Voltammetric and Spectroscopic Determination of Toxic Metals in Sediments and Sea Water of Salerno Gulf

In this present work the distribution of heavy metals in sea water and sediments of the Salerno Gulf is measured. The elements determined were Cu, Pb, Cd, Zn and Hg, employing, as instrumental techniques, either differential pulse anodic stripping voltammetry (DPASV) or graphite furnace atomic absorption spectroscopy (GFAAS). A comparison of the results of the two analytical techniques is also made. Mercury determination was carried out employing the cold vapour atomic absorption spectroscopy (CVAAS) technique, with SnCl₂ as the reducing agent. The sample digestion was performed by a new procedure using concentrated suprapure H₂SO₄–K₂Cr₂O₇ mixture. The accuracy and precision of the analytical procedure were evaluated employing Sea Water BCR-CRM 403 and Estuarine Sediment BCR-CRM 277 as reference materials. Accuracy, expressed as relative error e and precision, expressed as relative standard deviation s_r, were in order of 2 to 5%. For both matrices, the detection limits, for all the elements, were in the range g g_-1 to ng g_-1.     

Solid phase extraction of Cu(II), Ni(II), Pb(II), Cd(II) and Mn(II) ions with 1-(2-thiazolylazo)-2-naphthol loaded Amberlite XAD-1180

A new method for separation and preconcentration of trace amounts of Cu(II), Ni(II), Pb(II), Cd(II) and Mn(II) ions in various matrices was proposed. The method is based on the adsorption and chelation of the metal ions on a column containing Amberlite XAD-1180 resin impregnated with 1-(2-thiazolylazo)-2-naphthol (TAN) reagent prior to their determination by flame atomic absorption spectrometry (FAAS). The effect of pH, type, concentration and volume of eluent, sample volume, flow rates of sample and elution solutions, and interfering ions have been investigated. The optimum pH for simultaneous retention of all the metal ions was 9. Eluent for quantitative elution was 20 ml of 2 mol l(-1) HNO(3). The optimum sample and eluent flow rates were found as 4 ml min(-1), and also sample volume was 500 ml, except for Mn (87% recovery). The sorption capacity of the resin was found to be 0.77, 0.41, 0.57, and 0.30 mg g(-1) for Cu(II), Ni(II), Cd(II), and Mn(II), respectively. The preconcentration factor of the method was 200 for Cu(II), 150 for Pb(II), 100 for Cd(II) and Ni(II), and 50 for Mn(II). The recovery values for all of the metal ions were > or = 95% and relative standard deviations (RSDs) were < or = 5.1%. The detection limit values were in the range of 0.03 and 1.19 microg l(-1). The accuracy of the method was confirmed by analysing the certified reference materials (TMDA 54.4 fortified lake water and GBW 07605 tea samples) and the recovery studies. This procedure was applied to the determination of Cu(II), Ni(II), Pb(II), Cd(II) and Mn(II) in waste water and lake water samples.     

Preconcentration of metal ions through chelation on a synthesized resin containing O, O donor atoms for quantitative analysis of environmental and biological samples

Nascent Amberlite XAD-4 has been used as the polymeric support for the synthesis of a stable extractor of metal ions, by incorporating phthalic acid through azo bridging. Elemental analyses and infra-red spectral and thermal studies were carried out for its characterization. The water regain value and hydrogen ion capacity were found to be 12.50 and 5.75 mmol g^?1, respectively. The optimum pH range for the maximum sorption of Ni(II), Mn(II), Cu(II), Zn(II), Cd(II), Cr(III), and Co(II) was observed at pH 5.5–8.0 with the corresponding half-loading time (t _1/2) of 9, 5, 9, 9, 3, 9, and 5 min, respectively. The preconcentration factor for Ni(II), Mn(II), Cu(II), Zn(II), Cd(II), Cr(III), and Co(II) are 190, 190, 190, 180, 180, 160, and 160, with the corresponding limit of preconcentration in the range of 5.25–6.25 μg L^?1. The detection limits, for flame atomic absorption spectrophotometry, were found to be 0.62, 0.60, 0.65, 0.75, 0.72, 0.84, and 0.85 μg L^?1, respectively. Method has been successfully applied to the analysis of water samples, multivitamin formulations, infant food substitutes, hydrogenated oil, and fishes.     

Influences of metal cations on the determination of the alpha-oxocarboxylates as the methyl esters of the O-(2,3,4,5,6-pentafluorobenzyl)oximes by gas chromatography: the importance of accounting for matrix effects

The alpha-oxocarboxylates alpha-ketocarboxylates) and the corresponding alpha-oxoacids (alpha-ketoacids) have been reported as disinfection byproducts of ozonation of potable water supplies. In this analytical method, the oxo moiety is derivatized with O-(2,3,4,5,6-pentafluorobenzyl)oxylamine (PFBOA) to form an oxime which is then extracted into tert-butyl methyl ether. The carboxylic acid moiety is esterified (methylated) with diazomethane. In this study, five analytes were investigated: oxoethanoate (glyoxylate), 2-oxopropanoate (pyruvate), 2-oxobutanoate (2-ketobutyrate), 2-oxopentanoate (2-ketovalerate), and oxopropanedioate (ketomalonate, mesoxalate). The influence of Lewis acid metal cations in the water matrix was evaluated for the gas chromatographic method commonly used for the quantitation of these analytes at concentrations < or = 150 ng mL(-1). Tested metals included Ca(II), Mg(II), Fe(III), Cu(II) and Zn(II). At typical concentrations, calcium, in particular, can have profound impact, especially on oxoethanoate quantitation. Oxopropanoate experiences an increase in recovery in the presence of metal cations. 2-Oxobutanoate and 2-oxopentanoate are the most resistant to these effects, but 2-oxopentanoate shows increased recoveries at higher concentrations when assayed in the presence of calcium ion. Oxopropanedioate generally shows poorer precision and recovery when determined in solutions containing metal ions. This investigation demonstrates the significance of metal effects in the quantitative determination of these analytes and further emphasizes the importance of thorough matrix characterization and careful recovery studies with fortified (spiked) samples and blanks.     

The effect of the presence of trace metals on the oxidation of Sb(III) by hydrogen peroxide in aqueous solution

Despite its importance for understanding the behaviour of antimony in the environment, the oxidation kinetics of Sb(III) with natural oxidants is still not well understood. We have studied the oxidation of Sb(III) by hydrogen peroxide on a time scale of hours in the presence of some trace metals, Cu(II), Mn(II), Zn(II) and Pb(II), under pH and concentration conditions close to natural ones. The effects that these trace metals have on Sb(iii) oxidation by hydrogen peroxide vary. Zn(II) had no catalytic effect at all, but Cu(II), Mn(II) and Pb(II) did, though their effects were not uniform. Cu(II) significantly accelerated the reaction, which remained first-order with respect to Sb(III) at any Cu(II) concentration tested. Pb(II) and Mn(II) also enhanced the reaction rates, but the apparent order of the reaction with respect to Sb(III) changed to two. The trace metal effect observed was concentration dependent for Pb(II). The addition of the hydroxyl radical scavenger 2-propanol suggests that the trace metal catalytic effect observed involves the action of hydroxyl radicals, but that they are not responsible for the oxidation of Sb(III) by H2O2 in the absence of trace metals. The fact that Sb(III) can be oxidized by hydroxyl radicals present in water, even if it is not capable of producing them, has important environmental implications because hydroxyl radicals are known to be abundant in many natural waters such as seawater, humic-rich surface waters or rainwater.     

Chromium speciation in groundwater of a tannery polluted area of Chennai City, India

Chromium speciation in groundwater of a tannery polluted area was investigated for the distribution of chromium species and the influence of redox couples such as Fe(III)/Fe(II) and Mn(IV)/Mn(II). Speciation analysis was carried out by ammonium pyrolidinedithiocarbamate (APDC)–methylisobutylketone (MIBK) procedure. The groundwater samples were analyzed for Cr(III), Cr(VI), and Cr(III)-organic complexes. The APDC could not extract the Cr(III)-organic complexes, but HNO₃ digestion of the groundwater samples released the Cr(III)-organic complexes. The groundwater of the area is relatively oxidizing with redox potential (E _h) and dissolved oxygen (DO) ranged between 65 and 299 mV and 0.25 and 4.65 mg L^???1, respectively. The Fe(II) reduction of Cr(VI) was observed in some wells, but several wells that had Fe(II)/Cr(VI) concentrations more than the stoichiometric ratio (3:1) of the reduction reaction also had appreciable concentration of Cr(VI). This could partly be due to the oxidation of Fe(II) to Fe(III) by DO. It appears that the occurrence of Mn more than the Fe(II) concentration was also responsible for the presence of Cr(VI). Other reasons could be the Fe(II) complexation by organic ligands and the loss of reducing capacity of Fe(II) due to aquifer materials, but could not be established in this study.     

Determination of Pb(II), Zn(II), Cd(II), and Co(II) ions by flame atomic absorption spectrometry in food and water samples after preconcentration by coprecipitation with Mo(VI)-diethyldithiocarbamate

A new, simple, and rapid separation and preconcentration procedure, for determination of Pb(II), Cd(II), Zn(II), and Co(II) ions in environmental real samples, has been developed. The method is based on the combination of coprecipitation of analyte ions by the aid of the Mo(VI)–diethyldithiocarbamate–(Mo(VI)-DDTC) precipitate and flame atomic absorption spectrometric determinations. The effects of experimental conditions like pH of the aqueous solution, amounts of DDTC and Mo(VI), standing time, centrifugation rate and time, sample volume, etc. and also the influences of some foreign ions were investigated in detail on the quantitative recoveries of the analyte ions. The preconcentration factors were found to be 150 for Pb(II), Zn(II) and Co(II), and 200 for Cd(II) ions. The detection limits were in the range of 0.1–2.2 μg L^?1 while the relative standard deviations were found to be lower than 5 % for the studied analyte ions. The accuracy of the method was checked by spiked/recovery tests and the analysis of certified reference material (CRM TMDW-500 Drinking Water). The procedure was successfully applied to seawater and stream water as liquid samples and baby food and dried eggplant as solid samples in order to determine the levels of Pb(II), Cd(II), Zn(II), and Co(II) ions.     

Novel solid-phase extractor based on functionalization of multi-walled carbon nano tubes with 5-aminosalicylic acid for preconcentration of Pb(II) in water samples prior to determination by ICP-OES

New solid-phase extractor (MWCNTs-5-ASA) was synthesized via covalent immobilization of 5-aminsalicylic acid onto multi-walled carbon nanotubes (MWCNs). The success of the functionalization process was confirmed using Fourier transform infrared spectroscopy, scanning electron microscope, and surface coverage determination. Batch experiments were conducted as a function of pH to explore MWCNTs-5-ASA efficiency to extract several metal ions viz., Cr(III), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Pb(II). It was found that Pb(II) exhibits the highest extraction percentage with maximum adsorption capacity 32.75 mg g^?1. Its binding performance was well fitted with Langmuir sorption isotherm. On the other hand, the selective separation and preconcentration of trace Pb(II) under dynamic conditions prior to determination by inductively coupled plasma-optical emission spectrometry was investigated under different parameters. These included the rate of flow and volume of sample solution, in addition to the type of the eluate, its volume and concentration. The effect of a variety of foreign ions on the recovery percentage was also evaluated. Trace Pb(II) ions present in 500 mL aqueous solution adjusted to pH 4.0 were retained on 50 mg of MWCNTs-5-ASA and completely eluted using 4.0 mL of 2 M HNO₃. The limit of detection and the precision of the method were 0.25 ng mL^?1 and 2.8 %, respectively (N?=?5). This methodology has been applied for the determination of Pb(II) in water samples with good results.     

Solid phase extraction of Cd,Pb, Ni,Cu, and Zn in environmental samples on multiwalled carbon nanotubes

A simple and sensitive solid phase extraction (SPE) method on multiwalled carbon nanotubes (MWCNTs) is presented for the determination of cadmium, lead, nickel, copper, and zinc at trace levels combined with flame atomic absorption spectrometry. The effects of parameters like pH, sample volume, sample and eluent flow rates, eluent concentration, and volume and type of eluent on the recovery of trace elements was examined. The metals retained on the nanotube at pH 6.5 as α-benzoin oxime complexes were eluted by 10 mL 2 M HNO₃ in acetone. The influence of matrix ions on the developed method was also evaluated. The preconcentration factor of the method was found to be 50. The detection limits for Cd(II), Pb(II), Ni(II), Cu(II), and Zn(II) were found as 1.7, 5.5, 6.0, 2.3, and 2.4 μg L^?1, respectively. To test the accuracy of the method, the method was applied to TMDA-70 fortified lake water and Spinach 1570A standard reference materials. Addition recovery studies were applied to tap water and cracked wheat samples, and determination of the analyte elements was carried out in some food samples with good results.     

Assessing metal sorption on the marine alga Pilayella littoralis

Increasing interest in the development of biological materials for metal sorption led us to investigate the brown marine alga, Pilayella littoralis, as a biological sorbent. This work focuses on the harvest, preparation and evaluation of P. littoralis from Nahant beaches for use as a metal biosorbent. This biomass was used in batch tests with synthetic solutions. Its metal uptake properties, including metal binding capacity, the pH dependence of metal uptake and the kinetics of metal sorption, were investigated. Most metal sorption occurred within the first 5 min of exposure and the metals were optimally bound to the algae at pH 5.5. The algal binding capacities for Al(III), Cd(II), Co(II), Cr(VI), Cu(II), Fe(III), Ni(II) and Zn(II), were 2,000, 430, 560, 90, 850, 700, 390 and 450 micromol g(-1) of dried biomass, respectively. Metals were desorbed with 0.12 mol l(-1) HCl and determined by inductively coupled plasma atomic emission spectrometry (ICP-AES).     

Water Quality Changes in Chini Lake, Pahang, West Malaysia

A study of the water quality changes of Chini Lake was conducted for 12 months, which began in May 2004 and ended in April 2005. Fifteen sampling stations were selected representing the open water body in the lake. A total of 14 water quality parameters were measured and Malaysian Department of Environment Water Quality Index (DOE-WQI) was calculated and classified according to the Interim National Water Quality Standard, Malaysia (INWQS). The physical and chemical variables were temperature, dissolved oxygen (DO), conductivity, pH, total dissolved solid (TDS), turbidity, chlorophyll-a, biochemical oxygen demand (BOD), chemical oxygen demand (COD), total suspended solid (TSS), ammonia-N, nitrate, phosphate and sulphate. Results show that base on Malaysian WQI, the water in Chini Lake is classified as class II, which is suitable for recreational activities and allows body contact. With respect to the Interim National Water Quality Standard (INWQS), temperature was within the normal range, conductivity, TSS, nitrate, sulphate and TDS are categorized under class I. Parameters for DO, pH, turbidity, BOD, COD and ammonia-N are categorized under class II. Comparison with eutrophic status indicates that chlorophyll-a concentration in the lake was in mesotrophic condition. In general water quality in Chini Lake varied temporally and spatially, and the most affected water quality parameters were TSS, turbidity, chlorophyll-a, sulphate, DO, ammonia-N, pH and conductivity.     

Mercury speciation in plankton from the Cabo Frio Bay,SE - Brazil

Mercury (Hg) is considered a global pollutant, and the scientific community has shown great concern about its toxicity as it may affect the biota of entire systems, through bioaccumulation and bioamplification processes of its organic form, methylmercury (MeHg), along food web. However, few research studies deal with bioaccumulation of Hg from marine primary producers and the first-order consumers. So, this study aims to determine Hg distribution and concentration levels in phytoplankton and zooplankton in the Cabo Frio Bay, Brazil, a site influenced by coastal upwelling. The results from Hg speciation analyses show that inorganic mercury Hg(II) was the predominant specie in plankton from this bay. The annual Hg species distribution in plankton shown mean concentration of 2.00?±?1.28 ng Hg(II)?g^?1 and 0.15?±?0.08 ng MeHg g^?1 wet weight (phytoplankton) and 2.5?±?2.03 ng Hg(II)?g^?1 and 0.25?±?0.09 ng MeHg g^?1 wet weight (zooplankton). Therefore, upwelling zones should be considered in the Hg biogeochemical cycle models as a process that enhances Hg(II) bioaccumulation in plankton, raising its bioavailability and shelf deposition.     

Simultaneous measurements of radon and thoron,and their progeny levels in dwellings on anticlinal structures of Assam,India

Radon and thoron, and their progeny concentrations along with equilibrium factors for gas progeny and radiological risks to the residents have been measured in dwellings of Digboi and Mashimpur areas located on anticlines during the winter season. In this present investigation, twin-cup dosemeters fitted with LR-115 (II) nuclear detectors have been employed. The present work has shown that there exist considerable house-to-house variations in values with maximum values in mud houses and minimum values in assam type (AT) houses. It has been found that mean (and geometric standard deviations (GSD)) radon concentrations are 83.8 (1.3), 113.5 (1.1) and 157.2 (1.2) Bq m^?3 in AT, reinforced cement concrete (RCC) and mud houses in Digboi area and 63.0 (1.1), 87.1 (1.4) and 182.1 (1.2) Bq m^?3 in AT, RCC and mud houses in Mashimpur area, respectively. The overall mean radon concentrations in Digboi and Mashimpur are estimated to be 114.4 (1.4) and 100.0 (1.7) Bq m^?3. The mean radon concentrations are found to be less than the lower reference level of 200 Bq m^?3 of the International Commission on Radiological Protection (ICRP 2007). The thoron concentrations in Digboi area are estimated to be 31.1 (1.3), 50.8 (1.4) and 67.0 (1.6) Bq m^?3 in AT, RCC and mud houses, respectively, whereas in Mashimpur area, the thoron concentrations are estimated to be 26.4 (1.3), 44.4 (1.3) and 77.7 (1.3) Bq m^?3 in AT, RCC and mud houses, respectively. The mean annual effective doses in Digboi area are found to be 1.9 (1.3), 2.7 (1.2) and 4.1 (1.4) mSv y^?1 in AT, RCC and mud houses, respectively, while in the case of Mashimpur area, the mean annual effective doses are found to be 1.5 (1.4), 2.2 (1.2) and 4.9 (1.3) mSv y^?1 in AT, RCC and mud houses, respectively. Nevertheless, the obtained results are much lower than the upper reference level of 10 mSv (ICRP 2007).     

Characterization and Identification of the Sources of Chromium, Zinc, Lead, Cadmium, Nickel, Manganese and Iron in Pm10 Particulates at the Two Sites of Kolkata, India

Monitoring of ambient PM₁₀ (particulate matter which passes through a size selective impactor inlet with a 50% efficiency cut-off at 10 μm aerodynamic diameter) has been done at residential (Kasba) and industrial (Cossipore) sites of an urban region of Kolkata during November 2003 to November 2004. These sites were selected depending on the dominant anthropogenic activities. Metal constituents of atmospheric PM₁₀ deposited on glass fibre filter paper were estimated using Inductively Coupled Plasma Atomic Emission Spectrometer (ICP-AES). Chromium (Cr), zinc (Zn), lead (Pb), cadmium (Cd), nickel (Ni), manganese (Mn) and iron (Fe) are the seven toxic trace metals quantified from the measured PM₁₀ concentrations. The 24 h average concentrations of Cr, Zn, Pb, Cd, Ni, Mn and Fe from ninety PM₁₀ particulate samples of Kolkata were found to be 6.9, 506.1, 79.1, 3.3, 7.4, 2.4 and 103.6 ng/m³, respectively. The 24 h average PM₁₀ concentration exceeded national ambient air quality standard (NAAQS) as specified by central pollution control board, India at both residential (Kasba) and industrial (Cossipore) areas with mean concentration of 140.1 and 196.6 μg/m³, respectively. A simultaneous meteorology study was performed to assess the influence of air masses by wind speed, wind direction, rainfall, relative humidity and temperature. The measured toxic trace metals generally showed inverse relationship with wind speed, relative humidity and temperature. Factor analysis, a receptor modeling technique has been used for identification of the possible sources contributing to the PM₁₀. Varimax rotated factor analysis identified four possible sources of measured trace metals comprising solid waste dumping, vehicular traffic with the influence of road dust, road dust and soil dust at residential site (Kasba), while vehicular traffic with the influence of soil dust, road dust, galvanizing and electroplating industry, and tanning industry at industrial site (Cossipore).     

Adsorption and removal of oxo-anions of arsenic and selenium on the zirconium(IV) loaded polymer resin functionalized with diethylenetriamine-N,N,N',N'-polyacetic acid

A polymer adsorbent in which a Zr(IV)-edta complex analogue is immobilized has been prepared and applied to the removal of oxo-anions of As(III), As(V) and Se(IV). Effective retention of these anions has been demonstrated with the proposed polymer complex system. The adsorption mechanism of oxo-anions onto the Zr(IV)-chelated polymer complex has been investigated using Zr(IV)-edta as the model compound. The formation of mixed complexes with oxo-anions has been exemplified by the isolation of the carbonato complex K2[Zr(CO3)edta].3H2O, the structure of which has been confirmed by X-ray crystallography. NMR study suggests that oxo-anions that form weak or moderate conjugate acids, including those of As(III), As(V) and Se(IV), can form mixed complexes with Zr(IV)-edta using the unsaturated coordination site. However, oxo-anions of strong conjugate acids did not show any appreciable interaction with this complex. According to these observations, retention of oxo-anions on the Zr(IV)-chelated polymer complex has been interpreted by a ligand substitution reaction. The adsorption characteristics of As(III), As(V) and Se(IV) on the Zr(IV)-loaded resin have been examined with respect to the equilibrium adsorption, percentage extraction and the effect of co-existing ions. The adsorption and desorption cycles of the oxo-anions have been demonstrated using a column packed with the proposed resin without any loss of column performance, which indicates the possibility for repeated use.     

Retention capacities of several bryophytes for Hg(II) with special reference to the elevation and morphology of moss growth

Hg(II) Retention capacities of nine bryophyte species, collected from Jinfo Mountains (JFM) in Chongqing, China, had been investigated with special reference to the effect of morphology and elevation of moss growth. Results indicated that adsorption capacities of bryophytes for Hg(II) became stronger with the increase of multi-branches and leafy-shoots, as well as the elevation of moss growth, which was observed both in adsorption isotherm and adsorption kinetics experiments. Contrarily, the desorption kinetics showed a decrease tendency with the increase of multi-branches and leafy-shoots and the elevation of moss growth. The results demonstrated that bryophytes with higher multi-branches and leafy-shoots and higher growth elevation had a stronger adsorption capacity and a weaker desorption tendency, and therefore had a stronger retention capacity to Hg(II). The results disclosed the different relative sensitivity and retention capacity of mosses to pollution resulting from heavy metals, due to the differences in growth elevation and morphology. These should be considered when bryophytes were chosen as a tool for biomonitoring materials to environmental pollution, especially caused by Hg(II).     

Silica glass modified with flavonoid derivatives for preconcentration of some toxic metal ions in water samples and their determination with ICP-MS

Quercetin (3,3^′,4^′,5,7-pentahydroxyflavone) chemically bonded through pyran rearrangement on modified controlled pore silica glass (QCPSG) with a capacity 0.213 mmol/g was used for solid phase extraction of some toxic metal and metalloid ions. The newly designed QCPSG quantitatively sorbs As(V), Cd(II), Hg(II), and Pb(II) at the pH range 7.5–8.5 after 10 min of stirring. HCl (1 mol L^???1) instantaneously elutes all the metal ions. The sorption capacity of the ion collector is 0.42, 0.46, 0.53, and 0.49 mmol g^???1 for As(V), Cd(II), Hg(II), and Pb(II), respectively, whereas the preconcentration factor is 200. The effect of NaCl, Na₂SO₄, NaF, NaBr, Na₃PO₄, and other interfering salts on the sorption of metal ions (50 μg L^???1) was reported. Analytical detection limits of As(V), Cd(II), Hg(II), and Pb(II) were 4.18, 2.44, 15.86, and 25.00 pg mL^???1, respectively. QCPSG was used in the separation of the investigated metal ions from some natural water samples collected from diverse origins followed by determination by inductively coupled plasma–mass spectrometry. The data were compared with those obtained by the standard methods of determination using atomic absorption (hydride generation, HGAAS and after solvent extraction with ammonium pyrolidine dithiocarbamate/methyl isobutyl ketone). The suggested solid phase extraction method was found accurate with no random error.     

The determination of cobalt(II) at DME using catalytic hydrogen current technique in various water samples, agricultural materials and pharmaceuticals

Two novel and facile ligands ammonium piperidine dithiocarbamate (Amm Pip-DTC) and ammonium morpholine dithiocarbamate (Amm Mor-DTC) were synthesized for the development of rapid and cost effective catalytic hydrogen current technique to analyze cobalt(II) in the presence of NH(4)Cl-NH(4)OH at pH 7.8 and 8.4 with Amm Pip-DTC and Amm Mor-DTC. These ligands produce catalytic hydrogen currents with Co(II) at peak potentials -1.24 V and -1.44 V vs. SCE respectively. Quantitative experimental conditions are developed by studying effect of pH, supporting electrolyte (NH(4)Cl), ligand and metal ion concentrations and effect of adverse ions on peak height to improve the sensitivity, selectivity and detection limits of the catalytic hydrogen current technique and compared it in terms of Student's t test and variance ratio f test with differential pulse polarographic (DPP) method. The developed technique was applied for the analysis of cobalt(II) in various water samples, agricultural materials and pharmaceuticals and the results obtained are in good agreement with the DPP data.     

Effects of bridge construction on songbirds and small mammals at Blennerhassett Island, Ohio River, USA

Construction of man-made objects such as roads and bridges may have impacts on wildlife depending on species or location. We investigated songbirds and small mammals along the Ohio River, WV, USA at a new bridge both before and after construction and at a bridge crossing that was present throughout the study. Comparisons were made at each site over three time periods (1985–1987 [Phase I] and 1998–2000 [Phase II] [pre-construction], 2007–2009 [Phase III] [post-construction]) and at three distances (0, 100, 300 m) from the bridge or proposed bridge location. Overall, 70 songbirds and 10 small mammals were detected during the study. Cliff swallows (Petrochelidon pyrrhonota) and rock pigeons (Columba livia) showed high affinity for bridges (P?<?0.05). Combined small mammal abundances increased between Phases I and II (P?<?0.05), but did not differ between Phases II and III (P?>?0.05). Species richness and diversity for songbirds and small mammals did not differ before and after bridge construction (P?>?0.05). We found that most species sampled did not respond to the bridge crossing, and believe that the bridge is not causing any measurable negative density impacts to the species we investigated. The new bridge does provide habitat for exotic rock pigeons that are adjusted to man-made structures for nesting.     

Biosorption properties of Cd(II), Pb(II), and Cu(II) of extracellular polymeric substances (EPS) extracted from Aspergillus fumigatus and determined by polarographic method

Extracellular polymeric substances (EPS) were extracted from Aspergillus fumigatus using cationic exchange resin technique. The EPS were mainly composed of polysaccharide and low quantities of protein and nucleic acid. Biosorption of Cd(II), Pb(II), and Cu(II) of EPS was investigated as a function of pH using differential pulse polarography and the Ruzic model. Results showed that the EPS biosorption capacity determined using either the direct titration curves i?=?f(C _M) or the method proposed by Ruzic (Analytica Chimica Acta 140:99–113, 1982) were coincident. Cu(II) had the highest affinity with EPS followed by Pb(II) and Cd(II). The total number of binding sites for Cu(II) and Cd(II) increased with pH in the range of 4.0–7.0. Similar trend was observed for Pb(II) at pH?4.0–5.0, while precipitates were observed at pH?6.0 and 7.0. The conditional binding constants of these three metals displayed low levels of fluctuation with pH and ranged from 4.02?±?0.02 to 5.54?±?0.05.