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.     

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.     

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.     

Sources of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and coplanar polychlorinated biphenyls (Co-PCBs), and their bioaccumulation through the marine food web in Sendai Bay,Japan

The concentrations of PCDD/F and Co-PCB congeners in seawater, sediment, Pacific oyster, Japanese anchovy, marbled sole, and Japanese flounder samples from Sendai Bay, Japan, were analyzed. The compositions of total PCDD/F and total Co-PCB concentrations in sediment and Pacific oyster reflected that in seawater--the compositions of total PCDD, PCDF, and Co-PCB concentrations were approximately 60, 10, and 30%, respectively. The compositions in Japanese anchovy, marbled sole, and Japanese flounder were different from those in seawater and sediment-the ratio of total Co-PCB concentration to total PCDD/F plus Co-PCB concentrations in Japanese anchovy, marbled sole, and Japanese flounder was above 90%. Tetrachlorinated PCDDs (T4CDDs), such as 1,3,6,8- and 1,3,7,9-T4CDD, were the predominant congeners in seawater and sediment; the total T4CDD concentrations in seawater and sediment were approximately 46 and 48% of the total PCDD concentration. Furthermore, shipments of the herbicide 1,3,5-trichloro-2-(4-nitrophenoxy)benzene to Miyagi Prefecture, the so-called granary of Japan, were the highest in Japan over the last 12 years. The major sources of PCDD/Fs and Co-PCBs in Sendai Bay, which is in Miyagi Prefecture, are impurities in chlorinated herbicides. The order of concentration of PCDD/Fs was Pacific oyster > Japanese anchovy = marbled sole > Japanese flounder; the concentration in Japanese flounder, which is a higher-trophic-level consumer in the marine food web, was lower than that in shellfish (Pacific oyster) and Japanese anchovy, which are lower-trophic-level consumers. The order of concentration of Co-PCBs was Pacific oyster < Japanese anchovy = marbled sole < Japanese flounder; the concentrations in the higher-trophic-level consumers were higher than the concentrations in the lower-trophic-level consumers. Different PCDD/F congeners tended to bioaccumulate in different organisms. On the other hand, all species of Co-PCB congener tended to bioaccumulate in all organisms.     

Comparison of arsenic, cadmium, chromium, lead, manganese, mercury and selenium in feathers in bald eagle (Haliaeetus leucocephalus), and comparison with common eider (Somateria mollissima), glaucous-winged gull (Larus glaucescens), pigeon guillemot (Cepphus columba), and tufted puffin (Fratercula cirrhata) from the Aleutian Chain of Alaska

There is an abundance of field data for levels of metals from a range of places, but relatively few from the North Pacific Ocean and Bering Sea. In this paper we examine the levels of arsenic, cadmium, chromium, lead, manganese, mercury and selenium in feathers from common eiders (Somateria mollissima), glaucous-winged gulls (Larus glaucescens), pigeon guillemots (Cepphus columba), tufted puffins (Fratercula cirrhata) and bald eagles (Haliaeetus leucocephalus) from the Aleutian Chain of Alaska. Our primary objective was to test the hypothesis that there are no trophic levels relationships for arsenic, cadmium, chromium, lead, manganese, mercury and selenium among these five species of birds breeding in the marine environment of the Aleutians. There were significant interspecific differences in all metal levels. As predicted bald eagles had the highest levels of arsenic, chromium, lead, and manganese, but puffins had the highest levels of selenium, and pigeon guillemot had higher levels of mercury than eagles (although the differences were not significant). Common eiders, at the lowest trophic level had the lowest levels of some metals (chromium, mercury and selenium). However, eiders had higher levels than all other species (except eagles) for arsenic, cadmium, lead, and manganese. Levels of lead were higher in breast than in wing feathers of bald eagles. Except for lead, there were no significant differences in metal levels in feathers of bald eagles nesting on Adak and Amchitka Island; lead was higher on Adak than Amchitka. Eagle chicks tended to have lower levels of manganese than older eagles.     

Emissions of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), and dioxin-like polychlorinated biphenyls (PCBs) to air from waste incinerators and high thermal processes in India

This study investigated dioxins and dioxin-like polychlorinated biphenyls in gasses emitted from waste incinerators and thermal processes in central and western parts of India. The concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDDs/DFs) ranged from 0.0070 to 26.8140 ng toxicity equivalent (TEQ)/Nm³, and those of dioxin-like polychlorinated biphenyls (PCBs) ranged from 0.0001?×?10^?1 to 0.0295 ng TEQ/Nm³. The characteristics of mean PCDD/F I-TEQ concentration and congener profiles were studied over all the samples of air. In particular, a pattern consisting of a low proportion of dioxin-like PCBs and high proportion of PCDDs/DFs was common for all the samples from incinerators and high-temperature processes.     

Effect of temperature on single and competitive adsorptions of Cu(II) and Zn(II) onto natural clays

This study conducted a combined adsorption-sequential extractionanalysis (CASA), by which five phases (i.e., exchangeable, carbonate, Mn-Oxide, organic, and Fe-Oxide phases) of adsorbed heavy metals were analyzed, to investigate temperature effects on single and competitive adsorptions of Zn(II) and Cu(II) ontonatural clays. In the case of single adsorption of Zn, the exchangeable phase adsorption decreased from 65 to 40%, but thecarbonate phase adsorption increased from 30 to 40%, with an increase in temperature from 15 to 55 °C. However, in itscompetitive adsorption with Cu, Zn was mostly present in the exchangeable phase (over 90%), and with an increase in temperature, the exchangeable phase adsorption decreased only 10%. In the case of Cu, over 50% among the total amount of adsorption was present in the carbonate phase in both cases ofsingle and competitive adsorptions. The carbonate phaseadsorption of Cu increased from 56 to 61% and from 60 to 66% in single and competitive adsorptions, respectively, with atemperature increase. These results show that in the case of Zn,the major mechanism of retention in natural clay soils might beexchangeable phase adsorption, especially in the case of competitive adsorption with Cu. However, in the case of Cu, the major mechanism might be carbonate phase adsorption, which is known to be a more immobile phase than exchangeable phase adsorption. It seems that the adsorption of Zn and Cu onto natural clays is an endothermic reaction, which represents thatthe adsorption equilibrium constants and capacities increase with a temperature increase, with the exception of exchangeablephase adsorption.     

The Bear Brook Watershed, Maine (BBWM), USA

The Bear Brook Watershed Manipulation project in Maine is a paired calibrated watershed study funded by the U. S. EPA. The research program is evaluating whole ecosystem response to elevated inputs of acidifying chemicals. The project consists of a 2.5 year calibration period (1987-1989), nine years of chemical additions of (NH4)2SO4 (15N- and 34S-enriched for several years) to West Bear watershed (1989-1998), followed by a recovery period. The other watershed, East Bear, serves as a reference. Dosing is in six equal treatments/yr of 1800 eq SO4 and NH4/ha/yr, a 200% increase over 1988 loading (wet plus dry) for SO4 and 300% for N (wet NO3 + NH4). The experimental and reference watersheds are forested with mixed hard- and softwoods, and have thin acidic soils, areas of 10.2 and 10.7 ha, and relief of 210 m. Thin till of variable composition is underlain by metasedimentary pelitic rocks and calc-silicate gneiss intruded by granite dikes and sills. For the period 1987-1995, precipitation averaged 1.4 m/yr, had a mean pH of 4.5, with SO4, NO3, and NH4 concentrations of 26, 14, and 7 eq/L, respectively. The nearly perrenial streams draining each watershed have discharges ranging from 0 (East Bear stops flowing for one to two months per year) to 150 L/sec. Prior to manipulation, East Bear and West Bear had a volume weighted annual mean pH of approximately 5.4, alkalinity = 0 to 4 eq/L, total base cations = 184 eq/L (sea-salt corrected = 118 eq/L), and SO4 = 100 to 111 eq/L. Nitrate ranged from 0 to 30 eq/L with an annual mean of 6 to 25 eq/L; dissolved organic carbon (DOC) ranged from 1 to 7 mg/L but was typically less than 3. Episodic acidification occurred at high discharge and was caused by dilution of cations, slightly increased DOC, significantly higher NO3, and the sea-salt effect. Depressions in pH were accompanied by increases in inorganic Al. The West Bear catchment responded to the chemical additions with increased export of base cations, Al, SO4, NO3, and decreased pH, ANC, and DOC. Silica remained relatively constant. Neutralization of the acidifying chemicals occurred dominantly by cation desorption and mobilization of Al.     

Residues of organochlorine compounds in starlings (Sturnus vulgaris), 1979

Starlings were collected for the National Pesticides Monitoring Program from 112 sites throughout the contiguous United States and analyzed for organochlorine compounds. Starling samples from 14 sites had greater than 1.0 ppm DDE residues with the highest DDE level being 15.8 ppm in a sample taken near Roswell, New Mexico. The occurrence of PCBs and chlordane isomers increased since the 1976 collection, but DDT, DDE, and dieldrin occurrence decreased. DDE and dieldrin levels decreased since the 1976 collection, but the level of PCBs has increased.     

Fast simultaneous determination of traces of Cu(II) and Co(II) in soils and sediments with the luminol/perborate chemiluminescent system

A flow injection analysis method based on ion chromatography and luminol chemiluminescence detection was used for the simultaneous determination of copper (II) and cobalt (II) trace levels in soils and sediments following microwave-assisted acid digestion. Detection was based on chemiluminescence (CL) of the luminol–perborate system in an alkaline medium, which is catalyzed by both transition metals. The concentration and pH of the eluent (oxalic acid) was found to affect CL intensities and retention times, both of which were inversely proportional to the oxalic acid concentration. The calibration curves for both metal ions were linear and allowed a limit of detection of 0.003 μg l^?1 for cobalt (II) and 0.014 μg l^?1 for cooper (II) to be calculated. The proposed method was successfully used to determine both metal ions in certified reference materials of stream and river sediments and soil samples. Based on the results, the determination is free of interferences from the usual concomitant ions.     

Polycyclic aromatic hydrocarbons (PAHs) in starfish body and bottom sediments in Mohang Harbor (Taean), South Korea

The concentrations of 27 polycyclic aromatic hydrocarbons (PAHs) were determined in bottom sediments and starfish from Mohang Harbor (MH) in Taean peninsula, South Korea. In December 2007, crude oil washed ashore from the M/V Hebei Spirit and was subsequently cleaned up within a few months of the incident. The ecological risk, bioaccumulation factor (BAF), and composition of the 27 PAHs were examined. The PAH concentrations in the bottom sediment ranged from 24 to 366 μg/kg dried weight, and the ecological risk was determined as minimal (mERL-Q?<?1). Total PAH concentrations in Asterina pectinifera (inside seawall) and Asterias amurensis (outside seawall) were 1,226 and 1,477 μg/kg dry weight (d.w.), respectively. The total BAFs (∑BAF) for A. amurensis was 3.8 times higher than that of A. pectinifera, and the PAH concentrations of 5–6 log K _OW were highest in the two starfish species. Further, PAH fingerprint analysis (nine alkyl-substituted PAHs fraction, low molecular weight (LMW)/high molecular weight (HMW), Phe/Ant, and Flu/Pyr), and principal component analysis (PCA) based on three crude oil samples from the M/V Hebei Spirit showed no remaining influence of crude oil.     

Streamflow variability and hydroclimatic change at the Bear Brook Watershed in Maine (BBWM), USA

Seasonal variations in streamflow and the associated hydrologic extremes impart significant temporal structure to watershed-scale chemical fluxes. Consequently, a careful characterization of the episodic-to-seasonal and longer-term streamflow variations is a first step toward developing a comprehensive view of the temporal dynamics of watershed processes in a changing climate. Here we analyze a nearly two-decade-long streamflow record for the East Bear subwatershed within the Bear Brook Watershed in Maine (BBWM) (USA) to understand the envelope of streamflow variability by season, with a particular focus on the high flow events that have a disproportionately large impact on the biogeochemical processes and fluxes. Interannual and longer-term variations in a number of derived statistical metrics of hydrologic variability are examined. Our analysis shows substantial interannual and longer-term variability in seasonal flow volumes and peak flows. Furthermore, a long, unimpaired streamflow record for the Narraguagus River (a proximate watershed to the BBWM) is examined with a view to understand the relative coherence in hydrologic variability, as well as quantifying the decadal and longer-term hydrologic variations in this region. We find that the streamflow variability in the two watersheds shows similarity in all seasons. A moving window analysis to assess the changing flood potential over time indicates upward trends in the recent decades. Spring season (March–May) flood estimates show a near-monotonic trend over the 1949–2008 record. Finally, empirical relationships between streamflow and large-scale atmospheric circulation patterns highlight the regional and global climatic drivers of hydrologic extremes in this region, including impacts from remnants of Atlantic hurricanes.     

Preliminary screening of polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCDD) and tetrabromobisphenol A (TBBPA) flame retardants in landfill leachate

The occurrence of selected brominated flame retardants, including nine polybrominated diphenyl ether (PBDE) congeners, hexabromocyclododecane (HBCDD) and tetrabromobisphenol A (TBBPA) in leachate samples from eight landfill sites in South Africa, were investigated. In addition, the possible influences of dissolved organic carbon on their levels were also evaluated. Filtered leachate samples were subjected to solid-phase extraction to isolate the various target compounds. PBDEs with six bromine substituents and above, as well as α-HBCDD, β-HBCDD and TBBPA, were generally found below the detection limit. However, the mean value of the total lower PBDE congeners ranged between 0.04 and 0.48 μg L^?1, and the concentrations of γ-HBCDD ranged from not detectable (ND) to 0.05 μg L^?1. No significant correlation was observed between the target compounds and dissolved organic carbon, although weak to moderate correlations were mostly observed for the lower PBDEs.     

Occurrence of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in Lake Maggiore (Italy and Switzerland)

Samples of air (gas and particulate phases), bulk deposition, aquatic settling material and sediments were collected in Lake Maggiore (LM) in order to determine their content of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs). Air (gas and particulate phases) concentrations were 0.5 pg m(-3), 80 pg m(-3), 13 pg m(-3) and 106 pg m(-3) for SigmaPCDD/Fs, SigmaPCBs, Sigma dioxin-like PCBs (DL-PCBs) and SigmaPBDEs, respectively. Deposition fluxes ranged from 0.7 ng m(-2) d(-1) for SigmaPCDD/Fs to 32 ng m(-2) d(-1) for SigmaPCBs. Aquatic settling material presented concentrations of 0.4 ng g(-1) dry weight (dw) for SigmaPCDD/Fs, 13 ng g(-1) dw for SigmaPCB, 3.4 ng g(-1) dw for SigmaDL-PCBs and 5.7 ng g(-1) dw for SigmaPBDEs. Mean sediment concentrations were 0.4 ng g(-1) dw for SigmaPCDD/Fs, 11 ng g(-1) dw for SigmaPCB, 3 ng g(-1) dw for SigmaDL-PCBs and 5.1 ng g(-1) dw for SigmaPBDEs. Similar PCDD/F and DL-PCB congener patterns in all the environmental compartments of LM point to an important, if not dominant, contribution of atmospheric deposition as source of these pollutants into LM. In contrast, PBDE congener distribution was not similar in the different environmental compartments. BDE 47 dominated air and settling material, while BDE 209 was the predominant congener in the bulk atmospheric deposition. Moreover, sediments showed two distinct PBDE congener profiles. Lower PBDE concentrated sediments were dominated by congeners 47 and 99, while BDE 209 dominated in higher PBDE concentrated samples. This suggests the influence of local sources as well as atmospheric input of PBDEs into LM.     

Environmental Specimen Bank in Ehime University (es-BANK), Japan for global monitoring

During the last 40 years, The Center for Marine Environmental Studies (CMES), Ehime University collected a variety of environmental and biological material comprising about 1000 species and 100,000 samples from many developing and developed countries and also open seas and oceans all over the world. They were categorically archived, catalogued and stocked in our Environment Specimen Bank (es-BANK) facility equipped with a -25 degrees C cold room. We have already exchanged specimens with many scientific institutions and are also eager to widen our collaboration with other specimen banks. In our survey using the air, water, wildlife and human samples, we found that the major emission sources for the industrial chemicals like polychlorinated biphenyls (PCBs) are in the developed nations while those of organochlorine (OC) pesticides like dichlorodiphenyltrichloroethane and its metabolites (DDTs), hexachlorocyclohexane isomers (HCHs), etc. are located in developing countries. However, significant emission of modern environmental contaminants such as polybrominated diphenyl ethers (PBDEs) also seems to occur predominantly in countries with high economic growth rates. Apart from the modern incinerators and other industrial installations in developed nations, the compounds, like dioxins and related compounds (DRCs), were also found to be released in significant levels from the municipal solid waste dumping sites of developing countries. By evaluating the distribution patterns of various persistent toxic substances (PTSs) in our studies, we could conclude that DRCs and DDTs are regional contaminants, while PCBs, PBDEs, HCHs and hexachlorobenzene (HCB) are global contaminants. We also found that the pollution by PBDEs has been increasing in the last two decades while that of the legacy OCs has been decreasing.     

Cytotoxicity and genotoxicity of Guaribas river water (Piauí, Brazil), influenced by anthropogenic action

In general, tropical rivers have a great impact on human activities. Bioaccumulation of toxins is a worldwide problem nowadays and has been, historically, overlooked by the supervisory authorities. This study evaluated cytogenotoxic effects of Guaribas river (a Brazilian river) water during dry and rainy seasons of 2014 by using the Allium cepa test system. The toxicogenetic variables, including root growth, mitotic index, and chromosomal aberrations, were analyzed in meristematic cells of A. cepa exposed to water samples taken from the up-, within, and downstream of the city Picos (state: Piauí). The physical-chemical parameters were also analyzed to explain water quality and possible anthropogenic action. Additionally, the presence of heavy metals was also analyzed to explain water quality and possible damaging effects on eukaryotic cells. The results suggest that the river water exerted cytotoxic, mutagenic, and genotoxic effects, regardless of the seasons. In addition, Guaribas river presented physico-chemical values outside the Brazilian laws, which can be a characteristic of human pollution (domestic sewage, industrial, and local agriculture). The genetic damage was positively correlated with higher levels of heavy metals. The pollution of the Guaribas river water may link to the chemical contamination, including the action of heavy metals and their impacts on genetic instability in the aquatic ecosystem. In conclusion, necessary steps should be taken into account for further toxicogenetic studies of the Guaribas river water, as it has an influence in human health of the same region of Brazil.