trace amounts are essential for biological processes in all organisms, but excessive levels can be detrimental by acting as enzyme inhibitors. Discharge of industrial wastewater, agriculture runoff and untreated sewage pose a particularly serious threat to the coastal environment of Kerala, but there is a dearth of studies in documenting the contaminant metals. This study aimed principally to assess such contamination by examining the results of heavy metal (Cu, Pb, Cr, Ni, Zn, Cd and Hg) analysis in seawater, sediment and benthic biota from a survey of five transects along the central and northern coast of Kerala in 2008 covering a 10.0 km stretch of near shore environment in each transect. Trophic transfer of metal contaminants from aquatic invertebrates to its predators was also assessed, by employing a suitable benthic food chain model in order to understand which all metals are undergoing biotransference (transfer of metals from a food source to consumer).The study of present contamination levels will be useful for potential environmental remediation and ecosystem restoration at contaminated sites and provides a scientific basis for standards and protective measures for the coastal waters and sediments. The usefulness of biomonitor proposed in this study would allow identification of different bioavailable metals as well as provide an assessment of the magnitude of metal contamination in the coastal marine milieu. The increments in concentration of certain metals between the predator and prey discerned through benthic food chain can be interpreted as evidence of biotransference.

"Effects of some heavy metals copper. zinc and lead on certain tissues of £153 Qarsia (Hamilton and Buchanan) in different environments

The research investigations on pollution, particularly in coastal/ estuarine environments are recent ones and started only in 1970s. Hence the informations available are fragmentary and scattered. They throw some light only on either the concentration of heavy metals in water or in sediment or in organisms. No concerted efforts have been made to consolidate and correlate the results between the environment and biota. Literature on the level of concentration of heavy metals in different tissues of organisms with regard to their availability in the living media, their ratio, their inter—relationship, tolerance limit of organisms, etc. are very few or rather nil. in view of the importance enumerated above, the candidate has selected the topic "Effects of some heavy metals copper, zinc and lead on certain tissues of E E (Hamilton and Buchanan) in different environments" for detailed studies and to understand systematically (i) the source of effluents and wastes, (ii) the concentration of heavy metals copper, zinc and lead in water, in sediments and in tissues of the test animal, (iii) their effects, (iv) capacity of tolerance and accumulation in different tissues of the animal, and (V) the "Bioaccumulation Factor", etc.

Application of primary haemocyte culture of Penaeus monodon in the assessment of cytotoxicity and genotoxicity of heavy metals and pesticides

Lack of shrimp cell lines has hindered the study of pollutants which adversely affects shrimp health and its export value. In this context a primary haemocyte culture developed from Penaeus monodon was employed for assessing the cytotoxicity and genotoxicity of two heavy metal compounds, cadmium chloride and mercuric chloride and two organophosphate insecticides, malathion and monocrotophos. Using MTT assay 12 h IC50 values calculated were 31.09 16.27 mM and 5.52 1.16 mM for cadmium chloride and mercuric chloride and 59.94 52.30 mg l 1 and 186.76 77.00 mg l 1 for malathion and monocrotophos respectively. Employing Comet assay, DNA damage inflicted by these pollutants on haemocytes were evaluated and the pollutants induced DNA damage in >60% of the cells. The study suggested that haemocyte culture could be used as a tool for quantifying cytotoxicity and genotoxicity of aquaculture drugs, management chemicals and pollutants

Spatial Variability and Contamination of Heavy Metals in the Inter-tidal Systems of a Tropical Environment

Heavy metals in the surface sediments of the two coastal ecosystems of Cochin, southwest India were assessed. The study intends to evaluate the degree of anthropogenic influence on heavy metal concentration in the sediments of the mangrove and adjacent estuarine stations using enrichment factor and geoaccumulation index. The inverse relationship of Cd and Zn with texture in the mangrove sediments suggested the anthropogenic enrichment of these metals in the mangrove systems. In the estuarine sediments, the absence of any significant correlation of the heavy metals with other sedimentary parameters and their strong interdependence revealed the possibility that the input is not through the natural weathering processes. The analysis of enrichment factor indicated a minor enrichment for Pb and Zn in mangrove sediments. While, extremely severe enrichment for Cd, moderate enrichment for Zn and minor enrichment of Pb were observed in estuarine system. The geo accumulation index exhibited very low values for all metals except Zn, indicating the sediments of the mangrove ecosystem are unpolluted to moderately polluted by anthropogenic activities. However, very strongly polluted condition for Cd and a moderately polluted condition for Zn were evident in estuarine sediments

Potential of Brassic rapa, Cannabis sativa, Helianthus annuus and Zea mays for phytoextraction of heavy metals from calcareous dredged sediment derived soils

Remediation of soil pollution is one of the many current environmental challenges. Anthropogenic activity has resulted in the contamination of extended areas of land, the remediation of which is both invasive and expensive by conventional means. Phytoextraction of heavy metals from contaminated soils has the prospect of being a more economic in situ alternative. In addition, phytoextraction targets ecotoxicologically the most relevant soil fraction of these metals, i.e. the bioavailable fraction. Greenhouse experiments were carried out to evaluate the potential of four high biomass crop species in their potential for phytoextraction of heavy metals, with or without with the use of soil amendments (EDTA or EDDS). A calcareous dredged sediment derived surface soil, with high organic matter and clay content and moderate levels of heavy metal pollution, was used in the experiments. No growth depression was observed in EDTA or EDDS treated pots in comparison to untreated controls. Metal accumulation was considered to be low for phytoextraction purposes, despite the use of chelating agents. The low observed shoot concentrations of heavy metals were attributed to the low phytoavailability of heavy metals in this particular soil substrate. The mobilising effects induced by EDTA in the soil were found to be too long-lived for application as a soil amendment in phytoextraction. Although EDDS was found to be more biodegradable, higher effect half lives were observed than reported in literature or observed in previous experiments. These findings caution against the use of any amendment, biodegradable or otherwise, without proper investigation of its effects and the longevity thereof. (C) 2005 Elsevier Ltd. All rights reserved.

An inventory of heavy metals inputs to agricultural soils in England and Wales

An inventory of heavy metal inputs (Zn, Cu, Ni, Pb, Cd, Cr, As and Hg) to agricultural soils in England and Wales in 2000 is presented, accounting for major sources including atmospheric deposition, sewage sludge, livestock manures, inorganic fertilisers and lime, agrochemicals, irrigation water, industrial by-product 'wastes' and composts. Across the whole agricultural land area, atmospheric deposition was the main source of most metals, ranging from 25 to 85% of total inputs. Livestock manures and sewage sludge were also important sources, responsible for an estimated 37-40 and 8-17% of total Zn and Cu inputs, respectively. However, at the individual field scale sewage sludge, livestock manures and industrial wastes could be the major source of many metals where these materials are applied. This work will assist in developing strategies for reducing heavy metal inputs to agricultural land and effectively targeting policies to protect soils from long-term heavy metal accumulation. (C) 2003 Elsevier Science B.V. All rights reserved.

Expression of metallothionein genes I and II in bank vole clethrionomys glareolus populations chronically exposed in situ to heavy metals

The expression of two metallothionein genes (Mt-I and Mt-II) in the liver, kidney, and gonad of bank voles collected at four metal-contaminated sites (Cd, Zn, Pb, and Fe) were measured using the quantitative real-time PCR method (QPCR). Relative Mt gene expression was calculated by applying a normalization factor (NF) using the expression of two housekeeping genes, ribosomal 18S and beta-actin. Relative Mt expression in tissues of animals from contaminated sites was up to 54.8-fold higher than those from the reference site for Mt-I and up to 91.6-fold higher for Mt-II. Mt-II gene expression in the livers of bank voles from contaminated sites was higher than Mt-I gene expression. Inversely, Mt-II expression in the kidneys of voles was lower than Mt-I expression. Positive correlations between cadmium levels in the tissues and Mt-I were obtained in all studied tissues. Zinc, which undergoes homeostatic regulation, correlated positively with both Mt-I and Mt-II gene expression only in the kidney. Results showed that animals living in chronically contaminated environments intensively activate detoxifying mechanisms such as metallothionein expression. This is the first time that QPCR techniques to measure MT gene expression have been applied to assess the impact of environmental metal pollution on field collected bank voles.

Fully electrochemical hyphenated flow system for preconcentration, cleanup, stripping, capillary electrophoresis with stacking and contactless conductivity detection of trace heavy metals

Successful coupling of electrochemical preconcentration (EPC) to capillary electrophoresis (CE) with contactless conductivity detection (C(4)D) is reported for the first time. The EPC-CE interface comprises a dual glassy carbon electrode (GCE) block, a spacer and an upper block with flow inlet and outlet, pseudo-reference electrode and a fitting for the CE silica column, consisting of an orifice perpendicular to the surface of a glassy carbon electrode with a bushing inside to ensure a tight press fit. The end of the capillary in contact with the GCE is slant polished, thus defining a reproducible distance from the electrode surface to the column bore. First results with EPC-CE-C(4)D are very promising, as revealed by enrichment factors of two orders of magnitude for Tl, Cu, Pb and Cd ion peak area signals. Detection limits for 10 min deposition time fall around 20 nmol L(-1) with linear calibration curves over a wide range. Besides preconcentration, easy matrix exchange between accumulation and stripping/injection favors procedures like sample cleanup and optimization of pH, ionic strength and complexing power. This was demonstrated for highly saline samples by using a low conductivity buffer for stripping/injection to improve separation and promote field-enhanced sample stacking during electromigration along the capillary. (C) 2010 Elsevier B.V. All rights reserved.